[Title 40 CFR ]
[Code of Federal Regulations (annual edition) - July 1, 2016 Edition]
[From the U.S. Government Publishing Office]

[[Page i]]

Title 40

Protection of Environment

________________________

Part 60 (Appendices)

Revised as of July 1, 2016

Containing a codification of documents of general
applicability and future effect

As of July 1, 2016
Published by the Office of the Federal Register
National Archives and Records Administration as a
Special Edition of the Federal Register

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Table of Contents

Page
Explanation................................................. v

Title 40:
Chapter I--Environmental Protection Agency
(Continued) 3
Finding Aids:
Table of CFR Titles and Chapters........................ 829
Alphabetical List of Agencies Appearing in the CFR...... 849
List of CFR sections Affected........................... 859

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----------------------------

Cite this Code: CFR
To cite the regulations in
this volume use title,
part and appendix letter.
Thus, 40 CFR 60,
appendices refers to title
40, part 60, appendix A.

----------------------------

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EXPLANATION

The Code of Federal Regulations is a codification of the general and
permanent rules published in the Federal Register by the Executive
departments and agencies of the Federal Government. The Code is divided
into 50 titles which represent broad areas subject to Federal
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name of the issuing agency. Each chapter is further subdivided into
parts covering specific regulatory areas.
Each volume of the Code is revised at least once each calendar year
and issued on a quarterly basis approximately as follows:

Title 1 through Title 16.................................as of January 1
Title 17 through Title 27..................................as of April 1
Title 28 through Title 41...................................as of July 1
Title 42 through Title 50................................as of October 1

The appropriate revision date is printed on the cover of each
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LEGAL STATUS

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HOW TO USE THE CODE OF FEDERAL REGULATIONS

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Federal agencies to display an OMB control number with their information
collection request.

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Many agencies have begun publishing numerous OMB control numbers as
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(a) The incorporation will substantially reduce the volume of
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(b) The matter incorporated is in fact available to the extent
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(c) The incorporating document is drafted and submitted for
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this volume.

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Oliver A. Potts,
Director,
Office of the Federal Register.
July 1, 2016.

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THIS TITLE

Title 40--Protection of Environment is composed of thirty-seven
volumes. The parts in these volumes are arranged in the following order:
Parts 1-49, parts 50-51, part 52 (52.01-52.1018), part 52 (52.1019-
52.2019), part 52 (52.2020-end of part 52), parts 53-59, part 60 (60.1-
60.499) , part 60 (60.500-end of part 60, sections), part 60
(Appendices), parts 61-62, part 63 (63.1-63.599), part 63 (63.600-
63.1199), part 63 (63.1200-63.1439), part 63 (63.1440-63.6175), part 63
(63.6580-63.8830), part 63 (63.8980-end of part 63), parts 64-71, parts
72-79, part 80, part 81, parts 82-86, parts 87-95, parts 96-99, parts
100-135, parts 136-149, parts 150-189, parts 190-259, parts 260-265,
parts 266-299, parts 300-399, parts 400-424, parts 425-699, parts 700-
722, parts 723-789, parts 790-999, parts 1000-1059, and parts 1060 to
end. The contents of these volumes represent all current regulations
codified under this title of the CFR as of July 1, 2016.

Chapter I--Environmental Protection Agency appears in all thirty-
seven volumes. Regulations issued by the Council on Environmental
Quality, including an Index to Parts 1500 through 1508, appear in the
volume containing parts 1060 to end. The OMB control numbers for title
40 appear in Sec. 9.1 of this chapter.

For this volume, Ann Worley was Chief Editor. The Code of Federal
Regulations publication program is under the direction of John Hyrum
Martinez, assisted by Stephen J. Frattini.

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TITLE 40--PROTECTION OF ENVIRONMENT

(This book contains part 60, appendices)

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Part

chapter i--Environmental Protection Agency (Continued)...... 60

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CHAPTER I--ENVIRONMENTAL PROTECTION AGENCY (CONTINUED)

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Editorial Note: Nomenclature changes to chapter I appear at 65 FR
47324, 47325, Aug. 2, 2000.

SUBCHAPTER C--AIR PROGRAMS (CONTINUED)
Part Page
60 Part 60--Standards of performance for new
stationary sources (Continued).......... 5

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SUBCHAPTER C_AIR PROGRAMS (CONTINUED)

PART 60_STANDARDS OF PERFORMANCE FOR NEW STATIONARY SOURCES
(CONTINUED)--Table of Contents

App.

Appendix A-1 to Part 60--Test Methods 1 through 2F
Appendix A-2 to Part 60--Test Methods 2G through 3C
Appendix A-3 to Part 60--Test Methods 4 through 5I
Appendix A-4 to Part 60--Test Methods 6 through 10B
Appendix A-5 to Part 60--Test Methods 11 through 15A
Appendix A-6 to Part 60--Test Methods 16 through 18
Appendix A-7 to Part 60--Test Methods 19 through 25E
Appendix A-8 to Part 60--Test Methods 26 through 29
Appendix B to Part 60--Performance Specifications
Appendix C to Part 60--Determination of Emission Rate Change
Appendix D to Part 60--Required Emission Inventory Information
Appendix E to Part 60 [Reserved]
Appendix F to Part 60--Quality Assurance Procedures
Appendix G to Part 60--Provisions for an Alternative Method of
Demonstrating Compliance with 40 CFR 60.43 for the Newton
Power Station of Central Illinois Public Service Company
Appendix H to Part 60 [Reserved]
Appendix I to Part 60--Owner's Manuals and Temporary Labels for Wood
Heaters Subject to Subparts AAA and QQQQ of Part 60

Authority: 42 U.S.C. 7401-7601.

Source: 36 FR 24877, Dec. 23, 1971, unless otherwise noted.

Sec. Appendix A-1 to Part 60--Test Methods 1 through 2F

Method 1--Sample and velocity traverses for stationary sources
Method 1A--Sample and velocity traverses for stationary sources with
small stacks or ducts
Method 2--Determination of stack gas velocity and volumetric flow rate
(Type S pitot tube)
Method 2A--Direct measurement of gas volume through pipes and small
ducts
Method 2B--Determination of exhaust gas volume flow rate from gasoline
vapor incinerators
Method 2C--Determination of gas velocity and volumetric flow rate in
small stacks or ducts (standard pitot tube)
Method 2D--Measurement of gas volume flow rates in small pipes and ducts
Method 2E--Determination of landfill gas production flow rate
Method 2F--Determination of Stack Gas Velocity and Volumetric Flow Rate
With Three-Dimensional Probes
The test methods in this appendix are referred to in Sec. 60.8
(Performance Tests) and Sec. 60.11 (Compliance With Standards and
Maintenance Requirements) of 40 CFR part 60, subpart A (General
Provisions). Specific uses of these test methods are described in the
standards of performance contained in the subparts, beginning with
Subpart D.
Within each standard of performance, a section title ``Test Methods
and Procedures'' is provided to: (1) Identify the test methods to be
used as reference methods to the facility subject to the respective
standard and (2) identify any special instructions or conditions to be
followed when applying a method to the respective facility. Such
instructions (for example, establish sampling rates, volumes, or
temperatures) are to be used either in addition to, or as a substitute
for procedures in a test method. Similarly, for sources subject to
emission monitoring requirements, specific instructions pertaining to
any use of a test method as a reference method are provided in the
subpart or in appendix B.
Inclusion of methods in this appendix is not intended as an
endorsement or denial of their applicability to sources that are not
subject to standards of performance. The methods are potentially
applicable to other sources; however, applicability should be confirmed
by careful and appropriate evaluation of the conditions prevalent at
such sources.
The approach followed in the formulation of the test methods
involves specifications for equipment, procedures, and performance. In
concept, a performance specification approach would be preferable in all
methods because this allows the greatest flexibility to the user. In
practice, however, this approach is impractical in most cases because
performance specifications cannot be established. Most of the methods
described herein, therefore, involve specific equipment specifications
and procedures, and only a few methods in this appendix rely on
performance criteria.
Minor changes in the test methods should not necessarily affect the
validity of the results and it is recognized that alternative and
equivalent methods exist. section 60.8 provides authority for the
Administrator to

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specify or approve (1) equivalent methods, (2) alternative methods, and
(3) minor changes in the methodology of the test methods. It should be
clearly understood that unless otherwise identified all such methods and
changes must have prior approval of the Administrator. An owner
employing such methods or deviations from the test methods without
obtaining prior approval does so at the risk of subsequent disapproval
and retesting with approved methods.
Within the test methods, certain specific equipment or procedures
are recognized as being acceptable or potentially acceptable and are
specifically identified in the methods. The items identified as
acceptable options may be used without approval but must be identified
in the test report. The potentially approvable options are cited as
``subject to the approval of the Administrator'' or as ``or
equivalent.'' Such potentially approvable techniques or alternatives may
be used at the discretion of the owner without prior approval. However,
detailed descriptions for applying these potentially approvable
techniques or alternatives are not provided in the test methods. Also,
the potentially approvable options are not necessarily acceptable in all
applications. Therefore, an owner electing to use such potentially
approvable techniques or alternatives is responsible for: (1) assuring
that the techniques or alternatives are in fact applicable and are
properly executed; (2) including a written description of the
alternative method in the test report (the written method must be clear
and must be capable of being performed without additional instruction,
and the degree of detail should be similar to the detail contained in
the test methods); and (3) providing any rationale or supporting data
necessary to show the validity of the alternative in the particular
application. Failure to meet these requirements can result in the
Administrator's disapproval of the alternative.

Method 1--Sample and Velocity Traverses for Stationary Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling) essential to its
performance. Some material is incorporated by reference from other
methods in this part. Therefore, to obtain reliable results, persons
using this method should have a thorough knowledge of at least the
following additional test method: Method 2.

1.0 Scope and Application

1.1 Measured Parameters. The purpose of the method is to provide
guidance for the selection of sampling ports and traverse points at
which sampling for air pollutants will be performed pursuant to
regulations set forth in this part. Two procedures are presented: a
simplified procedure, and an alternative procedure (see section 11.5).
The magnitude of cyclonic flow of effluent gas in a stack or duct is the
only parameter quantitatively measured in the simplified procedure.
1.2 Applicability. This method is applicable to gas streams flowing
in ducts, stacks, and flues. This method cannot be used when: (1) the
flow is cyclonic or swirling; or (2) a stack is smaller than 0.30 meter
(12 in.) in diameter, or 0.071 m\2\ (113 in.\2\) in cross-sectional
area. The simplified procedure cannot be used when the measurement site
is less than two stack or duct diameters downstream or less than a half
diameter upstream from a flow disturbance.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

Note: The requirements of this method must be considered before
construction of a new facility from which emissions are to be measured;
failure to do so may require subsequent alterations to the stack or
deviation from the standard procedure. Cases involving variants are
subject to approval by the Administrator.

2.0 Summary of Method

2.1 This method is designed to aid in the representative measurement
of pollutant emissions and/or total volumetric flow rate from a
stationary source. A measurement site where the effluent stream is
flowing in a known direction is selected, and the cross-section of the
stack is divided into a number of equal areas. Traverse points are then
located within each of these equal areas.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies.

6.1 Apparatus. The apparatus described below is required only when
utilizing the alternative site selection procedure described in section
11.5 of this method.
6.1.1 Directional Probe. Any directional probe, such as United
Sensor Type DA Three-Dimensional Directional Probe, capable of measuring
both the pitch and yaw angles of gas flows is acceptable. Before using
the probe, assign an identification number to the

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directional probe, and permanently mark or engrave the number on the
body of the probe. The pressure holes of directional probes are
susceptible to plugging when used in particulate-laden gas streams.
Therefore, a procedure for cleaning the pressure holes by ``back-
purging'' with pressurized air is required.
6.1.2 Differential Pressure Gauges. Inclined manometers, U-tube
manometers, or other differential pressure gauges (e.g., magnehelic
gauges) that meet the specifications described in Method 2, section 6.2.

Note: If the differential pressure gauge produces both negative and
positive readings, then both negative and positive pressure readings
shall be calibrated at a minimum of three points as specified in Method
2, section 6.2.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection, Preservation, Storage, and Transport [Reserved]

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Procedure

11.1 Selection of Measurement Site.
11.1.1 Sampling and/or velocity measurements are performed at a site
located at least eight stack or duct diameters downstream and two
diameters upstream from any flow disturbance such as a bend, expansion,
or contraction in the stack, or from a visible flame. If necessary, an
alternative location may be selected, at a position at least two stack
or duct diameters downstream and a half diameter upstream from any flow
disturbance.
11.1.2 An alternative procedure is available for determining the
acceptability of a measurement location not meeting the criteria above.
This procedure described in section 11.5 allows for the determination of
gas flow angles at the sampling points and comparison of the measured
results with acceptability criteria.
11.2 Determining the Number of Traverse Points.
11.2.1 Particulate Traverses.
11.2.1.1 When the eight- and two-diameter criterion can be met, the
minimum number of traverse points shall be: (1) twelve, for circular or
rectangular stacks with diameters (or equivalent diameters) greater than
0.61 meter (24 in.); (2) eight, for circular stacks with diameters
between 0.30 and 0.61 meter (12 and 24 in.); and (3) nine, for
rectangular stacks with equivalent diameters between 0.30 and 0.61 meter
(12 and 24 in.).
11.2.1.2 When the eight- and two-diameter criterion cannot be met,
the minimum number of traverse points is determined from Figure 1-1.
Before referring to the figure, however, determine the istances from the
measurement site to the nearest upstream and downstream disturbances,
and divide each distance by the stack diameter or equivalent diameter,
to determine the distance in terms of the number of duct diameters.
Then, determine from Figure 1-1 the minimum number of traverse points
that corresponds: (1) to the number of duct diameters upstream; and (2)
to the number of diameters downstream. Select the higher of the two
minimum numbers of traverse points, or a greater value, so that for
circular stacks the number is a multiple of 4, and for rectangular
stacks, the number is one of those shown in Table 1-1.
11.2.2 Velocity (Non-Particulate) Traverses. When velocity or
volumetric flow rate is to be determined (but not particulate matter),
the same procedure as that used for particulate traverses (Section
11.2.1) is followed, except that Figure 1-2 may be used instead of
Figure 1-1.
11.3 Cross-Sectional Layout and Location of Traverse Points.
11.3.1 Circular Stacks.
11.3.1.1 Locate the traverse points on two perpendicular diameters
according to Table 1-2 and the example shown in Figure 1-3. Any equation
(see examples in References 2 and 3 in section 16.0) that gives the same
values as those in Table 1-2 may be used in lieu of Table 1-2.
11.3.1.2 For particulate traverses, one of the diameters must
coincide with the plane containing the greatest expected concentration
variation (e.g., after bends); one diameter shall be congruent to the
direction of the bend. This requirement becomes less critical as the
distance from the disturbance increases; therefore, other diameter
locations may be used, subject to the approval of the Administrator.
11.3.1.3 In addition, for elliptical stacks having unequal
perpendicular diameters, separate traverse points shall be calculated
and located along each diameter. To determine the cross-sectional area
of the elliptical stack, use the following equation:

Square Area = D1 x D2 x 0.7854

Where: D1 = Stack diameter 1
D2 = Stack diameter 2

11.3.1.4 In addition, for stacks having diameters greater than 0.61
m (24 in.), no traverse points shall be within 2.5 centimeters (1.00
in.) of the stack walls; and for stack diameters equal to or less than
0.61 m (24 in.), no traverse points shall be located within 1.3 cm (0.50
in.) of the stack walls. To meet these criteria, observe the procedures
given below.
11.3.2 Stacks With Diameters Greater Than 0.61 m (24 in.).
11.3.2.1 When any of the traverse points as located in section
11.3.1 fall within 2.5 cm (1.0 in.) of the stack walls, relocate them
away

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from the stack walls to: (1) a distance of 2.5 cm (1.0 in.); or (2) a
distance equal to the nozzle inside diameter, whichever is larger. These
relocated traverse points (on each end of a diameter) shall be the
``adjusted'' traverse points.
11.3.2.2 Whenever two successive traverse points are combined to
form a single adjusted traverse point, treat the adjusted point as two
separate traverse points, both in the sampling and/or velocity
measurement procedure, and in recording of the data.
11.3.3 Stacks With Diameters Equal To or Less Than 0.61 m (24 in.).
Follow the procedure in section 11.3.1.1, noting only that any
``adjusted'' points should be relocated away from the stack walls to:
(1) a distance of 1.3 cm (0.50 in.); or (2) a distance equal to the
nozzle inside diameter, whichever is larger.
11.3.4 Rectangular Stacks.
11.3.4.1 Determine the number of traverse points as explained in
sections 11.1 and 11.2 of this method. From Table 1-1, determine the
grid configuration. Divide the stack cross-section into as many equal
rectangular elemental areas as traverse points, and then locate a
traverse point at the centroid of each equal area according to the
example in Figure 1-4.
11.3.4.2 To use more than the minimum number of traverse points,
expand the ``minimum number of traverse points'' matrix (see Table 1-1)
by adding the extra traverse points along one or the other or both legs
of the matrix; the final matrix need not be balanced. For example, if a
4 x 3 ``minimum number of points'' matrix were expanded to 36 points,
the final matrix could be 9 x 4 or 12 x 3, and would not necessarily
have to be 6 x 6. After constructing the final matrix, divide the stack
cross-section into as many equal rectangular, elemental areas as
traverse points, and locate a traverse point at the centroid of each
equal area.
11.3.4.3 The situation of traverse points being too close to the
stack walls is not expected to arise with rectangular stacks. If this
problem should ever arise, the Administrator must be contacted for
resolution of the matter.
11.4 Verification of Absence of Cyclonic Flow.
11.4.1 In most stationary sources, the direction of stack gas flow
is essentially parallel to the stack walls. However, cyclonic flow may
exist (1) after such devices as cyclones and inertial demisters
following venturi scrubbers, or (2) in stacks having tangential inlets
or other duct configurations which tend to induce swirling; in these
instances, the presence or absence of cyclonic flow at the sampling
location must be determined. The following techniques are acceptable for
this determination.
11.4.2 Level and zero the manometer. Connect a Type S pitot tube to
the manometer and leak-check system. Position the Type S pitot tube at
each traverse point, in succession, so that the planes of the face
openings of the pitot tube are perpendicular to the stack cross-
sectional plane; when the Type S pitot tube is in this position, it is
at ``0[deg] reference.'' Note the differential pressure (Fp) reading at
each traverse point. If a null (zero) pitot reading is obtained at
0[deg] reference at a given traverse point, an acceptable flow condition
exists at that point. If the pitot reading is not zero at 0[deg]
reference, rotate the pitot tube (up to 90[deg] yaw angle), until a
null reading is obtained. Carefully determine and record the value of
the rotation angle (a) to the nearest degree. After the null technique
has been applied at each traverse point, calculate the average of the
absolute values of a; assign a values of 0[deg] to those points for
which no rotation was required, and include these in the overall
average. If the average value of a is greater than 20[deg], the overall
flow condition in the stack is unacceptable, and alternative
methodology, subject to the approval of the Administrator, must be used
to perform accurate sample and velocity traverses.
11.5 The alternative site selection procedure may be used to
determine the rotation angles in lieu of the procedure outlined in
section 11.4.
11.5.1 Alternative Measurement Site Selection Procedure. This
alternative applies to sources where measurement locations are less than
2 equivalent or duct diameters downstream or less than one-half duct
diameter upstream from a flow disturbance. The alternative should be
limited to ducts larger than 24 in. in diameter where blockage and wall
effects are minimal. A directional flow-sensing probe is used to measure
pitch and yaw angles of the gas flow at 40 or more traverse points; the
resultant angle is calculated and compared with acceptable criteria for
mean and standard deviation.

Note: Both the pitch and yaw angles are measured from a line passing
through the traverse point and parallel to the stack axis. The pitch
angle is the angle of the gas flow component in the plane that INCLUDES
the traverse line and is parallel to the stack axis. The yaw angle is
the angle of the gas flow component in the plane PERPENDICULAR to the
traverse line at the traverse point and is measured from the line
passing through the traverse point and parallel to the stack axis.

11.5.2 Traverse Points. Use a minimum of 40 traverse points for
circular ducts and 42 points for rectangular ducts for the gas flow
angle determinations. Follow the procedure outlined in section 11.3 and
Table 1-1 or 1-2 for the location and layout of the traverse points. If
the measurement location is determined to be acceptable according to the
criteria in this alternative procedure, use the

[[Page 9]]

same traverse point number and locations for sampling and velocity
measurements.
11.5.3 Measurement Procedure.
11.5.3.1 Prepare the directional probe and differential pressure
gauges as recommended by the manufacturer. Capillary tubing or surge
tanks may be used to dampen pressure fluctuations. It is recommended,
but not required, that a pretest leak check be conducted. To perform a
leak check, pressurize or use suction on the impact opening until a
reading of at least 7.6 cm (3 in.) H2O registers on the
differential pressure gauge, then plug the impact opening. The pressure
of a leak-free system will remain stable for at least 15 seconds.
11.5.3.2 Level and zero the manometers. Since the manometer level
and zero may drift because of vibrations and temperature changes,
periodically check the level and zero during the traverse.
11.5.3.3 Position the probe at the appropriate locations in the gas
stream, and rotate until zero deflection is indicated for the yaw angle
pressure gauge. Determine and record the yaw angle. Record the pressure
gauge readings for the pitch angle, and determine the pitch angle from
the calibration curve. Repeat this procedure for each traverse point.
Complete a ``back-purge'' of the pressure lines and the impact openings
prior to measurements of each traverse point.
11.5.3.4 A post-test check as described in section 11.5.3.1 is
required. If the criteria for a leak-free system are not met, repair the
equipment, and repeat the flow angle measurements.
11.5.4 Calibration. Use a flow system as described in sections
10.1.2.1 and 10.1.2.2 of Method 2. In addition, the flow system shall
have the capacity to generate two test-section velocities: one between
365 and 730 m/min (1,200 and 2,400 ft/min) and one between 730 and 1,100
m/min (2,400 and 3,600 ft/min).
11.5.4.1 Cut two entry ports in the test section. The axes through
the entry ports shall be perpendicular to each other and intersect in
the centroid of the test section. The ports should be elongated slots
parallel to the axis of the test section and of sufficient length to
allow measurement of pitch angles while maintaining the pitot head
position at the test-section centroid. To facilitate alignment of the
directional probe during calibration, the test section should be
constructed of plexiglass or some other transparent material. All
calibration measurements should be made at the same point in the test
section, preferably at the centroid of the test section.
11.5.4.2 To ensure that the gas flow is parallel to the central axis
of the test section, follow the procedure outlined in section 11.4 for
cyclonic flow determination to measure the gas flow angles at the
centroid of the test section from two test ports located 90[deg] apart.
The gas flow angle measured in each port must be 2[deg] of 0[deg].
Straightening vanes should be installed, if necessary, to meet this
criterion.
11.5.4.3 Pitch Angle Calibration. Perform a calibration traverse
according to the manufacturer's recommended protocol in 5[deg]
increments for angles from -60[deg] to + 60[deg] at one velocity in each
of the two ranges specified above. Average the pressure ratio values
obtained for each angle in the two flow ranges, and plot a calibration
curve with the average values of the pressure ratio (or other suitable
measurement factor as recommended by the manufacturer) versus the pitch
angle. Draw a smooth line through the data points. Plot also the data
values for each traverse point. Determine the differences between the
measured data values and the angle from the calibration curve at the
same pressure ratio. The difference at each comparison must be within
2[deg] for angles between 0[deg] and 40[deg] and within 3[deg] for
angles between 40[deg] and 60[deg].
11.5.4.4 Yaw Angle Calibration. Mark the three-dimensional probe to
allow the determination of the yaw position of the probe. This is
usually a line extending the length of the probe and aligned with the
impact opening. To determine the accuracy of measurements of the yaw
angle, only the zero or null position need be calibrated as follows:
Place the directional probe in the test section, and rotate the probe
until the zero position is found. With a protractor or other angle
measuring device, measure the angle indicated by the yaw angle indicator
on the three-dimensional probe. This should be within 2[deg] of 0[deg].
Repeat this measurement for any other points along the length of the
pitot where yaw angle measurements could be read in order to account for
variations in the pitot markings used to indicate pitot head positions.

12.0 Data Analysis and Calculations

12.1 Nomenclature.
L = length.
n = total number of traverse points.
Pi = pitch angle at traverse point i, degree.
Ravg = average resultant angle, degree.
Ri = resultant angle at traverse point i, degree.
Sd = standard deviation, degree.
W = width.
Yi = yaw angle at traverse point i, degree.
12.2 For a rectangular cross section, an equivalent diameter
(De) shall be calculated using the following equation, to
determine the upstream and downstream distances:
[GRAPHIC] [TIFF OMITTED] TR17OC00.037

12.3 If use of the alternative site selection procedure (Section
11.5 of this method) is required, perform the following calculations
using the equations below: the resultant

[[Page 10]]

angle at each traverse point, the average resultant angle, and the
standard deviation. Complete the calculations retaining at least one
extra significant figure beyond that of the acquired data. Round the
values after the final calculations.
12.3.1 Calculate the resultant angle at each traverse point:
[GRAPHIC] [TIFF OMITTED] TR17OC00.038

12.3.2 Calculate the average resultant for the measurements:
[GRAPHIC] [TIFF OMITTED] TR17OC00.039

12.3.3 Calculate the standard deviations:
[GRAPHIC] [TIFF OMITTED] TR17OC00.040

12.3.4 Acceptability Criteria. The measurement location is
acceptable if Ravg 20[deg] and Sd
10[deg].

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Determining Dust Concentration in a Gas Stream, ASME Performance
Test Code No. 27. New York. 1957.
2. DeVorkin, Howard, et al. Air Pollution Source Testing Manual. Air
Pollution Control District. Los Angeles, CA. November 1963.
3. Methods for Determining of Velocity, Volume, Dust and Mist
Content of Gases. Western Precipitation Division of Joy Manufacturing
Co. Los Angeles, CA. Bulletin WP-50. 1968.
4. Standard Method for Sampling Stacks for Particulate Matter. In:
1971 Book of ASTM Standards, Part 23. ASTM Designation D 2928-71.
Philadelphia, PA. 1971.
5. Hanson, H.A., et al. Particulate Sampling Strategies for Large
Power Plants Including Nonuniform Flow. USEPA, ORD, ESRL, Research
Triangle Park, NC. EPA-600/2-76-170. June 1976.
6. Entropy Environmentalists, Inc. Determination of the Optimum
Number of Sampling Points: An Analysis of Method 1 Criteria.
Environmental Protection Agency. Research Triangle Park, NC. EPA
Contract No. 68-01-3172, Task 7.
7. Hanson, H.A., R.J. Davini, J.K. Morgan, and A.A. Iversen.
Particulate Sampling Strategies for Large Power Plants Including
Nonuniform Flow. USEPA, Research Triangle Park, NC. Publication No. EPA-
600/2-76-170. June 1976. 350 pp.
8. Brooks, E.F., and R.L. Williams. Flow and Gas Sampling Manual.
U.S. Environmental Protection Agency. Research Triangle Park, NC.
Publication No. EPA-600/2-76-203. July 1976. 93 pp.
9. Entropy Environmentalists, Inc. Traverse Point Study. EPA
Contract No. 68-02-3172. June 1977. 19 pp.
10. Brown, J. and K. Yu. Test Report: Particulate Sampling Strategy
in Circular Ducts. Emission Measurement Branch. U.S. Environmental
Protection Agency, Research Triangle Park, NC 27711. July 31, 1980. 12
pp.
11. Hawksley, P.G.W., S. Badzioch, and J.H. Blackett. Measurement of
Solids in Flue Gases. Leatherhead, England, The British Coal Utilisation
Research Association. 1961. pp. 129-133.
12. Knapp, K.T. The Number of Sampling Points Needed for
Representative Source Sampling. In: Proceedings of the Fourth National
Conference on Energy and Environment. Theodore, L. et al. (ed). Dayton,
Dayton section of the American Institute of Chemical Engineers. October
3-7, 1976. pp. 563-568.
13. Smith, W.S. and D.J. Grove. A Proposed Extension of EPA Method 1
Criteria. Pollution Engineering. XV (8):36-37. August 1983.
14. Gerhart, P.M. and M.J. Dorsey. Investigation of Field Test
Procedures for Large Fans. University of Akron. Akron, OH. (EPRI
Contract CS-1651). Final Report (RP-1649-5). December 1980.
15. Smith, W.S. and D.J. Grove. A New Look at Isokinetic Sampling--
Theory and Applications. Source Evaluation Society Newsletter. VIII
(3):19-24. August 1983.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 11]]

[GRAPHIC] [TIFF OMITTED] TR27FE14.007

Table 1-1 Cross-Section Layout for Rectangular Stacks
------------------------------------------------------------------------
Number of tranverse points layout Matrix
------------------------------------------------------------------------
9...................................... 3 x 3
12..................................... 4 x 3
16..................................... 4 x 4
20..................................... 5 x 4
25..................................... 5 x 5
30..................................... 6 x 5
36..................................... 6 x 6
42..................................... 7 x 6
49..................................... 7 x 7
------------------------------------------------------------------------

[[Page 12]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.042

Table 1-2--Location of Traverse Points in Circular Stacks
[Percent of stack diameter from inside wall to tranverse point]
--------------------------------------------------------------------------------------------------------------------------------------------------------
Number of traverse points on a diameter
Traverse point number on a diameter -----------------------------------------------------------------------------------------------
2 4 6 8 10 12 14 16 18 20 22 24
--------------------------------------------------------------------------------------------------------------------------------------------------------
1....................................................... 14.6 6.7 4.4 3.2 2.6 2.1 1.8 1.6 1.4 1.3 1.1 1.1
2....................................................... 85.4 25.0 14.6 10.5 8.2 6.7 5.7 4.9 4.4 3.9 3.5 3.2
3....................................................... ...... 75.0 29.6 19.4 14.6 11.8 9.9 8.5 7.5 6.7 6.0 5.5
4....................................................... ...... 93.3 70.4 32.3 22.6 17.7 14.6 12.5 10.9 9.7 8.7 7.9
5....................................................... ...... ...... 85.4 67.7 34.2 25.0 20.1 16.9 14.6 12.9 11.6 10.5

[[Page 13]]

6....................................................... ...... ...... 95.6 80.6 65.8 35.6 26.9 22.0 18.8 16.5 14.6 13.2
7....................................................... ...... ...... ...... 89.5 77.4 64.4 36.6 28.3 23.6 20.4 18.0 16.1
8....................................................... ...... ...... ...... 96.8 85.4 75.0 63.4 37.5 29.6 25.0 21.8 19.4
9....................................................... ...... ...... ...... ...... 91.8 82.3 73.1 62.5 38.2 30.6 26.2 23.0
10...................................................... ...... ...... ...... ...... 97.4 88.2 79.9 71.7 61.8 38.8 31.5 27.2
11...................................................... ...... ...... ...... ...... ...... 93.3 85.4 78.0 70.4 61.2 39.3 32.3
12...................................................... ...... ...... ...... ...... ...... 97.9 90.1 83.1 76.4 69.4 60.7 39.8
13...................................................... ...... ...... ...... ...... ...... ...... 94.3 87.5 81.2 75.0 68.5 60.2
14...................................................... ...... ...... ...... ...... ...... ...... 98.2 91.5 85.4 79.6 73.8 67.7
15...................................................... ...... ...... ...... ...... ...... ...... ...... 95.1 89.1 83.5 78.2 72.8
16...................................................... ...... ...... ...... ...... ...... ...... ...... 98.4 92.5 87.1 82.0 77.0
17...................................................... ...... ...... ...... ...... ...... ...... ...... ...... 95.6 90.3 85.4 80.6
18...................................................... ...... ...... ...... ...... ...... ...... ...... ...... 98.6 93.3 88.4 83.9
19...................................................... ...... ...... ...... ...... ...... ...... ...... ...... ...... 96.1 91.3 86.8
20...................................................... ...... ...... ...... ...... ...... ...... ...... ...... ...... 98.7 94.0 89.5
21...................................................... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... 96.5 92.1
22...................................................... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... 98.9 94.5
23...................................................... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... 96.8
24...................................................... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... 99.9
--------------------------------------------------------------------------------------------------------------------------------------------------------

[GRAPHIC] [TIFF OMITTED] TR17OC00.043

Method 1A--Sample and Velocity Traverses for Stationary Sources With
Small Stacks or Ducts

1.0 Scope and Application

1.1 Measured Parameters. The purpose of the method is to provide
guidance for the selection of sampling ports and traverse points at
which sampling for air pollutants will be performed pursuant to
regulations set forth in this part.
1.2 Applicability. The applicability and principle of this method
are identical to Method 1, except its applicability is limited to stacks
or ducts. This method is applicable to flowing gas streams in ducts,
stacks, and flues of less than about 0.30 meter (12 in.) in diameter, or
0.071 m\2\ (113 in.\2\) in cross-sectional area, but equal to or greater
than about 0.10 meter (4 in.) in diameter, or 0.0081 m\2\ (12.57 in.\2\)
in cross-sectional area. This method cannot be used when the flow is
cyclonic or swirling.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

[[Page 14]]

2.0 Summary of Method

2.1 The method is designed to aid in the representative measurement
of pollutant emissions and/or total volumetric flow rate from a
stationary source. A measurement site or a pair of measurement sites
where the effluent stream is flowing in a known direction is (are)
selected. The cross-section of the stack is divided into a number of
equal areas. Traverse points are then located within each of these equal
areas.
2.2 In these small diameter stacks or ducts, the conventional Method
5 stack assembly (consisting of a Type S pitot tube attached to a
sampling probe, equipped with a nozzle and thermocouple) blocks a
significant portion of the cross-section of the duct and causes
inaccurate measurements. Therefore, for particulate matter (PM) sampling
in small stacks or ducts, the gas velocity is measured using a standard
pitot tube downstream of the actual emission sampling site. The straight
run of duct between the PM sampling and velocity measurement sites
allows the flow profile, temporarily disturbed by the presence of the
sampling probe, to redevelop and stabilize.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies [Reserved]

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection, Preservation, Storage, and Transport [Reserved]

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Procedure

11.1 Selection of Measurement Site.
11.1.1 Particulate Measurements--Steady or Unsteady Flow. Select a
particulate measurement site located preferably at least eight
equivalent stack or duct diameters downstream and 10 equivalent
diameters upstream from any flow disturbances such as bends, expansions,
or contractions in the stack, or from a visible flame. Next, locate the
velocity measurement site eight equivalent diameters downstream of the
particulate measurement site (see Figure 1A-1). If such locations are
not available, select an alternative particulate measurement location at
least two equivalent stack or duct diameters downstream and two and one-
half diameters upstream from any flow disturbance. Then, locate the
velocity measurement site two equivalent diameters downstream from the
particulate measurement site. (See section 12.2 of Method 1 for
calculating equivalent diameters for a rectangular cross-section.)
11.1.2 PM Sampling (Steady Flow) or Velocity (Steady or Unsteady
Flow) Measurements. For PM sampling when the volumetric flow rate in a
duct is constant with respect to time, section 11.1.1 of Method 1 may be
followed, with the PM sampling and velocity measurement performed at one
location. To demonstrate that the flow rate is constant (within 10
percent) when PM measurements are made, perform complete velocity
traverses before and after the PM sampling run, and calculate the
deviation of the flow rate derived after the PM sampling run from the
one derived before the PM sampling run. The PM sampling run is
acceptable if the deviation does not exceed 10 percent.
11.2 Determining the Number of Traverse Points.
11.2.1 Particulate Measurements (Steady or Unsteady Flow). Use
Figure 1-1 of Method 1 to determine the number of traverse points to use
at both the velocity measurement and PM sampling locations. Before
referring to the figure, however, determine the distances between both
the velocity measurement and PM sampling sites to the nearest upstream
and downstream disturbances. Then divide each distance by the stack
diameter or equivalent diameter to express the distances in terms of the
number of duct diameters. Then, determine the number of traverse points
from Figure 1-1 of Method 1 corresponding to each of these four
distances. Choose the highest of the four numbers of traverse points (or
a greater number) so that, for circular ducts the number is a multiple
of four; and for rectangular ducts, the number is one of those shown in
Table 1-1 of Method 1. When the optimum duct diameter location criteria
can be satisfied, the minimum number of traverse points required is
eight for circular ducts and nine for rectangular ducts.
11.2.2 PM Sampling (Steady Flow) or only Velocity (Non-Particulate)
Measurements. Use Figure 1-2 of Method 1 to determine number of traverse
points, following the same procedure used for PM sampling as described
in section 11.2.1 of Method 1. When the optimum duct diameter location
criteria can be satisfied, the minimum number of traverse points
required is eight for circular ducts and nine for rectangular ducts.

[[Page 15]]

11.3 Cross-sectional Layout, Location of Traverse Points, and
Verification of the Absence of Cyclonic Flow. Same as Method 1, sections
11.3 and 11.4, respectively.

12.0 Data Analysis and Calculations [Reserved]

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as Method 1, section 16.0, References 1 through 6, with the
addition of the following:
1. Vollaro, Robert F. Recommended Procedure for Sample Traverses in
Ducts Smaller Than 12 Inches in Diameter. U.S. Environmental Protection
Agency, Emission Measurement Branch, Research Triangle Park, North
Carolina. January 1977.

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.044

Method 2--Determination of Stack Gas Velocity and Volumetric Flow Rate
(Type S Pitot Tube)

1.0 Scope and Application.

1.1 This method is applicable for the determination of the average
velocity and the volumetric flow rate of a gas stream.
1.2 This method is not applicable at measurement sites that fail to
meet the criteria of Method 1, section 11.1. Also, the method cannot be
used for direct measurement in cyclonic or swirling gas streams; section
11.4 of Method 1 shows how to determine cyclonic or swirling flow
conditions. When unacceptable conditions exist, alternative procedures,
subject to the approval of the Administrator, must be employed to
produce accurate flow rate determinations. Examples of such alternative
procedures are: (1) to install straightening vanes; (2) to calculate the
total volumetric flow rate stoichiometrically, or (3) to move to another
measurement site at which the flow is acceptable.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method.

2.1 The average gas velocity in a stack is determined from the gas
density and from measurement of the average velocity head with a Type S
(Stausscheibe or reverse type) pitot tube.

[[Page 16]]

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Specifications for the apparatus are given below. Any other
apparatus that has been demonstrated (subject to approval of the
Administrator) to be capable of meeting the specifications will be
considered acceptable.
6.1 Type S Pitot Tube.
6.1.1 Pitot tube made of metal tubing (e.g., stainless steel) as
shown in Figure 2-1. It is recommended that the external tubing diameter
(dimension Dt, Figure 2-2b) be between 0.48 and 0.95 cm (\3/
16\ and \3/8\ inch). There shall be an equal distance from the base of
each leg of the pitot tube to its face-opening plane (dimensions
PA and PB, Figure 2-2b); it is recommended that
this distance be between 1.05 and 1.50 times the external tubing
diameter. The face openings of the pitot tube shall, preferably, be
aligned as shown in Figure 2-2; however, slight misalignments of the
openings are permissible (see Figure 2-3).
6.1.2 The Type S pitot tube shall have a known coefficient,
determined as outlined in section 10.0. An identification number shall
be assigned to the pitot tube; this number shall be permanently marked
or engraved on the body of the tube. A standard pitot tube may be used
instead of a Type S, provided that it meets the specifications of
sections 6.7 and 10.2. Note, however, that the static and impact
pressure holes of standard pitot tubes are susceptible to plugging in
particulate-laden gas streams. Therefore, whenever a standard pitot tube
is used to perform a traverse, adequate proof must be furnished that the
openings of the pitot tube have not plugged up during the traverse
period. This can be accomplished by comparing the velocity head (Fp)
measurement recorded at a selected traverse point (readable Fp value)
with a second Fp measurement recorded after ``back purging'' with
pressurized air to clean the impact and static holes of the standard
pitot tube. If the before and after Fp measurements are within 5
percent, then the traverse data are acceptable. Otherwise, the data
should be rejected and the traverse measurements redone. Note that the
selected traverse point should be one that demonstrates a readable Fp
value. If ``back purging'' at regular intervals is part of a routine
procedure, then comparative Fp measurements shall be conducted as above
for the last two traverse points that exhibit suitable Fp measurements.
6.2 Differential Pressure Gauge. An inclined manometer or equivalent
device. Most sampling trains are equipped with a 10 in. (water column)
inclined-vertical manometer, having 0.01 in. H20 divisions on
the 0 to 1 in. inclined scale, and 0.1 in. H20 divisions on
the 1 to 10 in. vertical scale. This type of manometer (or other gauge
of equivalent sensitivity) is satisfactory for the measurement of Fp
values as low as 1.27 mm (0.05 in.) H20. However, a
differential pressure gauge of greater sensitivity shall be used
(subject to the approval of the Administrator), if any of the following
is found to be true: (1) the arithmetic average of all Fp readings at
the traverse points in the stack is less than 1.27 mm (0.05 in.)
H20; (2) for traverses of 12 or more points, more than 10
percent of the individual Fp readings are below 1.27 mm (0.05 in.)
H20; or (3) for traverses of fewer than 12 points, more than
one Fp reading is below 1.27 mm (0.05 in.) H20. Reference 18
(see section 17.0) describes commercially available instrumentation for
the measurement of low-range gas velocities.
6.2.1 As an alternative to criteria (1) through (3) above, Equation
2-1 (Section 12.2) may be used to determine the necessity of using a
more sensitive differential pressure gauge. If T is greater than 1.05,
the velocity head data are unacceptable and a more sensitive
differential pressure gauge must be used.

Note: If differential pressure gauges other than inclined manometers
are used (e.g., magnehelic gauges), their calibration must be checked
after each test series. To check the calibration of a differential
pressure gauge, compare Fp readings of the gauge with those of a gauge-
oil manometer at a minimum of three points, approximately representing
the range of Fp values in the stack. If, at each point, the values of Fp
as read by the differential pressure gauge and gauge-oil manometer agree
to within 5 percent, the differential pressure gauge shall be considered
to be in proper calibration. Otherwise, the test series shall either be
voided, or procedures to adjust the measured Fp values and final results
shall be used, subject to the approval of the Administrator.

6.3 Temperature Sensor. A thermocouple, liquid-filled bulb
thermometer, bimetallic thermometer, mercury-in-glass thermometer, or
other gauge capable of measuring temperatures to within 1.5 percent of
the minimum absolute stack temperature. The temperature sensor shall be
attached to the pitot tube such that the sensor tip does not touch any
metal; the gauge shall be in an interference-free arrangement with
respect to the pitot tube face openings (see Figure 2-1 and Figure 2-4).
Alternative positions may

[[Page 17]]

be used if the pitot tube-temperature gauge system is calibrated
according to the procedure of section 10.0. Provided that a difference
of not more than 1 percent in the average velocity measurement is
introduced, the temperature gauge need not be attached to the pitot
tube. This alternative is subject to the approval of the Administrator.
6.4 Pressure Probe and Gauge. A piezometer tube and mercury- or
water-filled U-tube manometer capable of measuring stack pressure to
within 2.5 mm (0.1 in.) Hg. The static tap of a standard type pitot tube
or one leg of a Type S pitot tube with the face opening planes
positioned parallel to the gas flow may also be used as the pressure
probe.
6.5 Barometer. A mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 2.54 mm (0.1 in.) Hg.

Note: The barometric pressure reading may be obtained from a nearby
National Weather Service station. In this case, the station value (which
is the absolute barometric pressure) shall be requested and an
adjustment for elevation differences between the weather station and
sampling point shall be made at a rate of minus 2.5 mm (0.1 in.) Hg per
30 m (100 ft) elevation increase or plus 2.5 mm (0.1 in.) Hg per 30 m
(100 ft.) for elevation decrease.

6.6 Gas Density Determination Equipment. Method 3 equipment, if
needed (see section 8.6), to determine the stack gas dry molecular
weight, and Method 4 (reference method) or Method 5 equipment for
moisture content determination. Other methods may be used subject to
approval of the Administrator.
6.7 Calibration Pitot Tube. When calibration of the Type S pitot
tube is necessary (see section 10.1), a standard pitot tube shall be
used for a reference. The standard pitot tube shall, preferably, have a
known coefficient, obtained either (1) directly from the National
Institute of Standards and Technology (NIST), Gaithersburg MD 20899,
(301) 975-2002, or (2) by calibration against another standard pitot
tube with an NIST-traceable coefficient. Alternatively, a standard pitot
tube designed according to the criteria given in sections 6.7.1 through
6.7.5 below and illustrated in Figure 2-5 (see also References 7, 8, and
17 in section 17.0) may be used. Pitot tubes designed according to these
specifications will have baseline coefficients of 0.99 0.01.
6.7.1 Standard Pitot Design.
6.7.1.1 Hemispherical (shown in Figure 2-5), ellipsoidal, or conical
tip.
6.7.1.2 A minimum of six diameters straight run (based upon D, the
external diameter of the tube) between the tip and the static pressure
holes.
6.7.1.3 A minimum of eight diameters straight run between the static
pressure holes and the centerline of the external tube, following the
90[deg] bend.
6.7.1.4 Static pressure holes of equal size (approximately 0.1 D),
equally spaced in a piezometer ring configuration.
6.7.1.5 90[deg] bend, with curved or mitered junction.
6.8 Differential Pressure Gauge for Type S Pitot Tube Calibration.
An inclined manometer or equivalent. If the single-velocity calibration
technique is employed (see section 10.1.2.3), the calibration
differential pressure gauge shall be readable to the nearest 0.127 mm
(0.005 in.) H20. For multivelocity calibrations, the gauge
shall be readable to the nearest 0.127 mm (0.005 in.) H20 for
Fp values between 1.27 and 25.4 mm (0.05 and 1.00 in.) H20,
and to the nearest 1.27 mm (0.05 in.) H20 for Fp values above
25.4 mm (1.00 in.) H20. A special, more sensitive gauge will
be required to read Fp values below 1.27 mm (0.05 in.) H20
(see Reference 18 in section 16.0).

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection and Analysis

8.1 Set up the apparatus as shown in Figure 2-1. Capillary tubing or
surge tanks installed between the manometer and pitot tube may be used
to dampen FP fluctuations. It is recommended, but not required, that a
pretest leak-check be conducted as follows: (1) blow through the pitot
impact opening until at least 7.6 cm (3.0 in.) H2O velocity
head registers on the manometer; then, close off the impact opening. The
pressure shall remain stable (2.5 mm H2O, 0.10 in.
H2O) for at least 15 seconds; (2) do the same for the static
pressure side, except using suction to obtain the minimum of 7.6 cm (3.0
in.) H2O. Other leak-check procedures, subject to the
approval of the Administrator, may be used.
8.2 Level and zero the manometer. Because the manometer level and
zero may drift due to vibrations and temperature changes, make periodic
checks during the traverse (at least once per hour). Record all
necessary data on a form similar to that shown in Figure 2-6.
8.3 Measure the velocity head and temperature at the traverse points
specified by Method 1. Ensure that the proper differential pressure
gauge is being used for the range of Fp values encountered (see section
6.2). If it is necessary to change to a more sensitive gauge, do so, and
remeasure the Fp and temperature readings at each traverse point.
Conduct a post-test leak-check (mandatory), as described in section 8.1
above, to validate the traverse run.
8.4 Measure the static pressure in the stack. One reading is usually
adequate.
8.5 Determine the atmospheric pressure.
8.6 Determine the stack gas dry molecular weight. For combustion
processes or processes that emit essentially CO2,
O2, CO, and

[[Page 18]]

N2, use Method 3. For processes emitting essentially air, an
analysis need not be conducted; use a dry molecular weight of 29.0. For
other processes, other methods, subject to the approval of the
Administrator, must be used.
8.7 Obtain the moisture content from Method 4 (reference method, or
equivalent) or from Method 5.
8.8 Determine the cross-sectional area of the stack or duct at the
sampling location. Whenever possible, physically measure the stack
dimensions rather than using blueprints. Do not assume that stack
diameters are equal. Measure each diameter distance to verify its
dimensions.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.1-10.4..................... Sampling Ensure accurate
equipment measurement of stack
calibration. gas flow rate,
sample volume.
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 Type S Pitot Tube. Before its initial use, carefully examine
the Type S pitot tube top, side, and end views to verify that the face
openings of the tube are aligned within the specifications illustrated
in Figures 2-2 and 2-3. The pitot tube shall not be used if it fails to
meet these alignment specifications. After verifying the face opening
alignment, measure and record the following dimensions of the pitot
tube: (a) the external tubing diameter (dimension Dt, Figure
2-2b); and (b) the base-to-opening plane distances (dimensions
PA and PB, Figure 2-2b). If Dt is
between 0.48 and 0.95 cm \3/16\ and \3/8\ in.), and if PA and
PB are equal and between 1.05 and 1.50 Dt, there
are two possible options: (1) the pitot tube may be calibrated according
to the procedure outlined in sections 10.1.2 through 10.1.5, or (2) a
baseline (isolated tube) coefficient value of 0.84 may be assigned to
the pitot tube. Note, however, that if the pitot tube is part of an
assembly, calibration may still be required, despite knowledge of the
baseline coefficient value (see section 10.1.1). If Dt,
PA, and PB are outside the specified limits, the
pitot tube must be calibrated as outlined in sections 10.1.2 through
10.1.5.
10.1.1 Type S Pitot Tube Assemblies. During sample and velocity
traverses, the isolated Type S pitot tube is not always used; in many
instances, the pitot tube is used in combination with other source-
sampling components (e.g., thermocouple, sampling probe, nozzle) as part
of an ``assembly.'' The presence of other sampling components can
sometimes affect the baseline value of the Type S pitot tube coefficient
(Reference 9 in section 17.0); therefore, an assigned (or otherwise
known) baseline coefficient value may or may not be valid for a given
assembly. The baseline and assembly coefficient values will be identical
only when the relative placement of the components in the assembly is
such that aerodynamic interference effects are eliminated. Figures 2-4,
2-7, and 2-8 illustrate interference-free component arrangements for
Type S pitot tubes having external tubing diameters between 0.48 and
0.95 cm (\3/16\ and \3/8\ in.). Type S pitot tube assemblies that fail
to meet any or all of the specifications of Figures 2-4, 2-7, and 2-8
shall be calibrated according to the procedure outlined in sections
10.1.2 through 10.1.5, and prior to calibration, the values of the
intercomponent spacings (pitot-nozzle, pitot-thermocouple, pitot-probe
sheath) shall be measured and recorded.

Note: Do not use a Type S pitot tube assembly that is constructed
such that the impact pressure opening plane of the pitot tube is below
the entry plane of the nozzle (see Figure 2-7B).

10.1.2 Calibration Setup. If the Type S pitot tube is to be
calibrated, one leg of the tube shall be permanently marked A, and the
other, B. Calibration shall be performed in a flow system having the
following essential design features:
10.1.2.1 The flowing gas stream must be confined to a duct of
definite cross-sectional area, either circular or rectangular. For
circular cross sections, the minimum duct diameter shall be 30.48 cm (12
in.); for rectangular cross sections, the width (shorter side) shall be
at least 25.4 cm (10 in.).
10.1.2.2 The cross-sectional area of the calibration duct must be
constant over a distance of 10 or more duct diameters. For a rectangular
cross section, use an equivalent diameter, calculated according to
Equation 2-2 (see section 12.3), to determine the number of duct
diameters. To ensure the presence of stable, fully developed flow
patterns at the calibration site, or ``test section,'' the site must be
located at least eight diameters downstream and two diameters upstream
from the nearest disturbances.

Note: The eight- and two-diameter criteria are not absolute; other
test section locations may be used (subject to approval of the
Administrator), provided that the flow at the test site has been
demonstrated to be or found stable and parallel to the duct axis.

10.1.2.3 The flow system shall have the capacity to generate a test-
section velocity around 910 m/min (3,000 ft/min). This velocity must be
constant with time to guarantee steady flow during calibration. Note
that Type S pitot tube coefficients obtained by

[[Page 19]]

single-velocity calibration at 910 m/min (3,000 ft/min) will generally
be valid to 3 percent for the measurement of velocities above 300 m/min
(1,000 ft/min) and to 6 percent for the measurement of velocities
between 180 and 300 m/min (600 and 1,000 ft/min). If a more precise
correlation between the pitot tube coefficient, (Cp), and
velocity is desired, the flow system should have the capacity to
generate at least four distinct, time-invariant test-section velocities
covering the velocity range from 180 to 1,500 m/min (600 to 5,000 ft/
min), and calibration data shall be taken at regular velocity intervals
over this range (see References 9 and 14 in section 17.0 for details).
10.1.2.4 Two entry ports, one for each of the standard and Type S
pitot tubes, shall be cut in the test section. The standard pitot entry
port shall be located slightly downstream of the Type S port, so that
the standard and Type S impact openings will lie in the same cross-
sectional plane during calibration. To facilitate alignment of the pitot
tubes during calibration, it is advisable that the test section be
constructed of Plexiglas \TM\ or some other transparent material.
10.1.3 Calibration Procedure. Note that this procedure is a general
one and must not be used without first referring to the special
considerations presented in section 10.1.5. Note also that this
procedure applies only to single-velocity calibration. To obtain
calibration data for the A and B sides of the Type S pitot tube, proceed
as follows:
10.1.3.1 Make sure that the manometer is properly filled and that
the oil is free from contamination and is of the proper density. Inspect
and leak-check all pitot lines; repair or replace if necessary.
10.1.3.2 Level and zero the manometer. Switch on the fan, and allow
the flow to stabilize. Seal the Type S pitot tube entry port.
10.1.3.3 Ensure that the manometer is level and zeroed. Position the
standard pitot tube at the calibration point (determined as outlined in
section 10.1.5.1), and align the tube so that its tip is pointed
directly into the flow. Particular care should be taken in aligning the
tube to avoid yaw and pitch angles. Make sure that the entry port
surrounding the tube is properly sealed.
10.1.3.4 Read Fpstd, and record its value in a data table
similar to the one shown in Figure 2-9. Remove the standard pitot tube
from the duct, and disconnect it from the manometer. Seal the standard
entry port.
10.1.3.5 Connect the Type S pitot tube to the manometer and leak-
check. Open the Type S tube entry port. Check the manometer level and
zero. Insert and align the Type S pitot tube so that its A side impact
opening is at the same point as was the standard pitot tube and is
pointed directly into the flow. Make sure that the entry port
surrounding the tube is properly sealed.
10.1.3.6 Read Fps, and enter its value in the data table.
Remove the Type S pitot tube from the duct, and disconnect it from the
manometer.
10.1.3.7 Repeat Steps 10.1.3.3 through 10.1.3.6 until three pairs of
Fp readings have been obtained for the A side of the Type S pitot tube.
10.1.3.8 Repeat Steps 10.1.3.3 through 10.1.3.7 for the B side of
the Type S pitot tube.
10.1.3.9 Perform calculations as described in section 12.4. Use the
Type S pitot tube only if the values of mA and mB
are less than or equal to 0.01 and if the absolute value of the
difference between Cp(A) and Cp(B) is 0.01 or
less.
10.1.4 Special Considerations.
10.1.4.1 Selection of Calibration Point.
10.1.4.1.1 When an isolated Type S pitot tube is calibrated, select
a calibration point at or near the center of the duct, and follow the
procedures outlined in section 10.1.3. The Type S pitot coefficients
measured or calculated, (i.e., Cp(A) and Cp(B))
will be valid, so long as either: (1) the isolated pitot tube is used;
or (2) the pitot tube is used with other components (nozzle,
thermocouple, sample probe) in an arrangement that is free from
aerodynamic interference effects (see Figures 2-4, 2-7, and 2-8).
10.1.4.1.2 For Type S pitot tube-thermocouple combinations (without
probe assembly), select a calibration point at or near the center of the
duct, and follow the procedures outlined in section 10.1.3. The
coefficients so obtained will be valid so long as the pitot tube-
thermocouple combination is used by itself or with other components in
an interference-free arrangement (Figures 2-4, 2-7, and 2-8).
10.1.4.1.3 For Type S pitot tube combinations with complete probe
assemblies, the calibration point should be located at or near the
center of the duct; however, insertion of a probe sheath into a small
duct may cause significant cross-sectional area interference and
blockage and yield incorrect coefficient values (Reference 9 in section
17.0). Therefore, to minimize the blockage effect, the calibration point
may be a few inches off-center if necessary. The actual blockage effect
will be negligible when the theoretical blockage, as determined by a
projected-area model of the probe sheath, is 2 percent or less of the
duct cross-sectional area for assemblies without external sheaths
(Figure 2-10a), and 3 percent or less for assemblies with external
sheaths (Figure 2-10b).
10.1.4.2 For those probe assemblies in which pitot tube-nozzle
interference is a factor (i.e., those in which the pitot-nozzle
separation distance fails to meet the specifications illustrated in
Figure 2-7A), the value of Cp(s) depends upon the amount of
free space between the tube and nozzle and, therefore, is a function of
nozzle size. In these instances, separate calibrations shall be
performed

[[Page 20]]

with each of the commonly used nozzle sizes in place. Note that the
single-velocity calibration technique is acceptable for this purpose,
even though the larger nozzle sizes (>0.635 cm or \1/4\ in.) are not
ordinarily used for isokinetic sampling at velocities around 910 m/min
(3,000 ft/min), which is the calibration velocity. Note also that it is
not necessary to draw an isokinetic sample during calibration (see
Reference 19 in section 17.0).
10.1.4.3 For a probe assembly constructed such that its pitot tube
is always used in the same orientation, only one side of the pitot tube
need be calibrated (the side which will face the flow). The pitot tube
must still meet the alignment specifications of Figure 2-2 or 2-3,
however, and must have an average deviation (m) value of 0.01 or less
(see section 10.1.4.4).
10.1.5 Field Use and Recalibration.
10.1.5.1 Field Use.
10.1.5.1.1 When a Type S pitot tube (isolated or in an assembly) is
used in the field, the appropriate coefficient value (whether assigned
or obtained by calibration) shall be used to perform velocity
calculations. For calibrated Type S pitot tubes, the A side coefficient
shall be used when the A side of the tube faces the flow, and the B side
coefficient shall be used when the B side faces the flow. Alternatively,
the arithmetic average of the A and B side coefficient values may be
used, irrespective of which side faces the flow.
10.1.5.1.2 When a probe assembly is used to sample a small duct,
30.5 to 91.4 cm (12 to 36 in.) in diameter, the probe sheath sometimes
blocks a significant part of the duct cross-section, causing a reduction
in the effective value of Cp(s). Consult Reference 9 (see
section 17.0) for details. Conventional pitot-sampling probe assemblies
are not recommended for use in ducts having inside diameters smaller
than 30.5 cm (12 in.) (see Reference 16 in section 17.0).
10.1.5.2 Recalibration.
10.1.5.2.1 Isolated Pitot Tubes. After each field use, the pitot
tube shall be carefully reexamined in top, side, and end views. If the
pitot face openings are still aligned within the specifications
illustrated in Figure 2-2 and Figure 2-3, it can be assumed that the
baseline coefficient of the pitot tube has not changed. If, however, the
tube has been damaged to the extent that it no longer meets the
specifications of Figure 2-2 and Figure 2-3, the damage shall either be
repaired to restore proper alignment of the face openings, or the tube
shall be discarded.
10.1.5.2.2 Pitot Tube Assemblies. After each field use, check the
face opening alignment of the pitot tube, as in section 10.1.5.2.1.
Also, remeasure the intercomponent spacings of the assembly. If the
intercomponent spacings have not changed and the face opening alignment
is acceptable, it can be assumed that the coefficient of the assembly
has not changed. If the face opening alignment is no longer within the
specifications of Figure 2-2 and Figure 2-3, either repair the damage or
replace the pitot tube (calibrating the new assembly, if necessary). If
the intercomponent spacings have changed, restore the original spacings,
or recalibrate the assembly.
10.2 Standard Pitot Tube (if applicable). If a standard pitot tube
is used for the velocity traverse, the tube shall be constructed
according to the criteria of section 6.7 and shall be assigned a
baseline coefficient value of 0.99. If the standard pitot tube is used
as part of an assembly, the tube shall be in an interference-free
arrangement (subject to the approval of the Administrator).
10.3 Temperature Sensors.
10.3.1 After each field use, calibrate dial thermometers, liquid-
filled bulb thermometers, thermocouple-potentiometer systems, and other
sensors at a temperature within 10 percent of the average absolute stack
temperature. For temperatures up to 405 [deg]C (761 [deg]F), use an ASTM
mercury-in-glass reference thermometer, or equivalent, as a reference.
Alternatively, either a reference thermocouple and potentiometer
(calibrated against NIST standards) or thermometric fixed points (e.g.,
ice bath and boiling water, corrected for barometric pressure) may be
used. For temperatures above 405 [deg]C (761 [deg]F), use a reference
thermocouple-potentiometer system calibrated against NIST standards or
an alternative reference, subject to the approval of the Administrator.
10.3.2 The temperature data recorded in the field shall be
considered valid. If, during calibration, the absolute temperature
measured with the sensor being calibrated and the reference sensor agree
within 1.5 percent, the temperature data taken in the field shall be
considered valid. Otherwise, the pollutant emission test shall either be
considered invalid or adjustments (if appropriate) of the test results
shall be made, subject to the approval of the Administrator.
10.4 Barometer. Calibrate the barometer used against a mercury
barometer or NIST-traceable barometer prior to each field test.

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this method (see
section 8.0).

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after final
calculation.
12.1 Nomenclature.
A = Cross-sectional area of stack, m\2\ (ft\2\).
Bws = Water vapor in the gas stream (from Method 4 (reference
method) or Method 5), proportion by volume.
Cp = Pitot tube coefficient, dimensionless.

[[Page 21]]

Cp(s) = Type S pitot tube coefficient, dimensionless.
Cp(std) = Standard pitot tube coefficient; use 0.99 if the
coefficient is unknown and the tube is designed according to
the criteria of sections 6.7.1 to 6.7.5 of this method.
De = Equivalent diameter.
K = 0.127 mm H2O (metric units). 0.005 in. H2O
(English units).
Kp = Velocity equation constant.
L = Length.
Md = Molecular weight of stack gas, dry basis (see section
8.6), g/g-mole (lb/lb-mole).
Ms = Molecular weight of stack gas, wet basis, g/g-mole (lb/
lb-mole).
n = Total number of traverse points.
Pbar = Barometric pressure at measurement site, mm Hg (in.
Hg).
Pg = Stack static pressure, mm Hg (in. Hg).
Ps = Absolute stack pressure (Pbar +
Pg), mm Hg (in. Hg),
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
Qsd = Dry volumetric stack gas flow rate corrected to
standard conditions, dscm/hr (dscf/hr).
T = Sensitivity factor for differential pressure gauges.
Ts(abavg) = Average absolute stack temperature, [deg]K
([deg]R).
= 273 + Ts for metric units,
= 460 + Ts for English units.
Ts = Stack temperature, [deg]C ([deg]F).
= 273 + Ts for metric units,
= 460 + Ts for English units.
Tstd = Standard absolute temperature, 293 [deg]K (528
[deg]R).
Vs = Average stack gas velocity, m/sec (ft/sec).
W = Width.
Fp = Velocity head of stack gas, mm H2O (in. H20).
Fpi = Individual velocity head reading at traverse point
``i'', mm (in.) H2O.
Fpstd = Velocity head measured by the standard pitot tube, cm
(in.) H2O.
Fps = Velocity head measured by the Type S pitot tube, cm
(in.) H2O.
3600 = Conversion Factor, sec/hr.
18.0 = Molecular weight of water, g/g-mole (lb/lb-mole).

12.2 Calculate T as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.045

12.3 Calculate De as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.046

12.4 Calibration of Type S Pitot Tube.
12.4.1 For each of the six pairs of Fp readings (i.e., three from
side A and three from side B) obtained in section 10.1.3, calculate the
value of the Type S pitot tube coefficient according to Equation 2-3:
[GRAPHIC] [TIFF OMITTED] TR17OC00.047

12.4.2 Calculate Cp(A), the mean A-side coefficient, and
Cp(B), the mean B-side coefficient. Calculate the difference
between these two average values.
12.4.3 Calculate the deviation of each of the three A-side values of
Cp(s) from Cp(A), and the deviation of each of the
three B-side values of Cp(s) from Cp(B), using
Equation 2-4:
[GRAPHIC] [TIFF OMITTED] TR17OC00.048

12.4.4 Calculate m the average deviation from the mean, for both the
A and B sides of the pitot tube. Use Equation 2-5:
[GRAPHIC] [TIFF OMITTED] TR17OC00.049

12.5 Molecular Weight of Stack Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.050

12.6 Average Stack Gas Velocity.

[[Page 22]]

[GRAPHIC] [TIFF OMITTED] TR27FE14.008

12.7 Average Stack Gas Dry Volumetric Flow Rate.
[GRAPHIC] [TIFF OMITTED] TR27FE14.027

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Mark, L.S. Mechanical Engineers' Handbook. New York. McGraw-Hill
Book Co., Inc. 1951.
2. Perry, J.H., ed. Chemical Engineers' Handbook. New York. McGraw-
Hill Book Co., Inc. 1960.
3. Shigehara, R.T., W.F. Todd, and W.S. Smith. Significance of
Errors in Stack Sampling Measurements. U.S. Environmental Protection
Agency, Research Triangle Park, N.C. (Presented at the Annual Meeting of
the Air Pollution Control Association, St. Louis, MO., June 14-19,
1970).
4. Standard Method for Sampling Stacks for Particulate Matter. In:
1971 Book of ASTM Standards, Part 23. Philadelphia, PA. 1971. ASTM
Designation D 2928-71.
5. Vennard, J.K. Elementary Fluid Mechanics. New York. John Wiley
and Sons, Inc. 1947.
6. Fluid Meters--Their Theory and Application. American Society of
Mechanical Engineers, New York, N.Y. 1959.
7. ASHRAE Handbook of Fundamentals. 1972. p. 208.
8. Annual Book of ASTM Standards, Part 26. 1974. p. 648.
9. Vollaro, R.F. Guidelines for Type S Pitot Tube Calibration. U.S.
Environmental Protection Agency, Research Triangle Park, N.C. (Presented
at 1st Annual Meeting, Source Evaluation Society, Dayton, OH, September
18, 1975.)
10. Vollaro, R.F. A Type S Pitot Tube Calibration Study. U.S.
Environmental Protection Agency, Emission Measurement Branch, Research
Triangle Park, N.C. July 1974.
11. Vollaro, R.F. The Effects of Impact Opening Misalignment on the
Value of the Type S Pitot Tube Coefficient. U.S. Environmental
Protection Agency, Emission Measurement Branch, Research Triangle Park,
NC. October 1976.
12. Vollaro, R.F. Establishment of a Baseline Coefficient Value for
Properly Constructed Type S Pitot Tubes. U.S. Environmental Protection
Agency, Emission Measurement Branch, Research Triangle Park, NC.
November 1976.
13. Vollaro, R.F. An Evaluation of Single-Velocity Calibration
Technique as a Means

[[Page 23]]

of Determining Type S Pitot Tube Coefficients. U.S. Environmental
Protection Agency, Emission Measurement Branch, Research Triangle Park,
NC. August 1975.
14. Vollaro, R.F. The Use of Type S Pitot Tubes for the Measurement
of Low Velocities. U.S. Environmental Protection Agency, Emission
Measurement Branch, Research Triangle Park, NC. November 1976.
15. Smith, Marvin L. Velocity Calibration of EPA Type Source
Sampling Probe. United Technologies Corporation, Pratt and Whitney
Aircraft Division, East Hartford, CT. 1975.
16. Vollaro, R.F. Recommended Procedure for Sample Traverses in
Ducts Smaller than 12 Inches in Diameter. U.S. Environmental Protection
Agency, Emission Measurement Branch, Research Triangle Park, NC.
November 1976.
17. Ower, E. and R.C. Pankhurst. The Measurement of Air Flow, 4th
Ed. London, Pergamon Press. 1966.
18. Vollaro, R.F. A Survey of Commercially Available Instrumentation
for the Measurement of Low-Range Gas Velocities. U.S. Environmental
Protection Agency, Emission Measurement Branch, Research Triangle Park,
NC. November 1976. (Unpublished Paper).
19. Gnyp, A.W., et al. An Experimental Investigation of the Effect
of Pitot Tube-Sampling Probe Configurations on the Magnitude of the S
Type Pitot Tube Coefficient for Commercially Available Source Sampling
Probes. Prepared by the University of Windsor for the Ministry of the
Environment, Toronto, Canada. February 1975.

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.055

[[Page 24]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.056

[[Page 25]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.057

[[Page 26]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.058

[GRAPHIC] [TIFF OMITTED] TR17OC00.059

PLANT___________________________________________________________________
DATE____________________________________________________________________

[[Page 27]]

RUN NO._________________________________________________________________
STACK DIA. OR DIMENSIONS, m (in.)_______________________________________
BAROMETRIC PRESS., mm Hg (in. Hg)_______________________________________
CROSS SECTIONAL AREA, m\2\ (ft\2\)______________________________________
OPERATORS_______________________________________________________________
PITOT TUBE I.D. NO._____________________________________________________
AVG. COEFFICIENT, Cp =__________________________________________________
LAST DATE CALIBRATED____________________________________________________

------------------------------------------------------------------------

-------------------------------------------------------------------------

------------------------------------------------------------------------

SCHEMATIC OF STACK CROSS SECTION

--------------------------------------------------------------------------------------------------------------------------------------------------------
Stack temperature
Traverse Pt. No. Vel. Hd., Fp mm (in.) ----------------------------------------------- Pg mm Hg (in. Hg) (Fp)\1/2\
H2O Ts, [deg]C ( [deg]F) Ts, [deg]K ([deg]R)
--------------------------------------------------------------------------------------------------------------------------------------------------------

--------------------------------------------------------------------------------------------------------------------------------------------------------

--------------------------------------------------------------------------------------------------------------------------------------------------------
Average(1)
--------------------------------------------------------------------------------------------------------------------------------------------------------

Figure 2-6. Velocity Traverse Data

[[Page 28]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.060

[GRAPHIC] [TIFF OMITTED] TR17OC00.061

PITOT TUBE IDENTIFICATION NUMBER:_______________________________________
DATE:___________________________________________________________________
CALIBRATED BY:__________________________________________________________

``A'' Side Calibration
----------------------------------------------------------------------------------------------------------------
FPstd cm H2O (in FP(s) cm H2O (in Deviation Cp(s)--
Run No. H2O) H2O) Cp(s) Cp(A)
----------------------------------------------------------------------------------------------------------------
1
----------------------------------------------------------------------------------------------------------------
2
----------------------------------------------------------------------------------------------------------------
3
----------------------------------------------------------------------------------------------------------------

[[Page 29]]

Cp, avg
(SIDE A)
----------------------------------------------------------------------------------------------------------------

``B'' Side Calibration
----------------------------------------------------------------------------------------------------------------
FPstd cm H2O (in FP(s) cm H2O (in Deviation Cp(s)--
Run No. H2O) H2O) Cp(s) Cp(B)
----------------------------------------------------------------------------------------------------------------
1
----------------------------------------------------------------------------------------------------------------
2
----------------------------------------------------------------------------------------------------------------
3
----------------------------------------------------------------------------------------------------------------
Cp, avg
(SIDE B)
----------------------------------------------------------------------------------------------------------------

[GRAPHIC] [TIFF OMITTED] TR17OC00.062

[Cp, avg (side A)--Cp, avg (side B)]*
*Must be less than or equal to 0.01

Figure 2-9. Pitot Tube Calibration Data

[[Page 30]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.063

Method 2A--Direct Measurement of Gas Volume Through Pipes and Small
Ducts

1.0 Scope and Application

1.1 This method is applicable for the determination of gas flow
rates in pipes and small ducts, either in-line or at exhaust positions,
within the temperature range of 0 to 50 [deg]C (32 to 122 [deg]F).
1.2 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas volume meter is used to measure gas volume directly.
Temperature and pressure measurements are made to allow correction of
the volume to standard conditions.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

[[Page 31]]

and health practices and determine the applicability of regulatory
limitations prior to performing this test method.

6.0 Equipment and Supplies

Specifications for the apparatus are given below. Any other
apparatus that has been demonstrated (subject to approval of the
Administrator) to be capable of meeting the specifications will be
considered acceptable.
6.1 Gas Volume Meter. A positive displacement meter, turbine meter,
or other direct measuring device capable of measuring volume to within 2
percent. The meter shall be equipped with a temperature sensor (accurate
to within 2 percent of the minimum absolute temperature) and a pressure
gauge (accurate to within 2.5 mm Hg). The manufacturer's recommended
capacity of the meter shall be sufficient for the expected maximum and
minimum flow rates for the sampling conditions. Temperature, pressure,
corrosive characteristics, and pipe size are factors necessary to
consider in selecting a suitable gas meter.
6.2 Barometer. A mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 2.5 mm Hg.

Note: In many cases, the barometric reading may be obtained from a
nearby National Weather Service station, in which case the station value
(which is the absolute barometric pressure) shall be requested and an
adjustment for elevation differences between the weather station and
sampling point shall be applied at a rate of minus 2.5 mm (0.1 in.) Hg
per 30 m (100 ft) elevation increase or vice versa for elevation
decrease.

6.3 Stopwatch. Capable of measurement to within 1 second.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection and Analysis

8.1 Installation. As there are numerous types of pipes and small
ducts that may be subject to volume measurement, it would be difficult
to describe all possible installation schemes. In general, flange
fittings should be used for all connections wherever possible. Gaskets
or other seal materials should be used to assure leak-tight connections.
The volume meter should be located so as to avoid severe vibrations and
other factors that may affect the meter calibration.
8.2 Leak Test.
8.2.1 A volume meter installed at a location under positive pressure
may be leak-checked at the meter connections by using a liquid leak
detector solution containing a surfactant. Apply a small amount of the
solution to the connections. If a leak exists, bubbles will form, and
the leak must be corrected.
8.2.2 A volume meter installed at a location under negative pressure
is very difficult to test for leaks without blocking flow at the inlet
of the line and watching for meter movement. If this procedure is not
possible, visually check all connections to assure leak-tight seals.
8.3 Volume Measurement.
8.3.1 For sources with continuous, steady emission flow rates,
record the initial meter volume reading, meter temperature(s), meter
pressure, and start the stopwatch. Throughout the test period, record
the meter temperatures and pressures so that average values can be
determined. At the end of the test, stop the timer, and record the
elapsed time, the final volume reading, meter temperature, and pressure.
Record the barometric pressure at the beginning and end of the test run.
Record the data on a table similar to that shown in Figure 2A-1.
8.3.2 For sources with noncontinuous, non-steady emission flow
rates, use the procedure in section 8.3.1 with the addition of the
following: Record all the meter parameters and the start and stop times
corresponding to each process cyclical or noncontinuous event.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.1-10.4..................... Sampling Ensure accurate
equipment measurement of stack
calibration. gas flow rate,
sample volume.
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 Volume Meter.
10.1.1 The volume meter is calibrated against a standard reference
meter prior to its initial use in the field. The reference meter is a
spirometer or liquid displacement meter with a capacity consistent with
that of the test meter.
10.1.2 Alternatively, a calibrated, standard pitot may be used as
the reference meter in conjunction with a wind tunnel assembly. Attach
the test meter to the wind tunnel so that the total flow passes through
the test meter. For each calibration run, conduct a 4-point traverse
along one stack diameter at a position at least eight diameters of
straight tunnel downstream and two diameters upstream of any bend,
inlet, or air mover. Determine the traverse point locations as specified
in Method 1. Calculate the reference volume using the velocity values
following the procedure in Method 2, the wind tunnel cross-sectional
area, and the run time.

[[Page 32]]

10.1.3 Set up the test meter in a configuration similar to that used
in the field installation (i.e., in relation to the flow moving device).
Connect the temperature sensor and pressure gauge as they are to be used
in the field. Connect the reference meter at the inlet of the flow line,
if appropriate for the meter, and begin gas flow through the system to
condition the meters. During this conditioning operation, check the
system for leaks.
10.1.4 The calibration shall be performed during at least three
different flow rates. The calibration flow rates shall be about 0.3,
0.6, and 0.9 times the rated maximum flow rate of the test meter.
10.1.5 For each calibration run, the data to be collected include:
reference meter initial and final volume readings, the test meter
initial and final volume reading, meter average temperature and
pressure, barometric pressure, and run time. Repeat the runs at each
flow rate at least three times.
10.1.6 Calculate the test meter calibration coefficient as indicated
in section 12.2.
10.1.7 Compare the three Ym values at each of the flow
rates tested and determine the maximum and minimum values. The
difference between the maximum and minimum values at each flow rate
should be no greater than 0.030. Extra runs may be required to complete
this requirement. If this specification cannot be met in six successive
runs, the test meter is not suitable for use. In addition, the meter
coefficients should be between 0.95 and 1.05. If these specifications
are met at all the flow rates, average all the Ym values from
runs meeting the specifications to obtain an average meter calibration
coefficient, Ym.
10.1.8 The procedure above shall be performed at least once for each
volume meter. Thereafter, an abbreviated calibration check shall be
completed following each field test. The calibration of the volume meter
shall be checked with the meter pressure set at the average value
encountered during the field test. Three calibration checks (runs) shall
be performed using this average flow rate value. Calculate the average
value of the calibration factor. If the calibration has changed by more
than 5 percent, recalibrate the meter over the full range of flow as
described above.

Note: If the volume meter calibration coefficient values obtained
before and after a test series differ by more than 5 percent, the test
series shall either be voided, or calculations for the test series shall
be performed using whichever meter coefficient value (i.e., before or
after) gives the greater value of pollutant emission rate.

10.2 Temperature Sensor. After each test series, check the
temperature sensor at ambient temperature. Use an American Society for
Testing and Materials (ASTM) mercury-in-glass reference thermometer, or
equivalent, as a reference. If the sensor being checked agrees within 2
percent (absolute temperature) of the reference, the temperature data
collected in the field shall be considered valid. Otherwise, the test
data shall be considered invalid or adjustments of the results shall be
made, subject to the approval of the Administrator.
10.3 Barometer. Calibrate the barometer used against a mercury
barometer or NIST-traceable barometer prior to the field test.

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this method (see
section 8.0).

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra decimal figure
beyond that of the acquired data. Round off figures after final
calculation.

12.1 Nomenclature.

f = Final reading.
i = Initial reading.
Pbar = Barometric pressure, mm Hg.
Pg = Average static pressure in volume meter, mm Hg.
Qs = Gas flow rate, m\3\/min, standard conditions.
s = Standard conditions, 20 [deg]C and 760 mm Hg.
Tr = Reference meter average temperature, [deg]K ([deg]R).
Tm = Test meter average temperature, [deg]K ([deg]R).
Vr = Reference meter volume reading, m\3\.
Vm = Test meter volume reading, m\3\.
Ym = Test meter calibration coefficient, dimensionless.
k = Elapsed test period time, min.
12.2 Test Meter Calibration Coefficient.
[GRAPHIC] [TIFF OMITTED] TR27FE14.009

12.3 Volume.

[[Page 33]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.065

12.4 Gas Flow Rate.
[GRAPHIC] [TIFF OMITTED] TR17OC00.066

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Rom, Jerome J. Maintenance, Calibration, and Operation of
Isokinetic Source Sampling Equipment. U.S. Environmental Protection
Agency, Research Triangle Park, NC. Publication No. APTD-0576. March
1972.
2. Wortman, Martin, R. Vollaro, and P.R. Westlin. Dry Gas Volume
Meter Calibrations. Source Evaluation Society Newsletter. Vol. 2, No. 2.
May 1977.
3. Westlin, P.R., and R.T. Shigehara. Procedure for Calibrating and
Using Dry Gas Volume Meters as Calibration Standards. Source Evaluation
Society Newsletter. Vol. 3, No. 1. February 1978.

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 2B--Determination of Exhaust Gas Volume Flow Rate From Gasoline
Vapor Incinerators

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should also have a thorough knowledge of at
least the following additional test methods: Method 1, Method 2, Method
2A, Method 10, Method 25A, Method 25B.

1.0 Scope and Application

1.1 This method is applicable for the determination of exhaust
volume flow rate from incinerators that process gasoline vapors
consisting primarily of alkanes, alkenes, and/or arenes (aromatic
hydrocarbons). It is assumed that the amount of auxiliary fuel is
negligible.
1.2 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Organic carbon concentration and volume flow rate are measured
at the incinerator inlet using either Method 25A or Method 25B and
Method 2A, respectively. Organic carbon, carbon dioxide
(CO2), and carbon monoxide (CO) concentrations are measured
at the outlet using either Method 25A or Method 25B and Method 10,
respectively. The ratio of total carbon at the incinerator inlet and
outlet is multiplied by the inlet volume to determine the exhaust volume
flow rate.

3.0 Definitions

Same as section 3.0 of Method 10 and Method 25A.

4.0 Interferences

Same as section 4.0 of Method 10.

5.0 Safety

6.0 Equipment and Supplies

Same as section 6.0 of Method 2A, Method 10, and Method 25A and/or
Method 25B as applicable, with the addition of the following:
6.1 This analyzer must meet the specifications set forth in section
6.1.2 of Method 10, except that the span shall be 15 percent
CO2 by volume.

7.0 Reagents and Standards

Same as section 7.0 of Method 10 and Method 25A, with the following
addition and exceptions:
7.1 Carbon Dioxide Analyzer Calibration. CO2 gases
meeting the specifications set forth in section 7 of Method 6C are
required.
7.2 Hydrocarbon Analyzer Calibration. Methane shall not be used as a
calibration gas when performing this method.
7.3 Fuel Gas. If Method 25B is used to measure the organic carbon
concentrations at both the inlet and exhaust, no fuel gas is required.

[[Page 34]]

8.0 Sample Collection and Analysis

8.1 Pre-test Procedures. Perform all pre-test procedures (e.g.,
system performance checks, leak checks) necessary to determine gas
volume flow rate and organic carbon concentration in the vapor line to
the incinerator inlet and to determine organic carbon, carbon monoxide,
and carbon dioxide concentrations at the incinerator exhaust, as
outlined in Method 2A, Method 10, and Method 25A and/or Method 25B as
applicable.
8.2 Sampling. At the beginning of the test period, record the
initial parameters for the inlet volume meter according to the
procedures in Method 2A and mark all of the recorder strip charts to
indicate the start of the test. Conduct sampling and analysis as
outlined in Method 2A, Method 10, and Method 25A and/or Method 25B as
applicable. Continue recording inlet organic and exhaust CO2,
CO, and organic concentrations throughout the test. During periods of
process interruption and halting of gas flow, stop the timer and mark
the recorder strip charts so that data from this interruption are not
included in the calculations. At the end of the test period, record the
final parameters for the inlet volume meter and mark the end on all of
the recorder strip charts.
8.3 Post-test Procedures. Perform all post-test procedures (e.g.,
drift tests, leak checks), as outlined in Method 2A, Method 10, and
Method 25A and/or Method 25B as applicable.

9.0 Quality Control

Same as section 9.0 of Method 2A, Method 10, and Method 25A.

10.0 Calibration and Standardization

Same as section 10.0 of Method 2A, Method 10, and Method 25A.

Note: If a manifold system is used for the exhaust analyzers, all
the analyzers and sample pumps must be operating when the analyzer
calibrations are performed.

10.1 If an analyzer output does not meet the specifications of the
method, invalidate the test data for the period. Alternatively,
calculate the exhaust volume results using initial calibration data and
using final calibration data and report both resulting volumes. Then,
for emissions calculations, use the volume measurement resulting in the
greatest emission rate or concentration.

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this method (see
section 8.0).

12.0 Data Analysis and Calculations

Carry out the calculations, retaining at least one extra decimal
figure beyond that of the acquired data. Round off figures after the
final calculation.
12.1 Nomenclature.

COe = Mean carbon monoxide concentration in system exhaust,
ppm.
(CO2)a = Ambient carbon dioxide concentration, ppm
(if not measured during the test period, may be assumed to
equal 380 ppm).
(CO2)e = Mean carbon dioxide concentration in
system exhaust, ppm.
HCe = Mean organic concentration in system exhaust as defined
by the calibration gas, ppm.
Hci = Mean organic concentration in system inlet as defined
by the calibration gas, ppm.
Ke = Hydrocarbon calibration gas factor for the exhaust
hydrocarbon analyzer, unitless [equal to the number of carbon
atoms per molecule of the gas used to calibrate the analyzer
(2 for ethane, 3 for propane, etc.)].
Ki = Hydrocarbon calibration gas factor for the inlet
hydrocarbon analyzer, unitless.
Ves = Exhaust gas volume, m\3\.
Vis = Inlet gas volume, m\3\.
Qes = Exhaust gas volume flow rate, m\3\/min.
Qis = Inlet gas volume flow rate, m\3\/min.
k = Sample run time, min.
S = Standard conditions: 20 [deg]C, 760 mm Hg.

12.2 Concentrations. Determine mean concentrations of inlet
organics, outlet CO2, outlet CO, and outlet organics
according to the procedures in the respective methods and the analyzers'
calibration curves, and for the time intervals specified in the
applicable regulations.
12.3 Exhaust Gas Volume. Calculate the exhaust gas volume as
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.067

12.4 Exhaust Gas Volume Flow Rate. Calculate the exhaust gas volume
flow rate as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.210

[[Page 35]]

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as section 16.0 of Method 2A, Method 10, and Method 25A.

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 2C--Determination of Gas Velocity and Volumetric Flow Rate in
Small Stacks or Ducts (Standard Pitot Tube)

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling) essential to its
performance. Some material is incorporated by reference from other
methods in this part. Therefore, to obtain reliable results, persons
using this method should also have a thorough knowledge of at least the
following additional test methods: Method 1, Method 2.

1.0 Scope and Application

1.1 This method is applicable for the determination of average
velocity and volumetric flow rate of gas streams in small stacks or
ducts. Limits on the applicability of this method are identical to those
set forth in Method 2, section 1.0, except that this method is limited
to stationary source stacks or ducts less than about 0.30 meter (12 in.)
in diameter, or 0.071 m\2\ (113 in.\2\) in cross-sectional area, but
equal to or greater than about 0.10 meter (4 in.) in diameter, or 0.0081
m\2\ (12.57 in.\2\) in cross-sectional area.
1.2 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 The average gas velocity in a stack or duct is determined from
the gas density and from measurement of velocity heads with a standard
pitot tube.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Same as Method 2, section 6.0, with the exception of the following:
6.1 Standard Pitot Tube (instead of Type S). A standard pitot tube
which meets the specifications of section 6.7 of Method 2. Use a
coefficient of 0.99 unless it is calibrated against another standard
pitot tube with a NIST-traceable coefficient (see section 10.2 of Method
2).
6.2 Alternative Pitot Tube. A modified hemispherical-nosed pitot
tube (see Figure 2C-1), which features a shortened stem and enlarged
impact and static pressure holes. Use a coefficient of 0.99 unless it is
calibrated as mentioned in section 6.1 above. This pitot tube is useful
in particulate liquid droplet-laden gas streams when a ``back purge'' is
ineffective.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection and Analysis

8.1 Follow the general procedures in section 8.0 of Method 2, except
conduct the measurements at the traverse points specified in Method 1A.
The static and impact pressure holes of standard pitot tubes are
susceptible to plugging in particulate-laden gas streams. Therefore,
adequate proof that the openings of the pitot tube have not plugged
during the traverse period must be furnished; this can be done by taking
the velocity head (Fp) heading at the final traverse point, cleaning out
the impact and static holes of the standard pitot tube by ``back-
purging'' with pressurized air, and then taking another Fp reading. If
the Fp readings made before and after the air purge are the same (within
5 percent) the traverse is acceptable. Otherwise, reject the run. Note
that if the Fp at the final traverse point is unsuitably low, another
point may be selected. If ``back purging'' at regular intervals is part
of the procedure, then take comparative Fp readings, as above, for the
last two back purges at which suitably high Fp readings are observed.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.0.......................... Sampling Ensure accurate
equipment measurement of stack
calibration. gas velocity head.
------------------------------------------------------------------------

[[Page 36]]

10.0 Calibration and Standardization

Same as Method 2, sections 10.2 through 10.4.

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this method (see
section 8.0).

12.0 Calculations and Data Analysis

Same as Method 2, section 12.0.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as Method 2, section 16.0.

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.068

Method 2D--Measurement of Gas Volume Flow Rates in Small Pipes and Ducts

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling) essential to its
performance. Some material is incorporated by reference from other
methods in this part. Therefore, to obtain reliable results, persons
using this method should also have a thorough knowledge of at least the
following additional test methods: Method 1, Method 2, and Method 2A.

1.0 Scope and Application

1.1 This method is applicable for the determination of the
volumetric flow rates of gas streams in small pipes and ducts. It can be
applied to intermittent or variable gas flows only with particular
caution.
1.2 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 All the gas flow in the pipe or duct is directed through a
rotameter, orifice plate or similar device to measure flow rate or
pressure drop. The device has been previously calibrated in a manner
that insures its proper calibration for the gas being measured. Absolute
temperature and pressure measurements are made to allow correction of
volumetric flow rates to standard conditions.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

[[Page 37]]

6.0 Equipment and Supplies

Specifications for the apparatus are given below. Any other
apparatus that has been demonstrated (subject to approval of the
Administrator) to be capable of meeting the specifications will be
considered acceptable.
6.1 Gas Metering Rate or Flow Element Device. A rotameter, orifice
plate, or other volume rate or pressure drop measuring device capable of
measuring the stack flow rate to within 5 percent. The metering device
shall be equipped with a temperature gauge accurate to within 2 percent
of the minimum absolute stack temperature and a pressure gauge (accurate
to within 5 mm Hg). The capacity of the metering device shall be
sufficient for the expected maximum and minimum flow rates at the stack
gas conditions. The magnitude and variability of stack gas flow rate,
molecular weight, temperature, pressure, dewpoint, and corrosive
characteristics, and pipe or duct size are factors to consider in
choosing a suitable metering device.
6.2 Barometer. Same as Method 2, section 6.5.
6.3 Stopwatch. Capable of measurement to within 1 second.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection and Analysis

8.1 Installation and Leak Check. Same as Method 2A, sections 8.1 and
8.2, respectively.
8.2 Volume Rate Measurement.
8.2.1 Continuous, Steady Flow. At least once an hour, record the
metering device flow rate or pressure drop reading, and the metering
device temperature and pressure. Make a minimum of 12 equally spaced
readings of each parameter during the test period. Record the barometric
pressure at the beginning and end of the test period. Record the data on
a table similar to that shown in Figure 2D-1.
8.2.2 Noncontinuous and Nonsteady Flow. Use volume rate devices with
particular caution. Calibration will be affected by variation in stack
gas temperature, pressure and molecular weight. Use the procedure in
section 8.2.1 with the addition of the following: Record all the
metering device parameters on a time interval frequency sufficient to
adequately profile each process cyclical or noncontinuous event. A
multichannel continuous recorder may be used.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.0.......................... Sampling Ensure accurate
equipment measurement of stack
calibration. gas flow rate or
sample volume.
------------------------------------------------------------------------

10.0 Calibration and Standardization

Same as Method 2A, section 10.0, with the following exception:
10.1 Gas Metering Device. Same as Method 2A, section 10.1, except
calibrate the metering device with the principle stack gas to be
measured (examples: air, nitrogen) against a standard reference meter. A
calibrated dry gas meter is an acceptable reference meter. Ideally,
calibrate the metering device in the field with the actual gas to be
metered. For metering devices that have a volume rate readout, calculate
the test metering device calibration coefficient, Ym, for
each run shown in Equation 2D-2 section 12.3.
10.2 For metering devices that do not have a volume rate readout,
refer to the manufacturer's instructions to calculate the Vm2
corresponding to each Vr.
10.3 Temperature Gauge. Use the procedure and specifications in
Method 2A, section 10.2. Perform the calibration at a temperature that
approximates field test conditions.
10.4 Barometer. Calibrate the barometer used against a mercury
barometer or NIST-traceable barometer prior to the field test.

11.0 Analytical Procedure.

Sample collection and analysis are concurrent for this method (see
section 8.0).

12.0 Data Analysis and Calculations

12.1 Nomenclature.
Pbar = Barometric pressure, mm Hg (in. Hg).
Pm = Test meter average static pressure, mm Hg (in. Hg).
Qr = Reference meter volume flow rate reading, m\3\/min
(ft\3\/min).
Qm = Test meter volume flow rate reading, m\3\/min (ft\3\/
min).
Tr = Absolute reference meter average temperature, [deg]K
([deg]R).
Tm = Absolute test meter average temperature, [deg]K
([deg]R).
Kl = 0.3855 [deg]K/mm Hg for metric units, = 17.65 [deg]R/in.
Hg for English units.
12.2 Gas Flow Rate.
[GRAPHIC] [TIFF OMITTED] TR17OC00.069

12.3 Test Meter Device Calibration Coefficient. Calculation for
testing metering device calibration coefficient, Ym.
[GRAPHIC] [TIFF OMITTED] TR17OC00.070

[[Page 38]]

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Spink, L.K. Principles and Practice of Flowmeter Engineering. The
Foxboro Company. Foxboro, MA. 1967.
2. Benedict, R.P. Fundamentals of Temperature, Pressure, and Flow
Measurements. John Wiley & Sons, Inc. New York, NY. 1969.
3. Orifice Metering of Natural Gas. American Gas Association.
Arlington, VA. Report No. 3. March 1978. 88 pp.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Plant___________________________________________________________________
Date____________________________________________________________________
Run No._________________________________________________________________
Sample location_________________________________________________________
Barometric pressure (mm Hg):
Start___________________________________________________________________
Finish__________________________________________________________________
Operators_______________________________________________________________
Metering device No._____________________________________________________
Calibration coefficient_________________________________________________
Calibration gas_________________________________________________________
Date to recalibrate_____________________________________________________

----------------------------------------------------------------------------------------------------------------
Temperature
Time Flow rate reading Static Pressure ---------------------------------------
[mm Hg (in. Hg)] [deg]C ([deg]F) [deg]K ([deg]R)
----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------

Figure 2D-1. Volume Flow Rate Measurement Data

Method 2E--Determination of Landfill Gas Production Flow Rate

1.0 Scope and Application

1.1 Applicability. This method applies to the measurement of
landfill gas (LFG) production flow rate from municipal solid waste
landfills and is used to calculate the flow rate of nonmethane organic
compounds (NMOC) from landfills.
1.2 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Extraction wells are installed either in a cluster of three or
at five dispersed locations in the landfill. A blower is used to extract
LFG from the landfill. LFG composition, landfill pressures, and orifice
pressure differentials from the wells are measured and the landfill gas
production flow rate is calculated.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

5.1 Since this method is complex, only experienced personnel should
perform the test. Landfill gas contains methane, therefore explosive
mixtures may exist at or near the landfill. It is advisable to take
appropriate

[[Page 39]]

safety precautions when testing landfills, such as refraining from
smoking and installing explosion-proof equipment.

6.0 Equipment and Supplies

6.1 Well Drilling Rig. Capable of boring a 0.61 m (24 in.) diameter
hole into the landfill to a minimum of 75 percent of the landfill depth.
The depth of the well shall not extend to the bottom of the landfill or
the liquid level.
6.2 Gravel. No fines. Gravel diameter should be appreciably larger
than perforations stated in sections 6.10 and 8.2.
6.3 Bentonite.
6.4 Backfill Material. Clay, soil, and sandy loam have been found to
be acceptable.
6.5 Extraction Well Pipe. Minimum diameter of 3 in., constructed of
polyvinyl chloride (PVC), high density polyethylene (HDPE), fiberglass,
stainless steel, or other suitable nonporous material capable of
transporting landfill gas.
6.6 Above Ground Well Assembly. Valve capable of adjusting gas flow,
such as a gate, ball, or butterfly valve; sampling ports at the well
head and outlet; and a flow measuring device, such as an in-line orifice
meter or pitot tube. A schematic of the aboveground well head assembly
is shown in Figure 2E-1.
6.7 Cap. Constructed of PVC or HDPE.
6.8 Header Piping. Constructed of PVC or HDPE.
6.9 Auger. Capable of boring a 0.15-to 0.23-m (6-to 9-in.) diameter
hole to a depth equal to the top of the perforated section of the
extraction well, for pressure probe installation.
6.10 Pressure Probe. Constructed of PVC or stainless steel (316),
0.025-m (1-in.). Schedule 40 pipe. Perforate the bottom two-thirds. A
minimum requirement for perforations is slots or holes with an open area
equivalent to four 0.006-m (\1/4\-in.) diameter holes spaced 90[deg]
apart every 0.15 m (6 in.).
6.11 Blower and Flare Assembly. Explosion-proof blower, capable of
extracting LFG at a flow rate of 8.5 m\3\/min (300 ft\3\/min), a water
knockout, and flare or incinerator.
6.12 Standard Pitot Tube and Differential Pressure Gauge for Flow
Rate Calibration with Standard Pitot. Same as Method 2, sections 6.7 and
6.8.
6.13 Orifice Meter. Orifice plate, pressure tabs, and pressure
measuring device to measure the LFG flow rate.
6.14 Barometer. Same as Method 4, section 6.1.5.
6.15 Differential Pressure Gauge. Water-filled U-tube manometer or
equivalent, capable of measuring within 0.02 mm Hg (0.01 in.
H2O), for measuring the pressure of the pressure probes.

7.0 Reagents and Standards. Not Applicable

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Placement of Extraction Wells. The landfill owner or operator
may install a single cluster of three extraction wells in a test area or
space five equal-volume wells over the landfill. The cluster wells are
recommended but may be used only if the composition, age of the refuse,
and the landfill depth of the test area can be determined.
8.1.1 Cluster Wells. Consult landfill site records for the age of
the refuse, depth, and composition of various sections of the landfill.
Select an area near the perimeter of the landfill with a depth equal to
or greater than the average depth of the landfill and with the average
age of the refuse between 2 and 10 years old. Avoid areas known to
contain nondecomposable materials, such as concrete and asbestos. Locate
the cluster wells as shown in Figure 2E-2.
8.1.1.1 The age of the refuse in a test area will not be uniform, so
calculate a weighted average age of the refuse as shown in section 12.2.
8.1.2 Equal Volume Wells. Divide the sections of the landfill that
are at least 2 years old into five areas representing equal volumes.
Locate an extraction well near the center of each area.
8.2 Installation of Extraction Wells. Use a well drilling rig to dig
a 0.6 m (24 in.) diameter hole in the landfill to a minimum of 75
percent of the landfill depth, not to extend to the bottom of the
landfill or the liquid level. Perforate the bottom two thirds of the
extraction well pipe. A minimum requirement for perforations is holes or
slots with an open area equivalent to 0.01-m (0.5-in.) diameter holes
spaced 90[deg] apart every 0.1 to 0.2 m (4 to 8 in.). Place the
extraction well in the center of the hole and backfill with gravel to a
level 0.30 m (1 ft) above the perforated section. Add a layer of
backfill material 1.2 m (4 ft) thick. Add a layer of bentonite 0.9 m (3
ft) thick, and backfill the remainder of the hole with cover material or
material equal in permeability to the existing cover material. The
specifications for extraction well installation are shown in Figure 2E-
3.
8.3 Pressure Probes. Shallow pressure probes are used in the check
for infiltration of air into the landfill, and deep pressure probes are
use to determine the radius of influence. Locate pressure probes along
three radial arms approximately 120[deg] apart at distances of 3, 15,
30, and 45 m (10, 50, 100, and 150 ft) from the extraction well. The
tester has the option of locating additional pressure probes at
distances every 15 m (50 feet) beyond 45 m (150 ft). Example placements
of probes are shown in Figure 2E-4. The 15-, 30-, and 45-m, (50-, 100-,
and 150-ft) probes from each well, and any additional probes located
along the three radial arms (deep probes),

[[Page 40]]

shall extend to a depth equal to the top of the perforated section of
the extraction wells. All other probes (shallow probes) shall extend to
a depth equal to half the depth of the deep probes.
8.3.1 Use an auger to dig a hole, 0.15- to 0.23-m (6-to 9-in.) in
diameter, for each pressure probe. Perforate the bottom two thirds of
the pressure probe. A minimum requirement for perforations is holes or
slots with an open area equivalent to four 0.006-m (0.25-in.) diameter
holes spaced 90[deg] apart every 0.15 m (6 in.). Place the pressure
probe in the center of the hole and backfill with gravel to a level 0.30
m (1 ft) above the perforated section. Add a layer of backfill material
at least 1.2 m (4 ft) thick. Add a layer of bentonite at least 0.3 m (1
ft) thick, and backfill the remainder of the hole with cover material or
material equal in permeability to the existing cover material. The
specifications for pressure probe installation are shown in Figure 2E-5.
8.4 LFG Flow Rate Measurement. Place the flow measurement device,
such as an orifice meter, as shown in Figure 2E-1. Attach the wells to
the blower and flare assembly. The individual wells may be ducted to a
common header so that a single blower, flare assembly, and flow meter
may be used. Use the procedures in section 10.1 to calibrate the flow
meter.
8.5 Leak-Check. A leak-check of the above ground system is required
for accurate flow rate measurements and for safety. Sample LFG at the
well head sample port and at the outlet sample port. Use Method 3C to
determine nitrogen (N2) concentrations. Determine the
difference between the well head and outlet N2 concentrations
using the formula in section 12.3. The system passes the leak-check if
the difference is less than 10,000 ppmv.
8.6 Static Testing. Close the control valves on the well heads
during static testing. Measure the gauge pressure (Pg) at
each deep pressure probe and the barometric pressure (Pbar)
every 8 hours (hr) for 3 days. Convert the gauge pressure of each deep
pressure probe to absolute pressure using the equation in section 12.4.
Record as Pi (initial absolute pressure).
8.6.1 For each probe, average all of the 8-hr deep pressure probe
readings (Pi) and record as Pia (average absolute
pressure). Pia is used in section 8.7.5 to determine the
maximum radius of influence.
8.6.2 Measure the static flow rate of each well once during static
testing.
8.7 Short-Term Testing. The purpose of short-term testing is to
determine the maximum vacuum that can be applied to the wells without
infiltration of ambient air into the landfill. The short-term testing is
performed on one well at a time. Burn all LFG with a flare or
incinerator.
8.7.1 Use the blower to extract LFG from a single well at a rate at
least twice the static flow rate of the respective well measured in
section 8.6.2. If using a single blower and flare assembly and a common
header system, close the control valve on the wells not being measured.
Allow 24 hr for the system to stabilize at this flow rate.
8.7.2 Test for infiltration of air into the landfill by measuring
the gauge pressures of the shallow pressure probes and using Method 3C
to determine the LFG N2 concentration. If the LFG
N2 concentration is less than 5 percent and all of the
shallow probes have a positive gauge pressure, increase the blower
vacuum by 3.7 mm Hg (2 in. H2O), wait 24 hr, and repeat the
tests for infiltration. Continue the above steps of increasing blower
vacuum by 3.7 mm Hg (2 in. H2O), waiting 24 hr, and testing
for infiltration until the concentration of N2 exceeds 5
percent or any of the shallow probes have a negative gauge pressure.
When this occurs,reduce the blower vacuum to the maximum setting at
which the N2 concentration was less than 5 percent and the
gauge pressures of the shallow probes are positive.
8.7.3 At this blower vacuum, measure atmospheric pressure
(Pbar) every 8 hr for 24 hr, and record the LFG flow rate
(Qs) and the probe gauge pressures (Pf) for all of
the probes. Convert the gauge pressures of the deep probes to absolute
pressures for each 8-hr reading at Qs as shown in section
12.4.
8.7.4 For each probe, average the 8-hr deep pressure probe absolute
pressure readings and record as Pfa (the final average
absolute pressure).
8.7.5 For each probe, compare the initial average pressure
(Pia) from section 8.6.1 to the final average pressure
(Pfa). Determine the furthermost point from the well head
along each radial arm where Pfa Pia.
This distance is the maximum radius of influence (Rm), which
is the distance from the well affected by the vacuum. Average these
values to determine the average maximum radius of influence
(Rma).
8.7.6 Calculate the depth (Dst) affected by the
extraction well during the short term test as shown in section 12.6. If
the computed value of Dst exceeds the depth of the landfill,
set Dst equal to the landfill depth.
8.7.7 Calculate the void volume (V) for the extraction well as shown
in section 12.7.
8.7.8 Repeat the procedures in section 8.7 for each well.
8.8 Calculate the total void volume of the test wells
(Vv) by summing the void volumes (V) of each well.
8.9 Long-Term Testing. The purpose of long-term testing is to
extract two void volumes of LFG from the extraction wells. Use the
blower to extract LFG from the wells. If a single Blower and flare
assembly and common header system are used, open all control valves and
set the blower vacuum equal to

[[Page 41]]

the highest stabilized blower vacuum demonstrated by any individual well
in section 8.7. Every 8 hr, sample the LFG from the well head sample
port, measure the gauge pressures of the shallow pressure probes, the
blower vacuum, the LFG flow rate, and use the criteria for infiltration
in section 8.7.2 and Method 3C to test for infiltration. If infiltration
is detected, do not reduce the blower vacuum, instead reduce the LFG
flow rate from the well by adjusting the control valve on the well head.
Adjust each affected well individually. Continue until the equivalent of
two total void volumes (Vv) have been extracted, or until
Vt = 2Vv.
8.9.1 Calculate Vt, the total volume of LFG extracted
from the wells, as shown in section 12.8.
8.9.2 Record the final stabilized flow rate as Qf and the
gauge pressure for each deep probe. If, during the long term testing,
the flow rate does not stabilize, calculate Qf by averaging
the last 10 recorded flow rates.
8.9.3 For each deep probe, convert each gauge pressure to absolute
pressure as in section 12.4. Average these values and record as
Psa. For each probe, compare Pia to
Psa. Determine the furthermost point from the well head along
each radial arm where Psa Pia. This
distance is the stabilized radius of influence. Average these values to
determine the average stabilized radius of influence (Rsa).
8.10 Determine the NMOC mass emission rate using the procedures in
section 12.9 through 12.15.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.1.......................... LFG flow rate Ensures accurate
meter measurement of LFG
calibration. flow rate and sample
volume
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 LFG Flow Rate Meter (Orifice) Calibration Procedure. Locate a
standard pitot tube in line with an orifice meter. Use the procedures in
section 8, 12.5, 12.6, and 12.7 of Method 2 to determine the average dry
gas volumetric flow rate for at least five flow rates that bracket the
expected LFG flow rates, except in section 8.1, use a standard pitot
tube rather than a Type S pitot tube. Method 3C may be used to determine
the dry molecular weight. It may be necessary to calibrate more than one
orifice meter in order to bracket the LFG flow rates. Construct a
calibration curve by plotting the pressure drops across the orifice
meter for each flow rate versus the average dry gas volumetric flow rate
in m\3\/min of the gas.

11.0 Procedures [Reserved]

12.0 Data Analysis and Calculations

12.1 Nomenclature.
A = Age of landfill, yr.
Aavg = Average age of the refuse tested, yr.
Ai = Age of refuse in the ith fraction, yr.
Ar = Acceptance rate, Mg/yr.
CNMOC = NMOC concentration, ppmv as hexane (CNMOC
= Ct/6).
Co = Concentration of N2 at the outlet, ppmv.
Ct = NMOC concentration, ppmv (carbon equivalent) from Method
25C.
Cw = Concentration of N2 at the wellhead, ppmv.
D = Depth affected by the test wells, m.
Dst = Depth affected by the test wells in the short-term
test, m.
e = Base number for natural logarithms (2.718).
f = Fraction of decomposable refuse in the landfill.
fi = Fraction of the refuse in the ith section.
k = Landfill gas generation constant, yr^-1.
Lo = Methane generation potential, m\3\/Mg.
Lo' = Revised methane generation potential to account for the
amount of nondecomposable material in the landfill, m\3\/Mg.
Mi = Mass of refuse in the ith section, Mg.
Mr = Mass of decomposable refuse affected by the test well,
Mg.
Pbar = Atmospheric pressure, mm Hg.
Pf = Final absolute pressure of the deep pressure probes
during short-term testing, mm Hg.
Pfa = Average final absolute pressure of the deep pressure
probes during short-term testing, mm Hg.
Pgf = final gauge pressure of the deep pressure probes, mm
Hg.
Pgi = Initial gauge pressure of the deep pressure probes, mm
Hg.
Pi = Initial absolute pressure of the deep pressure probes
during static testing, mm Hg.
Pia = Average initial absolute pressure of the deep pressure
probes during static testing, mm Hg.
Ps = Final absolute pressure of the deep pressure probes
during long-term testing, mm Hg.
Psa = Average final absolute pressure of the deep pressure
probes during long-term testing, mm Hg.
Qf = Final stabilized flow rate, m\3\/min.
Qi = LFG flow rate measured at orifice meter during the ith
interval, m\3\/min.
Qs = Maximum LFG flow rate at each well determined by short-
term test, m\3\/min.

[[Page 42]]

Qt = NMOC mass emission rate, m\3\/min.
Rm = Maximum radius of influence, m.
Rma = Average maximum radius of influence, m.
Rs = Stabilized radius of influence for an individual well,
m.
Rsa = Average stabilized radius of influence, m.
ti = Age of section i, yr.
tt = Total time of long-term testing, yr.
tvi = Time of the ith interval (usually 8), hr.
V = Void volume of test well, m\3\.
Vr = Volume of refuse affected by the test well, m\3\.
Vt = Total volume of refuse affected by the long-term
testing, m\3\.
Vv = Total void volume affected by test wells, m\3\.
WD = Well depth, m.
n = Refuse density, Mg/m\3\ (Assume 0.64 Mg/m\3\ if data are
unavailable).

12.2 Use the following equation to calculate a weighted average age
of landfill refuse.
[GRAPHIC] [TIFF OMITTED] TR17OC00.071

12.3 Use the following equation to determine the difference in
N2 concentrations (ppmv) at the well head and outlet
location.
[GRAPHIC] [TIFF OMITTED] TR17OC00.072

12.4 Use the following equation to convert the gauge pressure
(Pg) of each initial deep pressure probe to absolute pressure
(Pi).
[GRAPHIC] [TIFF OMITTED] TR17OC00.073

12.5 Use the following equation to convert the gauge pressures of
the deep probes to absolute pressures for each 8-hr reading at
Qs.
[GRAPHIC] [TIFF OMITTED] TR17OC00.074

12.6 Use the following equation to calculate the depth
(Dst) affected by the extraction well during the short-term
test.
[GRAPHIC] [TIFF OMITTED] TR17OC00.075

12.7 Use the following equation to calculate the void volume for the
extraction well (V).
[GRAPHIC] [TIFF OMITTED] TR17OC00.076

12.8 Use the following equation to calculate Vt, the
total volume of LFG extracted from the wells.
[GRAPHIC] [TIFF OMITTED] TR17OC00.077

12.9 Use the following equation to calculate the depth affected by
the test well. If using cluster wells, use the average depth of the
wells for WD. If the value of D is greater than the depth of the
landfill, set D equal to the landfill depth.
[GRAPHIC] [TIFF OMITTED] TR17OC00.078

12.10 Use the following equation to calculate the volume of refuse
affected by the test well.
[GRAPHIC] [TIFF OMITTED] TR17OC00.079

12.11 Use the following equation to calculate the mass affected by
the test well.
[GRAPHIC] [TIFF OMITTED] TR17OC00.080

12.12 Modify Lo to account for the nondecomposable refuse
in the landfill.
[GRAPHIC] [TIFF OMITTED] TR17OC00.081

12.13 In the following equation, solve for k (landfill gas
generation constant) by iteration. A suggested procedure is to select a
value for k, calculate the left side of the equation, and if not equal
to zero, select another value for k. Continue this process until the
left hand side of the equation equals zero, 0.001.
[GRAPHIC] [TIFF OMITTED] TR17OC00.082

12.14 Use the following equation to determine landfill NMOC mass
emission rate if the yearly acceptance rate of refuse has been
consistent (10 percent) over the life of the landfill.
[GRAPHIC] [TIFF OMITTED] TR17OC00.083

12.15 Use the following equation to determine landfill NMOC mass
emission rate if the acceptance rate has not been consistent over the
life of the landfill.

[[Page 43]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.084

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Same as Method 2, Appendix A, 40 CFR Part 60.
2. Emcon Associates, Methane Generation and Recovery from Landfills.
Ann Arbor Science, 1982.
3. The Johns Hopkins University, Brown Station Road Landfill Gas
Resource Assessment, Volume 1: Field Testing and Gas Recovery
Projections. Laurel, Maryland: October 1982.
4. Mandeville and Associates, Procedure Manual for Landfill Gases
Emission Testing.
5. Letter and attachments from Briggum, S., Waste Management of
North America, to Thorneloe, S., EPA. Response to July 28, 1988 request
for additional information. August 18, 1988.
6. Letter and attachments from Briggum, S., Waste Management of
North America, to Wyatt, S., EPA. Response to December 7, 1988 request
for additional information. January 16, 1989.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

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[GRAPHIC] [TIFF OMITTED] TR17OC00.086

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[GRAPHIC] [TIFF OMITTED] TR17OC00.087

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[GRAPHIC] [TIFF OMITTED] TR17OC00.088

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[GRAPHIC] [TIFF OMITTED] TR17OC00.089

Method 2F--Determination of Stack Gas Velocity And Volumetric Flow Rate
With Three-Dimensional Probes

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling) essential to its
performance. Some material has been incorporated from other methods in
this part. Therefore, to obtain reliable results, those using this
method should have a thorough knowledge of at least the following
additional test methods: Methods 1, 2, 3 or 3A, and 4.

1.0 Scope and Application

1.1 This method is applicable for the determination of yaw angle, pitch
angle, axial velocity and the volumetric flow rate of a gas

[[Page 49]]

stream in a stack or duct using a three-dimensional (3-D) probe. This
method may be used only when the average stack or duct gas velocity is
greater than or equal to 20 ft/sec. When the above condition cannot be
met, alternative procedures, approved by the Administrator, U.S.
Environmental Protection Agency, shall be used to make accurate flow
rate determinations.

2.0 Summary of Method

2.1 A 3-D probe is used to determine the velocity pressure and the
yaw and pitch angles of the flow velocity vector in a stack or duct. The
method determines the yaw angle directly by rotating the probe to null
the pressure across a pair of symmetrically placed ports on the probe
head. The pitch angle is calculated using probe-specific calibration
curves. From these values and a determination of the stack gas density,
the average axial velocity of the stack gas is calculated. The average
gas volumetric flow rate in the stack or duct is then determined from
the average axial velocity.

3.0 Definitions

3.1. Angle-measuring Device Rotational Offset (RADO). The rotational
position of an angle-measuring device relative to the reference scribe
line, as determined during the pre-test rotational position check
described in section 8.3.
3.2 Axial Velocity. The velocity vector parallel to the axis of the
stack or duct that accounts for the yaw and pitch angle components of
gas flow. The term ``axial'' is used herein to indicate that the
velocity and volumetric flow rate results account for the measured yaw
and pitch components of flow at each measurement point.
3.3 Calibration Pitot Tube. The standard (Prandtl type) pitot tube
used as a reference when calibrating a 3-D probe under this method.
3.4 Field Test. A set of measurements conducted at a specific unit
or exhaust stack/duct to satisfy the applicable regulation (e.g., a
three-run boiler performance test, a single-or multiple-load nine-run
relative accuracy test).
3.5 Full Scale of Pressure-measuring Device. Full scale refers to
the upper limit of the measurement range displayed by the device. For
bi-directional pressure gauges, full scale includes the entire pressure
range from the lowest negative value to the highest positive value on
the pressure scale.
3.6 Main probe. Refers to the probe head and that section of probe
sheath directly attached to the probe head. The main probe sheath is
distinguished from probe extensions, which are sections of sheath added
onto the main probe to extend its reach.
3.7 ``May,'' ``Must,'' ``Shall,'' ``Should,'' and the imperative
form of verbs.
3.7.1 ``May'' is used to indicate that a provision of this method is
optional.
3.7.2 ``Must,'' ``Shall,'' and the imperative form of verbs (such as
``record'' or ``enter'') are used to indicate that a provision of this
method is mandatory.
3.7.3 ``Should'' is used to indicate that a provision of this method
is not mandatory, but is highly recommended as good practice.
3.8 Method 1. Refers to 40 CFR part 60, appendix A, ``Method 1--
Sample and velocity traverses for stationary sources.''
3.9 Method 2. Refers to 40 CFR part 60, appendix A, ``Method 2--
Determination of stack gas velocity and volumetric flow rate (Type S
pitot tube).''
3.10 Method 2G. Refers to 40 CFR part 60, appendix A, ``Method 2G--
Determination of stack gas velocity and volumetric flow rate with two-
dimensional probes.''
3.11 Nominal Velocity. Refers to a wind tunnel velocity setting that
approximates the actual wind tunnel velocity to within 1.5 m/sec (5
ft/sec).
3.12 Pitch Angle. The angle between the axis of the stack or duct
and the pitch component of flow, i.e., the component of the total
velocity vector in a plane defined by the traverse line and the axis of
the stack or duct. (Figure 2F-1 illustrates the ``pitch plane.'') From
the standpoint of a tester facing a test port in a vertical stack, the
pitch component of flow is the vector of flow moving from the center of
the stack toward or away from that test port. The pitch angle is the
angle described by this pitch component of flow and the vertical axis of
the stack.
3.13 Readability. For the purposes of this method, readability for
an analog measurement device is one half of the smallest scale division.
For a digital measurement device, it is the number of decimals displayed
by the device.
3.14 Reference Scribe Line. A line permanently inscribed on the main
probe sheath (in accordance with section 6.1.6.1) to serve as a
reference mark for determining yaw angles.
3.15 Reference Scribe Line Rotational Offset (RSLO). The
rotational position of a probe's reference scribe line relative to the
probe's yaw-null position, as determined during the yaw angle
calibration described in section 10.5.
3.16 Response Time. The time required for the measurement system to
fully respond to a change from zero differential pressure and ambient
temperature to the stable stack or duct pressure and temperature
readings at a traverse point.
3.17 Tested Probe. A 3-D probe that is being calibrated.
3.18 Three-dimensional (3-D) Probe. A directional probe used to
determine the velocity pressure and yaw and pitch angles in a flowing
gas stream.

[[Page 50]]

3.19 Traverse Line. A diameter or axis extending across a stack or
duct on which measurements of differential pressure and flow angles are
made.
3.20 Wind Tunnel Calibration Location. A point, line, area, or
volume within the wind tunnel test section at, along, or within which
probes are calibrated. At a particular wind tunnel velocity setting, the
average velocity pressures at specified points at, along, or within the
calibration location shall vary by no more than 2 percent or 0.3 mm
H2O (0.01 in. H2O), whichever is less restrictive,
from the average velocity pressure at the calibration pitot tube
location. Air flow at this location shall be axial, i.e., yaw and pitch
angles within 3[deg]. Compliance with these flow criteria shall be
demonstrated by performing the procedures prescribed in sections 10.1.1
and 10.1.2. For circular tunnels, no part of the calibration location
may be closer to the tunnel wall than 10.2 cm (4 in.) or 25 percent of
the tunnel diameter, whichever is farther from the wall. For elliptical
or rectangular tunnels, no part of the calibration location may be
closer to the tunnel wall than 10.2 cm (4 in.) or 25 percent of the
applicable cross-sectional axis, whichever is farther from the wall.
3.21 Wind Tunnel with Documented Axial Flow. A wind tunnel facility
documented as meeting the provisions of sections 10.1.1 (velocity
pressure cross-check) and 10.1.2 (axial flow verification) using the
procedures described in these sections or alternative procedures
determined to be technically equivalent.
3.22 Yaw Angle. The angle between the axis of the stack or duct and
the yaw component of flow, i.e., the component of the total velocity
vector in a plane perpendicular to the traverse line at a particular
traverse point. (Figure 2F-1 illustrates the ``yaw plane.'') From the
standpoint of a tester facing a test port in a vertical stack, the yaw
component of flow is the vector of flow moving to the left or right from
the center of the stack as viewed by the tester. (This is sometimes
referred to as ``vortex flow,'' i.e., flow around the centerline of a
stack or duct.) The yaw angle is the angle described by this yaw
component of flow and the vertical axis of the stack. The algebraic sign
convention is illustrated in Figure 2F-2.
3.23 Yaw Nulling. A procedure in which a probe is rotated about its
axis in a stack or duct until a zero differential pressure reading
(``yaw null'') is obtained. When a 3-D probe is yaw-nulled, its impact
pressure port (P1) faces directly into the direction of flow
in the stack or duct and the differential pressure between pressure
ports P2 and P3 is zero.

4.0 Interferences [Reserved]

5.0 Safety

5.1 This test method may involve hazardous operations and the use of
hazardous materials or equipment. This method does not purport to
address all of the safety problems associated with its use. It is the
responsibility of the user to establish and implement appropriate safety
and health practices and to determine the applicability of regulatory
limitations before using this test method.

6.0 Equipment and Supplies

6.1 Three-dimensional Probes. The 3-D probes as specified in
subsections 6.1.1 through 6.1.3 below qualify for use based on
comprehensive wind tunnel and field studies involving both inter-and
intra-probe comparisons by multiple test teams. Other types of probes
shall not be used unless approved by the Administrator. Each 3-D probe
shall have a unique identification number or code permanently marked on
the main probe sheath. The minimum recommended diameter of the sensing
head of any probe used under this method is 2.5 cm (1 in.). Each probe
shall be calibrated prior to use according to the procedures in section
10. Manufacturer-supplied calibration data shall be used as example
information only, except when the manufacturer calibrates the 3-D probe
as specified in section 10 and provides complete documentation.
6.1.1 Five-hole prism-shaped probe. This type of probe consists of
five pressure taps in the flat facets of a prism-shaped sensing head.
The pressure taps are numbered 1 through 5, with the pressures measured
at each hole referred to as P1, P2, P3,
P4, and P5, respectively. Figure 2F-3 is an
illustration of the placement of pressure taps on a commonly available
five-hole prism-shaped probe, the 2.5-cm (1-in.) DAT probe. (Note:
Mention of trade names or specific products does not constitute
endorsement by the U.S. Environmental Protection Agency.) The numbering
arrangement for the prism-shaped sensing head presented in Figure 2F-3
shall be followed for correct operation of the probe. A brief
description of the probe measurements involved is as follows: the
differential pressure P2-P3 is used to yaw null
the probe and determine the yaw angle; the differential pressure
P4-P5 is a function of pitch angle; and the
differential pressure P1-P2 is a function of total
velocity.
6.1.2 Five-hole spherical probe. This type of probe consists of five
pressure taps in a spherical sensing head. As with the prism-shaped
probe, the pressure taps are numbered 1 through 5, with the pressures
measured at each hole referred to as P1, P2,
P3, P4, and P5, respectively. However,
the P4 and P5 pressure taps are in the reverse
location

[[Page 51]]

from their respective positions on the prism-shaped probe head. The
differential pressure P2-P3 is used to yaw null
the probe and determine the yaw angle; the differential pressure
P4-P5 is a function of pitch angle; and the
differential pressure P1-P2 is a function of total
velocity. A diagram of a typical spherical probe sensing head is
presented in Figure 2F-4. Typical probe dimensions are indicated in the
illustration.
6.1.3 A manual 3-D probe refers to a five-hole prism-shaped or
spherical probe that is positioned at individual traverse points and yaw
nulled manually by an operator. An automated 3-D probe refers to a
system that uses a computer-controlled motorized mechanism to position
the five-hole prism-shaped or spherical head at individual traverse
points and perform yaw angle determinations.
6.1.4 Other three-dimensional probes. [Reserved]
6.1.5 Probe sheath. The probe shaft shall include an outer sheath
to: (1) provide a surface for inscribing a permanent reference scribe
line, (2) accommodate attachment of an angle-measuring device to the
probe shaft, and (3) facilitate precise rotational movement of the probe
for determining yaw angles. The sheath shall be rigidly attached to the
probe assembly and shall enclose all pressure lines from the probe head
to the farthest position away from the probe head where an angle-
measuring device may be attached during use in the field. The sheath of
the fully assembled probe shall be sufficiently rigid and straight at
all rotational positions such that, when one end of the probe shaft is
held in a horizontal position, the fully extended probe meets the
horizontal straightness specifications indicated in section 8.2 below.
6.1.6 Scribe lines.
6.1.6.1 Reference scribe line. A permanent line, no greater than 1.6
mm (1/16 in.) in width, shall be inscribed on each manual probe that
will be used to determine yaw angles of flow. This line shall be placed
on the main probe sheath in accordance with the procedures described in
section 10.4 and is used as a reference position for installation of the
yaw angle-measuring device on the probe. At the discretion of the
tester, the scribe line may be a single line segment placed at a
particular position on the probe sheath (e.g., near the probe head),
multiple line segments placed at various locations along the length of
the probe sheath (e.g., at every position where a yaw angle-measuring
device may be mounted), or a single continuous line extending along the
full length of the probe sheath.
6.1.6.2 Scribe line on probe extensions. A permanent line may also
be inscribed on any probe extension that will be attached to the main
probe in performing field testing. This allows a yaw angle-measuring
device mounted on the extension to be readily aligned with the reference
scribe line on the main probe sheath.
6.1.6.3 Alignment specifications. This specification shall be met
separately, using the procedures in section 10.4.1, on the main probe
and on each probe extension. The rotational position of the scribe line
or scribe line segments on the main probe or any probe extension must
not vary by more than 2[deg]. That is, the difference between the
minimum and maximum of all of the rotational angles that are measured
along the full length of the main probe or the probe extension must not
exceed 2[deg].
6.1.7 Probe and system characteristics to ensure horizontal
stability.
6.1.7.1 For manual probes, it is recommended that the effective
length of the probe (coupled with a probe extension, if necessary) be at
least 0.9 m (3 ft.) longer than the farthest traverse point mark on the
probe shaft away from the probe head. The operator should maintain the
probe's horizontal stability when it is fully inserted into the stack or
duct. If a shorter probe is used, the probe should be inserted through a
bushing sleeve, similar to the one shown in Figure 2F-5, that is
installed on the test port; such a bushing shall fit snugly around the
probe and be secured to the stack or duct entry port in such a manner as
to maintain the probe's horizontal stability when fully inserted into
the stack or duct.
6.1.7.2 An automated system that includes an external probe casing
with a transport system shall have a mechanism for maintaining
horizontal stability comparable to that obtained by manual probes
following the provisions of this method. The automated probe assembly
shall also be constructed to maintain the alignment and position of the
pressure ports during sampling at each traverse point. The design of the
probe casing and transport system shall allow the probe to be removed
from the stack or duct and checked through direct physical measurement
for angular position and insertion depth.
6.1.8 The tubing that is used to connect the probe and the pressure-
measuring device should have an inside diameter of at least 3.2 mm (1/8
in.), to reduce the time required for pressure equilibration, and should
be as short as practicable.
6.2 Yaw Angle-measuring Device. One of the following devices shall
be used for measurement of the yaw angle of flow.
6.2.1 Digital inclinometer. This refers to a digital device capable
of measuring and displaying the rotational position of the probe to
within 1[deg]. The device shall be able to be locked into position on
the probe sheath or probe extension, so that it indicates the probe's
rotational position throughout the test. A rotational position collar
block that can be attached to the probe sheath (similar

[[Page 52]]

to the collar shown in Figure 2F-6) may be required to lock the digital
inclinometer into position on the probe sheath.
6.2.2 Protractor wheel and pointer assembly. This apparatus, similar
to that shown in Figure 2F-7, consists of the following components.
6.2.2.1 A protractor wheel that can be attached to a port opening
and set in a fixed rotational position to indicate the yaw angle
position of the probe's scribe line relative to the longitudinal axis of
the stack or duct. The protractor wheel must have a measurement ring on
its face that is no less than 17.8 cm (7 in.) in diameter, shall be able
to be rotated to any angle and then locked into position on the stack or
duct port, and shall indicate angles to a resolution of 1[deg].
6.2.2.2 A pointer assembly that includes an indicator needle mounted
on a collar that can slide over the probe sheath and be locked into a
fixed rotational position on the probe sheath. The pointer needle shall
be of sufficient length, rigidity, and sharpness to allow the tester to
determine the probe's angular position to within 1[deg] from the
markings on the protractor wheel. Corresponding to the position of the
pointer, the collar must have a scribe line to be used in aligning the
pointer with the scribe line on the probe sheath.
6.2.3 Other yaw angle-measuring devices. Other angle-measuring
devices with a manufacturer's specified precision of 1[deg] or better
may be used, if approved by the Administrator.
6.3 Probe Supports and Stabilization Devices. When probes are used
for determining flow angles, the probe head should be kept in a stable
horizontal position. For probes longer than 3.0 m (10 ft.), the section
of the probe that extends outside the test port shall be secured. Three
alternative devices are suggested for maintaining the horizontal
position and stability of the probe shaft during flow angle
determinations and velocity pressure measurements: (1) Monorails
installed above each port, (2) probe stands on which the probe shaft may
be rested, or (3) bushing sleeves of sufficient length secured to the
test ports to maintain probes in a horizontal position. Comparable
provisions shall be made to ensure that automated systems maintain the
horizontal position of the probe in the stack or duct. The physical
characteristics of each test platform may dictate the most suitable type
of stabilization device. Thus, the choice of a specific stabilization
device is left to the judgment of the testers.
6.4 Differential Pressure Gauges. The pressure (FP) measuring
devices used during wind tunnel calibrations and field testing shall be
either electronic manometers (e.g., pressure transducers), fluid
manometers, or mechanical pressure gauges (e.g., MagnehelicF
gauges). Use of electronic manometers is recommended. Under low velocity
conditions, use of electronic manometers may be necessary to obtain
acceptable measurements.
6.4.1 Differential pressure-measuring device. This refers to a
device capable of measuring pressure differentials and having a
readability of 1 percent of full scale. The device shall be capable of
accurately measuring the maximum expected pressure differential. Such
devices are used to determine the following pressure measurements:
velocity pressure, static pressure, yaw-null pressure, and pitch-angle
pressure. For an inclined-vertical manometer, the readability
specification of 1 percent shall be met separately using the respective
full-scale upper limits of the inclined and vertical portions of the
scales. To the extent practicable, the device shall be selected such
that most of the pressure readings are between 10 and 90 percent of the
device's full-scale measurement range (as defined in section 3.5).
Typical velocity pressure (P1-P2) ranges for both
the prism-shaped probe and the spherical probe are 0 to 1.3 cm
H2O (0 to 0.5 in. H2O), 0 to 5.1 cm H2O
(0 to 2 in. H2O), and 0 to 12.7 cm H2O (0 to 5 in.
H2O). The pitch angle (P4-P5) pressure
range is typically - 6.4 to + 6.4 mm H2O (- 0.25 to + 0.25
in. H2O) or - 12.7 to + 12.7 mm H2O (- 0.5 to +
0.5 in. H2O) for the prism-shaped probe, and - 12.7 to + 12.7
mm H2O (- 0.5 to + 0.5 in. H2O) or - 5.1 to + 5.1
cm H2O (- 2 to + 2 in. H2O) for the spherical
probe. The pressure range for the yaw null (P2-
P3) readings is typically - 12.7 to + 12.7 mm H2O
(- 0.5 to + 0.5 in. H2O) for both probe types. In addition,
pressure-measuring devices should be selected such that the zero does
not drift by more than 5 percent of the average expected pressure
readings to be encountered during the field test. This is particularly
important under low pressure conditions.
6.4.2 Gauge used for yaw nulling. The differential pressure-
measuring device chosen for yaw nulling the probe during the wind tunnel
calibrations and field testing shall be bi-directional, i.e., capable of
reading both positive and negative differential pressures. If a
mechanical, bi-directional pressure gauge is chosen, it shall have a
full-scale range no greater than 2.6 cm H2O (1 in.
H2O) [i.e., - 1.3 to + 1.3 cm H2O (- 0.5 in. to +
0.5 in.)].
6.4.3 Devices for calibrating differential pressure-measuring
devices. A precision manometer (e.g., a U-tube, inclined, or inclined-
vertical manometer, or micromanometer) or NIST (National Institute of
Standards and Technology) traceable pressure source shall be used for
calibrating differential pressure-measuring devices. The device shall be
maintained under laboratory conditions or in a similar protected
environment (e.g., a climate-controlled trailer). It shall not be used
in field tests. The precision manometer shall have a scale gradation of
0.3 mm H2O (0.01 in. H2O), or less, in the range
of 0 to 5.1 cm H2O

[[Page 53]]

(0 to 2 in. H2O) and 2.5 mm H2O (0.1 in.
H2O), or less, in the range of 5.1 to 25.4 cm H2O
(2 to 10 in. H2O). The manometer shall have manufacturer's
documentation that it meets an accuracy specification of at least 0.5
percent of full scale. The NIST-traceable pressure source shall be
recertified annually.
6.4.4 Devices used for post-test calibration check. A precision
manometer meeting the specifications in section 6.4.3, a pressure-
measuring device or pressure source with a documented calibration
traceable to NIST, or an equivalent device approved by the Administrator
shall be used for the post-test calibration check. The pressure-
measuring device shall have a readability equivalent to or greater than
the tested device. The pressure source shall be capable of generating
pressures between 50 and 90 percent of the range of the tested device
and known to within 1 percent of the full scale of the tested device.
The pressure source shall be recertified annually.
6.5 Data Display and Capture Devices. Electronic manometers (if
used) shall be coupled with a data display device (such as a digital
panel meter, personal computer display, or strip chart) that allows the
tester to observe and validate the pressure measurements taken during
testing. They shall also be connected to a data recorder (such as a data
logger or a personal computer with data capture software) that has the
ability to compute and retain the appropriate average value at each
traverse point, identified by collection time and traverse point.
6.6 Temperature Gauges. For field tests, a thermocouple or
resistance temperature detector (RTD) capable of measuring temperature
to within 3 [deg]C (5 [deg]F) of the stack or duct temperature shall
be used. The thermocouple shall be attached to the probe such that the
sensor tip does not touch any metal and is located on the opposite side
of the probe head from the pressure ports so as not to interfere with
the gas flow around the probe head. The position of the thermocouple
relative to the pressure port face openings shall be in the same
configuration as used for the probe calibrations in the wind tunnel.
Temperature gauges used for wind tunnel calibrations shall be capable of
measuring temperature to within 0.6 [deg]C (1 [deg]F) of the
temperature of the flowing gas stream in the wind tunnel.
6.7 Stack or Duct Static Pressure Measurement. The pressure-
measuring device used with the probe shall be as specified in section
6.4 of this method. The static tap of a standard (Prandtl type) pitot
tube or one leg of a Type S pitot tube with the face opening planes
positioned parallel to the gas flow may be used for this measurement.
Also acceptable is the pressure differential reading of P1-
Pbar from a five-hole prism-shaped probe (e.g., Type DA or
DAT probe) with the P1 pressure port face opening positioned
parallel to the gas flow in the same manner as the Type S probe.
However, the spherical probe, as specified in section 6.1.2, is unable
to provide this measurement and shall not be used to take static
pressure measurements. Static pressure measurement is further described
in section 8.11.
6.8 Barometer. Same as Method 2, section 2.5.
6.9 Gas Density Determination Equipment. Method 3 or 3A shall be
used to determine the dry molecular weight of the stack gas. Method 4
shall be used for moisture content determination and computation of
stack gas wet molecular weight. Other methods may be used, if approved
by the Administrator.
6.10 Calibration Pitot Tube. Same as Method 2, section 2.7.
6.11 Wind Tunnel for Probe Calibration. Wind tunnels used to
calibrate velocity probes must meet the following design specifications.
6.11.1 Test section cross-sectional area. The flowing gas stream
shall be confined within a circular, rectangular, or elliptical duct.
The cross-sectional area of the tunnel must be large enough to ensure
fully developed flow in the presence of both the calibration pitot tube
and the tested probe. The calibration site, or ``test section,'' of the
wind tunnel shall have a minimum diameter of 30.5 cm (12 in.) for
circular or elliptical duct cross-sections or a minimum width of 30.5 cm
(12 in.) on the shorter side for rectangular cross-sections. Wind
tunnels shall meet the probe blockage provisions of this section and the
qualification requirements prescribed in section 10.1. The projected
area of the portion of the probe head, shaft, and attached devices
inside the wind tunnel during calibration shall represent no more than 4
percent of the cross-sectional area of the tunnel. The projected area
shall include the combined area of the calibration pitot tube and the
tested probe if both probes are placed simultaneously in the same cross-
sectional plane in the wind tunnel, or the larger projected area of the
two probes if they are placed alternately in the wind tunnel.
6.11.2 Velocity range and stability. The wind tunnel should be
capable of maintaining velocities between 6.1 m/sec and 30.5 m/sec (20
ft/sec and 100 ft/sec). The wind tunnel shall produce fully developed
flow patterns that are stable and parallel to the axis of the duct in
the test section.
6.11.3 Flow profile at the calibration location. The wind tunnel
shall provide axial flow within the test section calibration location
(as defined in section 3.20). Yaw and pitch angles in the calibration
location shall be within 3[deg] of 0[deg]. The procedure for
determining that this requirement has been met is described in section
10.1.2.
6.11.4 Entry ports in the wind tunnel test section.

[[Page 54]]

6.11.4.1 Port for tested probe. A port shall be constructed for the
tested probe. The port should have an elongated slot parallel to the
axis of the duct at the test section. The elongated slot should be of
sufficient length to allow attaining all the pitch angles at which the
probe will be calibrated for use in the field. To facilitate alignment
of the probe during calibration, the test section should include a
window constructed of a transparent material to allow the tested probe
to be viewed. This port shall be located to allow the head of the tested
probe to be positioned within the calibration location (as defined in
section 3.20) at all pitch angle settings.
6.11.4.2 Port for verification of axial flow. Depending on the
equipment selected to conduct the axial flow verification prescribed in
section 10.1.2, a second port, located 90[deg] from the entry port for
the tested probe, may be needed to allow verification that the gas flow
is parallel to the central axis of the test section. This port should be
located and constructed so as to allow one of the probes described in
section 10.1.2.2 to access the same test point(s) that are accessible
from the port described in section 6.11.4.1.
6.11.4.3 Port for calibration pitot tube. The calibration pitot tube
shall be used in the port for the tested probe or a separate entry port.
In either case, all measurements with the calibration pitot tube shall
be made at the same point within the wind tunnel over the course of a
probe calibration. The measurement point for the calibration pitot tube
shall meet the same specifications for distance from the wall and for
axial flow as described in section 3.20 for the wind tunnel calibration
location.
6.11.5 Pitch angle protractor plate. A protractor plate shall be
attached directly under the port used with the tested probe and set in a
fixed position to indicate the pitch angle position of the probe
relative to the longitudinal axis of the wind tunnel duct (similar to
Figure 2F- 8). The protractor plate shall indicate angles in 5[deg]
increments with a minimum resolution of 2[deg]. The tested probe shall
be able to be locked into position at the desired pitch angle delineated
on the protractor. The probe head position shall be maintained within
the calibration location (as defined in section 3.20) in the test
section of the wind tunnel during all tests across the range of pitch
angles.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection and Analysis

8.1 Equipment Inspection and Set-Up
8.1.1 All probes, differential pressure-measuring devices, yaw
angle-measuring devices, thermocouples, and barometers shall have a
current, valid calibration before being used in a field test. (See
sections 10.3.3, 10.3.4, and 10.5 through10.10 for the applicable
calibration requirements.)
8.1.2 Before each field use of a 3-D probe, perform a visual
inspection to verify the physical condition of the probe head according
to the procedures in section 10.2. Record the inspection results on a
form similar to Table 2F-1. If there is visible damage to the 3-D probe,
the probe shall not be used until it is recalibrated.
8.1.3 After verifying that the physical condition of the probe head
is acceptable, set up the apparatus using lengths of flexible tubing
that are as short as practicable. Surge tanks installed between the
probe and pressure-measuring device may be used to dampen pressure
fluctuations provided that an adequate measurement response time (see
section 8.8) is maintained.
8.2 Horizontal Straightness Check. A horizontal straightness check
shall be performed before the start of each field test, except as
otherwise specified in this section. Secure the fully assembled probe
(including the probe head and all probe shaft extensions) in a
horizontal position using a stationary support at a point along the
probe shaft approximating the location of the stack or duct entry port
when the probe is sampling at the farthest traverse point from the stack
or duct wall. The probe shall be rotated to detect bends. Use an angle-
measuring device or trigonometry to determine the bend or sag between
the probe head and the secured end. (See Figure 2F-9.) Probes that are
bent or sag by more than 5[deg] shall not be used. Although this check
does not apply when the probe is used for a vertical traverse, care
should be taken to avoid the use of bent probes when conducting vertical
traverses. If the probe is constructed of a rigid steel material and
consists of a main probe without probe extensions, this check need only
be performed before the initial field use of the probe, when the probe
is recalibrated, when a change is made to the design or material of the
probe assembly, and when the probe becomes bent. With such probes, a
visual inspection shall be made of the fully assembled probe before each
field test to determine if a bend is visible. The probe shall be rotated
to detect bends. The inspection results shall be documented in the field
test report. If a bend in the probe is visible, the horizontal
straightness check shall be performed before the probe is used.
8.3 Rotational Position Check. Before each field test, and each time
an extension is added to the probe during a field test, a rotational
position check shall be performed on all manually operated probes
(except as noted in section 8.3.5, below) to ensure that, throughout
testing, the angle-measuring device is either: aligned to within 1[deg]
of the rotational position of the reference scribe line; or is affixed
to the probe such that the rotational offset of the device from the
reference scribe line is known to within 1[deg]. This check shall
consist of direct measurements of the

[[Page 55]]

rotational positions of the reference scribe line and angle-measuring
device sufficient to verify that these specifications are met. Annex A
in section 18 of this method gives recommended procedures for performing
the rotational position check, and Table 2F-2 gives an example data
form. Procedures other than those recommended in Annex A in section 18
may be used, provided they demonstrate whether the alignment
specification is met and are explained in detail in the field test
report.
8.3.1 Angle-measuring device rotational offset. The tester shall
maintain a record of the angle-measuring device rotational offset,
RADO, as defined in section 3.1. Note that RADO is
assigned a value of 0[deg] when the angle-measuring device is aligned to
within 1[deg] of the rotational position of the reference scribe line.
The RADO shall be used to determine the yaw angle of flow in
accordance with section 8.9.4.
8.3.2 Sign of angle-measuring device rotational offset. The sign of
RADO is positive when the angle-measuring device (as viewed
from the ``tail'' end of the probe) is positioned in a clockwise
direction from the reference scribe line and negative when the device is
positioned in a counterclockwise direction from the reference scribe
line.
8.3.3 Angle-measuring devices that can be independently adjusted
(e.g., by means of a set screw), after being locked into position on the
probe sheath, may be used. However, the RADO must also take
into account this adjustment.
8.3.4 Post-test check. If probe extensions remain attached to the
main probe throughout the field test, the rotational position check
shall be repeated, at a minimum, at the completion of the field test to
ensure that the angle-measuring device has remained within 2[deg] of
its rotational position established prior to testing. At the discretion
of the tester, additional checks may be conducted after completion of
testing at any sample port or after any test run. If the 2[deg]
specification is not met, all measurements made since the last
successful rotational position check must be repeated. section 18.1.1.3
of Annex A provides an example procedure for performing the post-test
check.
8.3.5 Exceptions.
8.3.5.1 A rotational position check need not be performed if, for
measurements taken at all velocity traverse points, the yaw angle-
measuring device is mounted and aligned directly on the reference scribe
line specified in sections 6.1.6.1 and 6.1.6.3 and no independent
adjustments, as described in section 8.3.3, are made to the device's
rotational position.
8.3.5.2 If extensions are detached and re-attached to the probe
during a field test, a rotational position check need only be performed
the first time an extension is added to the probe, rather than each time
the extension is re-attached, if the probe extension is designed to be
locked into a mechanically fixed rotational position (e.g., through use
of interlocking grooves) that can re-establish the initial rotational
position to within 1[deg].
8.4 Leak Checks. A pre-test leak check shall be conducted before
each field test. A post-test check shall be performed at the end of the
field test, but additional leak checks may be conducted after any test
run or group of test runs. The post-test check may also serve as the
pre-test check for the next group of test runs. If any leak check is
failed, all runs since the last passed leak check are invalid. While
performing the leak check procedures, also check each pressure device's
responsiveness to the changes in pressure.
8.4.1 To perform the leak check, pressurize the probe's
P1 pressure port until at least 7.6 cm H2O (3 in.
H2O) pressure, or a pressure corresponding to approximately
75 percent of the pressure-measuring device's measurement scale,
whichever is less, registers on the device; then, close off the pressure
port. The pressure shall remain stable [2.5 mm H2O (0.10
in. H2O)] for at least 15 seconds. Check the P2,
P3, P4, and P5 pressure ports in the
same fashion. Other leak-check procedures may be used, if approved by
the Administrator.
8.5 Zeroing the Differential Pressure-measuring Device. Zero each
differential pressure-measuring device, including the device used for
yaw nulling, before each field test. At a minimum, check the zero after
each field test. A zero check may also be performed after any test run
or group of test runs. For fluid manometers and mechanical pressure
gauges (e.g., MagnehelicF gauges), the zero reading shall not
deviate from zero by more than 0.8 mm H2O (0.03 in.
H2O) or one minor scale division, whichever is greater,
between checks. For electronic manometers, the zero reading shall not
deviate from zero between checks by more than: 0.3 mm H2O
(0.01 in. H2O), for full scales less than or equal to 5.1 cm
H2O (2.0 in. H2O); or 0.8 mm H2O
(0.03 in. H2O), for full scales greater than 5.1 cm
H2O (2.0 in. H2O). (Note: If negative zero drift
is not directly readable, estimate the reading based on the position of
the gauge oil in the manometer or of the needle on the pressure gauge.)
In addition, for all pressure-measuring devices except those used
exclusively for yaw nulling, the zero reading shall not deviate from
zero by more than 5 percent of the average measured differential
pressure at any distinct process condition or load level. If any zero
check is failed at a specific process condition or load level, all runs
conducted at that process condition or load level since the last passed
zero check are invalid.
8.6 Traverse Point Verification. The number and location of the
traverse points shall be selected based on Method 1 guidelines.

[[Page 56]]

The stack or duct diameter and port nipple lengths, including any
extension of the port nipples into stack or duct, shall be verified the
first time the test is performed; retain and use this information for
subsequent field tests, updating it as required. Physically measure the
stack or duct dimensions or use a calibrated laser device; do not use
engineering drawings of the stack or duct. The probe length necessary to
reach each traverse point shall be recorded to within 6.4 mm (1/4 in.)
and, for manual probes, marked on the probe sheath. In determining these
lengths, the tester shall take into account both the distance that the
port flange projects outside of the stack and the depth that any port
nipple extends into the gas stream. The resulting point positions shall
reflect the true distances from the inside wall of the stack or duct, so
that when the tester aligns any of the markings with the outside face of
the stack port, the probe's impact port shall be located at the
appropriate distance from the inside wall for the respective Method 1
traverse point. Before beginning testing at a particular location, an
out-of-stack or duct verification shall be performed on each probe that
will be used to ensure that these position markings are correct. The
distances measured during the verification must agree with the
previously calculated distances to within 1/4 in. For manual probes,
the traverse point positions shall be verified by measuring the distance
of each mark from the probe's P1 pressure port. A comparable
out-of-stack test shall be performed on automated probe systems. The
probe shall be extended to each of the prescribed traverse point
positions. Then, the accuracy of the positioning for each traverse point
shall be verified by measuring the distance between the port flange and
the probe's P1 pressure port.
8.7 Probe Installation. Insert the probe into the test port. A solid
material shall be used to seal the port.
8.8 System Response Time. Determine the response time of the probe
measurement system. Insert and position the ``cold'' probe (at ambient
temperature and pressure) at any Method 1 traverse point. Read and
record the probe's P1- P2 differential pressure,
temperature, and elapsed time at 15-second intervals until stable
readings for both pressure and temperature are achieved. The response
time is the longer of these two elapsed times. Record the response time.
8.9 Sampling.
8.9.1 Yaw angle measurement protocol. With manual probes, yaw angle
measurements may be obtained in two alternative ways during the field
test, either by using a yaw angle-measuring device (e.g., digital
inclinometer) affixed to the probe, or using a protractor wheel and
pointer assembly. For horizontal traversing, either approach may be
used. For vertical traversing, i.e., when measuring from on top or into
the bottom of a horizontal duct, only the protractor wheel and pointer
assembly may be used. With automated probes, curve-fitting protocols may
be used to obtain yaw-angle measurements.
8.9.1.1 If a yaw angle-measuring device affixed to the probe is to
be used, lock the device on the probe sheath, aligning it either on the
reference scribe line or in the rotational offset position established
under section 8.3.1.
8.9.1.2 If a protractor wheel and pointer assembly is to be used,
follow the procedures in Annex B of this method.
8.9.1.3 Other yaw angle-determination procedures. If approved by the
Administrator, other procedures for determining yaw angle may be used,
provided that they are verified in a wind tunnel to be able to perform
the yaw angle calibration procedure as described in section 10.5.
8.9.2 Sampling strategy. At each traverse point, first yaw-null the
probe, as described in section 8.9.3, below. Then, with the probe
oriented into the direction of flow, measure and record the yaw angle,
the differential pressures and the temperature at the traverse point,
after stable readings are achieved, in accordance with sections 8.9.4
and 8.9.5. At the start of testing in each port (i.e., after a probe has
been inserted into the flue gas stream), allow at least the response
time to elapse before beginning to take measurements at the first
traverse point accessed from that port. Provided that the probe is not
removed from the flue gas stream, measurements may be taken at
subsequent traverse points accessed from the same test port without
waiting again for the response time to elapse.
8.9.3 Yaw-nulling procedure. In preparation for yaw angle
determination, the probe must first be yaw nulled. After positioning the
probe at the appropriate traverse point, perform the following
procedures.
8.9.3.1 Rotate the probe until a null differential pressure reading
(the difference in pressures across the P2 and P3
pressure ports is zero, i.e., P2 = P3) is
indicated by the yaw angle pressure gauge. Read and record the angle
displayed by the angle-measuring device.
8.9.3.2 Sign of the measured angle. The angle displayed on the
angle-measuring device is considered positive when the probe's impact
pressure port (as viewed from the ``tail'' end of the probe) is oriented
in a clockwise rotational position relative to the stack or duct axis
and is considered negative when the probe's impact pressure port is
oriented in a counterclockwise rotational position (see Figure 2F-10).
8.9.4 Yaw angle determination. After performing the yaw-nulling
procedure in section

[[Page 57]]

8.9.3, determine the yaw angle of flow according to one of the following
procedures. Special care must be observed to take into account the signs
of the recorded angle and all offsets.
8.9.4.1 Direct-reading. If all rotational offsets are zero or if the
angle-measuring device rotational offset (RADO) determined in
section 8.3 exactly compensates for the scribe line rotational offset
(RSLO) determined in section 10.5, then the magnitude of the
yaw angle is equal to the displayed angle-measuring device reading from
section 8.9.3.1. The algebraic sign of the yaw angle is determined in
accordance with section 8.9.3.2.

Note: Under certain circumstances (e.g., testing of horizontal
ducts), a 90[deg] adjustment to the angle-measuring device readings may
be necessary to obtain the correct yaw angles.

8.9.4.2 Compensation for rotational offsets during data reduction.
When the angle-measuring device rotational offset does not compensate
for reference scribe line rotational offset, the following procedure
shall be used to determine the yaw angle:
(a) Enter the reading indicated by the angle-measuring device from
section 8.9.3.1.
(b) Associate the proper algebraic sign from section 8.9.3.2 with
the reading in step (a).
(c) Subtract the reference scribe line rotational offset,
RSLO, from the reading in step (b).
(d) Subtract the angle-measuring device rotational offset,
RADO, if any, from the result obtained in step (c).
(e) The final result obtained in step (d) is the yaw angle of flow.

Note: It may be necessary to first apply a 90[deg] adjustment to the
reading in step (a), in order to obtain the correct yaw angle.

8.9.4.3 Record the yaw angle measurements on a form similar to Table
2F-3.
8.9.5 Velocity determination. Maintain the probe rotational position
established during the yaw angle determination. Then, begin recording
the pressure-measuring device readings for the impact pressure
(P1- P2) and pitch angle pressure (P4-
P5). These pressure measurements shall be taken over a
sampling period of sufficiently long duration to ensure representative
readings at each traverse point. If the pressure measurements are
determined from visual readings of the pressure device or display, allow
sufficient time to observe the pulsation in the readings to obtain a
sight-weighted average, which is then recorded manually. If an automated
data acquisition system (e.g., data logger, computer-based data
recorder, strip chart recorder) is used to record the pressure
measurements, obtain an integrated average of all pressure readings at
the traverse point. Stack or duct gas temperature measurements shall be
recorded, at a minimum, once at each traverse point. Record all
necessary data as shown in the example field data form (Table 2F-3).
8.9.6 Alignment check. For manually operated probes, after the
required yaw angle and differential pressure and temperature
measurements have been made at each traverse point, verify (e.g., by
visual inspection) that the yaw angle-measuring device has remained in
proper alignment with the reference scribe line or with the rotational
offset position established in section 8.3. If, for a particular
traverse point, the angle-measuring device is found to be in proper
alignment, proceed to the next traverse point; otherwise, re-align the
device and repeat the angle and differential pressure measurements at
the traverse point. In the course of a traverse, if a mark used to
properly align the angle-measuring device (e.g., as described in section
18.1.1.1) cannot be located, re-establish the alignment mark before
proceeding with the traverse.
8.10 Probe Plugging. Periodically check for plugging of the pressure
ports by observing the responses on pressure differential readouts.
Plugging causes erratic results or sluggish responses. Rotate the probe
to determine whether the readouts respond in the expected direction. If
plugging is detected, correct the problem and repeat the affected
measurements.
8.11 Static Pressure. Measure the static pressure in the stack or
duct using the equipment described in section 6.7.
8.11.1 If a Type DA or DAT probe is used for this measurement,
position the probe at or between any traverse point(s) and rotate the
probe until a null differential pressure reading is obtained at
P2- P3. Rotate the probe 90[deg]. Disconnect the
P2 pressure side of the probe and read the pressure
P1-Pbar and record as the static pressure. (Note:
The spherical probe, specified in section 6.1.2, is unable to provide
this measurement and shall not be used to take static pressure
measurements.)
8.11.2 If a Type S probe is used for this measurement, position the
probe at or between any traverse point(s) and rotate the probe until a
null differential pressure reading is obtained. Disconnect the tubing
from one of the pressure ports; read and record the FP. For pressure
devices with one-directional scales, if a deflection in the positive
direction is noted with the negative side disconnected, then the static
pressure is positive. Likewise, if a deflection in the positive
direction is noted with the positive side disconnected, then the static
pressure is negative.
8.12 Atmospheric Pressure. Determine the atmospheric pressure at the
sampling elevation during each test run following the procedure
described in section 2.5 of Method 2.

[[Page 58]]

8.13 Molecular Weight. Determine the stack gas dry molecular weight.
For combustion processes or processes that emit essentially
CO2, O2, CO, and N2, use Method 3 or
3A. For processes emitting essentially air, an analysis need not be
conducted; use a dry molecular weight of 29.0. Other methods may be
used, if approved by the Administrator.
8.14 Moisture. Determine the moisture content of the stack gas using
Method 4 or equivalent.
8.15 Data Recording and Calculations. Record all required data on a
form similar to Table 2F-3.
8.15.1 Selection of appropriate calibration curves. Choose the
appropriate pair of F1 and F2 versus pitch angle
calibration curves, created as described in section 10.6.
8.15.2 Pitch angle derivation. Use the appropriate calculation
procedures in section 12.2 to find the pitch angle ratios that are
applicable at each traverse point. Then, find the pitch angles
corresponding to these pitch angle ratios on the ``F1 versus
pitch angle'' curve for the probe.
8.15.3 Velocity calibration coefficient derivation. Use the pitch
angle obtained following the procedures described in section 8.15.2 to
find the corresponding velocity calibration coefficients from the
``F2 versus pitch angle'' calibration curve for the probe.
8.15.4 Calculations. Calculate the axial velocity at each traverse
point using the equations presented in section 12.2 to account for the
yaw and pitch angles of flow. Calculate the test run average stack gas
velocity by finding the arithmetic average of the point velocity results
in accordance with sections 12.3 and 12.4, and calculate the stack gas
volumetric flow rate in accordance with section 12.5 or 12.6, as
applicable.

9.0 Quality Control

9.1 Quality Control Activities. In conjunction with the yaw angle
determination and the pressure and temperature measurements specified in
section 8.9, the following quality control checks should be performed.
9.1.1 Range of the differential pressure gauge. In accordance with
the specifications in section 6.4, ensure that the proper differential
pressure gauge is being used for the range of FP values encountered. If
it is necessary to change to a more sensitive gauge, replace the gauge
with a gauge calibrated according to section 10.3.3, perform the leak
check described in section 8.4 and the zero check described in section
8.5, and repeat the differential pressure and temperature readings at
each traverse point.
9.1.2 Horizontal stability check. For horizontal traverses of a
stack or duct, visually check that the probe shaft is maintained in a
horizontal position prior to taking a pressure reading. Periodically,
during a test run, the probe's horizontal stability should be verified
by placing a carpenter's level, a digital inclinometer, or other angle-
measuring device on the portion of the probe sheath that extends outside
of the test port. A comparable check should be performed by automated
systems.

10.0 Calibration

10.1 Wind Tunnel Qualification Checks. To qualify for use in
calibrating probes, a wind tunnel shall have the design features
specified in section 6.11 and satisfy the following qualification
criteria. The velocity pressure cross-check in section 10.1.1 and axial
flow verification in section 10.1.2 shall be performed before the
initial use of the wind tunnel and repeated immediately after any
alteration occurs in the wind tunnel's configuration, fans, interior
surfaces, straightening vanes, controls, or other properties that could
reasonably be expected to alter the flow pattern or velocity stability
in the tunnel. The owner or operator of a wind tunnel used to calibrate
probes according to this method shall maintain records documenting that
the wind tunnel meets the requirements of sections 10.1.1 and 10.1.2 and
shall provide these records to the Administrator upon request.
10.1.1 Velocity pressure cross-check. To verify that the wind tunnel
produces the same velocity at the tested probe head as at the
calibration pitot tube impact port, perform the following cross-check.
Take three differential pressure measurements at the fixed calibration
pitot tube location, using the calibration pitot tube specified in
section 6.10, and take three measurements with the calibration pitot
tube at the wind tunnel calibration location, as defined in section
3.20. Alternate the measurements between the two positions. Perform this
procedure at the lowest and highest velocity settings at which the
probes will be calibrated. Record the values on a form similar to Table
2F-4. At each velocity setting, the average velocity pressure obtained
at the wind tunnel calibration location shall be within 2 percent or
2.5 mm H2O (0.01 in. H2O), whichever is less
restrictive, of the average velocity pressure obtained at the fixed
calibration pitot tube location. This comparative check shall be
performed at 2.5-cm (1-in.), or smaller, intervals across the full
length, width, and depth (if applicable) of the wind tunnel calibration
location. If the criteria are not met at every tested point, the wind
tunnel calibration location must be redefined, so that acceptable
results are obtained at every point. Include the results of the velocity
pressure cross-check in the calibration data section of the field test
report. (See section 16.1.4.)
10.1.2 Axial flow verification. The following procedures shall be
performed to demonstrate that there is fully developed axial flow within
the calibration location and at

[[Page 59]]

the calibration pitot tube location. Two testing options are available
to conduct this check.
10.1.2.1 Using a calibrated 3-D probe. A 3-D probe that has been
previously calibrated in a wind tunnel with documented axial flow (as
defined in section 3.21) may be used to conduct this check. Insert the
calibrated 3-D probe into the wind tunnel test section using the tested
probe port. Following the procedures in sections 8.9 and 12.2 of this
method, determine the yaw and pitch angles at all the point(s) in the
test section where the velocity pressure cross-check, as specified in
section 10.1.1, is performed. This includes all the points in the
calibration location and the point where the calibration pitot tube will
be located. Determine the yaw and pitch angles at each point. Repeat
these measurements at the highest and lowest velocities at which the
probes will be calibrated. Record the values on a form similar to Table
2F-5. Each measured yaw and pitch angle shall be within 3[deg] of
0[deg]. Exceeding the limits indicates unacceptable flow in the test
section. Until the problem is corrected and acceptable flow is verified
by repetition of this procedure, the wind tunnel shall not be used for
calibration of probes. Include the results of the axial flow
verification in the calibration data section of the field test report.
(See section 16.1.4.)
10.1.2.2 Using alternative probes. Axial flow verification may be
performed using an uncalibrated prism-shaped 3-D probe (e.g., DA or DAT
probe) or an uncalibrated wedge probe. (Figure 2F-11 illustrates a
typical wedge probe.) This approach requires use of two ports: the
tested probe port and a second port located 90[deg] from the tested
probe port. Each port shall provide access to all the points within the
wind tunnel test section where the velocity pressure cross-check, as
specified in section 10.1.1, is conducted. The probe setup shall include
establishing a reference yaw-null position on the probe sheath to serve
as the location for installing the angle-measuring device. Physical
design features of the DA, DAT, and wedge probes are relied on to
determine the reference position. For the DA or DAT probe, this
reference position can be determined by setting a digital inclinometer
on the flat facet where the P1 pressure port is located and
then identifying the rotational position on the probe sheath where a
second angle-measuring device would give the same angle reading. The
reference position on a wedge probe shaft can be determined either
geometrically or by placing a digital inclinometer on each side of the
wedge and rotating the probe until equivalent readings are obtained.
With the latter approach, the reference position is the rotational
position on the probe sheath where an angle-measuring device would give
a reading of 0[deg]. After installing the angle-measuring device in the
reference yaw-null position on the probe sheath, determine the yaw angle
from the tested port. Repeat this measurement using the 90[deg] offset
port, which provides the pitch angle of flow. Determine the yaw and
pitch angles at all the point(s) in the test section where the velocity
pressure cross-check, as specified in section 10.1.1, is performed. This
includes all the points in the wind tunnel calibration location and the
point where the calibration pitot tube will be located. Perform this
check at the highest and lowest velocities at which the probes will be
calibrated. Record the values on a form similar to Table 2F-5. Each
measured yaw and pitch angle shall be within 3[deg] of 0[deg].
Exceeding the limits indicates unacceptable flow in the test section.
Until the problem is corrected and acceptable flow is verified by
repetition of this procedure, the wind tunnel shall not be used for
calibration of probes. Include the results in the probe calibration
report.
10.1.3 Wind tunnel audits.
10.1.3.1 Procedure. Upon the request of the Administrator, the owner
or operator of a wind tunnel shall calibrate a 3-D audit probe in
accordance with the procedures described in sections 10.3 through 10.6.
The calibration shall be performed at two velocities and over a pitch
angle range that encompasses the velocities and pitch angles typically
used for this method at the facility. The resulting calibration data and
curves shall be submitted to the Agency in an audit test report. These
results shall be compared by the Agency to reference calibrations of the
audit probe at the same velocity and pitch angle settings obtained at
two different wind tunnels.
10.1.3.2 Acceptance criteria. The audited tunnel's calibration is
acceptable if all of the following conditions are satisfied at each
velocity and pitch setting for the reference calibration obtained from
at least one of the wind tunnels. For pitch angle settings between -
15[deg] and + 15[deg], no velocity calibration coefficient (i.e.,
F2) may differ from the corresponding reference value by more
than 3 percent. For pitch angle settings outside of this range (i.e.,
less than - 15[deg] and greater than + 15[deg]), no velocity calibration
coefficient may differ by more than 5 percent from the corresponding
reference value. If the acceptance criteria are not met, the audited
wind tunnel shall not be used to calibrate probes for use under this
method until the problems are resolved and acceptable results are
obtained upon completion of a subsequent audit.
10.2 Probe Inspection. Before each calibration of a 3-D probe,
carefully examine the physical condition of the probe head. Particular
attention shall be paid to the edges of the pressure ports and the
surfaces surrounding these ports. Any dents, scratches, or asymmetries
on the edges of the pressure ports and any scratches or indentations on

[[Page 60]]

the surfaces surrounding the pressure ports shall be noted because of
the potential effect on the probe's pressure readings. If the probe has
been previously calibrated, compare the current condition of the probe's
pressure ports and surfaces to the results of the inspection performed
during the probe's most recent wind tunnel calibration. Record the
results of this inspection on a form and in diagrams similar to Table
2F-1. The information in Table 2F-1 will be used as the basis for
comparison during the probe head inspections performed before each
subsequent field use.
10.3 Pre-Calibration Procedures. Prior to calibration, a scribe line
shall have been placed on the probe in accordance with section 10.4. The
yaw angle and velocity calibration procedures shall not begin until the
pre-test requirements in sections 10.3.1 through 10.3.4 have been met.
10.3.1 Perform the horizontal straightness check described in
section 8.2 on the probe assembly that will be calibrated in the wind
tunnel.
10.3.2 Perform a leak check in accordance with section 8.4.
10.3.3 Except as noted in section 10.3.3.3, calibrate all
differential pressure-measuring devices to be used in the probe
calibrations, using the following procedures. At a minimum, calibrate
these devices on each day that probe calibrations are performed.
10.3.3.1 Procedure. Before each wind tunnel use, all differential
pressure-measuring devices shall be calibrated against the reference
device specified in section 6.4.3 using a common pressure source.
Perform the calibration at three reference pressures representing 30,
60, and 90 percent of the full-scale range of the pressure-measuring
device being calibrated. For an inclined-vertical manometer, perform
separate calibrations on the inclined and vertical portions of the
measurement scale, considering each portion of the scale to be a
separate full-scale range. [For example, for a manometer with a 0- to
2.5-cm H2O (0- to 1-in. H2O) inclined scale and a
2.5- to 12.7-cm H2O (1- to 5-in. H2O) vertical
scale, calibrate the inclined portion at 7.6, 15.2, and 22.9 mm
H2O (0.3, 0.6, and 0.9 in. H2O), and calibrate the
vertical portion at 3.8, 7.6, and 11.4 cm H2O (1.5, 3.0, and
4.5 in. H2O).] Alternatively, for the vertical portion of the
scale, use three evenly spaced reference pressures, one of which is
equal to or higher than the highest differential pressure expected in
field applications.
10.3.3.2 Acceptance criteria. At each pressure setting, the two
pressure readings made using the reference device and the pressure-
measuring device being calibrated shall agree to within 2 percent of
full scale of the device being calibrated or 0.5 mm H2O (0.02
in. H2O), whichever is less restrictive. For an inclined-
vertical manometer, these requirements shall be met separately using the
respective full-scale upper limits of the inclined and vertical portions
of the scale. Differential pressure-measuring devices not meeting the #2
percent of full scale or 0.5 mm H2O (0.02 in. H2O)
calibration requirement shall not be used.
10.3.3.3 Exceptions. Any precision manometer that meets the
specifications for a reference device in section 6.4.3 and that is not
used for field testing does not require calibration, but must be leveled
and zeroed before each wind tunnel use. Any pressure device used
exclusively for yaw nulling does not require calibration, but shall be
checked for responsiveness to rotation of the probe prior to each wind
tunnel use.
10.3.4 Calibrate digital inclinometers on each day of wind tunnel or
field testing (prior to beginning testing) using the following
procedures. Calibrate the inclinometer according to the manufacturer's
calibration procedures. In addition, use a triangular block (illustrated
in Figure 2F-12) with a known angle, k independently determined using a
protractor or equivalent device, between two adjacent sides to verify
the inclinometer readings.

Note: If other angle-measuring devices meeting the provisions of
section 6.2.3 are used in place of a digital inclinometer, comparable
calibration procedures shall be performed on such devices.)

Secure the triangular block in a fixed position. Place the inclinometer
on one side of the block (side A) to measure the angle of inclination
(R1). Repeat this measurement on the adjacent side of the
block (side B) using the inclinometer to obtain a second angle reading
(R2). The difference of the sum of the two readings from
180[deg] (i.e., 180[deg] -R1 - R2) shall be within
2[deg] of the known angle, K
10.4 Placement of Reference Scribe Line. Prior to the first
calibration of a probe, a line shall be permanently inscribed on the
main probe sheath to serve as a reference mark for determining yaw
angles. Annex C in section 18 of this method gives a guideline for
placement of the reference scribe line.
10.4.1 This reference scribe line shall meet the specifications in
sections 6.1.6.1 and 6.1.6.3 of this method. To verify that the
alignment specification in section 6.1.6.3 is met, secure the probe in a
horizontal position and measure the rotational angle of each scribe line
and scribe line segment using an angle-measuring device that meets the
specifications in section 6.2.1 or 6.2.3. For any scribe line that is
longer than 30.5 cm (12 in.), check the line's rotational position at
30.5-cm (12-in.) intervals. For each line segment that is 30.5 cm (12
in.) or less in length, check the rotational position at the two
endpoints of the segment. To meet the alignment specification in section
6.1.6.3, the minimum and maximum of all of the rotational angles that
are measured along the full

[[Page 61]]

length of the main probe must not differ by more than 2[deg].

Note: A short reference scribe line segment [e.g., 15.2 cm (6 in.)
or less in length] meeting the alignment specifications in section
6.1.6.3 is fully acceptable under this method. See section 18.1.1.1 of
Annex A for an example of a probe marking procedure, suitable for use
with a short reference scribe line.

10.4.2 The scribe line should be placed on the probe first and then
its offset from the yaw-null position established (as specified in
section 10.5). The rotational position of the reference scribe line
relative to the yaw-null position of the probe, as determined by the yaw
angle calibration procedure in section 10.5, is defined as the reference
scribe line rotational offset, RSLO. The reference scribe
line rotational offset shall be recorded and retained as part of the
probe's calibration record.
10.4.3 Scribe line for automated probes. A scribe line may not be
necessary for an automated probe system if a reference rotational
position of the probe is built into the probe system design. For such
systems, a ``flat'' (or comparable, clearly identifiable physical
characteristic) should be provided on the probe casing or flange plate
to ensure that the reference position of the probe assembly remains in a
vertical or horizontal position. The rotational offset of the flat (or
comparable, clearly identifiable physical characteristic) needed to
orient the reference position of the probe assembly shall be recorded
and maintained as part of the automated probe system's specifications.
10.5 Yaw Angle Calibration Procedure. For each probe used to measure
yaw angles with this method, a calibration procedure shall be performed
in a wind tunnel meeting the specifications in section 10.1 to determine
the rotational position of the reference scribe line relative to the
probe's yaw-null position. This procedure shall be performed on the main
probe with all devices that will be attached to the main probe in the
field [such as thermocouples or resistance temperature detectors (RTDs)]
that may affect the flow around the probe head. Probe shaft extensions
that do not affect flow around the probe head need not be attached
during calibration. At a minimum, this procedure shall include the
following steps.
10.5.1 Align and lock the angle-measuring device on the reference
scribe line. If a marking procedure (such as that described in section
18.1.1.1) is used, align the angle-measuring device on a mark within
1[deg] of the rotational position of the reference scribe line. Lock
the angle-measuring device onto the probe sheath at this position.
10.5.2 Zero the pressure-measuring device used for yaw nulling.
10.5.3 Insert the probe assembly into the wind tunnel through the
entry port, positioning the probe's impact port at the calibration
location. Check the responsiveness of the pressure-measurement device to
probe rotation, taking corrective action if the response is
unacceptable.
10.5.4 Ensure that the probe is in a horizontal position, using a
carpenter's level.
10.5.5 Rotate the probe either clockwise or counterclockwise until a
yaw null (P2 = P3) is obtained.
10.5.6 Use the reading displayed by the angle-measuring device at
the yaw-null position to determine the magnitude of the reference scribe
line rotational offset, RSLO, as defined in section 3.15.
Annex D in section 18 of this method provides a recommended procedure
for determining the magnitude of RSLO with a digital
inclinometer and a second procedure for determining the magnitude of
RSLO with a protractor wheel and pointer device. Table 2F-6
presents an example data form and Table 2F-7 is a look-up table with the
recommended procedure. Procedures other than those recommended in Annex
D in section 18 may be used, if they can determine RSLO to
within 1[deg] and are explained in detail in the field test report. The
algebraic sign of RSLO will either be positive, if the
rotational position of the reference scribe line (as viewed from the
``tail'' end of the probe) is clockwise, or negative, if
counterclockwise with respect to the probe's yaw-null position. (This is
illustrated in Figure 2F-13.)
10.5.7 The steps in sections 10.5.3 through 10.5.6 shall be
performed twice at each of the velocities at which the probe will be
calibrated (in accordance with section 10.6). Record the values of
RSLO.
10.5.8 The average of all of the RSLO values shall be
documented as the reference scribe line rotational offset for the probe.
10.5.9 Use of reference scribe line offset. The reference scribe
line rotational offset shall be used to determine the yaw angle of flow
in accordance with section 8.9.4.
10.6 Pitch Angle and Velocity Pressure Calibrations. Use the
procedures in sections 10.6.1 through 10.6.16 to generate an appropriate
set (or sets) of pitch angle and velocity pressure calibration curves
for each probe. The calibration procedure shall be performed on the main
probe and all devices that will be attached to the main probe in the
field (e.g., thermocouple or RTDs) that may affect the flow around the
probe head. Probe shaft extensions that do not affect flow around the
probe head need not be attached during calibration. (Note: If a sampling
nozzle is part of the assembly, a wind tunnel demonstration shall be
performed that shows the probe's ability to measure velocity and yaw
null is not impaired when the nozzle is drawing a sample.) The
calibration

[[Page 62]]

procedure involves generating two calibration curves, F1
versus pitch angle and F2 versus pitch angle. To generate
these two curves, F1 and F2 shall be derived using
Equations 2F-1 and 2F-2, below. Table 2F-8 provides an example wind
tunnel calibration data sheet, used to log the measurements needed to
derive these two calibration curves.
10.6.1 Calibration velocities. The tester may calibrate the probe at
two nominal wind tunnel velocity settings of 18.3 m/sec and 27.4 m/sec
(60 ft/sec and 90 ft/sec) and average the results of these calibrations,
as described in section 10.6.16.1, in order to generate a set of
calibration curves. If this option is selected, this single set of
calibration curves may be used for all field applications over the
entire velocity range allowed by the method. Alternatively, the tester
may customize the probe calibration for a particular field test
application (or for a series of applications), based on the expected
average velocity(ies) at the test site(s). If this option is selected,
generate each set of calibration curves by calibrating the probe at two
nominal wind tunnel velocity settings, at least one of which is greater
than or equal to the expected average velocity(ies) for the field
application(s), and average the results as described in section
10.6.16.1. Whichever calibration option is selected, the probe
calibration coefficients (F2 values) obtained at the two
nominal calibration velocities shall, for the same pitch angle setting,
meet the conditions specified in section 10.6.16.
10.6.2 Pitch angle calibration curve (F1 versus pitch
angle). The pitch angle calibration involves generating a calibration
curve of calculated F1 values versus tested pitch angles,
where F1 is the ratio of the pitch pressure to the velocity
pressure, i.e.,
[GRAPHIC] [TIFF OMITTED] TR14MY99.049

See Figure 2F-14 for an example F1 versus pitch angle
calibration curve.
10.6.3 Velocity calibration curve (F2 versus pitch
angle). The velocity calibration involves generating a calibration curve
of the 3-D probe's F2 coefficient against the tested pitch
angles, where
[GRAPHIC] [TIFF OMITTED] TR14MY99.050

and
Cp = calibration pitot tube coefficient, and
FPstd = velocity pressure from the calibration pitot tube.

See Figure 2F-15 for an example F2 versus pitch angle
calibration curve.
10.6.4 Connect the tested probe and calibration pitot probe to their
respective pressure-measuring devices. Zero the pressure-measuring
devices. Inspect and leak-check all pitot lines; repair or replace, if
necessary. Turn on the fan, and allow the wind tunnel air flow to
stabilize at the first of the two selected nominal velocity settings.
10.6.5 Position the calibration pitot tube at its measurement
location (determined as outlined in section 6.11.4.3), and align the
tube so that its tip is pointed directly into the flow. Ensure that the
entry port surrounding the tube is properly sealed. The calibration
pitot tube may either remain in the wind tunnel throughout the
calibration, or be removed from the wind tunnel while measurements are
taken with the probe being calibrated.
10.6.6 Set up the pitch protractor plate on the tested probe's entry
port to establish the pitch angle positions of the probe to within
2[deg].
10.6.7 Check the zero setting of each pressure-measuring device.
10.6.8 Insert the tested probe into the wind tunnel and align it so
that its P1 pressure port is pointed directly into the flow
and is positioned within the calibration location (as defined in section
3.20). Secure the probe at the 0[deg] pitch angle position. Ensure that
the entry port surrounding the probe is properly sealed.
10.6.9 Read the differential pressure from the calibration pitot
tube (FPstd), and record its value. Read the barometric
pressure to within 2.5 mm Hg (0.1 in. Hg) and the temperature in the
wind tunnel to within 0.6 [deg]C (1 [deg]F). Record these values on a
data form similar to Table 2F-8.
10.6.10 After the tested probe's differential pressure gauges have
had sufficient time to stabilize, yaw null the probe, then obtain
differential pressure readings for (P1- P2) and
(P4- P5). Record the yaw angle and differential
pressure readings. After taking these readings, ensure that the tested
probe has remained at the yaw-null position.
10.6.11 Either take paired differential pressure measurements with
both the calibration pitot tube and tested probe (according to sections
10.6.9 and 10.6.10) or take readings only with the tested probe
(according to section 10.6.10) in 5[deg] increments over the pitch-angle
range for which the probe is to be calibrated. The calibration pitch-
angle range shall be symmetric around 0[deg] and shall exceed the
largest pitch angle expected in the field by 5[deg]. At a minimum,
probes shall be calibrated over the range of -15[deg] to + 15[deg]. If
paired calibration pitot tube and tested probe measurements are not
taken at each pitch angle setting, the differential pressure from the
calibration pitot tube shall be read, at a minimum, before taking the
tested probe's differential pressure reading at the first pitch angle
setting and after taking the tested probe's differential pressure
readings at the last pitch angle setting in each replicate.

[[Page 63]]

10.6.12 Perform a second replicate of the procedures in sections
10.6.5 through 10.6.11 at the same nominal velocity setting.
10.6.13 For each replicate, calculate the F1 and
F2 values at each pitch angle. At each pitch angle, calculate
the percent difference between the two F2 values using
Equation 2F-3.
[GRAPHIC] [TIFF OMITTED] TR14MY99.051

If the percent difference is less than or equal to 2 percent,
calculate an average F1 value and an average F2
value at that pitch angle. If the percent difference is greater than 2
percent and less than or equal to 5 percent, perform a third repetition
at that angle and calculate an average F1 value and an
average F2 value using all three repetitions. If the percent
difference is greater than 5 percent, perform four additional
repetitions at that angle and calculate an average F1 value
and an average F2 value using all six repetitions. When
additional repetitions are required at any pitch angle, move the probe
by at least 5[deg] and then return to the specified pitch angle before
taking the next measurement. Record the average values on a form similar
to Table 2F-9.
10.6.14 Repeat the calibration procedures in sections 10.6.5 through
10.6.13 at the second selected nominal wind tunnel velocity setting.
10.6.15 Velocity drift check. The following check shall be
performed, except when paired calibration pitot tube and tested probe
pressure measurements are taken at each pitch angle setting. At each
velocity setting, calculate the percent difference between consecutive
differential pressure measurements made with the calibration pitot tube.
If a measurement differs from the previous measurement by more than 2
percent or 0.25 mm H2O (0.01 in. H2O), whichever
is less restrictive, the calibration data collected between these
calibration pitot tube measurements may not be used, and the
measurements shall be repeated.
10.6.16 Compare the averaged F2 coefficients obtained
from the calibrations at the two selected nominal velocities, as
follows. At each pitch angle setting, use Equation 2F-3 to calculate the
difference between the corresponding average F2 values at the
two calibration velocities. At each pitch angle in the - 15[deg] to +
15[deg] range, the percent difference between the average F2
values shall not exceed 3.0 percent. For pitch angles outside this range
(i.e., less than - 15[deg]0 and greater than + 15[deg]), the percent
difference shall not exceed 5.0 percent.
10.6.16.1 If the applicable specification in section 10.6.16 is met
at each pitch angle setting, average the results obtained at the two
nominal calibration velocities to produce a calibration record of
F1 and F2 at each pitch angle tested. Record these
values on a form similar to Table 2F-9. From these values, generate one
calibration curve representing F1 versus pitch angle and a
second curve representing F2 versus pitch angle. Computer
spreadsheet programs may be used to graph the calibration data and to
develop polynomial equations that can be used to calculate pitch angles
and axial velocities.
10.6.16.2 If the applicable specification in section 10.6.16 is
exceeded at any pitch angle setting, the probe shall not be used unless:
(1) the calibration is repeated at that pitch angle and acceptable
results are obtained or (2) values of F1 and F2
are obtained at two nominal velocities for which the specifications in
section 10.6.16 are met across the entire pitch angle range.
10.7 Recalibration. Recalibrate the probe using the procedures in
section 10 either within 12 months of its first field use after its most
recent calibration or after 10 field tests (as defined in section 3.4),
whichever occurs later. In addition, whenever there is visible damage to
the 3-D head, the probe shall be recalibrated before it is used again.
10.8 Calibration of pressure-measuring devices used in field tests.
Before its initial use in a field test, calibrate each pressure-
measuring device (except those used exclusively for yaw nulling) using
the three-point calibration procedure described in section 10.3.3. The
device shall be recalibrated according to the procedure in section
10.3.3 no later than 90 days after its first field use following its
most recent calibration. At the discretion of the tester, more frequent
calibrations (e.g., after a field test) may be performed. No
adjustments, other than adjustments to the zero setting, shall be made
to the device between calibrations.
10.8.1 Post-test calibration check. A single-point calibration check
shall be performed on each pressure-measuring device after completion of
each field test. At the discretion of the tester, more frequent single-
point calibration checks (e.g., after one or more field test runs) may
be performed. It is recommended that the post-test check be performed
before leaving the field test site. The check shall be performed at a
pressure between 50 and 90 percent of full scale by taking a common
pressure reading with the tested device and a reference pressure-
measuring device (as described in section 6.4.4) or by challenging the
tested device with a reference pressure source (as described in section
6.4.4) or by performing an equivalent check using a reference device
approved by the Administrator.
10.8.2 Acceptance criterion. At the selected pressure setting, the
pressure readings made using the reference device and the tested device
shall agree to within 3 percent of full scale of the tested device or
0.8 mm H2O (0.03 in. H2O), whichever is less
restrictive. If this

[[Page 64]]

specification is met, the test data collected during the field test are
valid. If the specification is not met, all test data collected since
the last successful calibration or calibration check are invalid and
shall be repeated using a pressure-measuring device with a current,
valid calibration. Any device that fails the calibration check shall not
be used in a field test until a successful recalibration is performed
according to the procedures in section 10.3.3.
10.9 Temperature Gauges. Same as Method 2, section 4.3. The
alternative thermocouple calibration procedures outlined in Emission
Measurement Center (EMC) Approved Alternative Method (ALT-011)
``Alternative Method 2 Thermocouple Calibration Procedure'' may be
performed. Temperature gauges shall be calibrated no more than 30 days
prior to the start of a field test or series of field tests and
recalibrated no more than 30 days after completion of a field test or
series of field tests.
10.10 Barometer. Same as Method 2, section 4.4. The barometer shall
be calibrated no more than 30 days prior to the start of a field test or
series of field tests.

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this method (see
section 8.0).

12.0 Data Analysis and Calculations

These calculations use the measured yaw angle, derived pitch angle,
and the differential pressure and temperature measurements at individual
traverse points to derive the axial flue gas velocity (va(i))
at each of those points. The axial velocity values at all traverse
points that comprise a full stack or duct traverse are then averaged to
obtain the average axial flue gas velocity (va (avg)). Round
off figures only in the final calculation of reported values.
12.1 Nomenclature

A = Cross-sectional area of stack or duct, m\2\ (ft \2\).
Bws = Water vapor in the gas stream (from Method 4 or
alternative), proportion by volume.
Kp Conversion factor (a constant),
[GRAPHIC] [TIFF OMITTED] TR14MY99.052

for the metric system, and
[GRAPHIC] [TIFF OMITTED] TR14MY99.053

for the English system.

Md = Molecular weight of stack or duct gas, dry basis (see
section 8.13), g/g-mole (lb/lb-mole).
Ms = Molecular weight of stack or duct gas, wet basis, g/g-
mole (lb/lb-mole).
[GRAPHIC] [TIFF OMITTED] TR14MY99.054

Pbar = Barometric pressure at measurement site, mm Hg (in.
Hg).
Pg = Stack or duct static pressure, mm H2O (in.
H2O).
Ps = Absolute stack or duct pressure, mm Hg (in. Hg),
[GRAPHIC] [TIFF OMITTED] TR14MY99.055

Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
13.6 = Conversion from mm H2O (in. H2O) to mm Hg
(in. Hg).
Qsd = Average dry-basis volumetric stack or duct gas flow
rate corrected to standard conditions, dscm/hr (dscf/hr).
Qsw = Average wet-basis volumetric stack or duct gas flow
rate corrected to standard conditions, wscm/hr (wscf/hr).
Ts(avg) = Average absolute stack or duct gas temperature
across all traverse points.
ts(i) = Stack or duct gas temperature, C (F), at traverse
point i.
Ts(i) = Absolute stack or duct gas temperature, K (R), at
traverse point i,
[GRAPHIC] [TIFF OMITTED] TR14MY99.056

for the metric system, and
[GRAPHIC] [TIFF OMITTED] TR14MY99.057

for the English system.
Tstd = Standard absolute temperature, 293 [deg]K (528
[deg]R).
F1(i) = Pitch angle ratio, applicable at traverse point i,
dimensionless.
F2(i) = 3-D probe velocity calibration coefficient,
applicable at traverse point i, dimensionless.
(P4-P5)i = Pitch differential pressure
of stack or duct gas flow, mm H2O (in.
H2O), at traverse point i.
(P1-P2)i = Velocity head (differential
pressure) of stack or duct gas flow, mm H2O (in.
H2O), at traverse point i.
va(i) = Reported stack or duct gas axial velocity, m/sec (ft/
sec), at traverse point i.
va(avg) = Average stack or duct gas axial velocity, m/sec
(ft/sec), across all traverse points.
3,600 = Conversion factor, sec/hr.
18.0 = Molecular weight of water, g/g-mole (lb/lb-mole).
ky(i) = Yaw angle, degrees, at traverse point i.
kp(i) = Pitch angle, degrees, at traverse point i.
n = Number of traverse points.

[[Page 65]]

12.2 Traverse Point Velocity Calculations. Perform the following
calculations from the measurements obtained at each traverse point.
12.2.1 Selection of calibration curves. Select calibration curves as
described in section 10.6.1.
12.2.2 Traverse point pitch angle ratio. Use Equation 2F-1, as
described in section 10.6.2, to calculate the pitch angle ratio,
F1(i), at each traverse point.
12.2.3 Pitch angle. Use the pitch angle ratio, F1(i), to
derive the pitch angle, kp(i), at traverse point i from the
F1 versus pitch angle calibration curve generated under
section 10.6.16.1.
12.2.4 Velocity calibration coefficient. Use the pitch angle,
kp(i), to obtain the probe velocity calibration coefficient,
F2(i), at traverse point i from the ``velocity pressure
calibration curve,'' i.e., the F2 versus pitch angle
calibration curve generated under section 10.6.16.1.
12.2.5 Axial velocity. Use the following equation to calculate the
axial velocity, va(i), from the differential pressure
(P1-P2)i and yaw angle,
ky(i), measured at traverse point i and the previously
calculated values for the velocity calibration coefficient,
F2(i), absolute stack or duct standard temperature,
Ts(i), absolute stack or duct pressure, Ps,
molecular weight, Ms, and pitch angle, ``kp(i).
[GRAPHIC] [TIFF OMITTED] TR14MY99.058

12.2.6 Handling multiple measurements at a traverse point. For
pressure or temperature devices that take multiple measurements at a
traverse point, the multiple measurements (or where applicable, their
square roots) may first be averaged and the resulting average values
used in the equations above. Alternatively, the individual measurements
may be used in the equations above and the resulting multiple calculated
values may then be averaged to obtain a single traverse point value.
With either approach, all of the individual measurements recorded at a
traverse point must be used in calculating the applicable traverse point
value.
12.3 Average Axial Velocity in Stack or Duct. Use the reported
traverse point axial velocity in the following equation.
[GRAPHIC] [TIFF OMITTED] TR14MY99.059

12.4 Acceptability of Results. The test results are acceptable and
the calculated value of va(avg) may be reported as the
average axial velocity for the test run if the conditions in either
section 12.4.1 or 12.4.2 are met.
12.4.1 The calibration curves were generated at nominal velocities
of 18.3 m/sec and 27.4 m/sec (60 ft/sec and 90 ft/sec).
12.4.2 The calibration curves were generated at nominal velocities
other than 18.3 m/sec and 27.4 m/sec (60 ft/sec and 90 ft/sec), and the
value of va(avg) obtained using Equation 2F-9 is less than or
equal to at least one of the nominal velocities used to derive the
F1 and F2 calibration curves.
12.4.3 If the conditions in neither section 12.4.1 nor section
12.4.2 are met, the test results obtained in Equation 2F-9 are not
acceptable, and the steps in sections 12.2 and 12.3 must be repeated
using a set of F1 and F2 calibration curves that
satisfies the conditions specified in section 12.4.1 or 12.4.2.
12.5 Average Gas Wet Volumetric Flow Rate in Stack or Duct. Use the
following equation to compute the average volumetric flow rate on a wet
basis.
[GRAPHIC] [TIFF OMITTED] TR14MY99.060

12.6 Average Gas Dry Volumetric Flow Rate in Stack or Duct. Use the
following equation to compute the average volumetric flow rate on a dry
basis.

[[Page 66]]

[GRAPHIC] [TIFF OMITTED] TR14MY99.061

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Reporting

16.1 Field Test Reports. Field test reports shall be submitted to
the Agency according to applicable regulatory requirements. Field test
reports should, at a minimum, include the following elements.
16.1.1 Description of the source. This should include the name and
location of the test site, descriptions of the process tested, a
description of the combustion source, an accurate diagram of stack or
duct cross-sectional area at the test site showing the dimensions of the
stack or duct, the location of the test ports, and traverse point
locations and identification numbers or codes. It should also include a
description and diagram of the stack or duct layout, showing the
distance of the test location from the nearest upstream and downstream
disturbances and all structural elements (including breachings, baffles,
fans, straighteners, etc.) affecting the flow pattern. If the source and
test location descriptions have been previously submitted to the Agency
in a document (e.g., a monitoring plan or test plan), referencing the
document in lieu of including this information in the field test report
is acceptable.
16.1.2 Field test procedures. These should include a description of
test equipment and test procedures. Testing conventions, such as
traverse point numbering and measurement sequence (e.g., sampling from
center to wall, or wall to center), should be clearly stated. Test port
identification and directional reference for each test port should be
included on the appropriate field test data sheets.
16.1.3 Field test data.
16.1.3.1 Summary of results. This summary should include the dates
and times of testing and the average axial gas velocity and the average
flue gas volumetric flow results for each run and tested condition.
16.1.3.2 Test data. The following values for each traverse point
should be recorded and reported:

(a) P1-P2 and P4-P5
differential pressures
(b) Stack or duct gas temperature at traverse point i
(ts(i))
(c) Absolute stack or duct gas temperature at traverse point i
(Ts(i))
(d) Yaw angle at each traverse point i (ky(i))
(e) Pitch angle at each traverse point i (kp(i))
(f) Stack or duct gas axial velocity at traverse point i
(va(i))

16.1.3.3 The following values should be reported once per run:

(a) Water vapor in the gas stream (from Method 4 or alternative),
proportion by volume (Bws), measured at the frequency
specified in the applicable regulation
(b) Molecular weight of stack or duct gas, dry basis (Md)
(c) Molecular weight of stack or duct gas, wet basis (Ms)
(d) Stack or duct static pressure (Pg)
(e) Absolute stack or duct pressure (Ps)
(f) Carbon dioxide concentration in the flue gas, dry basis (\0/
0\d CO2)
(g) Oxygen concentration in the flue gas, dry basis (\0/
0\d O2)
(h) Average axial stack or duct gas velocity (va(avg))
across all traverse points
(i) Gas volumetric flow rate corrected to standard conditions, dry
or wet basis as required by the applicable regulation (Qsd or
Qsw)

16.1.3.4 The following should be reported once per complete set of test
runs:

(a) Cross-sectional area of stack or duct at the test location (A)
(b) Measurement system response time (sec)
(c) Barometric pressure at measurement site (Pbar)

16.1.4 Calibration data. The field test report should include
calibration data for all probes and test equipment used in the field
test. At a minimum, the probe calibration data reported to the Agency
should include the following:

(a) Date of calibration
(b) Probe type
(c) Probe identification number(s) or code(s)
(d) Probe inspection sheets
(e) Pressure measurements and intermediate calculations of
F1 and F2 at each pitch angle used to obtain
calibration curves in accordance with section 10.6 of this method
(f) Calibration curves (in graphic or equation format) obtained in
accordance with sections 10.6.11 of this method
(g) Description and diagram of wind tunnel used for the calibration,
including dimensions of cross-sectional area and position and size of
the test section
(h) Documentation of wind tunnel qualification tests performed in
accordance with section 10.1 of this method

[[Page 67]]

16.1.5 Quality Assurance. Specific quality assurance and quality
control procedures used during the test should be described.

17.0 Bibliography

(1) 40 CFR Part 60, Appendix A, Method 1--Sample and velocity
traverses for stationary sources.
(2) 40 CFR Part 60, Appendix A, Method 2H--Determination of stack
gas velocity taking into account velocity decay near the stack wall.
(3) 40 CFR Part 60, Appendix A, Method 2--Determination of stack gas
velocity and volumetric flow rate (Type S pitot tube).
(4) 40 CFR Part 60, Appendix A, Method 3--Gas analysis for carbon
dioxide, oxygen, excess air, and dry molecular weight.
(5) 40 CFR Part 60, Appendix A, Method 3A--Determination of oxygen
and carbon dioxide concentrations in emissions from stationary sources
(instrumental analyzer procedure).
(6) 40 CFR Part 60, Appendix A, Method 4--Determination of moisture
content in stack gases.
(7) Emission Measurement Center (EMC) Approved Alternative Method
(ALT-011) ``Alternative Method 2 Thermocouple Calibration Procedure.''
(8) Electric Power Research Institute, Interim Report EPRI TR-
106698, ``Flue Gas Flow Rate Measurement Errors,'' June 1996.
(9) Electric Power Research Institute, Final Report EPRI TR-108110,
``Evaluation of Heat Rate Discrepancy from Continuous Emission
Monitoring Systems,'' August 1997.
(10) Fossil Energy Research Corporation, Final Report, ``Velocity
Probe Tests in Non-axial Flow Fields,'' November 1998, Prepared for the
U.S. Environmental Protection Agency.
(11) Fossil Energy Research Corporation, ``Additional Swirl Tunnel
Tests: E-DAT and T-DAT Probes,'' February 24, 1999, Technical Memorandum
Prepared for U.S. Environmental Protection Agency, P.O. No. 7W-1193-
NALX.
(12) Massachusetts Institute of Technology, Report WBWT-TR-1317,
``Calibration of Eight Wind Speed Probes Over a Reynolds Number Range of
46,000 to 725,000 Per Foot, Text and Summary Plots,'' Plus appendices,
October 15, 1998, Prepared for The Cadmus Group, Inc.
(13) National Institute of Standards and Technology, Special
Publication 250, ``NIST Calibration Services Users Guide 1991,'' Revised
October 1991, U.S. Department of Commerce, p. 2.
(14) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Four Prandtl Probes, Four
S-Type Probes, Four French Probes, Four Modified Kiel Probes,'' Prepared
for the U.S. Environmental Protection Agency under IAG #DW13938432-01-0.
(15) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Five Autoprobes,''
Prepared for the U.S. Environmental Protection Agency under IAG
#DW13938432-01-0.
(16) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Eight Spherical Probes,''
Prepared for the U.S. Environmental Protection Agency under IAG
#DW13938432-01-0.
(17) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Four DAT Probes,''
Prepared for the U.S. Environmental Protection Agency under IAG
#DW13938432-01-0.
(18) Norfleet, S.K., ``An Evaluation of Wall Effects on Stack Flow
Velocities and Related Overestimation Bias in EPA's Stack Flow Reference
Methods,'' EPRI CEMS User's Group Meeting, New Orleans, Louisiana, May
13-15, 1998.
(19) Page, J.J., E.A. Potts, and R.T. Shigehara, ``3-D Pitot Tube
Calibration Study,'' EPA Contract No. 68-D1-0009, Work Assignment No. I-
121, March 11, 1993.
(20) Shigehara, R.T., W.F. Todd, and W.S. Smith, ``Significance of
Errors in Stack Sampling Measurements,'' Presented at the Annual Meeting
of the Air Pollution Control Association, St. Louis, Missouri, June 14-
19, 1970.
(21) The Cadmus Group, Inc., May 1999, ``EPA Flow Reference Method
Testing and Analysis: Findings Report,'' EPA/430-R-99-009.
(22) The Cadmus Group, Inc., 1998, ``EPA Flow Reference Method
Testing and Analysis: Data Report, Texas Utilities, DeCordova Steam
Electric Station, Volume I: Test Description and Appendix A (Data
Distribution Package),'' EPA/430-R-98-015a.
(23) The Cadmus Group, Inc., 1998, ``EPA Flow Reference Method
Testing and Analysis: Data Report, Texas Utilities, Lake Hubbard Steam
Electric Station, Volume I: Test Description and Appendix A (Data
Distribution Package),'' EPA/430-R-98-017a.
(24) The Cadmus Group, Inc., 1998, ``EPA Flow Reference Method
Testing and Analysis: Data Report, Pennsylvania Electric Co., G.P.U.
Genco Homer City Station: Unit 1, Volume I: Test Description and
Appendix A (Data Distribution Package),'' EPA/430-R-98-018a.
(25) The Cadmus Group, Inc., 1997, ``EPA Flow Reference Method
Testing and Analysis: Wind Tunnel Experimental Results,'' EPA/430-R-97-
013.

18.0 Annexes

Annex A, C, and D describe recommended procedures for meeting
certain provisions in sections 8.3, 10.4, and 10.5 of this method. Annex
B describes procedures to be followed

[[Page 68]]

when using the protractor wheel and pointer assembly to measure yaw
angles, as provided under section 8.9.1.
18.1 Annex A--Rotational Position Check. The following are
recommended procedures that may be used to satisfy the rotational
position check requirements of section 8.3 of this method and to
determine the angle-measuring device rotational offset RADO.
18.1.1 Rotational position check with probe outside stack. Where
physical constraints at the sampling location allow full assembly of the
probe outside the stack and insertion into the test port, the following
procedures should be performed before the start of testing. Two angle-
measuring devices that meet the specifications in section 6.2.1 or 6.2.3
are required for the rotational position check. An angle measuring
device whose position can be independently adjusted (e.g., by means of a
set screw) after being locked into position on the probe sheath shall
not be used for this check unless the independent adjustment is set so
that the device performs exactly like a device without the capability
for independent adjustment. That is, when aligned on the probe such a
device must give the same reading as a device that does not have the
capability of being independently adjusted. With the fully assembled
probe (including probe shaft extensions, if any) secured in a horizontal
position, affix one yaw angle-measuring device to the probe sheath and
lock it into position on the reference scribe line specified in section
6.1.6.1. Position the second angle-measuring device using the procedure
in section 18.1.1.1 or 18.1.1.2.
18.1.1.1 Marking procedure. The procedures in this section should be
performed at each location on the fully assembled probe where the yaw
angle-measuring device will be mounted during the velocity traverse.
Place the second yaw angle-measuring device on the main probe sheath (or
extension) at the position where a yaw angle will be measured during the
velocity traverse. Adjust the position of the second angle-measuring
device until it indicates the same angle (1[deg]) as the reference
device, and affix the second device to the probe sheath (or extension).
Record the angles indicated by the two angle-measuring devices on a form
similar to Table 2F-2. In this position, the second angle-measuring
device is considered to be properly positioned for yaw angle
measurement. Make a mark, no wider than 1.6 mm (1/16 in.), on the probe
sheath (or extension), such that the yaw angle-measuring device can be
re-affixed at this same properly aligned position during the velocity
traverse.
18.1.1.2 Procedure for probe extensions with scribe lines. If,
during a velocity traverse the angle-measuring device will be affixed to
a probe extension having a scribe line as specified in section 6.1.6.2,
the following procedure may be used to align the extension's scribe line
with the reference scribe line instead of marking the extension as
described in section 18.1.1.1. Attach the probe extension to the main
probe. Align and lock the second angle-measuring device on the probe
extension's scribe line. Then, rotate the extension until both measuring
devices indicate the same angle (1[deg]). Lock the extension at this
rotational position. Record the angles indicated by the two angle-
measuring devices on a form similar to Table 2F-2. An angle-measuring
device may be aligned at any position on this scribe line during the
velocity traverse, if the scribe line meets the alignment specification
in section 6.1.6.3.
18.1.1.3 Post-test rotational position check. If the fully assembled
probe includes one or more extensions, the following check should be
performed immediately after the completion of a velocity traverse. At
the discretion of the tester, additional checks may be conducted after
completion of testing at any sample port. Without altering the alignment
of any of the components of the probe assembly used in the velocity
traverse, secure the fully assembled probe in a horizontal position.
Affix an angle-measuring device at the reference scribe line specified
in section 6.1.6.1. Use the other angle-measuring device to check the
angle at each location where the device was checked prior to testing.
Record the readings from the two angle-measuring devices.
18.1.2 Rotational position check with probe in stack. This section
applies only to probes that, due to physical constraints, cannot be
inserted into the test port as fully assembled with all necessary
extensions needed to reach the inner-most traverse point(s).
18.1.2.1 Perform the out-of-stack procedure in section 18.1.1 on the
main probe and any attached extensions that will be initially inserted
into the test port.
18.1.2.2 Use the following procedures to perform additional
rotational position check(s) with the probe in the stack, each time a
probe extension is added. Two angle-measuring devices are required. The
first of these is the device that was used to measure yaw angles at the
preceding traverse point, left in its properly aligned measurement
position. The second angle-measuring device is positioned on the added
probe extension. Use the applicable procedures in section 18.1.1.1 or
18.1.1.2 to align, adjust, lock, and mark (if necessary) the position of
the second angle-measuring device to within 1[deg] of the first device.
Record the readings of the two devices on a form similar to Table 2F-2.
18.1.2.3 The procedure in section 18.1.2.2 should be performed at
the first port where measurements are taken. The procedure should be
repeated each time a probe extension is re-attached at a subsequent
port, unless the probe extensions are designed to be locked into a
mechanically fixed rotational position (e.g., through use of
interlocking

[[Page 69]]

grooves), which can be reproduced from port to port as specified in
section 8.3.5.2.
18.2 Annex B--Angle Measurement Protocol for Protractor Wheel and
Pointer Device. The following procedure shall be used when a protractor
wheel and pointer assembly, such as the one described in section 6.2.2
and illustrated in Figure 2F-7 is used to measure the yaw angle of flow.
With each move to a new traverse point, unlock, re-align, and re-lock
the probe, angle-pointer collar, and protractor wheel to each other. At
each such move, particular attention is required to ensure that the
scribe line on the angle pointer collar is either aligned with the
reference scribe line on the main probe sheath or is at the rotational
offset position established under section 8.3.1. The procedure consists
of the following steps:
18.2.1 Affix a protractor wheel to the entry port for the test probe
in the stack or duct.
18.2.2 Orient the protractor wheel so that the 0[deg] mark
corresponds to the longitudinal axis of the stack or duct. For stacks,
vertical ducts, or ports on the side of horizontal ducts, use a digital
inclinometer meeting the specifications in section 6.2.1 to locate the
0[deg] orientation. For ports on the top or bottom of horizontal ducts,
identify the longitudinal axis at each test port and permanently mark
the duct to indicate the 0[deg] orientation. Once the protractor wheel
is properly aligned, lock it into position on the test port.
18.2.3 Move the pointer assembly along the probe sheath to the
position needed to take measurements at the first traverse point. Align
the scribe line on the pointer collar with the reference scribe line or
at the rotational offset position established under section 8.3.1.
Maintaining this rotational alignment, lock the pointer device onto the
probe sheath. Insert the probe into the entry port to the depth needed
to take measurements at the first traverse point.
18.2.4 Perform the yaw angle determination as specified in sections
8.9.3 and 8.9.4 and record the angle as shown by the pointer on the
protractor wheel. Then, take velocity pressure and temperature
measurements in accordance with the procedure in section 8.9.5. Perform
the alignment check described in section 8.9.6.
18.2.5 After taking velocity pressure measurements at that traverse
point, unlock the probe from the collar and slide the probe through the
collar to the depth needed to reach the next traverse point.
18.2.6 Align the scribe line on the pointer collar with the
reference scribe line on the main probe or at the rotational offset
position established under section 8.3.1. Lock the collar onto the
probe.
18.2.7 Repeat the steps in sections 18.2.4 through 18.2.6 at the
remaining traverse points accessed from the current stack or duct entry
port.
18.2.8 After completing the measurement at the last traverse point
accessed from a port, verify that the orientation of the protractor
wheel on the test port has not changed over the course of the traverse
at that port. For stacks, vertical ducts, or ports on the side of
horizontal ducts, use a digital inclinometer meeting the specifications
in section 6.2.1 to check the rotational position of the 0[deg] mark on
the protractor wheel. For ports on the top or bottom of horizontal
ducts, observe the alignment of the angle wheel 0[deg] mark relative to
the permanent 0[deg] mark on the duct at that test port. If these
observed comparisons exceed 2[deg] of 0[deg], all angle and pressure
measurements taken at that port since the protractor wheel was last
locked into position on the port shall be repeated.
18.2.9 Move to the next stack or duct entry port and repeat the
steps in sections 18.2.1 through 18.2.8.
18.3 Annex C--Guideline for Reference Scribe Line Placement. Use of
the following guideline is recommended to satisfy the requirements of
section 10.4 of this method. The rotational position of the reference
scribe line should be either 90[deg] or 180[deg] from the probe's impact
pressure port.
18.4 Annex D--Determination of Reference Scribe Line Rotational
Offset. The following procedures are recommended for determining the
magnitude and sign of a probe's reference scribe line rotational offset,
RSLO. Separate procedures are provided for two types of
angle-measuring devices: digital inclinometers and protractor wheel and
pointer assemblies.
18.4.1 Perform the following procedures on the main probe with all
devices that will be attached to the main probe in the field [such as
thermocouples or resistance temperature detectors (RTDs)] that may
affect the flow around the probe head. Probe shaft extensions that do
not affect flow around the probe head need not be attached during
calibration.
18.4.2 The procedures below assume that the wind tunnel duct used
for probe calibration is horizontal and that the flow in the calibration
wind tunnel is axial as determined by the axial flow verification check
described in section 10.1.2. Angle-measuring devices are assumed to
display angles in alternating 0[deg] to 90[deg] and 90[deg] to 0[deg]
intervals. If angle-measuring devices with other readout conventions are
used or if other calibration wind tunnel duct configurations are used,
make the appropriate calculational corrections.
18.4.2.1 Position the angle-measuring device in accordance with one
of the following procedures.
18.4.2.1.1 If using a digital inclinometer, affix the calibrated
digital inclinometer to the probe. If the digital inclinometer can be
independently adjusted after being locked

[[Page 70]]

into position on the probe sheath (e.g., by means of a set screw), the
independent adjustment must be set so that the device performs exactly
like a device without the capability for independent adjustment. That
is, when aligned on the probe the device must give the same readings as
a device that does not have the capability of being independently
adjusted. Either align it directly on the reference scribe line or on a
mark aligned with the scribe line determined according to the procedures
in section 18.1.1.1. Maintaining this rotational alignment, lock the
digital inclinometer onto the probe sheath.
18.4.2.1.2 If using a protractor wheel and pointer device, orient
the protractor wheel on the test port so that the 0[deg] mark is aligned
with the longitudinal axis of the wind tunnel duct. Maintaining this
alignment, lock the wheel into place on the wind tunnel test port. Align
the scribe line on the pointer collar with the reference scribe line or
with a mark aligned with the reference scribe line, as determined under
section 18.1.1.1. Maintaining this rotational alignment, lock the
pointer device onto the probe sheath.
18.4.2.2 Zero the pressure-measuring device used for yaw nulling.
18.4.2.3 Insert the probe assembly into the wind tunnel through the
entry port, positioning the probe's impact port at the calibration
location. Check the responsiveness of the pressure-measuring device to
probe rotation, taking corrective action if the response is
unacceptable.
18.4.2.4 Ensure that the probe is in a horizontal position using a
carpenter's level.
18.4.2.5 Rotate the probe either clockwise or counterclockwise until
a yaw null (P2 = P3) is obtained.
18.4.2.6 Read and record the value of knull, the angle
indicated by the angle-measuring device at the yaw-null position. Record
the angle reading on a form similar to Table 2F-6. Do not associate an
algebraic sign with this reading.
18.4.2.7 Determine the magnitude and algebraic sign of the reference
scribe line rotational offset, RSLO. The magnitude of
RSLO will be equal to either knull or (90[deg]-
knull), depending on the angle-measuring device used. (See
Table 2F-7 for a summary.) The algebraic sign of RSLO will
either be positive, if the rotational position of the reference scribe
line is clockwise, or negative, if counterclockwise with respect to the
probe's yaw-null position. Figure 2F-13 illustrates how the magnitude
and sign of RSLO are determined.
18.4.2.8 Perform the steps in sections 18.4.2.3 through 18.4.2.7
twice at each of the two calibration velocities selected for the probe
under section 10.6. Record the values of RSLO in a form
similar to Table 2F-6.
18.4.2.9 The average of all RSLO values is the reference
scribe line rotational offset for the probe.

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[36 FR 24877, Dec. 23, 1971]

Editorial Note: For Federal Register citations affecting appendix A-
1 to part 60, see the List of CFR sections Affected, which appears in
the Finding Aids section of the printed volume and at www.fdsys.gov.

[[Page 90]]

Editorial Note: At 79 FR 11257, Feb. 27, 2014, Figure 1-2 was added
to part 60, appendix A-1, method 1, section 17. However, this amendment
could not be performed because Figure 1-2 already existed.

Sec. Appendix A-2 to Part 60--Test Methods 2G through 3C

Method 2G--Determination of Stack Gas Velocity and Volumetric Flow Rate
With Two-Dimensional Probes
Method 2H--Determination of Stack Gas Velocity Taking Into Account
Velocity Decay Near the Stack Wall
Method 3--Gas analysis for the determination of dry molecular weight
Method 3A--Determination of Oxygen and Carbon Dioxide Concentrations in
Emissions From Stationary Sources (Instrumental Analyzer
Procedure)
Method 3B--Gas analysis for the determination of emission rate
correction factor or excess air
Method 3C--Determination of carbon dioxide, methane, nitrogen, and
oxygen from stationary sources
The test methods in this appendix are referred to in Sec. 60.8
(Performance Tests) and Sec. 60.11 (Compliance With Standards and
Maintenance Requirements) of 40 CFR part 60, subpart A (General
Provisions). Specific uses of these test methods are described in the
standards of performance contained in the subparts, beginning with
Subpart D.
Within each standard of performance, a section title ``Test Methods
and Procedures'' is provided to: (1) Identify the test methods to be
used as reference methods to the facility subject to the respective
standard and (2) identify any special instructions or conditions to be
followed when applying a method to the respective facility. Such
instructions (for example, establish sampling rates, volumes, or
temperatures) are to be used either in addition to, or as a substitute
for procedures in a test method. Similarly, for sources subject to
emission monitoring requirements, specific instructions pertaining to
any use of a test method as a reference method are provided in the
subpart or in Appendix B.
Inclusion of methods in this appendix is not intended as an
endorsement or denial of their applicability to sources that are not
subject to standards of performance. The methods are potentially
applicable to other sources; however, applicability should be confirmed
by careful and appropriate evaluation of the conditions prevalent at
such sources.
The approach followed in the formulation of the test methods
involves specifications for equipment, procedures, and performance. In
concept, a performance specification approach would be preferable in all
methods because this allows the greatest flexibility to the user. In
practice, however, this approach is impractical in most cases because
performance specifications cannot be established. Most of the methods
described herein, therefore, involve specific equipment specifications
and procedures, and only a few methods in this appendix rely on
performance criteria.
Minor changes in the test methods should not necessarily affect the
validity of the results and it is recognized that alternative and
equivalent methods exist. section 60.8 provides authority for the
Administrator to specify or approve (1) equivalent methods, (2)
alternative methods, and (3) minor changes in the methodology of the
test methods. It should be clearly understood that unless otherwise
identified all such methods and changes must have prior approval of the
Administrator. An owner employing such methods or deviations from the
test methods without obtaining prior approval does so at the risk of
subsequent disapproval and retesting with approved methods.
Within the test methods, certain specific equipment or procedures
are recognized as being acceptable or potentially acceptable and are
specifically identified in the methods. The items identified as
acceptable options may be used without approval but must be identified
in the test report. The potentially approvable options are cited as
``subject to the approval of the Administrator'' or as ``or
equivalent.'' Such potentially approvable techniques or alternatives may
be used at the discretion of the owner without prior approval. However,
detailed descriptions for applying these potentially approvable
techniques or alternatives are not provided in the test methods. Also,
the potentially approvable options are not necessarily acceptable in all
applications. Therefore, an owner electing to use such potentially
approvable techniques or alternatives is responsible for: (1) assuring
that the techniques or alternatives are in fact applicable and are
properly executed; (2) including a written description of the
alternative method in the test report (the written method must be clear
and must be capable of being performed without additional instruction,
and the degree of detail should be similar to the detail contained in
the test methods); and (3) providing any rationale or supporting data
necessary to show the validity of the alternative in the particular
application. Failure to meet these requirements can result in the
Administrator's disapproval of the alternative.

[[Page 91]]

Method 2G--Determination of Stack Gas Velocity and Volumetric Flow Rate
With Two-Dimensional Probes

1.0 Scope and Application

1.1 This method is applicable for the determination of yaw angle,
near-axial velocity, and the volumetric flow rate of a gas stream in a
stack or duct using a two-dimensional (2-D) probe.

2.0 Summary of Method

2.1 A 2-D probe is used to measure the velocity pressure and the yaw
angle of the flow velocity vector in a stack or duct. Alternatively,
these measurements may be made by operating one of the three-dimensional
(3-D) probes described in Method 2F, in yaw determination mode only.
From these measurements and a determination of the stack gas density,
the average near-axial velocity of the stack gas is calculated. The
near-axial velocity accounts for the yaw, but not the pitch, component
of flow. The average gas volumetric flow rate in the stack or duct is
then determined from the average near-axial velocity.

3.0 Definitions

3.1. Angle-measuring Device Rotational Offset (RADO). The rotational
position of an angle-measuring device relative to the reference scribe
line, as determined during the pre-test rotational position check
described in section 8.3.
3.2 Calibration Pitot Tube. The standard (Prandtl type) pitot tube
used as a reference when calibrating a probe under this method.
3.3 Field Test. A set of measurements conducted at a specific unit
or exhaust stack/duct to satisfy the applicable regulation (e.g., a
three-run boiler performance test, a single-or multiple-load nine-run
relative accuracy test).
3.4 Full Scale of Pressure-measuring Device. Full scale refers to
the upper limit of the measurement range displayed by the device. For
bi-directional pressure gauges, full scale includes the entire pressure
range from the lowest negative value to the highest positive value on
the pressure scale.
3.5 Main probe. Refers to the probe head and that section of probe
sheath directly attached to the probe head. The main probe sheath is
distinguished from probe extensions, which are sections of sheath added
onto the main probe to extend its reach.
3.6 ``May,'' ``Must,'' ``Shall,'' ``Should,'' and the imperative
form of verbs.
3.6.1 ``May'' is used to indicate that a provision of this method is
optional.
3.6.2 ``Must,'' ``Shall,'' and the imperative form of verbs (such as
``record'' or ``enter'') are used to indicate that a provision of this
method is mandatory.
3.6.3 ``Should'' is used to indicate that a provision of this method
is not mandatory, but is highly recommended as good practice.
3.7 Method 1. Refers to 40 CFR part 60, appendix A, ``Method 1--
Sample and velocity traverses for stationary sources.''
3.8 Method 2. Refers to 40 CFR part 60, appendix A, ``Method 2--
Determination of stack gas velocity and volumetric flow rate (Type S
pitot tube).''
3.9 Method 2F. Refers to 40 CFR part 60, appendix A, ``Method 2F--
Determination of stack gas velocity and volumetric flow rate with three-
dimensional probes.''
3.10 Near-axial Velocity. The velocity vector parallel to the axis
of the stack or duct that accounts for the yaw angle component of gas
flow. The term ``near-axial'' is used herein to indicate that the
velocity and volumetric flow rate results account for the measured yaw
angle component of flow at each measurement point.
3.11 Nominal Velocity. Refers to a wind tunnel velocity setting that
approximates the actual wind tunnel velocity to within 1.5 m/sec (5
ft/sec).
3.12 Pitch Angle. The angle between the axis of the stack or duct
and the pitch component of flow, i.e., the component of the total
velocity vector in a plane defined by the traverse line and the axis of
the stack or duct. (Figure 2G-1 illustrates the ``pitch plane.'') From
the standpoint of a tester facing a test port in a vertical stack, the
pitch component of flow is the vector of flow moving from the center of
the stack toward or away from that test port. The pitch angle is the
angle described by this pitch component of flow and the vertical axis of
the stack.
3.13 Readability. For the purposes of this method, readability for
an analog measurement device is one half of the smallest scale division.
For a digital measurement device, it is the number of decimals displayed
by the device.
3.14 Reference Scribe Line. A line permanently inscribed on the main
probe sheath (in accordance with section 6.1.5.1) to serve as a
reference mark for determining yaw angles.
3.15 Reference Scribe Line Rotational Offset (RSLO). The rotational
position of a probe's reference scribe line relative to the probe's yaw-
null position, as determined during the yaw angle calibration described
in section 10.5.

[[Page 92]]

3.16 Response Time. The time required for the measurement system to
fully respond to a change from zero differential pressure and ambient
temperature to the stable stack or duct pressure and temperature
readings at a traverse point.
3.17 Tested Probe. A probe that is being calibrated.
3.18 Three-dimensional (3-D) Probe. A directional probe used to
determine the velocity pressure and the yaw and pitch angles in a
flowing gas stream.
3.19 Two-dimensional (2-D) Probe. A directional probe used to
measure velocity pressure and yaw angle in a flowing gas stream.
3.20 Traverse Line. A diameter or axis extending across a stack or
duct on which measurements of velocity pressure and flow angles are
made.
3.21 Wind Tunnel Calibration Location. A point, line, area, or
volume within the wind tunnel test section at, along, or within which
probes are calibrated. At a particular wind tunnel velocity setting, the
average velocity pressures at specified points at, along, or within the
calibration location shall vary by no more than 2 percent or 0.3 mm
H20 (0.01 in. H2O), whichever is less restrictive,
from the average velocity pressure at the calibration pitot tube
location. Air flow at this location shall be axial, i.e., yaw and pitch
angles within 3[deg] of 0[deg]. Compliance with these flow criteria
shall be demonstrated by performing the procedures prescribed in
sections 10.1.1 and 10.1.2. For circular tunnels, no part of the
calibration location may be closer to the tunnel wall than 10.2 cm (4
in.) or 25 percent of the tunnel diameter, whichever is farther from the
wall. For elliptical or rectangular tunnels, no part of the calibration
location may be closer to the tunnel wall than 10.2 cm (4 in.) or 25
percent of the applicable cross-sectional axis, whichever is farther
from the wall.
3.22 Wind Tunnel with Documented Axial Flow. A wind tunnel facility
documented as meeting the provisions of sections 10.1.1 (velocity
pressure cross-check) and 10.1.2 (axial flow verification) using the
procedures described in these sections or alternative procedures
determined to be technically equivalent.
3.23 Yaw Angle. The angle between the axis of the stack or duct and
the yaw component of flow, i.e., the component of the total velocity
vector in a plane perpendicular to the traverse line at a particular
traverse point. (Figure 2G-1 illustrates the ``yaw plane.'') From the
standpoint of a tester facing a test port in a vertical stack, the yaw
component of flow is the vector of flow moving to the left or right from
the center of the stack as viewed by the tester. (This is sometimes
referred to as ``vortex flow,'' i.e., flow around the centerline of a
stack or duct.) The yaw angle is the angle described by this yaw
component of flow and the vertical axis of the stack. The algebraic sign
convention is illustrated in Figure 2G-2.
3.24 Yaw Nulling. A procedure in which a Type-S pitot tube or a 3-D
probe is rotated about its axis in a stack or duct until a zero
differential pressure reading (``yaw null'') is obtained. When a Type S
probe is yaw-nulled, the rotational position of its impact port is
90[deg] from the direction of flow in the stack or duct and the FP
reading is zero. When a 3-D probe is yaw-nulled, its impact pressure
port (P1) faces directly into the direction of flow in the
stack or duct and the differential pressure between pressure ports
P2 and P3 is zero.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Two-dimensional Probes. Probes that provide both the velocity
pressure and the yaw angle of the flow vector in a stack or duct, as
listed in sections 6.1.1 and 6.1.2, qualify for use based on
comprehensive wind tunnel and field studies involving both inter-and
intra-probe comparisons by multiple test teams. Each 2-D probe shall
have a unique identification number or code permanently marked on the
main probe sheath. Each probe shall be calibrated prior to use according
to the procedures in section 10. Manufacturer-supplied calibration data
shall be used as example information only, except when the manufacturer
calibrates the probe as specified in section 10 and provides complete
documentation.
6.1.1 Type S (Stausscheibe or reverse type) pitot tube. This is the
same as specified in Method 2, section 2.1, except for the following
additional specifications that enable the pitot tube to accurately
determine the yaw component of flow. For the purposes of this method,
the external diameter of the tubing used to construct the Type S pitot
tube (dimension Dt in Figure 2-2 of Method 2) shall be no
less than 9.5 mm (3/8 in.). The pitot tube shall also meet the following
alignment specifications. The angles a1, a2,
1, and 2, as shown in
Method 2, Figure 2-3, shall not exceed 2[deg]. The dimensions w and z,
shown in Method 2, Figure 2-3 shall not exceed 0.5 mm (0.02 in.).

[[Page 93]]

6.1.1.1 Manual Type S probe. This refers to a Type S probe that is
positioned at individual traverse points and yaw nulled manually by an
operator.
6.1.1.2 Automated Type S probe. This refers to a system that uses a
computer-controlled motorized mechanism to position the Type S pitot
head at individual traverse points and perform yaw angle determinations.
6.1.2 Three-dimensional probes used in 2-D mode. A 3-D probe, as
specified in sections 6.1.1 through 6.1.3 of Method 2F, may, for the
purposes of this method, be used in a two-dimensional mode (i.e.,
measuring yaw angle, but not pitch angle). When the 3-D probe is used as
a 2-D probe, only the velocity pressure and yaw-null pressure are
obtained using the pressure taps referred to as P1,
P2, and P3. The differential pressure
P1- P2 is a function of total velocity and
corresponds to the FP obtained using the Type S probe. The differential
pressure P2- P3 is used to yaw null the probe and
determine the yaw angle. The differential pressure P4-
P5, which is a function of pitch angle, is not measured when
the 3-D probe is used in 2-D mode.
6.1.3 Other probes. [Reserved]
6.1.4 Probe sheath. The probe shaft shall include an outer sheath
to: (1) provide a surface for inscribing a permanent reference scribe
line, (2) accommodate attachment of an angle-measuring device to the
probe shaft, and (3) facilitate precise rotational movement of the probe
for determining yaw angles. The sheath shall be rigidly attached to the
probe assembly and shall enclose all pressure lines from the probe head
to the farthest position away from the probe head where an angle-
measuring device may be attached during use in the field. The sheath of
the fully assembled probe shall be sufficiently rigid and straight at
all rotational positions such that, when one end of the probe shaft is
held in a horizontal position, the fully extended probe meets the
horizontal straightness specifications indicated in section 8.2 below.
6.1.5 Scribe lines.
6.1.5.1 Reference scribe line. A permanent line, no greater than 1.6
mm (1/16 in.) in width, shall be inscribed on each manual probe that
will be used to determine yaw angles of flow. This line shall be placed
on the main probe sheath in accordance with the procedures described in
section 10.4 and is used as a reference position for installation of the
yaw angle-measuring device on the probe. At the discretion of the
tester, the scribe line may be a single line segment placed at a
particular position on the probe sheath (e.g., near the probe head),
multiple line segments placed at various locations along the length of
the probe sheath (e.g., at every position where a yaw angle-measuring
device may be mounted), or a single continuous line extending along the
full length of the probe sheath.
6.1.5.2 Scribe line on probe extensions. A permanent line may also
be inscribed on any probe extension that will be attached to the main
probe in performing field testing. This allows a yaw angle-measuring
device mounted on the extension to be readily aligned with the reference
scribe line on the main probe sheath.
6.1.5.3 Alignment specifications. This specification shall be met
separately, using the procedures in section 10.4.1, on the main probe
and on each probe extension. The rotational position of the scribe line
or scribe line segments on the main probe or any probe extension must
not vary by more than 2[deg]. That is, the difference between the
minimum and maximum of all of the rotational angles that are measured
along the full length of the main probe or the probe extension must not
exceed 2[deg].
6.1.6 Probe and system characteristics to ensure horizontal
stability.
6.1.6.1 For manual probes, it is recommended that the effective
length of the probe (coupled with a probe extension, if necessary) be at
least 0.9 m (3 ft.) longer than the farthest traverse point mark on the
probe shaft away from the probe head. The operator should maintain the
probe's horizontal stability when it is fully inserted into the stack or
duct. If a shorter probe is used, the probe should be inserted through a
bushing sleeve, similar to the one shown in Figure 2G-3, that is
installed on the test port; such a bushing shall fit snugly around the
probe and be secured to the stack or duct entry port in such a manner as
to maintain the probe's horizontal stability when fully inserted into
the stack or duct.
6.1.6.2 An automated system that includes an external probe casing
with a transport system shall have a mechanism for maintaining
horizontal stability comparable to that obtained by manual probes
following the provisions of this method. The automated probe assembly
shall also be constructed to maintain the alignment and position of the
pressure ports during sampling at each traverse point. The design of the
probe casing and transport system shall allow the probe to be removed
from the stack or duct and checked through direct physical measurement
for angular position and insertion depth.
6.1.7 The tubing that is used to connect the probe and the pressure-
measuring device should have an inside diameter of at least 3.2 mm (\1/
8\ in.), to reduce the time required for pressure equilibration, and
should be as short as practicable.
6.1.8 If a detachable probe head without a sheath [e.g., a pitot
tube, typically 15.2 to 30.5 cm (6 to 12 in.) in length] is coupled with
a probe sheath and calibrated in a wind tunnel in accordance with the
yaw angle calibration procedure in section 10.5, the probe head shall
remain attached to the probe

[[Page 94]]

sheath during field testing in the same configuration and orientation as
calibrated. Once the detachable probe head is uncoupled or re-oriented,
the yaw angle calibration of the probe is no longer valid and must be
repeated before using the probe in subsequent field tests.
6.2 Yaw Angle-measuring Device. One of the following devices shall
be used for measurement of the yaw angle of flow.
6.2.1 Digital inclinometer. This refers to a digital device capable
of measuring and displaying the rotational position of the probe to
within 1[deg]. The device shall be able to be locked into position on
the probe sheath or probe extension, so that it indicates the probe's
rotational position throughout the test. A rotational position collar
block that can be attached to the probe sheath (similar to the collar
shown in Figure 2G-4) may be required to lock the digital inclinometer
into position on the probe sheath.
6.2.2 Protractor wheel and pointer assembly. This apparatus, similar
to that shown in Figure 2G-5, consists of the following components.
6.2.2.1 A protractor wheel that can be attached to a port opening
and set in a fixed rotational position to indicate the yaw angle
position of the probe's scribe line relative to the longitudinal axis of
the stack or duct. The protractor wheel must have a measurement ring on
its face that is no less than 17.8 cm (7 in.) in diameter, shall be able
to be rotated to any angle and then locked into position on the stack or
duct test port, and shall indicate angles to a resolution of 1[deg].
6.2.2.2 A pointer assembly that includes an indicator needle mounted
on a collar that can slide over the probe sheath and be locked into a
fixed rotational position on the probe sheath. The pointer needle shall
be of sufficient length, rigidity, and sharpness to allow the tester to
determine the probe's angular position to within 1[deg] from the
markings on the protractor wheel. Corresponding to the position of the
pointer, the collar must have a scribe line to be used in aligning the
pointer with the scribe line on the probe sheath.
6.2.3 Other yaw angle-measuring devices. Other angle-measuring
devices with a manufacturer's specified precision of 1[deg] or better
may be used, if approved by the Administrator.
6.3 Probe Supports and Stabilization Devices. When probes are used
for determining flow angles, the probe head should be kept in a stable
horizontal position. For probes longer than 3.0 m (10 ft.), the section
of the probe that extends outside the test port shall be secured. Three
alternative devices are suggested for maintaining the horizontal
position and stability of the probe shaft during flow angle
determinations and velocity pressure measurements: (1) monorails
installed above each port, (2) probe stands on which the probe shaft may
be rested, or (3) bushing sleeves of sufficient length secured to the
test ports to maintain probes in a horizontal position. Comparable
provisions shall be made to ensure that automated systems maintain the
horizontal position of the probe in the stack or duct. The physical
characteristics of each test platform may dictate the most suitable type
of stabilization device. Thus, the choice of a specific stabilization
device is left to the judgement of the testers.
6.4 Differential Pressure Gauges. The velocity pressure (FP)
measuring devices used during wind tunnel calibrations and field testing
shall be either electronic manometers (e.g., pressure transducers),
fluid manometers, or mechanical pressure gauges (e.g.,
MagnehelicF gauges). Use of electronic manometers is
recommended. Under low velocity conditions, use of electronic manometers
may be necessary to obtain acceptable measurements.
6.4.1 Differential pressure-measuring device. This refers to a
device capable of measuring pressure differentials and having a
readability of 1 percent of full scale. The device shall be capable of
accurately measuring the maximum expected pressure differential. Such
devices are used to determine the following pressure measurements:
velocity pressure, static pressure, and yaw-null pressure. For an
inclined-vertical manometer, the readability specification of 1 percent
shall be met separately using the respective full-scale upper limits of
the inclined anvertical portions of the scales. To the extent
practicable, the device shall be selected such that most of the pressure
readings are between 10 and 90 percent of the device's full-scale
measurement range (as defined in section 3.4). In addition, pressure-
measuring devices should be selected such that the zero does not drift
by more than 5 percent of the average expected pressure readings to be
encountered during the field test. This is particularly important under
low pressure conditions.
6.4.2 Gauge used for yaw nulling. The differential pressure-
measuring device chosen for yaw nulling the probe during the wind tunnel
calibrations and field testing shall be bi-directional, i.e., capable of
reading both positive and negative differential pressures. If a
mechanical, bi-directional pressure gauge is chosen, it shall have a
full-scale range no greater than 2.6 cm (i.e., - 1.3 to + 1.3 cm) [1 in.
H2O (i.e., - 0.5 in. to + 0.5 in.)].
6.4.3 Devices for calibrating differential pressure-measuring
devices. A precision manometer (e.g., a U-tube, inclined, or inclined-
vertical manometer, or micromanometer) or NIST (National Institute of
Standards and Technology) traceable pressure source shall be used for
calibrating differential pressure-measuring devices. The device shall be
maintained under laboratory conditions or in a similar protected
environment (e.g., a climate-controlled trailer). It shall not be used

[[Page 95]]

in field tests. The precision manometer shall have a scale gradation of
0.3 mm H2O (0.01 in. H2O), or less, in the range
of 0 to 5.1 cm H2O (0 to 2 in. H2O) and 2.5 mm
H2O (0.1 in. H2O), or less, in the range of 5.1 to
25.4 cm H2O (2 to 10 in. H2O). The manometer shall
have manufacturer's documentation that it meets an accuracy
specification of at least 0.5 percent of full scale. The NIST-traceable
pressure source shall be recertified annually.
6.4.4 Devices used for post-test calibration check. A precision
manometer meeting the specifications in section 6.4.3, a pressure-
measuring device or pressure source with a documented calibration
traceable to NIST, or an equivalent device approved by the Administrator
shall be used for the post-test calibration check. The pressure-
measuring device shall have a readability equivalent to or greater than
the tested device. The pressure source shall be capable of generating
pressures between 50 and 90 percent of the range of the tested device
and known to within 1 percent of the full scale of the tested device.
The pressure source shall be recertified annually.
6.5 Data Display and Capture Devices. Electronic manometers (if
used) shall be coupled with a data display device (such as a digital
panel meter, personal computer display, or strip chart) that allows the
tester to observe and validate the pressure measurements taken during
testing. They shall also be connected to a data recorder (such as a data
logger or a personal computer with data capture software) that has the
ability to compute and retain the appropriate average value at each
traverse point, identified by collection time and traverse point.
6.6 Temperature Gauges. For field tests, a thermocouple or
resistance temperature detector (RTD) capable of measuring temperature
to within 3 [deg]C (5 [deg]F) of the stack or duct temperature shall
be used. The thermocouple shall be attached to the probe such that the
sensor tip does not touch any metal. The position of the thermocouple
relative to the pressure port face openings shall be in the same
configuration as used for the probe calibrations in the wind tunnel.
Temperature gauges used for wind tunnel calibrations shall be capable of
measuring temperature to within 0.6 [deg]C (1 [deg]F) of the
temperature of the flowing gas stream in the wind tunnel.
6.7 Stack or Duct Static Pressure Measurement. The pressure-
measuring device used with the probe shall be as specified in section
6.4 of this method. The static tap of a standard (Prandtl type) pitot
tube or one leg of a Type S pitot tube with the face opening planes
positioned parallel to the gas flow may be used for this measurement.
Also acceptable is the pressure differential reading of P1-
Pbar from a five-hole prism-shaped 3-D probe, as specified in
section 6.1.1 of Method 2F (such as the Type DA or DAT probe), with the
P1 pressure port face opening positioned parallel to the gas
flow in the same manner as the Type S probe. However, the 3-D spherical
probe, as specified in section 6.1.2 of Method 2F, is unable to provide
this measurement and shall not be used to take static pressure
measurements. Static pressure measurement is further described in
section 8.11.
6.8 Barometer. Same as Method 2, section 2.5.
6.9 Gas Density Determination Equipment. Method 3 or 3A shall be
used to determine the dry molecular weight of the stack or duct gas.
Method 4 shall be used for moisture content determination and
computation of stack or duct gas wet molecular weight. Other methods may
be used, if approved by the Administrator.
6.10 Calibration Pitot Tube. Same as Method 2, section 2.7.
6.11 Wind Tunnel for Probe Calibration. Wind tunnels used to
calibrate velocity probes must meet the following design specifications.
6.11.1 Test section cross-sectional area. The flowing gas stream
shall be confined within a circular, rectangular, or elliptical duct.
The cross-sectional area of the tunnel must be large enough to ensure
fully developed flow in the presence of both the calibration pitot tube
and the tested probe. The calibration site, or ``test section,'' of the
wind tunnel shall have a minimum diameter of 30.5 cm (12 in.) for
circular or elliptical duct cross-sections or a minimum width of 30.5 cm
(12 in.) on the shorter side for rectangular cross-sections. Wind
tunnels shall meet the probe blockage provisions of this section and the
qualification requirements prescribed in section 10.1. The projected
area of the portion of the probe head, shaft, and attached devices
inside the wind tunnel during calibration shall represent no more than 4
percent of the cross-sectional area of the tunnel. The projected area
shall include the combined area of the calibration pitot tube and the
tested probe if both probes are placed simultaneously in the same cross-
sectional plane in the wind tunnel, or the larger projected area of the
two probes if they are placed alternately in the wind tunnel.
6.11.2 Velocity range and stability. The wind tunnel should be
capable of maintaining velocities between 6.1 m/sec and 30.5 m/sec (20
ft/sec and 100 ft/sec). The wind tunnel shall produce fully developed
flow patterns that are stable and parallel to the axis of the duct in
the test section.
6.11.3 Flow profile at the calibration location. The wind tunnel
shall provide axial flow within the test section calibration location
(as defined in section 3.21). Yaw and pitch angles in the calibration
location shall be within 3[deg] of 0[deg]. The procedure for
determining that this requirement has been met is described in section
10.1.2.

[[Page 96]]

6.11.4 Entry ports in the wind tunnel test section.
6.11.4.1 Port for tested probe. A port shall be constructed for the
tested probe. This port shall be located to allow the head of the tested
probe to be positioned within the wind tunnel calibration location (as
defined in section 3.21). The tested probe shall be able to be locked
into the 0[deg] pitch angle position. To facilitate alignment of the
probe during calibration, the test section should include a window
constructed of a transparent material to allow the tested probe to be
viewed.
6.11.4.2 Port for verification of axial flow. Depending on the
equipment selected to conduct the axial flow verification prescribed in
section 10.1.2, a second port, located 90[deg] from the entry port for
the tested probe, may be needed to allow verification that the gas flow
is parallel to the central axis of the test section. This port should be
located and constructed so as to allow one of the probes described in
section 10.1.2.2 to access the same test point(s) that are accessible
from the port described in section 6.11.4.1.
6.11.4.3 Port for calibration pitot tube. The calibration pitot tube
shall be used in the port for the tested probe or in a separate entry
port. In either case, all measurements with the calibration pitot tube
shall be made at the same point within the wind tunnel over the course
of a probe calibration. The measurement point for the calibration pitot
tube shall meet the same specifications for distance from the wall and
for axial flow as described in section 3.21 for the wind tunnel
calibration location.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection and Analysis

8.1 Equipment Inspection and Set Up
8.1.1 All 2-D and 3-D probes, differential pressure-measuring
devices, yaw angle-measuring devices, thermocouples, and barometers
shall have a current, valid calibration before being used in a field
test. (See sections 10.3.3, 10.3.4, and 10.5 through 10.10 for the
applicable calibration requirements.)
8.1.2 Before each field use of a Type S probe, perform a visual
inspection to verify the physical condition of the pitot tube. Record
the results of the inspection. If the face openings are noticeably
misaligned or there is visible damage to the face openings, the probe
shall not be used until repaired, the dimensional specifications
verified (according to the procedures in section 10.2.1), and the probe
recalibrated.
8.1.3 Before each field use of a 3-D probe, perform a visual
inspection to verify the physical condition of the probe head according
to the procedures in section 10.2 of Method 2F. Record the inspection
results on a form similar to Table 2F-1 presented in Method 2F. If there
is visible damage to the 3-D probe, the probe shall not be used until it
is recalibrated.
8.1.4 After verifying that the physical condition of the probe head
is acceptable, set up the apparatus using lengths of flexible tubing
that are as short as practicable. Surge tanks installed between the
probe and pressure-measuring device may be used to dampen pressure
fluctuations provided that an adequate measurement system response time
(see section 8.8) is maintained.
8.2 Horizontal Straightness Check. A horizontal straightness check
shall be performed before the start of each field test, except as
otherwise specified in this section. Secure the fully assembled probe
(including the probe head and all probe shaft extensions) in a
horizontal position using a stationary support at a point along the
probe shaft approximating the location of the stack or duct entry port
when the probe is sampling at the farthest traverse point from the stack
or duct wall. The probe shall be rotated to detect bends. Use an angle-
measuring device or trigonometry to determine the bend or sag between
the probe head and the secured end. (See Figure 2G-6.) Probes that are
bent or sag by more than 5[deg] shall not be used. Although this check
does not apply when the probe is used for a vertical traverse, care
should be taken to avoid the use of bent probes when conducting vertical
traverses. If the probe is constructed of a rigid steel material and
consists of a main probe without probe extensions, this check need only
be performed before the initial field use of the probe, when the probe
is recalibrated, when a change is made to the design or material of the
probe assembly, and when the probe becomes bent. With such probes, a
visual inspection shall be made of the fully assembled probe before each
field test to determine if a bend is visible. The probe shall be rotated
to detect bends. The inspection results shall be documented in the field
test report. If a bend in the probe is visible, the horizontal
straightness check shall be performed before the probe is used.
8.3 Rotational Position Check. Before each field test, and each time
an extension is added to the probe during a field test, a rotational
position check shall be performed on all manually operated probes
(except as noted in section 8.3.5 below) to ensure that, throughout
testing, the angle-measuring device is either: aligned to within 1[deg]
of the rotational position of the reference scribe line; or is affixed
to the probe such that the rotational offset of the device from the
reference scribe line is known to within 1[deg]. This check shall
consist of direct measurements of the rotational positions of the
reference scribe line and angle-measuring device sufficient to verify
that these specifications are met. Annex A in section 18 of this method
gives recommended procedures for performing the rotational position
check, and Table 2G-2

[[Page 97]]

gives an example data form. Procedures other than those recommended in
Annex A in section 18 may be used, provided they demonstrate whether the
alignment specification is met and are explained in detail in the field
test report.
8.3.1 Angle-measuring device rotational offset. The tester shall
maintain a record of the angle-measuring device rotational offset,
RADO, as defined in section 3.1. Note that RADO is
assigned a value of 0[deg] when the angle-measuring device is aligned to
within 1[deg] of the rotational position of the reference scribe line.
The RADO shall be used to determine the yaw angle of flow in
accordance with section 8.9.4.
8.3.2 Sign of angle-measuring device rotational offset. The sign of
RADO is positive when the angle-measuring device (as viewed
from the ``tail'' end of the probe) is positioned in a clockwise
direction from the reference scribe line and negative when the device is
positioned in a counterclockwise direction from the reference scribe
line.
8.3.3 Angle-measuring devices that can be independently adjusted
(e.g., by means of a set screw), after being locked into position on the
probe sheath, may be used. However, the RADO must also take
into account this adjustment.
8.3.4 Post-test check. If probe extensions remain attached to the
main probe throughout the field test, the rotational position check
shall be repeated, at a minimum, at the completion of the field test to
ensure that the angle-measuring device has remained within 2[deg] of
its rotational position established prior to testing. At the discretion
of the tester, additional checks may be conducted after completion of
testing at any sample port or after any test run. If the 2[deg]
specification is not met, all measurements made since the last
successful rotational position check must be repeated. section 18.1.1.3
of Annex A provides an example procedure for performing the post-test
check.
8.3.5 Exceptions.
8.3.5.1 A rotational position check need not be performed if, for
measurements taken at all velocity traverse points, the yaw angle-
measuring device is mounted and aligned directly on the reference scribe
line specified in sections 6.1.5.1 and 6.1.5.3 and no independent
adjustments, as described in section 8.3.3, are made to device's
rotational position.
8.3.5.2 If extensions are detached and re-attached to the probe
during a field test, a rotational position check need only be performed
the first time an extension is added to the probe, rather than each time
the extension is re-attached, if the probe extension is designed to be
locked into a mechanically fixed rotational position (e.g., through the
use of interlocking grooves), that can re-establish the initial
rotational position to within 1[deg].
8.4 Leak Checks. A pre-test leak check shall be conducted before
each field test. A post-test check shall be performed at the end of the
field test, but additional leak checks may be conducted after any test
run or group of test runs. The post-test check may also serve as the
pre-test check for the next group of test runs. If any leak check is
failed, all runs since the last passed leak check are invalid. While
performing the leak check procedures, also check each pressure device's
responsiveness to changes in pressure.
8.4.1 To perform the leak check on a Type S pitot tube, pressurize
the pitot impact opening until at least 7.6 cm H2O (3 in.
H2O) velocity pressure, or a pressure corresponding to
approximately 75 percent of the pressure device's measurement scale,
whichever is less, registers on the pressure device; then, close off the
impact opening. The pressure shall remain stable (2.5 mm
H2O, 0.10 in. H2O) for at least 15 seconds.
Repeat this procedure for the static pressure side, except use suction
to obtain the required pressure. Other leak-check procedures may be
used, if approved by the Administrator.
8.4.2 To perform the leak check on a 3-D probe, pressurize the
probe's impact (P1) opening until at least 7.6 cm
H2O (3 in. H2O) velocity pressure, or a pressure
corresponding to approximately 75 percent of the pressure device's
measurement scale, whichever is less, registers on the pressure device;
then, close off the impact opening. The pressure shall remain stable
(2.5 mm H2O, 0.10 in. H2O) for at least 15
seconds. Check the P2 and P3 pressure ports in the
same fashion. Other leak-check procedures may be used, if approved by
the Administrator.
8.5 Zeroing the Differential Pressure-measuring Device. Zero each
differential pressure-measuring device, including the device used for
yaw nulling, before each field test. At a minimum, check the zero after
each field test. A zero check may also be performed after any test run
or group of test runs. For fluid manometers and mechanical pressure
gauges (e.g., MagnehelicF gauges), the zero reading shall not
deviate from zero by more than 0.8 mm H2O (0.03 in.
H2O) or one minor scale division, whichever is greater,
between checks. For electronic manometers, the zero reading shall not
deviate from zero between checks by more than: 0.3 mm H2O
(0.01 in. H2O), for full scales less than or equal to 5.1 cm
H2O (2.0 in. H2O); or 0.8 mm H2O
(0.03 in. H2O), for full scales greater than 5.1 cm
H2O (2.0 in. H2O). (Note: If negative zero drift
is not directly readable, estimate the reading based on the position of
the gauge oil in the manometer or of the needle on the pressure gauge.)
In addition, for all pressure-measuring devices except those used
exclusively for yaw nulling, the zero

[[Page 98]]

reading shall not deviate from zero by more than 5 percent of the
average measured differential pressure at any distinct process condition
or load level. If any zero check is failed at a specific process
condition or load level, all runs conducted at that process condition or
load level since the last passed zero check are invalid.
8.6 Traverse Point Verification. The number and location of the
traverse points shall be selected based on Method 1 guidelines. The
stack or duct diameter and port nipple lengths, including any extension
of the port nipples into the stack or duct, shall be verified the first
time the test is performed; retain and use this information for
subsequent field tests, updating it as required. Physically measure the
stack or duct dimensions or use a calibrated laser device; do not use
engineering drawings of the stack or duct. The probe length necessary to
reach each traverse point shall be recorded to within 6.4 mm (\1/4\
in.) and, for manual probes, marked on the probe sheath. In determining
these lengths, the tester shall take into account both the distance that
the port flange projects outside of the stack and the depth that any
port nipple extends into the gas stream. The resulting point positions
shall reflect the true distances from the inside wall of the stack or
duct, so that when the tester aligns any of the markings with the
outside face of the stack port, the probe's impact port shall be located
at the appropriate distance from the inside wall for the respective
Method 1 traverse point. Before beginning testing at a particular
location, an out-of-stack or duct verification shall be performed on
each probe that will be used to ensure that these position markings are
correct. The distances measured during the verification must agree with
the previously calculated distances to within \1/4\ in. For manual
probes, the traverse point positions shall be verified by measuring the
distance of each mark from the probe's impact pressure port (the
P1 port for a 3-D probe). A comparable out-of-stack test
shall be performed on automated probe systems. The probe shall be
extended to each of the prescribed traverse point positions. Then, the
accuracy of the positioning for each traverse point shall be verified by
measuring the distance between the port flange and the probe's impact
pressure port.
8.7 Probe Installation. Insert the probe into the test port. A solid
material shall be used to seal the port.
8.8 System Response Time. Determine the response time of the probe
measurement system. Insert and position the ``cold'' probe (at ambient
temperature and pressure) at any Method 1 traverse point. Read and
record the probe differential pressure, temperature, and elapsed time at
15-second intervals until stable readings for both pressure and
temperature are achieved. The response time is the longer of these two
elapsed times. Record the response time.
8.9 Sampling.
8.9.1 Yaw angle measurement protocol. With manual probes, yaw angle
measurements may be obtained in two alternative ways during the field
test, either by using a yaw angle-measuring device (e.g., digital
inclinometer) affixed to the probe, or using a protractor wheel and
pointer assembly. For horizontal traversing, either approach may be
used. For vertical traversing, i.e., when measuring from on top or into
the bottom of a horizontal duct, only the protractor wheel and pointer
assembly may be used. With automated probes, curve-fitting protocols may
be used to obtain yaw-angle measurements.
8.9.1.1 If a yaw angle-measuring device affixed to the probe is to
be used, lock the device on the probe sheath, aligning it either on the
reference scribe line or in the rotational offset position established
under section 8.3.1.
8.9.1.2 If a protractor wheel and pointer assembly is to be used,
follow the procedures in Annex B of this method.
8.9.1.3 Curve-fitting procedures. Curve-fitting routines sweep
through a range of yaw angles to create curves correlating pressure to
yaw position. To find the zero yaw position and the yaw angle of flow,
the curve found in the stack is computationally compared to a similar
curve that was previously generated under controlled conditions in a
wind tunnel. A probe system that uses a curve-fitting routine for
determining the yaw-null position of the probe head may be used,
provided that it is verified in a wind tunnel to be able to determine
the yaw angle of flow to within 1[deg].
8.9.1.4 Other yaw angle determination procedures. If approved by the
Administrator, other procedures for determining yaw angle may be used,
provided that they are verified in a wind tunnel to be able to perform
the yaw angle calibration procedure as described in section 10.5.
8.9.2 Sampling strategy. At each traverse point, first yaw-null the
probe, as described in section 8.9.3, below. Then, with the probe
oriented into the direction of flow, measure and record the yaw angle,
the differential pressure and the temperature at the traverse point,
after stable readings are achieved, in accordance with sections 8.9.4
and 8.9.5. At the start of testing in each port (i.e., after a probe has
been inserted into the flue gas stream), allow at least the response
time to elapse before beginning to take measurements at the first
traverse point accessed from that port. Provided that the probe is not
removed from the flue gas stream, measurements may be taken at
subsequent traverse points accessed from the same test port without
waiting again for the response time to elapse.

[[Page 99]]

8.9.3 Yaw-nulling procedure. In preparation for yaw angle
determination, the probe must first be yaw nulled. After positioning the
probe at the appropriate traverse point, perform the following
procedures.
8.9.3.1 For Type S probes, rotate the probe until a null
differential pressure reading is obtained. The direction of the probe
rotation shall be such that the thermocouple is located downstream of
the probe pressure ports at the yaw-null position. Rotate the probe
90[deg] back from the yaw-null position to orient the impact pressure
port into the direction of flow. Read and record the angle displayed by
the angle-measuring device.
8.9.3.2 For 3-D probes, rotate the probe until a null differential
pressure reading (the difference in pressures across the P2
and P3 pressure ports is zero, i.e., P2 =
P3) is indicated by the yaw angle pressure gauge. Read and
record the angle displayed by the angle-measuring device.
8.9.3.3 Sign of the measured angle. The angle displayed on the
angle-measuring device is considered positive when the probe's impact
pressure port (as viewed from the ``tail'' end of the probe) is oriented
in a clockwise rotational position relative to the stack or duct axis
and is considered negative when the probe's impact pressure port is
oriented in a counterclockwise rotational position (see Figure 2G-7).
8.9.4 Yaw angle determination. After performing the applicable yaw-
nulling procedure in section 8.9.3, determine the yaw angle of flow
according to one of the following procedures. Special care must be
observed to take into account the signs of the recorded angle reading
and all offsets.
8.9.4.1 Direct-reading. If all rotational offsets are zero or if the
angle-measuring device rotational offset (RADO) determined in
section 8.3 exactly compensates for the scribe line rotational offset
(RSLO) determined in section 10.5, then the magnitude of the
yaw angle is equal to the displayed angle-measuring device reading from
section 8.9.3.1 or 8.9.3.2. The algebraic sign of the yaw angle is
determined in accordance with section 8.9.3.3. [Note: Under certain
circumstances (e.g., testing of horizontal ducts) a 90[deg] adjustment
to the angle-measuring device readings may be necessary to obtain the
correct yaw angles.]
8.9.4.2 Compensation for rotational offsets during data reduction.
When the angle-measuring device rotational offset does not compensate
for reference scribe line rotational offset, the following procedure
shall be used to determine the yaw angle:
(a) Enter the reading indicated by the angle-measuring device from
section 8.9.3.1 or 8.9.3.2.
(b) Associate the proper algebraic sign from section 8.9.3.3 with
the reading in step (a).
(c) Subtract the reference scribe line rotational offset,
RSLO, from the reading in step (b).
(d) Subtract the angle-measuring device rotational offset,
RADO, if any, from the result obtained in step (c).
(e) The final result obtained in step (d) is the yaw angle of flow.

[Note: It may be necessary to first apply a 90[deg] adjustment to
the reading in step (a), in order to obtain the correct yaw angle.]

8.9.4.3 Record the yaw angle measurements on a form similar to Table
2G-3.
8.9.5 Impact velocity determination. Maintain the probe rotational
position established during the yaw angle determination. Then, begin
recording the pressure-measuring device readings. These pressure
measurements shall be taken over a sampling period of sufficiently long
duration to ensure representative readings at each traverse point. If
the pressure measurements are determined from visual readings of the
pressure device or display, allow sufficient time to observe the
pulsation in the readings to obtain a sight-weighted average, which is
then recorded manually. If an automated data acquisition system (e.g.,
data logger, computer-based data recorder, strip chart recorder) is used
to record the pressure measurements, obtain an integrated average of all
pressure readings at the traverse point. Stack or duct gas temperature
measurements shall be recorded, at a minimum, once at each traverse
point. Record all necessary data as shown in the example field data form
(Table 2G-3).
8.9.6 Alignment check. For manually operated probes, after the
required yaw angle and differential pressure and temperature
measurements have been made at each traverse point, verify (e.g., by
visual inspection) that the yaw angle-measuring device has remained in
proper alignment with the reference scribe line or with the rotational
offset position established in section 8.3. If, for a particular
traverse point, the angle-measuring device is found to be in proper
alignment, proceed to the next traverse point; otherwise, re-align the
device and repeat the angle and differential pressure measurements at
the traverse point. In the course of a traverse, if a mark used to
properly align the angle-measuring device (e.g., as described in section
18.1.1.1) cannot be located, re-establish the alignment mark before
proceeding with the traverse.
8.10 Probe Plugging. Periodically check for plugging of the pressure
ports by observing the responses on the pressure differential readouts.
Plugging causes erratic results or sluggish responses. Rotate the probe
to determine whether the readouts respond in the expected direction. If
plugging is detected, correct the problem and repeat the affected
measurements.

[[Page 100]]

8.11 Static Pressure. Measure the static pressure in the stack or
duct using the equipment described in section 6.7.
8.11.1 If a Type S probe is used for this measurement, position the
probe at or between any traverse point(s) and rotate the probe until a
null differential pressure reading is obtained. Disconnect the tubing
from one of the pressure ports; read and record the FP. For pressure
devices with one-directional scales, if a deflection in the positive
direction is noted with the negative side disconnected, then the static
pressure is positive. Likewise, if a deflection in the positive
direction is noted with the positive side disconnected, then the static
pressure is negative.
8.11.2 If a 3-D probe is used for this measurement, position the
probe at or between any traverse point(s) and rotate the probe until a
null differential pressure reading is obtained at P2-
P3. Rotate the probe 90[deg]. Disconnect the P2
pressure side of the probe and read the pressure P1-
Pbar and record as the static pressure. (Note: The spherical
probe, specified in section 6.1.2 of Method 2F, is unable to provide
this measurement and shall not be used to take static pressure
measurements.)
8.12 Atmospheric Pressure. Determine the atmospheric pressure at the
sampling elevation during each test run following the procedure
described in section 2.5 of Method 2.
8.13 Molecular Weight. Determine the stack or duct gas dry molecular
weight. For combustion processes or processes that emit essentially
CO2, O2, CO, and N2, use Method 3 or
3A. For processes emitting essentially air, an analysis need not be
conducted; use a dry molecular weight of 29.0. Other methods may be
used, if approved by the Administrator.
8.14 Moisture. Determine the moisture content of the stack gas using
Method 4 or equivalent.
8.15 Data Recording and Calculations. Record all required data on a
form similar to Table 2G-3.
8.15.1 2-D probe calibration coefficient. When a Type S pitot tube
is used in the field, the appropriate calibration coefficient as
determined in section 10.6 shall be used to perform velocity
calculations. For calibrated Type S pitot tubes, the A-side coefficient
shall be used when the A-side of the tube faces the flow, and the B-side
coefficient shall be used when the B-side faces the flow.
8.15.2 3-D calibration coefficient. When a 3-D probe is used to
collect data with this method, follow the provisions for the calibration
of 3-D probes in section 10.6 of Method 2F to obtain the appropriate
velocity calibration coefficient (F2 as derived using
Equation 2F-2 in Method 2F) corresponding to a pitch angle position of
0[deg].
8.15.3 Calculations. Calculate the yaw-adjusted velocity at each
traverse point using the equations presented in section 12.2. Calculate
the test run average stack gas velocity by finding the arithmetic
average of the point velocity results in accordance with sections 12.3
and 12.4, and calculate the stack gas volumetric flow rate in accordance
with section 12.5 or 12.6, as applicable.

9.0 Quality Control

10.0 Calibration

[[Page 101]]

differential pressure measurements at the fixed calibration pitot tube
location, using the calibration pitot tube specified in section 6.10,
and take three measurements with the calibration pitot tube at the wind
tunnel calibration location, as defined in section 3.21. Alternate the
measurements between the two positions. Perform this procedure at the
lowest and highest velocity settings at which the probes will be
calibrated. Record the values on a form similar to Table 2G-4. At each
velocity setting, the average velocity pressure obtained at the wind
tunnel calibration location shall be within 2 percent or 2.5 mm
H2O (0.01 in. H2O), whichever is less restrictive,
of the average velocity pressure obtained at the fixed calibration pitot
tube location. This comparative check shall be performed at 2.5-cm (1-
in.), or smaller, intervals across the full length, width, and depth (if
applicable) of the wind tunnel calibration location. If the criteria are
not met at every tested point, the wind tunnel calibration location must
be redefined, so that acceptable results are obtained at every point.
Include the results of the velocity pressure cross-check in the
calibration data section of the field test report. (See section 16.1.4.)
10.1.2 Axial flow verification. The following procedures shall be
performed to demonstrate that there is fully developed axial flow within
the wind tunnel calibration location and at the calibration pitot tube
location. Two options are available to conduct this check.
10.1.2.1 Using a calibrated 3-D probe. A probe that has been
previously calibrated in a wind tunnel with documented axial flow (as
defined in section 3.22) may be used to conduct this check. Insert the
calibrated 3-D probe into the wind tunnel test section using the tested
probe port. Following the procedures in sections 8.9 and 12.2 of Method
2F, determine the yaw and pitch angles at all the point(s) in the test
section where the velocity pressure cross-check, as specified in section
10.1.1, is performed. This includes all the points in the calibration
location and the point where the calibration pitot tube will be located.
Determine the yaw and pitch angles at each point. Repeat these
measurements at the highest and lowest velocities at which the probes
will be calibrated. Record the values on a form similar to Table 2G-5.
Each measured yaw and pitch angle shall be within 3[deg] of 0[deg].
Exceeding the limits indicates unacceptable flow in the test section.
Until the problem is corrected and acceptable flow is verified by
repetition of this procedure, the wind tunnel shall not be used for
calibration of probes. Include the results of the axial flow
verification in the calibration data section of the field test report.
(See section 16.1.4.)
10.1.2.2 Using alternative probes. Axial flow verification may be
performed using an uncalibrated prism-shaped 3-D probe (e.g., DA or DAT
probe) or an uncalibrated wedge probe. (Figure 2G-8 illustrates a
typical wedge probe.) This approach requires use of two ports: the
tested probe port and a second port located 90[deg] from the tested
probe port. Each port shall provide access to all the points within the
wind tunnel test section where the velocity pressure cross-check, as
specified in section 10.1.1, is conducted. The probe setup shall include
establishing a reference yaw-null position on the probe sheath to serve
as the location for installing the angle-measuring device. Physical
design features of the DA, DAT, and wedge probes are relied on to
determine the reference position. For the DA or DAT probe, this
reference position can be determined by setting a digital inclinometer
on the flat facet where the P1 pressure port is located and
then identifying the rotational position on the probe sheath where a
second angle-measuring device would give the same angle reading. The
reference position on a wedge probe shaft can be determined either
geometrically or by placing a digital inclinometer on each side of the
wedge and rotating the probe until equivalent readings are obtained.
With the latter approach, the reference position is the rotational
position on the probe sheath where an angle-measuring device would give
a reading of 0[deg]. After installation of the angle-measuring device in
the reference yaw-null position on the probe sheath, determine the yaw
angle from the tested port. Repeat this measurement using the 90[deg]
offset port, which provides the pitch angle of flow. Determine the yaw
and pitch angles at all the point(s) in the test section where the
velocity pressure cross-check, as specified in section 10.1.1, is
performed. This includes all the points in the wind tunnel calibration
location and the point where the calibration pitot tube will be located.
Perform this check at the highest and lowest velocities at which the
probes will be calibrated. Record the values on a form similar to Table
2G-5. Each measured yaw and pitch angle shall be within 3[deg] of
0[deg]. Exceeding the limits indicates unacceptable flow in the test
section. Until the problem is corrected and acceptable flow is verified
by repetition of this procedure, the wind tunnel shall not be used for
calibration of probes. Include the results in the probe calibration
report.
10.1.3 Wind tunnel audits.
10.1.3.1 Procedure. Upon the request of the Administrator, the owner
or operator of a wind tunnel shall calibrate a 2-D audit probe in
accordance with the procedures described in sections 10.3 through 10.6.
The calibration shall be performed at two velocities that encompass the
velocities typically used for this method at the facility. The resulting
calibration data shall be submitted to the Agency in an audit test
report. These results shall be

[[Page 102]]

compared by the Agency to reference calibrations of the audit probe at
the same velocity settings obtained at two different wind tunnels.
10.1.3.2 Acceptance criterion. The audited tunnel's calibration
coefficient is acceptable if it is within 3 percent of the reference
calibrations obtained at each velocity setting by one (or both) of the
wind tunnels. If the acceptance criterion is not met at each calibration
velocity setting, the audited wind tunnel shall not be used to calibrate
probes for use under this method until the problems are resolved and
acceptable results are obtained upon completion of a subsequent audit.
10.2 Probe Inspection.
10.2.1 Type S probe. Before each calibration of a Type S probe,
verify that one leg of the tube is permanently marked A, and the other,
B. Carefully examine the pitot tube from the top, side, and ends.
Measure the angles (a1, a2,
1, and 2) and the
dimensions (w and z) illustrated in Figures 2-2 and 2-3 in Method 2.
Also measure the dimension A, as shown in the diagram in Table 2G-1, and
the external tubing diameter (dimension Dt, Figure 2-2b in
Method 2). For the purposes of this method, Dt shall be no
less than 9.5 mm (\3/8\ in.). The base-to-opening plane distances
PA and PB in Figure 2-3 of Method 2 shall be
equal, and the dimension A in Table 2G-1 should be between
2.10Dt and 3.00Dt. Record the inspection findings
and probe measurements on a form similar to Table CD2-1 of the ``Quality
Assurance Handbook for Air Pollution Measurement Systems: Volume III,
Stationary Source-Specific Methods'' (EPA/600/R-94/038c, September
1994). For reference, this form is reproduced herein as Table 2G-1. The
pitot tube shall not be used under this method if it fails to meet the
specifications in this section and the alignment specifications in
section 6.1.1. All Type S probes used to collect data with this method
shall be calibrated according to the procedures outlined in sections
10.3 through 10.6 below. During calibration, each Type S pitot tube
shall be configured in the same manner as used, or planned to be used,
during the field test, including all components in the probe assembly
(e.g., thermocouple, probe sheath, sampling nozzle). Probe shaft
extensions that do not affect flow around the probe head need not be
attached during calibration.
10.2.2 3-D probe. If a 3-D probe is used to collect data with this
method, perform the pre-calibration inspection according to procedures
in Method 2F, section 10.2.
10.3 Pre-Calibration Procedures. Prior to calibration, a scribe line
shall have been placed on the probe in accordance with section 10.4. The
yaw angle and velocity calibration procedures shall not begin until the
pre-test requirements in sections 10.3.1 through 10.3.4 have been met.
10.3.1 Perform the horizontal straightness check described in
section 8.2 on the probe assembly that will be calibrated in the wind
tunnel.
10.3.2 Perform a leak check in accordance with section 8.4.
10.3.3 Except as noted in section 10.3.3.3, calibrate all
differential pressure-measuring devices to be used in the probe
calibrations, using the following procedures. At a minimum, calibrate
these devices on each day that probe calibrations are performed.
10.3.3.1 Procedure. Before each wind tunnel use, all differential
pressure-measuring devices shall be calibrated against the reference
device specified in section 6.4.3 using a common pressure source.
Perform the calibration at three reference pressures representing 30,
60, and 90 percent of the full-scale range of the pressure-measuring
device being calibrated. For an inclined-vertical manometer, perform
separate calibrations on the inclined and vertical portions of the
measurement scale, considering each portion of the scale to be a
separate full-scale range. [For example, for a manometer with a 0-to
2.5-cm H2O (0-to 1-in. H2O) inclined scale and a
2.5-to 12.7-cm H2O (1-to 5-in. H2O) vertical
scale, calibrate the inclined portion at 7.6, 15.2, and 22.9 mm
H2O (0.3, 0.6, and 0.9 in. H2O), and calibrate the
vertical portion at 3.8, 7.6, and 11.4 cm H2O (1.5, 3.0, and
4.5 in. H2O).] Alternatively, for the vertical portion of the
scale, use three evenly spaced reference pressures, one of which is
equal to or higher than the highest differential pressure expected in
field applications.
10.3.3.2 Acceptance criteria. At each pressure setting, the two
pressure readings made using the reference device and the pressure-
measuring device being calibrated shall agree to within 2 percent of
full scale of the device being calibrated or 0.5 mm H2O (0.02
in. H2O), whichever is less restrictive. For an inclined-
vertical manometer, these requirements shall be met separately using the
respective full-scale upper limits of the inclined and vertical portions
of the scale. Differential pressure-measuring devices not meeting the 2
percent of full scale or 0.5 mm H2O (0.02 in. H2O)
calibration requirement shall not be used.
10.3.3.3 Exceptions. Any precision manometer that meets the
specifications for a reference device in section 6.4.3 and that is not
used for field testing does not require calibration, but must be leveled
and zeroed before each wind tunnel use. Any pressure device used
exclusively for yaw nulling does not require calibration, but shall be
checked for responsiveness to rotation of the probe prior to each wind
tunnel use.
10.3.4 Calibrate digital inclinometers on each day of wind tunnel or
field testing

[[Page 103]]

(prior to beginning testing) using the following procedures. Calibrate
the inclinometer according to the manufacturer's calibration procedures.
In addition, use a triangular block (illustrated in Figure 2G-9) with a
known angle k, independently determined using a protractor or equivalent
device, between two adjacent sides to verify the inclinometer readings.
(Note: If other angle-measuring devices meeting the provisions of
section 6.2.3 are used in place of a digital inclinometer, comparable
calibration procedures shall be performed on such devices.) Secure the
triangular block in a fixed position. Place the inclinometer on one side
of the block (side A) to measure the angle of inclination
(R1). Repeat this measurement on the adjacent side of the
block (side B) using the inclinometer to obtain a second angle reading
(R2). The difference of the sum of the two readings from
180[deg] (i.e., 180[deg]-R1-R2) shall be within
2[deg] of the known angle, k.
10.4 Placement of Reference Scribe Line. Prior to the first
calibration of a probe, a line shall be permanently inscribed on the
main probe sheath to serve as a reference mark for determining yaw
angles. Annex C in section 18 of this method gives a guideline for
placement of the reference scribe line.
10.4.1 This reference scribe line shall meet the specifications in
sections 6.1.5.1 and 6.1.5.3 of this method. To verify that the
alignment specification in section 6.1.5.3 is met, secure the probe in a
horizontal position and measure the rotational angle of each scribe line
and scribe line segment using an angle-measuring device that meets the
specifications in section 6.2.1 or 6.2.3. For any scribe line that is
longer than 30.5 cm (12 in.), check the line's rotational position at
30.5-cm (12-in.) intervals. For each line segment that is 12 in. or less
in length, check the rotational position at the two endpoints of the
segment. To meet the alignment specification in section 6.1.5.3, the
minimum and maximum of all of the rotational angles that are measured
along the full length of main probe must not differ by more than 2[deg].
(Note: A short reference scribe line segment [e.g., 15.2 cm (6 in.) or
less in length] meeting the alignment specifications in section 6.1.5.3
is fully acceptable under this method. See section 18.1.1.1 of Annex A
for an example of a probe marking procedure, suitable for use with a
short reference scribe line.)
10.4.2 The scribe line should be placed on the probe first and then
its offset from the yaw-null position established (as specified in
section 10.5). The rotational position of the reference scribe line
relative to the yaw-null position of the probe, as determined by the yaw
angle calibration procedure in section 10.5, is the reference scribe
line rotational offset, RSLO. The reference scribe line
rotational offset shall be recorded and retained as part of the probe's
calibration record.
10.4.3 Scribe line for automated probes. A scribe line may not be
necessary for an automated probe system if a reference rotational
position of the probe is built into the probe system design. For such
systems, a ``flat'' (or comparable, clearly identifiable physical
characteristic) should be provided on the probe casing or flange plate
to ensure that the reference position of the probe assembly remains in a
vertical or horizontal position. The rotational offset of the flat (or
comparable, clearly identifiable physical characteristic) needed to
orient the reference position of the probe assembly shall be recorded
and maintained as part of the automated probe system's specifications.
10.5 Yaw Angle Calibration Procedure. For each probe used to measure
yaw angles with this method, a calibration procedure shall be performed
in a wind tunnel meeting the specifications in section 10.1 to determine
the rotational position of the reference scribe line relative to the
probe's yaw-null position. This procedure shall be performed on the main
probe with all devices that will be attached to the main probe in the
field [such as thermocouples, resistance temperature detectors (RTDs),
or sampling nozzles] that may affect the flow around the probe head.
Probe shaft extensions that do not affect flow around the probe head
need not be attached during calibration. At a minimum, this procedure
shall include the following steps.
10.5.1 Align and lock the angle-measuring device on the reference
scribe line. If a marking procedure (such as described in section
18.1.1.1) is used, align the angle-measuring device on a mark within
1[deg] of the rotational position of the reference scribe line. Lock
the angle-measuring device onto the probe sheath at this position.
10.5.2 Zero the pressure-measuring device used for yaw nulling.
10.5.3 Insert the probe assembly into the wind tunnel through the
entry port, positioning the probe's impact port at the calibration
location. Check the responsiveness of the pressure-measurement device to
probe rotation, taking corrective action if the response is
unacceptable.
10.5.4 Ensure that the probe is in a horizontal position, using a
carpenter's level.
10.5.5 Rotate the probe either clockwise or counterclockwise until a
yaw null [zero FP for a Type S probe or zero (P2-
P3) for a 3-D probe] is obtained. If using a Type S probe
with an attached thermocouple, the direction of the probe rotation shall
be such that the thermocouple is located downstream of the probe
pressure ports at the yaw-null position.
10.5.6 Use the reading displayed by the angle-measuring device at
the yaw-null position to determine the magnitude of the reference scribe
line rotational offset, RSLO, as defined in section 3.15.
Annex D in section 18

[[Page 104]]

of this method gives a recommended procedure for determining the
magnitude of RSLO with a digital inclinometer and a second
procedure for determining the magnitude of RSLO with a
protractor wheel and pointer device. Table 2G-6 gives an example data
form and Table 2G-7 is a look-up table with the recommended procedure.
Procedures other than those recommended in Annex D in section 18 may be
used, if they can determine RSLO to within 1[deg] and are
explained in detail in the field test report. The algebraic sign of
RSLO will either be positive if the rotational position of
the reference scribe line (as viewed from the ``tail'' end of the probe)
is clockwise, or negative, if counterclockwise with respect to the
probe's yaw-null position. (This is illustrated in Figure 2G-10.)
10.5.7 The steps in sections 10.5.3 through 10.5.6 shall be
performed twice at each of the velocities at which the probe will be
calibrated (in accordance with section 10.6). Record the values of
RSLO.
10.5.8 The average of all of the RSLO values shall be
documented as the reference scribe line rotational offset for the probe.
10.5.9 Use of reference scribe line offset. The reference scribe
line rotational offset shall be used to determine the yaw angle of flow
in accordance with section 8.9.4.
10.6 Velocity Calibration Procedure. When a 3-D probe is used under
this method, follow the provisions for the calibration of 3-D probes in
section 10.6 of Method 2F to obtain the necessary velocity calibration
coefficients (F2 as derived using Equation 2F-2 in Method 2F)
corresponding to a pitch angle position of 0[deg]. The following
procedure applies to Type S probes. This procedure shall be performed on
the main probe and all devices that will be attached to the main probe
in the field (e.g., thermocouples, RTDs, sampling nozzles) that may
affect the flow around the probe head. Probe shaft extensions that do
not affect flow around the probe head need not be attached during
calibration. (Note: If a sampling nozzle is part of the assembly, two
additional requirements must be satisfied before proceeding. The
distance between the nozzle and the pitot tube shall meet the minimum
spacing requirement prescribed in Method 2, and a wind tunnel
demonstration shall be performed that shows the probe's ability to yaw
null is not impaired when the nozzle is drawing sample.) To obtain
velocity calibration coefficient(s) for the tested probe, proceed as
follows.
10.6.1 Calibration velocities. The tester may calibrate the probe at
two nominal wind tunnel velocity settings of 18.3 m/sec and 27.4 m/sec
(60 ft/sec and 90 ft/sec) and average the results of these calibrations,
as described in sections 10.6.12 through 10.6.14, in order to generate
the calibration coefficient, Cp. If this option is selected,
this calibration coefficient may be used for all field applications
where the velocities are 9.1 m/sec (30 ft/sec) or greater.
Alternatively, the tester may customize the probe calibration for a
particular field test application (or for a series of applications),
based on the expected average velocity(ies) at the test site(s). If this
option is selected, generate the calibration coefficients by calibrating
the probe at two nominal wind tunnel velocity settings, one of which is
less than or equal to and the other greater than or equal to the
expected average velocity(ies) for the field application(s), and average
the results as described in sections 10.6.12 through 10.6.14. Whichever
calibration option is selected, the probe calibration coefficient(s)
obtained at the two nominal calibration velocities shall meet the
conditions specified in sections 10.6.12 through 10.6.14.
10.6.2 Connect the tested probe and calibration pitot tube to their
respective pressure-measuring devices. Zero the pressure-measuring
devices. Inspect and leak-check all pitot lines; repair or replace them,
if necessary. Turn on the fan, and allow the wind tunnel air flow to
stabilize at the first of the selected nominal velocity settings.
10.6.3 Position the calibration pitot tube at its measurement
location (determined as outlined in section 6.11.4.3), and align the
tube so that its tip is pointed directly into the flow. Ensure that the
entry port surrounding the tube is properly sealed. The calibration
pitot tube may either remain in the wind tunnel throughout the
calibration, or be removed from the wind tunnel while measurements are
taken with the probe being calibrated.
10.6.4 Check the zero setting of each pressure-measuring device.
10.6.5 Insert the tested probe into the wind tunnel and align it so
that the designated pressure port (e.g., either the A-side or B-side of
a Type S probe) is pointed directly into the flow and is positioned
within the wind tunnel calibration location (as defined in section
3.21). Secure the probe at the 0[deg] pitch angle position. Ensure that
the entry port surrounding the probe is properly sealed.
10.6.6 Read the differential pressure from the calibration pitot
tube (FPstd), and record its value. Read the barometric
pressure to within 2.5 mm Hg (0.1 in. Hg) and the temperature in the
wind tunnel to within 0.6 [deg]C (1 [deg]F). Record these values on a
data form similar to Table 2G-8.
10.6.7 After the tested probe's differential pressure gauges have
had sufficient time to stabilize, yaw null the probe (and then rotate it
back 90[deg] for Type S probes), then obtain the differential pressure
reading (FP). Record the yaw angle and differential pressure readings.
10.6.8 Take paired differential pressure measurements with the
calibration pitot tube and tested probe (according to sections 10.6.6
and 10.6.7). The paired measurements in

[[Page 105]]

each replicate can be made either simultaneously (i.e., with both probes
in the wind tunnel) or by alternating the measurements of the two probes
(i.e., with only one probe at a time in the wind tunnel).
10.6.9 Repeat the steps in sections 10.6.6 through 10.6.8 at the
same nominal velocity setting until three pairs of FP readings have been
obtained from the calibration pitot tube and the tested probe.
10.6.10 Repeat the steps in sections 10.6.6 through 10.6.9 above for
the A-side and B-side of the Type S pitot tube. For a probe assembly
constructed such that its pitot tube is always used in the same
orientation, only one side of the pitot tube need be calibrated (the
side that will face the flow). However, the pitot tube must still meet
the alignment and dimension specifications in section 6.1.1 and must
have an average deviation (m) value of 0.01 or less as provided in
section 10.6.12.4.
10.6.11 Repeat the calibration procedures in sections 10.6.6 through
10.6.10 at the second selected nominal wind tunnel velocity setting.
10.6.12 Perform the following calculations separately on the A-side
and B-side values.
10.6.12.1 Calculate a Cp value for each of the three
replicates performed at the lower velocity setting where the
calibrations were performed using Equation 2-2 in section 4.1.4 of
Method 2.
10.6.12.2 Calculate the arithmetic average, Cp(avg-low),
of the three Cp values.
10.6.12.3 Calculate the deviation of each of the three individual
values of Cp from the A-side average Cp(avg-low)
value using Equation 2-3 in Method 2.
10.6.12.4 Calculate the average deviation (m) of the three
individual Cp values from Cp(avg-low) using
Equation 2-4 in Method 2. Use the Type S pitot tube only if the values
of m (side A) and m (side B) are less than or equal to 0.01. If both A-
side and B-side calibration coefficients are calculated, the absolute
value of the difference between Cp(avg-low) (side A) and
Cp(avg-low) (side B) must not exceed 0.01.
10.6.13 Repeat the calculations in section 10.6.12 using the data
obtained at the higher velocity setting to derive the arithmetic
Cp values at the higher velocity setting,
Cp(avg-high), and to determine whether the conditions in
10.6.12.4 are met by both the A-side and B-side calibrations at this
velocity setting.
10.6.14 Use equation 2G-1 to calculate the percent difference of the
averaged Cp values at the two calibration velocities.
[GRAPHIC] [TIFF OMITTED] TR14MY99.062

The percent difference between the averaged Cp values shall
not exceed 3 percent. If the specification is met, average the A-side
values of Cp(avg-low) and Cp(avg-high) to produce
a single A-side calibration coefficient, Cp. Repeat for the
B-side values if calibrations were performed on that side of the pitot.
If the specification is not met, make necessary adjustments in the
selected velocity settings and repeat the calibration procedure until
acceptable results are obtained.
10.6.15 If the two nominal velocities used in the calibration were
18.3 and 27.4 m/sec (60 and 90 ft/sec), the average Cp from
section 10.6.14 is applicable to all velocities 9.1 m/sec (30 ft/sec) or
greater. If two other nominal velocities were used in the calibration,
the resulting average Cp value shall be applicable only in
situations where the velocity calculated using the calibration
coefficient is neither less than the lower nominal velocity nor greater
than the higher nominal velocity.
10.7 Recalibration. Recalibrate the probe using the procedures in
section 10 either within 12 months of its first field use after its most
recent calibration or after 10 field tests (as defined in section 3.3),
whichever occurs later. In addition, whenever there is visible damage to
the probe head, the probe shall be recalibrated before it is used again.
10.8 Calibration of pressure-measuring devices used in the field.
Before its initial use in a field test, calibrate each pressure-
measuring device (except those used exclusively for yaw nulling) using
the three-point calibration procedure described in section 10.3.3. The
device shall be recalibrated according to the procedure in section
10.3.3 no later than 90 days after its first field use following its
most recent calibration. At the discretion of the tester, more frequent
calibrations (e.g., after a field test) may be performed. No
adjustments, other than adjustments to the zero setting, shall be made
to the device between calibrations.
10.8.1 Post-test calibration check. A single-point calibration check
shall be performed on each pressure-measuring device after completion of
each field test. At the discretion of the tester, more frequent single-
point calibration checks (e.g., after one or more field test runs) may
be performed. It is recommended that the post-test check be performed
before leaving the field test site. The

[[Page 106]]

check shall be performed at a pressure between 50 and 90 percent of full
scale by taking a common pressure reading with the tested probe and a
reference pressure-measuring device (as described in section 6.4.4) or
by challenging the tested device with a reference pressure source (as
described in section 6.4.4) or by performing an equivalent check using a
reference device approved by the Administrator.
10.8.2 Acceptance criterion. At the selected pressure setting, the
pressure readings made using the reference device and the tested device
shall agree to within 3 percent of full scale of the tested device or
0.8 mm H2O (0.03 in. H2O), whichever is less
restrictive. If this specification is met, the test data collected
during the field test are valid. If the specification is not met, all
test data collected since the last successful calibration or calibration
check are invalid and shall be repeated using a pressure-measuring
device with a current, valid calibration. Any device that fails the
calibration check shall not be used in a field test until a successful
recalibration is performed according to the procedures in section
10.3.3.
10.9 Temperature Gauges. Same as Method 2, section 4.3. The
alternative thermocouple calibration procedures outlined in Emission
Measurement Center (EMC) Approved Alternative Method (ALT-011)
``Alternative Method 2 Thermocouple Calibration Procedure'' may be
performed. Temperature gauges shall be calibrated no more than 30 days
prior to the start of a field test or series of field tests and
recalibrated no more than 30 days after completion of a field test or
series of field tests.
10.10 Barometer. Same as Method 2, section 4.4. The barometer shall
be calibrated no more than 30 days prior to the start of a field test or
series of field tests.

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this method (see
section 8.0).

12.0 Data Analysis and Calculations

These calculations use the measured yaw angle and the differential
pressure and temperature measurements at individual traverse points to
derive the near-axial flue gas velocity (va(i)) at each of
those points. The near-axial velocity values at all traverse points that
comprise a full stack or duct traverse are then averaged to obtain the
average near-axial stack or duct gas velocity (va(avg)).

12.1 Nomenclature

A = Cross-sectional area of stack or duct at the test port location,
m\2\ (ft \2\).
Bws = Water vapor in the gas stream (from Method 4 or
alternative), proportion by volume.
Cp = Pitot tube calibration coefficient, dimensionless.
F2(i) = 3-D probe velocity coefficient at 0 pitch, applicable
at traverse point i.
Kp = Pitot tube constant,
[GRAPHIC] [TIFF OMITTED] TR14MY99.063

for the metric system, and
[GRAPHIC] [TIFF OMITTED] TR14MY99.064

for the English system.

Pbar = Barometric pressure at velocity measurement site, mm
Hg (in. Hg).
Pg = Stack or duct static pressure, mm H2O (in.
H2O).
Ps = Absolute stack or duct pressure, mm Hg (in. Hg),
[GRAPHIC] [TIFF OMITTED] TR14MY99.066

Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
13.6 = Conversion from mm H2O (in. H2O) to mm Hg
(in. Hg).
Qsd = Average dry-basis volumetric stack or duct gas flow
rate corrected to standard conditions, dscm/hr (dscf/hr).
Qsw = Average wet-basis volumetric stack or duct gas flow
rate corrected to standard conditions, wscm/hr (wscf/hr).
ts(i) = Stack or duct temperature, [deg]C ([deg]F), at
traverse point i.
Ts(i) = Absolute stack or duct temperature, [deg]K ([deg]R),
at traverse point i.
[GRAPHIC] [TIFF OMITTED] TR14MY99.067

for the metric system, and
[GRAPHIC] [TIFF OMITTED] TR14MY99.068

for the English system.

Ts(avg) = Average absolute stack or duct gas temperature
across all traverse points.
Tstd = Standard absolute temperature, 293 [deg]K (528
[deg]R).
va(i) = Measured stack or duct gas impact velocity, m/sec
(ft/sec), at traverse point i.
va(avg) = Average near-axial stack or duct gas velocity, m/
sec (ft/sec) across all traverse points.

[[Page 107]]

FPi = Velocity head (differential pressure) of stack or duct
gas, mm H2O (in. H2O), applicable at
traverse point i.
(P1-P2) = Velocity head (differential pressure) of
stack or duct gas measured by a 3-D probe, mm H2O
(in. H2O), applicable at traverse point i.
3,600 = Conversion factor, sec/hr.
18.0 = Molecular weight of water, g/g-mole (lb/lb-mole).
ky(i) = Yaw angle of the flow velocity vector, at traverse
point i.
n = Number of traverse points.

12.2 Traverse Point Velocity Calculations. Perform the following
calculations from the measurements obtained at each traverse point.
12.2.1 Selection of calibration coefficient. Select the calibration
coefficient as described in section 10.6.1.
12.2.2 Near-axial traverse point velocity. When using a Type S
probe, use the following equation to calculate the traverse point near-
axial velocity (va(i)) from the differential pressure
(FPi), yaw angle (ky(i)), absolute stack or duct
standard temperature (Ts(i)) measured at traverse point i,
the absolute stack or duct pressure (Ps), and molecular
weight (Ms).
[GRAPHIC] [TIFF OMITTED] TR14MY99.069

Use the following equation when using a 3-D probe.
[GRAPHIC] [TIFF OMITTED] TR14MY99.070

12.2.3 Handling multiple measurements at a traverse point. For
pressure or temperature devices that take multiple measurements at a
traverse point, the multiple measurements (or where applicable, their
square roots) may first be averaged and the resulting average values
used in the equations above. Alternatively, the individual measurements
may be used in the equations above and the resulting calculated values
may then be averaged to obtain a single traverse point value. With
either approach, all of the individual measurements recorded at a
traverse point must be used in calculating the applicable traverse point
value.
12.3 Average Near-Axial Velocity in Stack or Duct. Use the reported
traverse point near-axial velocity in the following equation.
[GRAPHIC] [TIFF OMITTED] TR14MY99.071

12.4 Acceptability of Results. The acceptability provisions in
section 12.4 of Method 2F apply to 3-D probes used under Method 2G. The
following provisions apply to Type S probes. For Type S probes, the test
results are acceptable and the calculated value of va(avg)
may be reported as the average near-axial velocity for the test run if
the conditions in either section 12.4.1 or 12.4.2 are met.
12.4.1 The average calibration coefficient Cp used in
Equation 2G-6 was generated at nominal velocities of 18.3 and 27.4 m/sec
(60 and 90 ft/sec) and the value of va(avg) calculated using
Equation 2G-8 is greater than or equal to 9.1 m/sec (30 ft/sec).
12.4.2 The average calibration coefficient Cp used in
Equation 2G-6 was generated at nominal velocities other than 18.3 or
27.4 m/sec (60 or 90 ft/sec) and the value of va(avg)
calculated using Equation 2G-8 is greater than or equal to the lower
nominal velocity and less than or equal to the higher nominal velocity
used to derive the average Cp.
12.4.3 If the conditions in neither section 12.4.1 nor section
12.4.2 are met, the test results obtained from Equation 2G-8 are not
acceptable, and the steps in sections 12.2 and 12.3 must be repeated
using an average calibration coefficient Cp that satisfies
the conditions in section 12.4.1 or 12.4.2.
12.5 Average Gas Volumetric Flow Rate in Stack or Duct (Wet Basis).
Use the following equation to compute the average volumetric flow rate
on a wet basis.

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[GRAPHIC] [TIFF OMITTED] TR14MY99.072

12.6 Average Gas Volumetric Flow Rate in Stack or Duct (Dry Basis).
Use the following equation to compute the average volumetric flow rate
on a dry basis.
[GRAPHIC] [TIFF OMITTED] TR14MY99.073

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Reporting.

16.1 Field Test Reports. Field test reports shall be submitted to
the Agency according to applicable regulatory requirements. Field test
reports should, at a minimum, include the following elements.
16.1.1 Description of the source. This should include the name and
location of the test site, descriptions of the process tested, a
description of the combustion source, an accurate diagram of stack or
duct cross-sectional area at the test site showing the dimensions of the
stack or duct, the location of the test ports, and traverse point
locations and identification numbers or codes. It should also include a
description and diagram of the stack or duct layout, showing the
distance of the test location from the nearest upstream and downstream
disturbances and all structural elements (including breachings, baffles,
fans, straighteners, etc.) affecting the flow pattern. If the source and
test location descriptions have been previously submitted to the Agency
in a document (e.g., a monitoring plan or test plan), referencing the
document in lieu of including this information in the field test report
is acceptable.
16.1.2 Field test procedures. These should include a description of
test equipment and test procedures. Testing conventions, such as
traverse point numbering and measurement sequence (e.g., sampling from
center to wall, or wall to center), should be clearly stated. Test port
identification and directional reference for each test port should be
included on the appropriate field test data sheets.
16.1.3 Field test data.
16.1.3.1 Summary of results. This summary should include the dates
and times of testing, and the average near-axial gas velocity and the
average flue gas volumetric flow results for each run and tested
condition.
16.1.3.2 Test data. The following values for each traverse point
should be recorded and reported:

(a) Differential pressure at traverse point i (FPi)
(b) Stack or duct temperature at traverse point i (ts(i))
(c) Absolute stack or duct temperature at traverse point i
(Ts(i))
(d) Yaw angle at traverse point i (ky(i))
(e) Stack gas near-axial velocity at traverse point i
(va(i))

16.1.3.3 The following values should be reported once per run:

(a) Water vapor in the gas stream (from Method 4 or alternative),
proportion by volume (Bws), measured at the frequency
specified in the applicable regulation
(b) Molecular weight of stack or duct gas, dry basis (Md)
(c) Molecular weight of stack or duct gas, wet basis (Ms)
(d) Stack or duct static pressure (Pg)
(e) Absolute stack or duct pressure (Ps)
(f) Carbon dioxide concentration in the flue gas, dry basis
(%d CO2)
(g) Oxygen concentration in the flue gas, dry basis (%d
O2)
(h) Average near-axial stack or duct gas velocity
(va(avg)) across all traverse points
(i) Gas volumetric flow rate corrected to standard conditions, dry
or wet basis as required by the applicable regulation (Qsd or
Qsw)

16.1.3.4 The following should be reported once per complete set of
test runs:

(a) Cross-sectional area of stack or duct at the test location (A)
(b) Pitot tube calibration coefficient (Cp)
(c) Measurement system response time (sec)
(d) Barometric pressure at measurement site (Pbar)

16.1.4 Calibration data. The field test report should include
calibration data for all

[[Page 109]]

probes and test equipment used in the field test. At a minimum, the
probe calibration data reported to the Agency should include the
following:

(a) Date of calibration
(b) Probe type
(c) Probe identification number(s) or code(s)
(d) Probe inspection sheets
(e) Pressure measurements and calculations used to obtain
calibration coefficients in accordance with section 10.6 of this method
(f) Description and diagram of wind tunnel used for the calibration,
including dimensions of cross-sectional area and position and size of
the test section
(g) Documentation of wind tunnel qualification tests performed in
accordance with section 10.1 of this method

16.1.5 Quality assurance. Specific quality assurance and quality
control procedures used during the test should be described.

17.0 Bibliography.

(1) 40 CFR Part 60, Appendix A, Method 1--Sample and velocity
traverses for stationary sources.
(2) 40 CFR Part 60, Appendix A, Method 2--Determination of stack gas
velocity and volumetric flow rate (Type S pitot tube) .
(3) 40 CFR Part 60, Appendix A, Method 2F--Determination of stack
gas velocity and volumetric flow rate with three-dimensional probes.
(4) 40 CFR Part 60, Appendix A, Method 2H--Determination of stack
gas velocity taking into account velocity decay near the stack wall.
(5) 40 CFR Part 60, Appendix A, Method 3--Gas analysis for carbon
dioxide, oxygen, excess air, and dry molecular weight.
(6) 40 CFR Part 60, Appendix A, Method 3A--Determination of oxygen
and carbon dioxide concentrations in emissions from stationary sources
(instrumental analyzer procedure).
(7) 40 CFR Part 60, Appendix A, Method 4--Determination of moisture
content in stack gases.
(8) Emission Measurement Center (EMC) Approved Alternative Method
(ALT-011) ``Alternative Method 2 Thermocouple Calibration Procedure.''
(9) Electric Power Research Institute, Interim Report EPRI TR-
106698, ``Flue Gas Flow Rate Measurement Errors,'' June 1996.
(10) Electric Power Research Institute, Final Report EPRI TR-108110,
``Evaluation of Heat Rate Discrepancy from Continuous Emission
Monitoring Systems,'' August 1997.
(11) Fossil Energy Research Corporation, Final Report, ``Velocity
Probe Tests in Non-axial Flow Fields,'' November 1998, Prepared for the
U.S. Environmental Protection Agency.
(12) Fossil Energy Research Corporation, ``Additional Swirl Tunnel
Tests: E-DAT and T-DAT Probes,'' February 24, 1999, Technical Memorandum
Prepared for U.S. Environmental Protection Agency, P.O. No. 7W-1193-
NALX.
(13) Massachusetts Institute of Technology, Report WBWT-TR-1317,
``Calibration of Eight Wind Speed Probes Over a Reynolds Number Range of
46,000 to 725,000 Per Foot, Text and Summary Plots,'' Plus appendices,
October 15, 1998, Prepared for The Cadmus Group, Inc.
(14) National Institute of Standards and Technology, Special
Publication 250, ``NIST Calibration Services Users Guide 1991,'' Revised
October 1991, U.S. Department of Commerce, p. 2.
(15) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Four Prandtl Probes, Four
S-Type Probes, Four French Probes, Four Modified Kiel Probes,'' Prepared
for the U.S. Environmental Protection Agency under IAG #DW13938432-01-0.
(16) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed In-strumentation, Five Autoprobes,''
Prepared for the U.S. Environmental Protection Agency under IAG
#DW13938432-01-0.
(17) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Eight Spherical Probes,''
Prepared for the U.S. Environmental Protection Agency under IAG
#DW13938432-01-0.
(18) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Four DAT Probes, ``
Prepared for the U.S. Environmental Protection Agency under IAG
#DW13938432-01-0.
(19) Norfleet, S.K., ``An Evaluation of Wall Effects on Stack Flow
Velocities and Related Overestimation Bias in EPA's Stack Flow Reference
Methods,'' EPRI CEMS User's Group Meeting, New Orleans, Louisiana, May
13-15, 1998.
(20) Page, J.J., E.A. Potts, and R.T. Shigehara, ``3-D Pitot Tube
Calibration Study,'' EPA Contract No. 68D10009, Work Assignment No. I-
121, March 11, 1993.
(21) Shigehara, R.T., W.F. Todd, and W.S. Smith, ``Significance of
Errors in Stack Sampling Measurements,'' Presented at the Annual Meeting
of the Air Pollution Control Association, St. Louis, Missouri, June
1419, 1970.
(22) The Cadmus Group, Inc., May 1999, ``EPA Flow Reference Method
Testing and Analysis: Findings Report,'' EPA/430-R-99-009.
(23) The Cadmus Group, Inc., 1998, ``EPA Flow Reference Method
Testing and Analysis: Data Report, Texas Utilities, DeCordova Steam
Electric Station, Volume

[[Page 110]]

I: Test Description and Appendix A (Data Distribution Package),'' EPA/
430-R-98-015a.
(24) The Cadmus Group, Inc., 1998, ``EPA Flow Reference Method
Testing and Analysis: Data Report, Texas Utilities, Lake Hubbard Steam
Electric Station, Volume I: Test Description and Appendix A (Data
Distribution Package),'' EPA/430-R-98-017a.
(25) The Cadmus Group, Inc., 1998, ``EPA Flow Reference Method
Testing and Analysis: Data Report, Pennsylvania Electric Co., G.P.U.
Genco Homer City Station: Unit 1, Volume I: Test Description and
Appendix A (Data Distribution Package),'' EPA/430-R-98-018a.
(26) The Cadmus Group, Inc., 1997, ``EPA Flow Reference Method
Testing and Analysis: Wind Tunnel Experimental Results,'' EPA/430-R-97-
013.

18.0 Annexes

Annex A, C, and D describe recommended procedures for meeting
certain provisions in sections 8.3, 10.4, and 10.5 of this method. Annex
B describes procedures to be followed when using the protractor wheel
and pointer assembly to measure yaw angles, as provided under section
8.9.1.
18.1 Annex A--Rotational Position Check. The following are
recommended procedures that may be used to satisfy the rotational
position check requirements of section 8.3 of this method and to
determine the angle-measuring device rotational offset
(RADO).
18.1.1 Rotational position check with probe outside stack. Where
physical constraints at the sampling location allow full assembly of the
probe outside the stack and insertion into the test port, the following
procedures should be performed before the start of testing. Two angle-
measuring devices that meet the specifications in section 6.2.1 or 6.2.3
are required for the rotational position check. An angle measuring
device whose position can be independently adjusted (e.g., by means of a
set screw) after being locked into position on the probe sheath shall
not be used for this check unless the independent adjustment is set so
that the device performs exactly like a device without the capability
for independent adjustment. That is, when aligned on the probe such a
device must give the same reading as a device that does not have the
capability of being independently adjusted. With the fully assembled
probe (including probe shaft extensions, if any) secured in a horizontal
position, affix one yaw angle-measuring device to the probe sheath and
lock it into position on the reference scribe line specified in section
6.1.5.1. Position the second angle-measuring device using the procedure
in section 18.1.1.1 or 18.1.1.2.
18.1.1.1 Marking procedure. The procedures in this section should be
performed at each location on the fully assembled probe where the yaw
angle-measuring device will be mounted during the velocity traverse.
Place the second yaw angle-measuring device on the main probe sheath (or
extension) at the position where a yaw angle will be measured during the
velocity traverse. Adjust the position of the second angle-measuring
device until it indicates the same angle (1[deg]) as the reference
device, and affix the second device to the probe sheath (or extension).
Record the angles indicated by the two angle-measuring devices on a form
similar to table 2G-2. In this position, the second angle-measuring
device is considered to be properly positioned for yaw angle
measurement. Make a mark, no wider than 1.6 mm (\1/16\ in.), on the
probe sheath (or extension), such that the yaw angle-measuring device
can be re-affixed at this same properly aligned position during the
velocity traverse.
18.1.1.2 Procedure for probe extensions with scribe lines. If,
during a velocity traverse the angle-measuring device will be affixed to
a probe extension having a scribe line as specified in section 6.1.5.2,
the following procedure may be used to align the extension's scribe line
with the reference scribe line instead of marking the extension as
described in section 18.1.1.1. Attach the probe extension to the main
probe. Align and lock the second angle-measuring device on the probe
extension's scribe line. Then, rotate the extension until both measuring
devices indicate the same angle (1[deg]). Lock the extension at this
rotational position. Record the angles indicated by the two angle-
measuring devices on a form similar to table 2G-2. An angle-measuring
device may be aligned at any position on this scribe line during the
velocity traverse, if the scribe line meets the alignment specification
in section 6.1.5.3.
18.1.1.3 Post-test rotational position check. If the fully assembled
probe includes one or more extensions, the following check should be
performed immediately after the completion of a velocity traverse. At
the discretion of the tester, additional checks may be conducted after
completion of testing at any sample port. Without altering the alignment
of any of the components of the probe assembly used in the velocity
traverse, secure the fully assembled probe in a horizontal position.
Affix an angle-measuring device at the reference scribe line specified
in section 6.1.5.1. Use the other angle-measuring device to check the
angle at each location where the device was checked prior to testing.
Record the readings from the two angle-measuring devices.
18.1.2 Rotational position check with probe in stack. This section
applies only to probes that, due to physical constraints, cannot be
inserted into the test port as fully assembled with all necessary
extensions needed to reach the inner-most traverse point(s).
18.1.2.1 Perform the out-of-stack procedure in section 18.1.1 on the
main probe and any

[[Page 111]]

attached extensions that will be initially inserted into the test port.
18.1.2.2 Use the following procedures to perform additional
rotational position check(s) with the probe in the stack, each time a
probe extension is added. Two angle-measuring devices are required. The
first of these is the device that was used to measure yaw angles at the
preceding traverse point, left in its properly aligned measurement
position. The second angle-measuring device is positioned on the added
probe extension. Use the applicable procedures in section 18.1.1.1 or
18.1.1.2 to align, adjust, lock, and mark (if necessary) the position of
the second angle-measuring device to within 1[deg] of the first device.
Record the readings of the two devices on a form similar to Table 2G-2.
18.1.2.3 The procedure in section 18.1.2.2 should be performed at
the first port where measurements are taken. The procedure should be
repeated each time a probe extension is re-attached at a subsequent
port, unless the probe extensions are designed to be locked into a
mechanically fixed rotational position (e.g., through use of
interlocking grooves), which can be reproduced from port to port as
specified in section 8.3.5.2.
18.2 Annex B--Angle Measurement Protocol for Protractor Wheel and
Pointer Device. The following procedure shall be used when a protractor
wheel and pointer assembly, such as the one described in section 6.2.2
and illustrated in Figure 2G-5 is used to measure the yaw angle of flow.
With each move to a new traverse point, unlock, re-align, and re-lock
the probe, angle-pointer collar, and protractor wheel to each other. At
each such move, particular attention is required to ensure that the
scribe line on the angle pointer collar is either aligned with the
reference scribe line on the main probe sheath or is at the rotational
offset position established under section 8.3.1. The procedure consists
of the following steps:
18.2.1 Affix a protractor wheel to the entry port for the test probe
in the stack or duct.
18.2.2 Orient the protractor wheel so that the 0[deg] mark
corresponds to the longitudinal axis of the stack or duct. For stacks,
vertical ducts, or ports on the side of horizontal ducts, use a digital
inclinometer meeting the specifications in section 6.2.1 to locate the
0[deg] orientation. For ports on the top or bottom of horizontal ducts,
identify the longitudinal axis at each test port and permanently mark
the duct to indicate the 0[deg] orientation. Once the protractor wheel
is properly aligned, lock it into position on the test port.
18.2.3 Move the pointer assembly along the probe sheath to the
position needed to take measurements at the first traverse point. Align
the scribe line on the pointer collar with the reference scribe line or
at the rotational offset position established under section 8.3.1.
Maintaining this rotational alignment, lock the pointer device onto the
probe sheath. Insert the probe into the entry port to the depth needed
to take measurements at the first traverse point.
18.2.4 Perform the yaw angle determination as specified in sections
8.9.3 and 8.9.4 and record the angle as shown by the pointer on the
protractor wheel. Then, take velocity pressure and temperature
measurements in accordance with the procedure in section 8.9.5. Perform
the alignment check described in section 8.9.6.
18.2.5 After taking velocity pressure measurements at that traverse
point, unlock the probe from the collar and slide the probe through the
collar to the depth needed to reach the next traverse point.
18.2.6 Align the scribe line on the pointer collar with the
reference scribe line on the main probe or at the rotational offset
position established under section 8.3.1. Lock the collar onto the
probe.
18.2.7 Repeat the steps in sections 18.2.4 through 18.2.6 at the
remaining traverse points accessed from the current stack or duct entry
port.
18.2.8 After completing the measurement at the last traverse point
accessed from a port, verify that the orientation of the protractor
wheel on the test port has not changed over the course of the traverse
at that port. For stacks, vertical ducts, or ports on the side of
horizontal ducts, use a digital inclinometer meeting the specifications
in section 6.2.1 to check the rotational position of the 0[deg] mark on
the protractor wheel. For ports on the top or bottom of horizontal
ducts, observe the alignment of the angle wheel 0[deg] mark relative to
the permanent 0[deg] mark on the duct at that test port. If these
observed comparisons exceed 2[deg] of 0[deg], all angle and pressure
measurements taken at that port since the protractor wheel was last
locked into position on the port shall be repeated.
18.2.9 Move to the next stack or duct entry port and repeat the
steps in sections 18.2.1 through 18.2.8.
18.3 Annex C--Guideline for Reference Scribe Line Placement. Use of
the following guideline is recommended to satisfy the requirements of
section 10.4 of this method. The rotational position of the reference
scribe line should be either 90[deg] or 180[deg] from the probe's impact
pressure port. For Type-S probes, place separate scribe lines, on
opposite sides of the probe sheath, if both the A and B sides of the
pitot tube are to be used for yaw angle measurements.
18.4 Annex D--Determination of Reference Scribe Line Rotational
Offset. The following procedures are recommended for determining the
magnitude and sign of a probe's reference scribe line rotational offset,
RSLO. Separate procedures are provided for two types of
angle-measuring devices: digital inclinometers and protractor wheel and
pointer assemblies.

[[Page 112]]

18.4.1 Perform the following procedures on the main probe with all
devices that will be attached to the main probe in the field [such as
thermocouples, resistance temperature detectors (RTDs), or sampling
nozzles] that may affect the flow around the probe head. Probe shaft
extensions that do not affect flow around the probe head need not be
attached during calibration.
18.4.2 The procedures below assume that the wind tunnel duct used
for probe calibration is horizontal and that the flow in the calibration
wind tunnel is axial as determined by the axial flow verification check
described in section 10.1.2. Angle-measuring devices are assumed to
display angles in alternating 0[deg] to 90[deg] and 90[deg] to 0[deg]
intervals. If angle-measuring devices with other readout conventions are
used or if other calibration wind tunnel duct configurations are used,
make the appropriate calculational corrections. For Type-S probes,
calibrate the A-side and B-sides separately, using the appropriate
scribe line (see section 18.3, above), if both the A and B sides of the
pitot tube are to be used for yaw angle determinations.
18.4.2.1 Position the angle-measuring device in accordance with one
of the following procedures.
18.4.2.1.1 If using a digital inclinometer, affix the calibrated
digital inclinometer to the probe. If the digital inclinometer can be
independently adjusted after being locked into position on the probe
sheath (e.g., by means of a set screw), the independent adjustment must
be set so that the device performs exactly like a device without the
capability for independent adjustment. That is, when aligned on the
probe the device must give the same readings as a device that does not
have the capability of being independently adjusted. Either align it
directly on the reference scribe line or on a mark aligned with the
scribe line determined according to the procedures in section 18.1.1.1.
Maintaining this rotational alignment, lock the digital inclinometer
onto the probe sheath.
18.4.2.1.2 If using a protractor wheel and pointer device, orient
the protractor wheel on the test port so that the 0[deg] mark is aligned
with the longitudinal axis of the wind tunnel duct. Maintaining this
alignment, lock the wheel into place on the wind tunnel test port. Align
the scribe line on the pointer collar with the reference scribe line or
with a mark aligned with the reference scribe line, as determined under
section 18.1.1.1. Maintaining this rotational alignment, lock the
pointer device onto the probe sheath.
18.4.2.2 Zero the pressure-measuring device used for yaw nulling.
18.4.2.3 Insert the probe assembly into the wind tunnel through the
entry port, positioning the probe's impact port at the calibration
location. Check the responsiveness of the pressure-measuring device to
probe rotation, taking corrective action if the response is
unacceptable.
18.4.2.4 Ensure that the probe is in a horizontal position using a
carpenter's level.
18.4.2.5 Rotate the probe either clockwise or counterclockwise until
a yaw null [zero FP for a Type S probe or zero (P2-
P3) for a 3-D probe] is obtained. If using a Type S probe
with an attached thermocouple, the direction of the probe rotation shall
be such that the thermocouple is located downstream of the probe
pressure ports at the yaw-null position.
18.4.2.6 Read and record the value of knull, the angle
indicated by the angle-measuring device at the yaw-null position. Record
the angle reading on a form similar to Table 2G-6. Do not associate an
algebraic sign with this reading.
18.4.2.7 Determine the magnitude and algebraic sign of the reference
scribe line rotational offset, RSLO. The magnitude of
RSLO will be equal to either knull or (90[deg]-
knull), depending on the type of probe being calibrated and
the type of angle-measuring device used. (See Table 2G-7 for a summary.)
The algebraic sign of RSLO will either be positive if the
rotational position of the reference scribe line is clockwise or
negative if counterclockwise with respect to the probe's yaw-null
position. Figure 2G-10 illustrates how the magnitude and sign of
RSLO are determined.
18.4.2.8 Perform the steps in sections 18.3.2.3 through 18.3.2.7
twice at each of the two calibration velocities selected for the probe
under section 10.6. Record the values of RSLO in a form
similar to Table 2G-6.
18.4.2.9 The average of all RSLO values is the reference
scribe line rotational offset for the probe.

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Method 2H--Determination of Stack Gas Velocity Taking Into Account
Velocity Decay Near the Stack Wall

1.0 Scope and Application

1.1 This method is applicable in conjunction with Methods 2, 2F, and
2G (40 CFR Part 60, Appendix A) to account for velocity decay near the
wall in circular stacks and ducts.
1.2 This method is not applicable for testing stacks and ducts less
than 3.3 ft (1.0 m) in diameter.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A wall effects adjustment factor is determined. It is used to
adjust the average stack gas velocity obtained under Method 2, 2F, or 2G
of this appendix to take into account velocity decay near the stack or
duct wall.
2.2 The method contains two possible procedures: a calculational
approach which derives an adjustment factor from velocity measurements
and a default procedure which assigns a generic adjustment factor based
on the construction of the stack or duct.
2.2.1 The calculational procedure derives a wall effects adjustment
factor from velocity measurements taken using Method 2, 2F, or 2G at 16
(or more) traverse points specified under Method 1 of this appendix and
a total of eight (or more) wall effects traverse points specified under
this method. The calculational procedure based on velocity measurements
is not applicable for horizontal circular ducts where build-up of
particulate matter or other material in the bottom of the duct is
present.
2.2.2 A default wall effects adjustment factor of 0.9900 for brick
and mortar stacks and 0.9950 for all other types of stacks and ducts may
be used without taking wall effects measurements in a stack or duct.
2.3 When the calculational procedure is conducted as part of a
relative accuracy test audit (RATA) or other multiple-run test
procedure, the wall effects adjustment factor derived from a single
traverse (i.e., single RATA run) may be applied to all runs of the same
RATA without repeating the wall effects measurements. Alternatively,
wall effects adjustment factors may be derived for several traverses and
an average wall effects adjustment factor applied to all runs of the
same RATA.

3.0 Definitions.

3.1 Complete wall effects traverse means a traverse in which
measurements are taken at drem (see section 3.3) and at 1-in.
intervals in each of the four Method 1 equal-area sectors closest to the
wall, beginning not farther than 4 in. (10.2 cm) from the wall and
extending either (1) across the entire width of the Method 1 equal-area
sector or (2) for stacks or ducts where this width exceeds 12 in. (30.5
cm) (i.e., stacks or ducts greater than or equal to 15.6 ft [4.8 m] in
diameter), to a distance of not less than 12 in. (30.5 cm) from the
wall. Note: Because this method specifies that measurements must be
taken at whole number multiples of 1 in. from a stack or duct wall, for
clarity numerical quantities in this method are expressed in English
units followed by metric units in parentheses. To enhance readability,
hyphenated terms such as ``1-in. intervals'' or ``1-in. incremented,''
are expressed in English units only.
3.2 dlast Depending on context, dlast means either (1) the distance
from the wall of the last 1-in. incremented wall effects traverse point
or (2) the traverse point located at that distance (see Figure 2H-2).
3.3 drem Depending on context, drem means either (1) the distance
from the wall of the centroid of the area between dlast and the interior
edge of the Method 1 equal-area sector closest to the wall or (2) the
traverse point located at that distance (see Figure 2H-2).
3.4 ``May,'' ``Must,'' ``Shall,'' ``Should,'' and the imperative
form of verbs.
3.4.1 ``May'' is used to indicate that a provision of this method is
optional.
3.4.2 ``Must,'' ``Shall,'' and the imperative form of verbs (such as
``record'' or ``enter'') are used to indicate that a provision of this
method is mandatory.
3.4.3 ``Should'' is used to indicate that a provision of this method
is not mandatory but is highly recommended as good practice.
3.5 Method 1 refers to 40 CFR part 60, appendix A, ``Method 1--
Sample and velocity traverses for stationary sources.''
3.6 Method 1 exterior equal-area sector and Method 1 equal-area
sector closest to the wall mean any one of the four equal-area sectors
that are closest to the wall for a circular stack or duct laid out in
accordance with section 2.3.1 of Method 1 (see Figure 2H-1).
3.7 Method 1 interior equal-area sector means any of the equal-area
sectors other than the Method 1 exterior equal-area sectors (as defined
in section 3.6) for a circular stack or duct laid out in accordance with
section 2.3.1 of Method 1 (see Figure 2H-1).
3.8 Method 1 traverse point and Method 1 equal-area traverse point
mean a traverse point located at the centroid of an equal-area sector of
a circular stack laid out in accordance with section 2.3.1 of Method 1.
3.9 Method 2 refers to 40 CFR part 60, appendix A, ``Method 2--
Determination of stack gas velocity and volumetric flow rate (Type S
pitot tube).''
3.10 Method 2F refers to 40 CFR part 60, appendix A, ``Method 2F--
Determination of stack gas velocity and volumetric flow rate with three-
dimensional probes.''

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3.11 Method 2G refers to 40 CFR part 60, appendix A, ``Method 2G--
Determination of stack gas velocity and volumetric flow rate with two-
dimensional probes.''
3.12 1-in. incremented wall effects traverse point means any of the
wall effects traverse points that are located at 1-in. intervals, i.e.,
traverse points d1 through dlast (see Figure 2H-2).
3.13 Partial wall effects traverse means a traverse in which
measurements are taken at fewer than the number of traverse points
required for a ``complete wall effects traverse'' (as defined in section
3.1), but are taken at a minimum of two traverse points in each Method 1
equal-area sector closest to the wall, as specified in section 8.2.2.
3.14 Relative accuracy test audit (RATA) is a field test procedure
performed in a stack or duct in which a series of concurrent
measurements of the same stack gas stream is taken by a reference method
and an installed monitoring system. A RATA usually consists of series of
9 to 12 sets of such concurrent measurements, each of which is referred
to as a RATA run. In a volumetric flow RATA, each reference method run
consists of a complete traverse of the stack or duct.
3.15 Wall effects-unadjusted average velocity means the average
stack gas velocity, not accounting for velocity decay near the wall, as
determined in accordance with Method 2, 2F, or 2G for a Method 1
traverse consisting of 16 or more points.
3.16 Wall effects-adjusted average velocity means the average stack
gas velocity, taking into account velocity decay near the wall, as
calculated from measurements at 16 or more Method 1 traverse points and
at the additional wall effects traverse points specified in this method.
3.17 Wall effects traverse point means a traverse point located in
accordance with sections 8.2.2 or 8.2.3 of this method.

4.0 Interferences [Reserved]

5.0 Safety

5.1 This method may involve hazardous materials, operations, and
equipment. This method does not purport to address all of the health and
safety considerations associated with its use. It is the responsibility
of the user of this method to establish appropriate health and safety
practices and to determine the applicability of occupational health and
safety regulatory requirements prior to performing this method.

6.0 Equipment and Supplies

6.1 The provisions pertaining to equipment and supplies in the
method that is used to take the traverse point measurements (i.e.,
Method 2, 2F, or 2G) are applicable under this method.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection and Analysis

8.1 Default Wall Effects Adjustment Factors. A default wall effects
adjustment factor of 0.9900 for brick and mortar stacks and 0.9950 for
all other types of stacks and ducts may be used without conducting the
following procedures.
8.2 Traverse Point Locations. Determine the location of the Method 1
traverse points in accordance with section 8.2.1 and the location of the
traverse points for either a partial wall effects traverse in accordance
with section 8.2.2 or a complete wall effects traverse in accordance
with section 8.2.3.
8.2.1 Method 1 equal-area traverse point locations. Determine the
location of the Method 1 equal-area traverse points for a traverse
consisting of 16 or more points using Table 1-2 (Location of Traverse
Points in Circular Stacks) of Method 1.
8.2.2 Partial wall effects traverse. For a partial wall effects
traverse, measurements must be taken at a minimum of the following two
wall effects traverse point locations in all four Method 1 equal-area
sectors closest to the wall: (1) 1 in. (2.5 cm) from the wall (except as
provided in section 8.2.2.1) and (2) drem, as determined
using Equation 2H-1 or 2H-2 (see section 8.2.2.2).
8.2.2.1 If the probe cannot be positioned at 1 in. (2.5 cm) from the
wall (e.g., because of insufficient room to withdraw the probe shaft) or
if velocity pressure cannot be detected at 1 in. (2.5 cm) from the wall
(for any reason other than build-up of particulate matter in the bottom
of a duct), take measurements at the 1-in. incremented wall effects
traverse point closest to the wall where the probe can be positioned and
velocity pressure can be detected.
8.2.2.2 Calculate the distance of drem from the wall to
within \1/4\ in. (6.4 mm) using Equation 2H-1 or Equation 2H-2 (for a
16-point traverse).
[GRAPHIC] [TIFF OMITTED] TR14MY99.074

Where:

r = the stack or duct radius determined from direct measurement of the
stack or duct diameter in accordance with section 8.6 of
Method 2F or Method 2G, in. (cm);
p = the number of Method 1 equal-area traverse points on a diameter, p
8 (e.g., for a 16-point traverse, p = 8); dlast and
drem are defined in sections 3.2 and 3.3 respectively, in.
(cm).

For a 16-point Method 1 traverse, Equation 2H-1 becomes:

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8.2.2.3 Measurements may be taken at any number of additional wall
effects traverse points, with the following provisions.
(a) dlast must not be closer to the center of the stack or duct than
the distance of the interior edge (boundary), db, of the Method 1 equal-
area sector closest to the wall (see Figure 2H-2 or 2H-3). That is,

Where:
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Table 2H-1 shows db as a function of the stack or duct radius, r, for
traverses ranging from 16 to 48 points (i.e., for values of p ranging
from 8 to 24).
(b) Each point must be located at a distance that is a whole number
(e.g., 1, 2, 3) multiple of 1 in. (2.5 cm).
(c) Points do not have to be located at consecutive 1-in. intervals.
That is, one or more 1-in. incremented points may be skipped. For
example, it would be acceptable for points to be located at 1 in. (2.5
cm), 3 in. (7.6 cm), 5 in. (12.7 cm), dlast, and drem; or at 1 in. (2.5
cm), 2 in. (5.1 cm), 4 in. (10.2 cm), 7 in. (17.8 cm), dlast, and drem.
Follow the instructions in section 8.7.1.2 of this method for recording
results for wall effects traverse points that are skipped. It should be
noted that the full extent of velocity decay may not be accounted for if
measurements are not taken at all 1-in. incremented points close to the
wall.
8.2.3 Complete wall effects traverse. For a complete wall effects
traverse, measurements must be taken at the following points in all four
Method 1 equal-area sectors closest to the wall.
(a) The 1-in. incremented wall effects traverse point closest to the
wall where the probe can be positioned and velocity can be detected, but
no farther than 4 in. (10.2 cm) from the wall.
(b) Every subsequent 1-in. incremented wall effects traverse point
out to the interior edge of the Method 1 equal-area sector or to 12 in.
(30.5 cm) from the wall, whichever comes first. Note: In stacks or ducts
with diameters greater than 15.6 ft (4.8 m) the interior edge of the
Method 1 equal-area sector is farther from the wall than 12 in. (30.5
cm).
(c) drem, as determined using Equation 2H-1 or 2H-2 (as
applicable). Note: For a complete traverse of a stack or duct with a
diameter less than 16.5 ft (5.0 m), the distance between drem
and dlast is less than or equal to \1/2\ in. (12.7 mm). As
discussed in section 8.2.4.2, when the distance between drem
and dlast is less than or equal to \1/2\ in. (12.7 mm), the
velocity measured at dlast may be used for drem.
Thus, it is not necessary to calculate the distance of drem
or to take measurements at drem when conducting a complete
traverse of a stack or duct with a diameter less than 16.5 ft (5.0 m).
8.2.4 Special considerations. The following special considerations
apply when the distance between traverse points is less than or equal to
\1/2\ in. (12.7 mm).
8.2.4.1 A wall effects traverse point and the Method 1 traverse
point. If the distance between a wall effects traverse point and the
Method 1 traverse point is less than or equal to \1/2\ in. (12.7 mm),
taking measurements at both points is allowed but not required or
recommended; if measurements are taken at only one point, take the
measurements at the point that is farther from the wall and use the
velocity obtained at that point as the value for both points (see
sections 8.2.3 and 9.2 for related requirements).
8.2.4.2 drem and dlast. If the distance
between drem and dlast is less than or equal to
\1/2\ in. (12.7 mm), taking measurements at drem is allowed
but not required or recommended; if measurements are not taken at
drem, the measured velocity value at dlast must be
used as the value for both dlast and drem.
8.3 Traverse Point Sampling Order and Probe Selection. Determine the
sampling order of the Method 1 and wall effects traverse points and
select the appropriate probe for the measurements, taking into account
the following considerations.
8.3.1 Traverse points on any radius may be sampled in either
direction (i.e., from the wall toward the center of the stack or duct,
or vice versa).
8.3.2 To reduce the likelihood of velocity variations during the
time of the traverse and the attendant potential impact on the wall
effects-adjusted and unadjusted average velocities, the following
provisions of this method shall be met.
8.3.2.1 Each complete set of Method 1 and wall effects traverse
points accessed from the same port shall be sampled without
interruption. Unless traverses are performed simultaneously in all ports
using separate probes at each port, this provision disallows first
sampling all Method 1 points at all ports and then sampling all the wall
effects points.
8.3.2.2 The entire integrated Method 1 and wall effects traverse
across all test ports shall be as short as practicable, consistent with
the measurement system response time

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(see section 8.4.1.1) and sampling (see section 8.4.1.2) provisions of
this method.
8.3.3 It is recommended but not required that in each Method 1
equal-area sector closest to the wall, the Method 1 equal-area traverse
point should be sampled in sequence between the adjacent wall effects
traverse points. For example, for the traverse point configuration shown
in Figure 2H-2, it is recommended that the Method 1 equal-area traverse
point be sampled between dlast and drem. In this
example, if the traverse is conducted from the wall toward the center of
the stack or duct, it is recommended that measurements be taken at
points in the following order: d1, d2,
dlast, the Method 1 traverse point, drem, and then
at the traverse points in the three Method 1 interior equal-area
sectors.
8.3.4 The same type of probe must be used to take measurements at
all Method 1 and wall effects traverse points. However, different copies
of the same type of probe may be used at different ports (e.g., Type S
probe 1 at port A, Type S probe 2 at port B) or at different traverse
points accessed from a particular port (e.g., Type S probe 1 for Method
1 interior traverse points accessed from port A, Type S probe 2 for wall
effects traverse points and the Method 1 exterior traverse point
accessed from port A). The identification number of the probe used to
obtain measurements at each traverse point must be recorded.
8.4 Measurements at Method 1 and Wall Effects Traverse Points.
Conduct measurements at Method 1 and wall effects traverse points in
accordance with Method 2, 2F, or 2G and in accordance with the
provisions of the following subsections (some of which are included in
Methods 2F and 2G but not in Method 2), which are particularly important
for wall effects testing.
8.4.1 Probe residence time at wall effects traverse points. Due to
the steep temperature and pressure gradients that can occur close to the
wall, it is very important for the probe residence time (i.e., the total
time spent at a traverse point) to be long enough to ensure collection
of representative temperature and pressure measurements. The provisions
of Methods 2F and 2G in the following subsections shall be observed.
8.4.1.1 System response time. Determine the response time of each
probe measurement system by inserting and positioning the ``cold'' probe
(at ambient temperature and pressure) at any Method 1 traverse point.
Read and record the probe differential pressure, temperature, and
elapsed time at 15-second intervals until stable readings for both
pressure and temperature are achieved. The response time is the longer
of these two elapsed times. Record the response time.
8.4.1.2 Sampling. At the start of testing in each port (i.e., after
a probe has been inserted into the stack gas stream), allow at least the
response time to elapse before beginning to take measurements at the
first traverse point accessed from that port. Provided that the probe is
not removed from the stack gas stream, measurements may be taken at
subsequent traverse points accessed from the same test port without
waiting again for the response time to elapse.
8.4.2 Temperature measurement for wall effects traverse points.
Either (1) take temperature measurements at each wall effects traverse
point in accordance with the applicable provisions of Method 2, 2F, or
2G; or (2) use the temperature measurement at the Method 1 traverse
point closest to the wall as the temperature measurement for all the
wall effects traverse points in the corresponding equal-area sector.
8.4.3 Non-detectable velocity pressure at wall effects traverse
points. If the probe cannot be positioned at a wall effects traverse
point or if no velocity pressure can be detected at a wall effects
point, measurements shall be taken at the first subsequent wall effects
traverse point farther from the wall where velocity can be detected.
Follow the instructions in section 8.7.1.2 of this method for recording
results for wall effects traverse points where velocity pressure cannot
be detected. It should be noted that the full extent of velocity decay
may not be accounted for if measurements are not taken at the 1-in.
incremented wall effects traverse points closest to the wall.
8.5 Data Recording. For each wall effects and Method 1 traverse
point where measurements are taken, record all pressure, temperature,
and attendant measurements prescribed in section 3 of Method 2 or
section 8.0 of Method 2F or 2G, as applicable.
8.6 Point Velocity Calculation. For each wall effects and Method 1
traverse point, calculate the point velocity value (vi) in accordance
with sections 12.1 and 12.2 of Method 2F for tests using Method 2F and
in accordance with sections 12.1 and 12.2 of Method 2G for tests using
Method 2 and Method 2G. (Note that the term (vi) in this method
corresponds to the term (va(i)) in Methods 2F and 2G.) When the
equations in the indicated sections of Method 2G are used in deriving
point velocity values for Method 2 tests, set the value of the yaw
angles appearing in the equations to 0[deg].
8.7 Tabulating Calculated Point Velocity Values for Wall Effects
Traverse Points. Enter the following values in a hardcopy or electronic
form similar to Form 2H-1 (for 16-point Method 1 traverses) or Form 2H-2
(for Method 1 traverses consisting of more than 16 points). A separate
form must be completed for each of the four Method 1 equal-area sectors
that are closest to the wall.
(a) Port ID (e.g., A, B, C, or D)
(b) Probe type
(c) Probe ID

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(d) Stack or duct diameter in ft (m) (determined in accordance with
section 8.6 of Method 2F or Method 2G)
(e) Stack or duct radius in in. (cm)
(f) Distance from the wall of wall effects traverse points at 1-in.
intervals, in ascending order starting with 1 in. (2.5 cm) (column A of
Form 2H-1 or 2H-2)
(g) Point velocity values (vd) for 1-in. incremented traverse points
(see section 8.7.1), including dlast (see section 8.7.2)
(h) Point velocity value (vdrem) at drem (see section 8.7.3).
8.7.1 Point velocity values at wall effects traverse points other
than dlast. For every 1-in. incremented wall effects traverse point
other than dlast, enter in column B of Form 2H-1 or 2H-2 either the
velocity measured at the point (see section 8.7.1.1) or the velocity
measured at the first subsequent traverse point farther from the wall
(see section 8.7.1.2). A velocity value must be entered in column B of
Form 2H-1 or 2H-2 for every 1-in. incremented traverse point from d1
(representing the wall effects traverse point 1 in. [2.5 cm] from the
wall) to dlast.
8.7.1.1 For wall effects traverse points where the probe can be
positioned and velocity pressure can be detected, enter the value
obtained in accordance with section 8.6.
8.7.1.2 For wall effects traverse points that were skipped [see
section 8.2.2.3(c)] and for points where the probe cannot be positioned
or where no velocity pressure can be detected, enter the value obtained
at the first subsequent traverse point farther from the wall where
velocity pressure was detected and measured and follow the entered value
with a ``flag,'' such as the notation ``NM,'' to indicate that ``no
measurements'' were actually taken at this point.
8.7.2 Point velocity value at dlast. For dlast, enter in column B of
Form 2H-1 or 2H-2 the measured value obtained in accordance with section
8.6.
8.7.3 Point velocity value (vdrem) at drem. Enter the point velocity
value obtained at drem in column G of row 4a in Form 2H-1 or 2H-2. If
the distance between drem and dlast is less than or equal to \1/2\ in.
(12.7 mm), the measured velocity value at dlast may be used as the value
at drem (see section 8.2.4.2).

9.0 Quality Control.

9.1 Particulate Matter Build-up in Horizontal Ducts. Wall effects
testing of horizontal circular ducts should be conducted only if build-
up of particulate matter or other material in the bottom of the duct is
not present.
9.2 Verifying Traverse Point Distances. In taking measurements at
wall effects traverse points, it is very important for the probe impact
pressure port to be positioned as close as practicable to the traverse
point locations in the gas stream. For this reason, before beginning
wall effects testing, it is important to calculate and record the
traverse point positions that will be marked on each probe for each
port, taking into account the distance that each port nipple (or probe
mounting flange for automated probes) extends out of the stack and any
extension of the port nipple (or mounting flange) into the gas stream.
To ensure that traverse point positions are properly identified, the
following procedures should be performed on each probe used.
9.2.1 Manual probes. Mark the probe insertion distance of the wall
effects and Method 1 traverse points on the probe sheath so that when a
mark is aligned with the outside face of the stack port, the probe
impact port is located at the calculated distance of the traverse point
from the stack inside wall. The use of different colored marks is
recommended for designating the wall effects and Method 1 traverse
points. Before the first use of each probe, check to ensure that the
distance of each mark from the center of the probe impact pressure port
agrees with the previously calculated traverse point positions to within
\1/4\ in. (6.4 mm).
9.2.2 Automated probe systems. For automated probe systems that
mechanically position the probe head at prescribed traverse point
positions, activate the system with the probe assemblies removed from
the test ports and sequentially extend the probes to the programmed
location of each wall effects traverse point and the Method 1 traverse
points. Measure the distance between the center of the probe impact
pressure port and the inside of the probe assembly mounting flange for
each traverse point. The measured distances must agree with the
previously calculated traverse point positions to within \1/4\ in. (6.4
mm).
9.3 Probe Installation. Properly sealing the port area is
particularly important in taking measurements at wall effects traverse
points. For testing involving manual probes, the area between the probe
sheath and the port should be sealed with a tightly fitting flexible
seal made of an appropriate material such as heavy cloth so that leakage
is minimized. For automated probe systems, the probe assembly mounting
flange area should be checked to verify that there is no leakage.
9.4 Velocity Stability. This method should be performed only when
the average gas velocity in the stack or duct is relatively constant
over the duration of the test. If the average gas velocity changes
significantly during the course of a wall effects test, the test results
should be discarded.

10.0 Calibration

10.1 The calibration coefficient(s) or curves obtained under Method
2, 2F, or 2G and used to perform the Method 1 traverse are applicable
under this method.

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11.0 Analytical Procedure

11.1 Sample collection and analysis are concurrent for this method
(see section 8).

12.0 Data Analysis and Calculations

12.1 The following calculations shall be performed to obtain a wall
effects adjustment factor (WAF) from (1) the wall effects-unadjusted
average velocity (T4avg), (2) the replacement velocity (vej) for each of
the four Method 1 sectors closest to the wall, and (3) the average stack
gas velocity that accounts for velocity decay near the wall (vavg).
12.2 Nomenclature. The following terms are listed in the order in
which they appear in Equations 2H-5 through 2H-21.

vavg = the average stack gas velocity, unadjusted for wall effects,
actual ft/sec (m/sec);
vii = stack gas point velocity value at Method 1 interior equal-area
sectors, actual ft/sec (m/sec);
vej = stack gas point velocity value, unadjusted for wall effects, at
Method 1 exterior equal-area sectors, actual ft/sec (m/sec);
i = index of Method 1 interior equal-area traverse points;
j = index of Method 1 exterior equal-area traverse points;
n = total number of traverse points in the Method 1 traverse;
vdecd = the wall effects decay velocity for a sub-sector located between
the traverse points at distances d^-1 (in metric
units, d^-2.5) and d from the wall, actual ft/sec
(m/sec);
vd = the measured stack gas velocity at distance d from the wall, actual
ft/sec (m/sec); Note: v0 = 0;
d = the distance of a 1-in. incremented wall effects traverse point from
the wall, for traverse points d1 through dlast, in. (cm);
Ad = the cross-sectional area of a sub-sector located between the
traverse points at distances d^-1 (in metric
units, d^-2.5) and d from the wall, in.\2\ (cm\2\)
( e.g., sub-sector A2 shown in Figures 2H-3 and 2H-
4);
r = the stack or duct radius, in. (cm);
Qd = the stack gas volumetric flow rate for a sub-sector located between
the traverse points at distances d^-1 (in metric
units, d^-2.5) and d from the wall, actual ft-
in.\2\/sec (m-cm\2\/sec);
Qd1dlast = the total stack gas volumetric flow rate for all
sub-sectors located between the wall and dlast, actual ft-
in.\2\/sec (m-cm\2\/sec);
dlast = the distance from the wall of the last 1-in. incremented wall
effects traverse point, in. (cm);
Adrem = the cross-sectional area of the sub-sector located between dlast
and the interior edge of the Method 1 equal-area sector
closest to the wall, in.\2\ (cm\2\) (see Figure 2H-4);
p = the number of Method 1 traverse points per diameter, p8
(e.g., for a 16-point traverse, p = 8);
drem = the distance from the wall of the centroid of the area between
dlast and the interior edge of the Method 1 equal-area sector
closest to the wall, in. (cm);
Qdrem = the total stack gas volumetric flow rate for the sub-sector
located between dlast and the interior edge of the Method 1
equal-area sector closest to the wall, actual ft-in.\2\/sec
(m-cm\2\/sec);
vdrem = the measured stack gas velocity at distance drem from the wall,
actual ft/sec (m/sec);
QT = the total stack gas volumetric flow rate for the Method 1 equal-
area sector closest to the wall, actual ft-in.\2\/sec (m-
cm\2\/sec);
vej = the replacement stack gas velocity for the Method 1 equal-area
sector closest to the wall, i.e., the stack gas point velocity
value, adjusted for wall effects, for the j\th\ Method 1
equal-area sector closest to the wall, actual ft/sec (m/sec);
vavg = the average stack gas velocity that accounts for velocity decay
near the wall, actual ft/sec (m/sec);
WAF = the wall effects adjustment factor derived from vavg and vavg for
a single traverse, dimensionless;
vfinal = the final wall effects-adjusted average stack gas velocity that
replaces the unadjusted average stack gas velocity obtained
using Method 2, 2F, or 2G for a field test consisting of a
single traverse, actual ft/sec (m/sec);
WAF = the wall effects adjustment factor that is applied to the average
velocity, unadjusted for wall effects, in order to obtain the
final wall effects-adjusted stack gas velocity, vfinal or,
vfinal(k), dimensionless;
vfinal(k) = the final wall effects-adjusted average stack gas velocity
that replaces the unadjusted average stack gas velocity
obtained using Method 2, 2F, or 2G on run k of a RATA or other
multiple-run field test procedure, actual ft/sec (m/sec);
vavg(k) = the average stack gas velocity, obtained on run k of a RATA or
other multiple-run procedure, unadjusted for velocity decay
near the wall, actual ft/sec (m/sec);
k=index of runs in a RATA or other multiple-run procedure.

12.3 Calculate the average stack gas velocity that does not account
for velocity decay near the wall (vavg) using Equation 2H-5.

[[Page 134]]

[GRAPHIC] [TIFF OMITTED] TR14MY99.077

(Note that vavg in Equation 2H-5 is the same as v(a)avg in Equations 2F-
9 and 2G-8 in Methods 2F and 2G, respectively.)
For a 16-point traverse, Equation 2H-5 may be written as follows:
[GRAPHIC] [TIFF OMITTED] TR14MY99.078

12.4 Calculate the replacement velocity, vej, for each of the four
Method 1 equal-area sectors closest to the wall using the procedures
described in sections 12.4.1 through 12.4.8. Forms 2H-1 and 2H-2 provide
sample tables that may be used in either hardcopy or spreadsheet format
to perform the calculations described in sections 12.4.1 through 12.4.8.
Forms 2H-3 and 2H-4 provide examples of Form 2H-1 filled in for partial
and complete wall effects traverses.
12.4.1 Calculate the average velocity (designated the ``decay
velocity,'' vdecd) for each sub-sector located between the
wall and dlast (see Figure 2H-3) using Equation 2H-7.
[GRAPHIC] [TIFF OMITTED] TR14MY99.079

For each line in column A of Form 2H-1 or 2H-2 that contains a value of
d, enter the corresponding calculated value of vdecd in
column C.
12.4.2 Calculate the cross-sectional area between the wall and the
first 1-in. incremented wall effects traverse point and between
successive 1-in. incremented wall effects traverse points, from the wall
to dlast (see Figure 2H-3), using Equation 2H-8.
[GRAPHIC] [TIFF OMITTED] TR14MY99.080

For each line in column A of Form 2H-1 or 2H-2 that contains a value of
d, enter the value of the expression \1/4\ (r - d + 1)\2\ in
column D, the value of the expression \1/4\ (r - d)\2\ in
column E, and the value of Ad in column F. Note that Equation
2H-8 is designed for use only with English units (in.). If metric units
(cm) are used, the first term, \1/4\ (r - d + 1)\2\, must be
changed to \1/4\ (r - d + 2.5)\2\. This change must also be
made in column D of Form 2H-1 or 2H-2.
12.4.3 Calculate the volumetric flow through each cross-sectional
area derived in section 12.4.2 by multiplying the values of vdecd,
derived according to section 12.4.1, by the cross-sectional areas
derived in section 12.4.2 using Equation 2H-9.
[GRAPHIC] [TIFF OMITTED] TR14MY99.081

For each line in column A of Form 2H-1 or 2H-2 that contains a value of
d, enter the corresponding calculated value of Qd in column G.
12.4.4 Calculate the total volumetric flow through all sub-sectors
located between the wall and dlast, using Equation 2H-10.
[GRAPHIC] [TIFF OMITTED] TN09JY99.003

Enter the calculated value of Qd1cdlast in line 3 of column G
of Form 2H-1 or 2H-2.
12.4.5 Calculate the cross-sectional area of the sub-sector located
between dlast and the interior edge of the Method 1 equal-area sector
(e.g., sub-sector Adrem shown in Figures 2H-3 and 2H-4) using Equation
2H-11.
[GRAPHIC] [TIFF OMITTED] TR14MY99.083

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For a 16-point traverse (eight points per diameter), Equation 2H-11 may
be written as follows:
[GRAPHIC] [TIFF OMITTED] TR14MY99.084

Enter the calculated value of Adrem in line 4b of column G of
Form 2H-1 or 2H-2.
12.4.6 Calculate the volumetric flow for the sub-sector located
between dlast and the interior edge of the Method 1 equal-
area sector, using Equation 2H-13.
[GRAPHIC] [TIFF OMITTED] TR14MY99.085

In Equation 2H-13, vdrem is either (1) the measured velocity
value at drem or (2) the measured velocity at
dlast, if the distance between drem and
dlast is less than or equal to \1/2\ in. (12.7 mm) and no
velocity measurement is taken at drem (see section 8.2.4.2).
Enter the calculated value of Qdrem in line 4c of column G of
Form 2H-1 or 2H-2.
12.4.7 Calculate the total volumetric flow for the Method 1 equal-
area sector closest to the wall, using Equation 2H-14.
[GRAPHIC] [TIFF OMITTED] TR14MY99.086

Enter the calculated value of QT in line 5a of column G of
Form 2H-1 or 2H-2.
12.4.8 Calculate the wall effects-adjusted replacement velocity
value for the Method 1 equal-area sector closest to the wall, using
Equation 2H-15.
[GRAPHIC] [TIFF OMITTED] TR14MY99.087

For a 16-point traverse (eight points per diameter), Equation 2H-15 may
be written as follows:
[GRAPHIC] [TIFF OMITTED] TR14MY99.088

Enter the calculated value of vej in line 5B of column G of Form 2H-1 or
2H-2.
12.5 Calculate the wall effects-adjusted average velocity, vavg, by
replacing the four values of vej shown in Equation 2H-5 with
the four wall effects-adjusted replacement velocity
values,vej, calculated according to section 12.4.8, using
Equation 2H-17.
[GRAPHIC] [TIFF OMITTED] TR14MY99.089

For a 16-point traverse, Equation 2H-17 may be written as follows:
[GRAPHIC] [TIFF OMITTED] TR14MY99.090

12.6 Calculate the wall effects adjustment factor, WAF, using
Equation 2H-19.
[GRAPHIC] [TIFF OMITTED] TR14MY99.091

12.6.1 Partial wall effects traverse. If a partial wall effects
traverse (see section 8.2.2) is conducted, the value obtained from
Equation 2H-19 is acceptable and may be reported as the wall effects
adjustment factor provided that the value is greater than or equal to
0.9800. If the value is less than 0.9800, it shall not be used and a
wall effects adjustment factor of 0.9800 may be used instead.
12.6.2 Complete wall effects traverse. If a complete wall effects
traverse (see section 8.2.3) is conducted, the value obtained from
Equation 2H-19 is acceptable and may be reported as the wall effects
adjustment factor provided that the value is greater than or equal to
0.9700. If the value is less than 0.9700, it shall not be used and a
wall effects adjustment factor of 0.9700 may be used instead. If the
wall effects adjustment factor for a particular stack or duct is less
than 0.9700, the tester may (1) repeat the wall effects test, taking
measurements at more Method 1 traverse points and (2) recalculate the
wall effects adjustment factor from these measurements, in an attempt to
obtain a wall effects adjustment factor that meets the 0.9700
specification and completely characterizes the wall effects.
12.7 Applying a Wall Effects Adjustment Factor. A default wall
effects adjustment factor, as specified in section 8.1, or a calculated
wall effects adjustment factor meeting the requirements of section
12.6.1 or 12.6.2

[[Page 136]]

may be used to adjust the average stack gas velocity obtained using
Methods 2, 2F, or 2G to take into account velocity decay near the wall
of circular stacks or ducts. Default wall effects adjustment factors
specified in section 8.1 and calculated wall effects adjustment factors
that meet the requirements of section 12.6.1 and 12.6.2 are summarized
in Table 2H-2.
12.7.1 Single-run tests. Calculate the final wall effects-adjusted
average stack gas velocity for field tests consisting of a single
traverse using Equation 2H-20.
[GRAPHIC] [TIFF OMITTED] TR14MY99.092

The wall effects adjustment factor, WAF, shown in Equation 2H-20, may be
(1) a default wall effects adjustment factor, as specified in section
8.1, or (2) a calculated adjustment factor that meets the specifications
in sections 12.6.1 or 12.6.2. If a calculated adjustment factor is used
in Equation 2H-20, the factor must have been obtained during the same
traverse in which vavg was obtained.
12.7.2 RATA or other multiple run test procedure. Calculate the
final wall effects-adjusted average stack gas velocity for any run k of
a RATA or other multiple-run procedure using Equation 2H-21.
[GRAPHIC] [TIFF OMITTED] TR14MY99.093

The wall effects adjustment factor, WAF, shown in Equation 2H-21 may be
(1) a default wall effects adjustment factor, as specified in section
8.1; (2) a calculated adjustment factor (meeting the specifications in
sections 12.6.1 or 12.6.2) obtained from any single run of the RATA that
includes run k; or (3) the arithmetic average of more than one WAF (each
meeting the specifications in sections 12.6.1 or 12.6.2) obtained
through wall effects testing conducted during several runs of the RATA
that includes run k. If wall effects adjustment factors (meeting the
specifications in sections 12.6.1 or 12.6.2) are determined for more
than one RATA run, the arithmetic average of all of the resulting
calculated wall effects adjustment factors must be used as the value of
WAF and applied to all runs of that RATA. If a calculated, not a
default, wall effects adjustment factor is used in Equation 2H-21, the
average velocity unadjusted for wall effects, vavg(k) must be
obtained from runs in which the number of Method 1 traverse points
sampled does not exceed the number of Method 1 traverse points in the
runs used to derive the wall effects adjustment factor, WAF, shown in
Equation 2H-21.
12.8 Calculating Volumetric Flow Using Final Wall Effects-Adjusted
Average Velocity Value. To obtain a stack gas flow rate that accounts
for velocity decay near the wall of circular stacks or ducts, replace
vs in Equation 2-10 in Method 2, or va(avg) in
Equations 2F-10 and 2F-11 in Method 2F, or va(avg) in
Equations 2G-9 and 2G-10 in Method 2G with one of the following.
12.8.1 For single-run test procedures, use the final wall effects-
adjusted average stack gas velocity, vfinal, calculated according to
Equation 2H-20.
12.8.2 For RATA and other multiple run test procedures, use the
final wall effects-adjusted average stack gas velocity, vfinal(k),
calculated according to Equation 2H-21.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Reporting

16.1 Field Test Reports. Field test reports shall be submitted to
the Agency according to the applicable regulatory requirements. When
Method 2H is performed in conjunction with Method 2, 2F, or 2G to derive
a wall effects adjustment factor, a single consolidated Method 2H/2F (or
2H/2G) field test report should be prepared. At a minimum, the
consolidated field test report should contain (1) all of the general
information, and data for Method 1 points, specified in section 16.0 of
Method 2F (when Method 2H is used in conjunction with Method 2F) or
section 16.0 of Method 2G (when Method 2H is used in conjunction with
Method 2 or 2G) and (2) the additional general information, and data for
Method 1 points and wall effects points, specified in this section (some
of which are included in section 16.0 of Methods 2F and 2G and are
repeated in this section to ensure complete reporting for wall effects
testing).
16.1.1 Description of the source and site. The field test report
should include the descriptive information specified in section 16.1.1
of Method 2F (when using Method 2F) or 2G (when using either Method 2 or
2G). It should also include a description of the stack or duct's
construction material along with the diagram showing the dimensions of
the stack or duct at the test port elevation prescribed in Methods 2F
and 2G. The diagram should indicate the location of all wall effects
traverse points where measurements were taken as well as the Method 1
traverse points. The diagram should provide a unique identification
number for each wall effects and Method 1 traverse point, its distance
from the wall, and its location relative to the probe entry ports.
16.1.2 Field test forms. The field test report should include a copy
of Form 2H-1, 2H-2, or an equivalent for each Method 1 exterior equal-
area sector.
16.1.3 Field test data. The field test report should include the
following data for the Method 1 and wall effects traverse.
16.1.3.1 Data for each traverse point. The field test report should
include the values

[[Page 137]]

specified in section 16.1.3.2 of Method 2F (when using Method 2F) or 2G
(when using either Method 2 or 2G) for each Method 1 and wall effects
traverse point. The provisions of section 8.4.2 of Method 2H apply to
the temperature measurements reported for wall effects traverse points.
For each wall effects and Method 1 traverse point, the following values
should also be included in the field test report.
(a) Traverse point identification number for each Method 1 and wall
effects traverse point.
(b) Probe type.
(c) Probe identification number.
(d) Probe velocity calibration coefficient (i.e., Cp when Method 2
or 2G is used; F2 when Method 2F is used).

For each Method 1 traverse point in an exterior equal-area sector,
the following additional value should be included.
(e) Calculated replacement velocity, vej, accounting for wall
effects.
16.1.3.2 Data for each run. The values specified in section 16.1.3.3
of Method 2F (when using Method 2F) or 2G (when using either Method 2 or
2G) should be included in the field test report once for each run. The
provisions of section 12.8 of Method 2H apply for calculating the
reported gas volumetric flow rate. In addition, the following Method 2H
run values should also be included in the field test report.
(a) Average velocity for run, accounting for wall effects, vavg.
(b) Wall effects adjustment factor derived from a test run, WAF.
16.1.3.3 Data for a complete set of runs. The values specified in
section 16.1.3.4 of Method 2F (when using Method 2F) or 2G (when using
either Method 2 or 2G) should be included in the field test report once
for each complete set of runs. In addition, the field test report should
include the wall effects adjustment factor, WAF, that is applied in
accordance with section 12.7.1 or 12.7.2 to obtain the final wall
effects-adjusted average stack gas velocity vfinal or vfinal(k).
16.1.4 Quality assurance and control. Quality assurance and control
procedures, specifically tailored to wall effects testing, should be
described.
16.2 Reporting a Default Wall Effects Adjustment Factor. When a
default wall effects adjustment factor is used in accordance with
section 8.1 of this method, its value and a description of the stack or
duct's construction material should be reported in lieu of submitting a
test report.

17.0 References.

[[Page 138]]

(16) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Eight Spherical Probes,''
Prepared for the U.S. Environmental Protection Agency under IAG No.
DW13938432-01-0.
(17) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Four DAT Probes,''
Prepared for the U.S. Environmental Protection Agency under IAG No.
DW13938432-01-0.
(18) Massachusetts Institute of Technology (MIT), 1998,
``Calibration of Eight Wind Speed Probes Over a Reynolds Number Range of
46,000 to 725,000 per Foot, Text and Summary Plots,'' Plus Appendices,
WBWT-TR-1317, Prepared for The Cadmus Group, Inc., under EPA Contract
68-W6-0050, Work Assignment 0007AA-3.
(19) Fossil Energy Research Corporation, Final Report, ``Velocity
Probe Tests in Non-axial Flow Fields,'' November 1998, Prepared for the
U.S. Environmental Protection Agency.
(20) Fossil Energy Research Corporation, ``Additional Swirl Tunnel
Tests: E-DAT and T-DAT Probes,'' February 24, 1999, Technical Memorandum
Prepared for U.S. Environmental Protection Agency, P.O. No. 7W-1193-
NALX.
[GRAPHIC] [TIFF OMITTED] TR14MY99.036

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[GRAPHIC] [TIFF OMITTED] TR14MY99.044

Method 3--Gas Analysis for the Determination of Dry Molecular Weight

1.0 Scope and Application

1.1 Analytes.

[[Page 147]]

------------------------------------------------------------------------
Analytes CAS No. Sensitivity
------------------------------------------------------------------------
Oxygen (O2)....................... 7782-44-7 2,000 ppmv.
Nitrogen (N2)..................... 7727-37-9 N/A.
Carbon dioxide (CO2).............. 124-38-9 2,000 ppmv.
Carbon monoxide (CO).............. 630-08-0 N/A.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of CO2 and O2 concentrations and dry molecular
weight of a sample from an effluent gas stream of a fossil-fuel
combustion process or other process.
1.3 Other methods, as well as modifications to the procedure
described herein, are also applicable for all of the above
determinations. Examples of specific methods and modifications include:
(1) A multi-point grab sampling method using an Orsat analyzer to
analyze the individual grab sample obtained at each point; (2) a method
for measuring either CO2 or O2 and using
stoichiometric calculations to determine dry molecular weight; and (3)
assigning a value of 30.0 for dry molecular weight, in lieu of actual
measurements, for processes burning natural gas, coal, or oil. These
methods and modifications may be used, but are subject to the approval
of the Administrator. The method may also be applicable to other
processes where it has been determined that compounds other than
CO2, O2, carbon monoxide (CO), and nitrogen
(N2) are not present in concentrations sufficient to affect
the results.
1.4 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted from a stack by one of the following
methods: (1) single-point, grab sampling; (2) single-point, integrated
sampling; or (3) multi-point, integrated sampling. The gas sample is
analyzed for percent CO2 and percent O2. For dry
molecular weight determination, either an Orsat or a Fyrite analyzer may
be used for the analysis.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Several compounds can interfere, to varying degrees, with the
results of Orsat or Fyrite analyses. Compounds that interfere with
CO2 concentration measurement include acid gases (e.g.,
sulfur dioxide, hydrogen chloride); compounds that interfere with
O2 concentration measurement include unsaturated hydrocarbons
(e.g., acetone, acetylene), nitrous oxide, and ammonia. Ammonia reacts
chemically with the O2 absorbing solution, and when present
in the effluent gas stream must be removed before analysis.

5.0 Safety

6.0 Equipment and Supplies

Note: As an alternative to the sampling apparatus and systems
described herein, other sampling systems (e.g., liquid displacement) may
be used, provided such systems are capable of obtaining a representative
sample and maintaining a constant sampling rate, and are, otherwise,
capable of yielding acceptable results. Use of such systems is subject
to the approval of the Administrator.

6.1 Grab Sampling (See Figure 3-1).
6.1.1 Probe. Stainless steel or borosilicate glass tubing equipped
with an in-stack or out-of-stack filter to remove particulate matter (a
plug of glass wool is satisfactory for this purpose). Any other
materials, resistant to temperature at sampling conditions and inert to
all components of the gas stream, may be used for the probe. Examples of
such materials may include aluminum, copper, quartz glass, and Teflon.
6.1.2 Pump. A one-way squeeze bulb, or equivalent, to transport the
gas sample to the analyzer.
6.2 Integrated Sampling (Figure 3-2).
6.2.1 Probe. Same as in section 6.1.1.

[[Page 148]]

6.2.2 Condenser. An air-cooled or water-cooled condenser, or other
condenser no greater than 250 ml that will not remove O2,
CO2, CO, and N2, to remove excess moisture which
would interfere with the operation of the pump and flowmeter.
6.2.3 Valve. A needle valve, to adjust sample gas flow rate.
6.2.4 Pump. A leak-free, diaphragm-type pump, or equivalent, to
transport sample gas to the flexible bag. Install a small surge tank
between the pump and rate meter to eliminate the pulsation effect of the
diaphragm pump on the rate meter.
6.2.5 Rate Meter. A rotameter, or equivalent, capable of measuring
flow rate to 2 percent of the selected flow rate. A flow rate range of
500 to 1000 ml/min is suggested.
6.2.6 Flexible Bag. Any leak-free plastic (e.g., Tedlar, Mylar,
Teflon) or plastic-coated aluminum (e.g., aluminized Mylar) bag, or
equivalent, having a capacity consistent with the selected flow rate and
duration of the test run. A capacity in the range of 55 to 90 liters
(1.9 to 3.2 ft\3\) is suggested. To leak-check the bag, connect it to a
water manometer, and pressurize the bag to 5 to 10 cm H2O (2
to 4 in. H2O). Allow to stand for 10 minutes. Any
displacement in the water manometer indicates a leak. An alternative
leak-check method is to pressurize the bag to 5 to 10 cm (2 to 4 in.)
H2O and allow to stand overnight. A deflated bag indicates a
leak.
6.2.7 Pressure Gauge. A water-filled U-tube manometer, or
equivalent, of about 30 cm (12 in.), for the flexible bag leak-check.
6.2.8 Vacuum Gauge. A mercury manometer, or equivalent, of at least
760 mm (30 in.) Hg, for the sampling train leak-check.
6.3 Analysis. An Orsat or Fyrite type combustion gas analyzer.

7.0 Reagents and Standards

7.1 Reagents. As specified by the Orsat or Fyrite-type combustion
analyzer manufacturer.
7.2 Standards. Two standard gas mixtures, traceable to National
Institute of Standards and Technology (NIST) standards, to be used in
auditing the accuracy of the analyzer and the analyzer operator
technique:
7.2.1. Gas cylinder containing 2 to 4 percent O2 and 14
to 18 percent CO2.
7.2.2. Gas cylinder containing 2 to 4 percent CO2 and
about 15 percent O2.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Single Point, Grab Sampling Procedure.
8.1.1 The sampling point in the duct shall either be at the centroid
of the cross section or at a point no closer to the walls than 1.0 m
(3.3 ft), unless otherwise specified by the Administrator.
8.1.2 Set up the equipment as shown in Figure 3-1, making sure all
connections ahead of the analyzer are tight. If an Orsat analyzer is
used, it is recommended that the analyzer be leak-checked by following
the procedure in section 11.5; however, the leak-check is optional.
8.1.3 Place the probe in the stack, with the tip of the probe
positioned at the sampling point. Purge the sampling line long enough to
allow at least five exchanges. Draw a sample into the analyzer, and
immediately analyze it for percent CO2 and percent
O2 according to section 11.2.
8.2 Single-Point, Integrated Sampling Procedure.
8.2.1 The sampling point in the duct shall be located as specified
in section 8.1.1.
8.2.2 Leak-check (optional) the flexible bag as in section 6.2.6.
Set up the equipment as shown in Figure 3-2. Just before sampling, leak-
check (optional) the train by placing a vacuum gauge at the condenser
inlet, pulling a vacuum of at least 250 mm Hg (10 in. Hg), plugging the
outlet at the quick disconnect, and then turning off the pump. The
vacuum should remain stable for at least 0.5 minute. Evacuate the
flexible bag. Connect the probe, and place it in the stack, with the tip
of the probe positioned at the sampling point. Purge the sampling line.
Next, connect the bag, and make sure that all connections are tight.
8.2.3 Sample Collection. Sample at a constant rate (10 percent).
The sampling run should be simultaneous with, and for the same total
length of time as, the pollutant emission rate determination. Collection
of at least 28 liters (1.0 ft\3\) of sample gas is recommended; however,
smaller volumes may be collected, if desired.
8.2.4 Obtain one integrated flue gas sample during each pollutant
emission rate determination. Within 8 hours after the sample is taken,
analyze it for percent CO2 and percent O2 using
either an Orsat analyzer or a Fyrite type combustion gas analyzer
according to section 11.3.

Note: When using an Orsat analyzer, periodic Fyrite readings may be
taken to verify/confirm the results obtained from the Orsat.

8.3 Multi-Point, Integrated Sampling Procedure.
8.3.1 Unless otherwise specified in an applicable regulation, or by
the Administrator, a minimum of eight traverse points shall be used for
circular stacks having diameters less than 0.61 m (24 in.), a minimum of
nine shall be used for rectangular stacks having equivalent diameters
less than 0.61 m (24 in.), and a minimum of 12 traverse points shall be
used for all other cases. The traverse points shall be located according
to Method 1.
8.3.2 Follow the procedures outlined in sections 8.2.2 through
8.2.4, except for the following: Traverse all sampling points, and
sample at each point for an equal length of

[[Page 149]]

time. Record sampling data as shown in Figure 3-3.

9.0 Quality Control

10.0 Calibration and Standardization

10.1 Analyzer. The analyzer and analyzer operator's technique should
be audited periodically as follows: take a sample from a manifold
containing a known mixture of CO2 and O2, and
analyze according to the procedure in section 11.3. Repeat this
procedure until the measured concentration of three consecutive samples
agrees with the stated value 0.5 percent. If necessary, take corrective
action, as specified in the analyzer users manual.
10.2 Rotameter. The rotameter need not be calibrated, but should be
cleaned and maintained according to the manufacturer's instruction.

11.0 Analytical Procedure

11.1 Maintenance. The Orsat or Fyrite-type analyzer should be
maintained and operated according to the manufacturers specifications.
11.2 Grab Sample Analysis. Use either an Orsat analyzer or a Fyrite-
type combustion gas analyzer to measure O2 and CO2
concentration for dry molecular weight determination, using procedures
as specified in the analyzer user's manual. If an Orsat analyzer is
used, it is recommended that the Orsat leak-check, described in section
11.5, be performed before this determination; however, the check is
optional. Calculate the dry molecular weight as indicated in section
12.0. Repeat the sampling, analysis, and calculation procedures until
the dry molecular weights of any three grab samples differ from their
mean by no more than 0.3 g/g-mole (0.3 lb/lb-mole). Average these three
molecular weights, and report the results to the nearest 0.1 g/g-mole
(0.1 lb/lb-mole).
11.3 Integrated Sample Analysis. Use either an Orsat analyzer or a
Fyrite-type combustion gas analyzer to measure O2 and
CO2 concentration for dry molecular weight determination,
using procedures as specified in the analyzer user's manual. If an Orsat
analyzer is used, it is recommended that the Orsat leak-check, described
in section 11.5, be performed before this determination; however, the
check is optional. Calculate the dry molecular weight as indicated in
section 12.0. Repeat the analysis and calculation procedures until the
individual dry molecular weights for any three analyses differ from
their mean by no more than 0.3 g/g-mole (0.3 lb/lb-mole). Average these
three molecular weights, and report the results to the nearest 0.1 g/g-
mole (0.1 lb/lb-mole).
11.4 Standardization. A periodic check of the reagents and of
operator technique should be conducted at least once every three series
of test runs as outlined in section 10.1.
11.5 Leak-Check Procedure for Orsat Analyzer. Moving an Orsat
analyzer frequently causes it to leak. Therefore, an Orsat analyzer
should be thoroughly leak-checked on site before the flue gas sample is
introduced into it. The procedure for leak-checking an Orsat analyzer is
as follows:
11.5.1 Bring the liquid level in each pipette up to the reference
mark on the capillary tubing, and then close the pipette stopcock.
11.5.2 Raise the leveling bulb sufficiently to bring the confining
liquid meniscus onto the graduated portion of the burette, and then
close the manifold stopcock.
11.5.3 Record the meniscus position.
11.5.4 Observe the meniscus in the burette and the liquid level in
the pipette for movement over the next 4 minutes.
11.5.5 For the Orsat analyzer to pass the leak-check, two conditions
must be met:
11.5.5.1 The liquid level in each pipette must not fall below the
bottom of the capillary tubing during this 4-minute interval.
11.5.5.2 The meniscus in the burette must not change by more than
0.2 ml during this 4-minute interval.
11.5.6 If the analyzer fails the leak-check procedure, check all
rubber connections and stopcocks to determine whether they might be the
cause of the leak. Disassemble, clean, and regrease any leaking
stopcocks. Replace leaking rubber connections. After the analyzer is
reassembled, repeat the leak-check procedure.

12.0 Calculations and Data Analysis

12.1 Nomenclature.

Md = Dry molecular weight, g/g-mole (lb/lb-mole).
%CO2 = Percent CO2 by volume, dry basis.
%O2 = Percent O2 by volume, dry basis.
%CO = Percent CO by volume, dry basis.
%N2 = Percent N2 by volume, dry basis.

[[Page 150]]

0.280 = Molecular weight of N2 or CO, divided by 100.
0.320 = Molecular weight of O2 divided by 100.
0.440 = Molecular weight of CO2 divided by 100.

12.2 Nitrogen, Carbon Monoxide Concentration. Determine the
percentage of the gas that is N2 and CO by subtracting the
sum of the percent CO2 and percent O2 from 100
percent.
12.3 Dry Molecular Weight. Use Equation 3-1 to calculate the dry
molecular weight of the stack gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.090

Note: The above Equation 3-1 does not consider the effect on
calculated dry molecular weight of argon in the effluent gas. The
concentration of argon, with a molecular weight of 39.9, in ambient air
is about 0.9 percent. A negative error of approximately 0.4 percent is
introduced. The tester may choose to include argon in the analysis using
procedures subject to approval of the Administrator.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Altshuller, A.P. Storage of Gases and Vapors in Plastic Bags.
International Journal of Air and Water Pollution. 6:75-81. 1963.
2. Conner, William D. and J.S. Nader. Air Sampling with Plastic
Bags. Journal of the American Industrial Hygiene Association. 25:291-
297. 1964.
3. Burrell Manual for Gas Analysts, Seventh edition. Burrell
Corporation, 2223 Fifth Avenue, Pittsburgh, PA. 15219. 1951.
4. Mitchell, W.J. and M.R. Midgett. Field Reliability of the Orsat
Analyzer. Journal of Air Pollution Control Association. 26:491-495. May
1976.
5. Shigehara, R.T., R.M. Neulicht, and W.S. Smith. Validating Orsat
Analysis Data from Fossil Fuel-Fired Units. Stack Sampling News.
4(2):21-26. August 1976.

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.091

[[Page 151]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.092

----------------------------------------------------------------------------------------------------------------
Time Traverse point Q (liter/min) % Deviation \a\
----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------
Average
----------------------------------------------------------------------------------------------------------------
\a\ % Dev.=[(Q-Qavg)/Qavg] x 100 (Must be 10%)

Figure 3-3. Sampling Rate Data

Method 3A--Determination of Oxygen and Carbon Dioxide Concentrations in
Emissions From Stationary Sources (Instrumental Analyzer Procedure)

1.0 Scope and Application

What is Method 3A?

Method 3A is a procedure for measuring oxygen (O2) and
carbon dioxide (CO2) in stationary source emissions using a
continuous instrumental analyzer. Quality assurance and quality control
requirements are included to assure that you, the tester, collect data
of known quality. You must document your adherence to these specific
requirements for equipment, supplies, sample collection and analysis,
calculations, and data analysis.
This method does not completely describe all equipment, supplies,
and sampling and

[[Page 152]]

analytical procedures you will need but refers to other methods for some
of the details. Therefore, to obtain reliable results, you should also
have a thorough knowledge of these additional test methods which are
found in appendix A to this part:
(a) Method 1--Sample and Velocity Traverses for Stationary Sources.
(b) Method 3--Gas Analysis for the Determination of Molecular
Weight.
(c) Method 4--Determination of Moisture Content in Stack Gases.
(d) Method 7E--Determination of Nitrogen Oxides Emissions from
Stationary Sources (Instrumental Analyzer Procedure).
1.1 Analytes. What does this method determine? This method measures
the concentration of oxygen and carbon dioxide.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Oxygen (O2).................... 7782-44-7 Typically <2% of
Calibration Span.
Carbon dioxide (CO2)........... 124-38-9 Typically <2% of
Calibration Span.
------------------------------------------------------------------------

1.2 Applicability. When is this method required? The use of Method
3A may be required by specific New Source Performance Standards, Clean
Air Marketing rules, State Implementation Plans and permits, where
measurements of O2 and CO2 concentrations in
stationary source emissions must be made, either to determine compliance
with an applicable emission standard or to conduct performance testing
of a continuous emission monitoring system (CEMS). Other regulations may
also require the use of Method 3A.
1.3 Data Quality Objectives. How good must my collected data be?
Refer to section 1.3 of Method 7E.

2.0 Summary of Method

In this method, you continuously or intermittently sample the
effluent gas and convey the sample to an analyzer that measures the
concentration of O2 or CO2. You must meet the
performance requirements of this method to validate your data.

3.0 Definitions

Refer to section 3.0 of Method 7E for the applicable definitions.

4.0 Interferences [Reserved]

5.0 Safety

Refer to section 5.0 of Method 7E.

6.0 Equipment and Supplies

Figure 7E-1 in Method 7E is a schematic diagram of an acceptable
measurement system.
6.1 What do I need for the measurement system? The components of the
measurement system are described (as applicable) in sections 6.1 and 6.2
of Method 7E, except that the analyzer described in section 6.2 of this
method must be used instead of the analyzer described in Method 7E. You
must follow the noted specifications in section 6.1 of Method 7E except
that the requirements to use stainless steel, Teflon, or non-reactive
glass filters do not apply. Also, a heated sample line is not required
to transport dry gases or for systems that measure the O2 or
CO2 concentration on a dry basis, provided that the system is
not also being used to concurrently measure SO2 and/or
NOX.
6.2 What analyzer must I use? You must use an analyzer that
continuously measures O2 or CO2 in the gas stream
and meets the specifications in section 13.0.

7.0 Reagents and Standards

7.1 Calibration Gas. What calibration gases do I need? Refer to
Section 7.1 of Method 7E for the calibration gas requirements. Example
calibration gas mixtures are listed below. Pre-cleaned or scrubbed air
may be used for the O2 high-calibration gas provided it does
not contain other gases that interfere with the O2
measurement.
(a) CO2 in Nitrogen (N2).
(b) CO2/SO2 gas mixture in N2.
(c) O2/SO2 gas mixture in N2.
(d) O2/CO2/SO2 gas mixture in
N2.
(e) CO2/NOX gas mixture in N2.
(f) CO2/SO2/NOX gas mixture in
N2.
The tests for analyzer calibration error and system bias require
high-, mid-, and low-level gases.
7.2 Interference Check. What reagents do I need for the interference
check? Potential interferences may vary among available analyzers. Table
7E-3 of Method 7E lists a number of gases that should be considered in
conducting the interference test.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sampling Site and Sampling Points. You must follow the
procedures of section 8.1 of Method 7E to determine the appropriate
sampling points, unless you are using Method 3A only to determine the
stack gas molecular weight and for no other purpose. In that case, you
may use single-point integrated sampling as described in section 8.2.1
of Method 3. If the stratification test provisions in section 8.1.2 of
Method 7E are used to reduce the number of required sampling points, the
alternative acceptance criterion for 3-

[[Page 153]]

point sampling will be 0.5 percent CO2 or O2, and
the alternative acceptance criterion for single-point sampling will be
0.3 percent CO2 or O2. In that case, you may use
single-point integrated sampling as described in section 8.2.1 of Method
3.
8.2 Initial Measurement System Performance Tests. You must follow
the procedures in section 8.2 of Method 7E. If a dilution-type
measurement system is used, the special considerations in section 8.3 of
Method 7E apply.
8.3 Interference Check. The O2 or CO2 analyzer
must be documented to show that interference effects to not exceed 2.5
percent of the calibration span. The interference test in section 8.2.7
of Method 7E is a procedure that may be used to show this. The effects
of all potential interferences at the concentrations encountered during
testing must be addressed and documented. This testing and documentation
may be done by the instrument manufacturer.
8.4 Sample Collection. You must follow the procedures in section 8.4
of Method 7E.
8.5 Post-Run System Bias Check and Drift Assessment. You must follow
the procedures in section 8.5 of Method 7E.

9.0 Quality Control

Follow quality control procedures in section 9.0 of Method 7E.

10.0 Calibration and Standardization

Follow the procedures for calibration and standardization in section
10.0 of Method 7E.

11.0 Analytical Procedures

Because sample collection and analysis are performed together (see
section 8), additional discussion of the analytical procedure is not
necessary.

12.0 Calculations and Data Analysis

You must follow the applicable procedures for calculations and data
analysis in section 12.0 of Method 7E, substituting percent
O2 and percent CO2 for ppmv of NOX as
appropriate.

13.0 Method Performance

The specifications for the applicable performance checks are the
same as in section 13.0 of Method 7E except for the alternative
specifications for system bias, drift, and calibration error. In these
alternative specifications, replace the term ``0.5 ppmv'' with the term
``0.5 percent O2'' or ``0.5 percent CO2'' (as
applicable).

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures [Reserved]

17.0 References

1. ``EPA Traceability Protocol for Assay and Certification of
Gaseous Calibration Standards'' September 1997 as amended, EPA-600/R-97/
121.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

Refer to section 18.0 of Method 7E.

Method 3B--Gas Analysis for the Determination of Emission Rate
Correction Factor or Excess Air

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Oxygen (O2)....................... 7782-44-7 2,000 ppmv.
Carbon Dioxide (CO2).............. 124-38-9 2,000 ppmv.
Carbon Monoxide (CO).............. 630-08-0 N/A.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of O2, CO2, and CO concentrations in the effluent
from fossil-fuel combustion processes for use in excess air or emission
rate correction factor calculations. Where compounds other than
CO2, O2, CO, and nitrogen (N2) are
present in concentrations sufficient to affect the results, the
calculation procedures presented in this method must be modified,
subject to the approval of the Administrator.
1.3 Other methods, as well as modifications to the procedure
described herein, are also applicable for all of the above
determinations. Examples of specific methods and modifications include:
(1) A multi-point sampling method using an Orsat analyzer to analyze
individual grab samples obtained at each point, and (2) a method using
CO2 or O2 and stoichiometric calculations to
determine excess air. These methods and modifications may be used, but
are subject to the approval of the Administrator.

[[Page 154]]

1.4 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted from a stack by one of the following
methods: (1) Single-point, grab sampling; (2) single-point, integrated
sampling; or (3) multi-point, integrated sampling. The gas sample is
analyzed for percent CO2, percent O2, and, if
necessary, percent CO using an Orsat combustion gas analyzer.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Several compounds can interfere, to varying degrees, with the
results of Orsat analyses. Compounds that interfere with CO2
concentration measurement include acid gases (e.g., sulfur dioxide,
hydrogen chloride); compounds that interfere with O2
concentration measurement include unsaturated hydrocarbons (e.g.,
acetone, acetylene), nitrous oxide, and ammonia. Ammonia reacts
chemically with the O2 absorbing solution, and when present
in the effluent gas stream must be removed before analysis.

5.0 Safety

6.0 Equipment and Supplies

6.1 Grab Sampling and Integrated Sampling. Same as in sections 6.1
and 6.2, respectively for Method 3.
6.2 Analysis. An Orsat analyzer only. For low CO2 (less
than 4.0 percent) or high O2 (greater than 15.0 percent)
concentrations, the measuring burette of the Orsat must have at least
0.1 percent subdivisions. For Orsat maintenance and operation
procedures, follow the instructions recommended by the manufacturer,
unless otherwise specified herein.

7.0 Reagents and Standards

7.1 Reagents. Same as in Method 3, section 7.1.
7.2 Standards. Same as in Method 3, section 7.2.

8.0 Sample Collection, Preservation, Storage, and Transport

Note: Each of the three procedures below shall be used only when
specified in an applicable subpart of the standards. The use of these
procedures for other purposes must have specific prior approval of the
Administrator. A Fyrite-type combustion gas analyzer is not acceptable
for excess air or emission rate correction factor determinations, unless
approved by the Administrator. If both percent CO2 and
percent O2 are measured, the analytical results of any of the
three procedures given below may also be used for calculating the dry
molecular weight (see Method 3).
8.1 Single-Point, Grab Sampling and Analytical Procedure.
8.1.1 The sampling point in the duct shall either be at the centroid
of the cross section or at a point no closer to the walls than 1.0 m
(3.3 ft), unless otherwise specified by the Administrator.
8.1.2 Set up the equipment as shown in Figure 3-1 of Method 3,
making sure all connections ahead of the analyzer are tight. Leak-check
the Orsat analyzer according to the procedure described in section 11.5
of Method 3. This leak-check is mandatory.
8.1.3 Place the probe in the stack, with the tip of the probe
positioned at the sampling point; purge the sampling line long enough to
allow at least five exchanges. Draw a sample into the analyzer. For
emission rate correction factor determinations, immediately analyze the
sample for percent CO2 or percent O2, as outlined
in section 11.2. For excess air determination, immediately analyze the
sample for percent CO2, O2, and CO, as outlined in
section 11.2, and calculate excess air as outlined in section 12.2.
8.1.4 After the analysis is completed, leak-check (mandatory) the
Orsat analyzer once again, as described in section 11.5 of Method 3. For
the results of the analysis to be valid, the Orsat analyzer must pass
this leak-test before and after the analysis.
8.2 Single-Point, Integrated Sampling and Analytical Procedure.

[[Page 155]]

8.2.1 The sampling point in the duct shall be located as specified
in section 8.1.1.
8.2.2 Leak-check (mandatory) the flexible bag as in section 6.2.6 of
Method 3. Set up the equipment as shown in Figure 3-2 of Method 3. Just
before sampling, leak-check (mandatory) the train by placing a vacuum
gauge at the condenser inlet, pulling a vacuum of at least 250 mm Hg (10
in. Hg), plugging the outlet at the quick disconnect, and then turning
off the pump. The vacuum should remain stable for at least 0.5 minute.
Evacuate the flexible bag. Connect the probe, and place it in the stack,
with the tip of the probe positioned at the sampling point; purge the
sampling line. Next, connect the bag, and make sure that all connections
are tight.
8.2.3 Sample at a constant rate, or as specified by the
Administrator. The sampling run must be simultaneous with, and for the
same total length of time as, the pollutant emission rate determination.
Collect at least 28 liters (1.0 ft\3\) of sample gas. Smaller volumes
may be collected, subject to approval of the Administrator.
8.2.4 Obtain one integrated flue gas sample during each pollutant
emission rate determination. For emission rate correction factor
determination, analyze the sample within 4 hours after it is taken for
percent CO2 or percent O2 (as outlined in section
11.2).
8.3 Multi-Point, Integrated Sampling and Analytical Procedure.
8.3.1 Unless otherwise specified in an applicable regulation, or by
the Administrator, a minimum of eight traverse points shall be used for
circular stacks having diameters less than 0.61 m (24 in.), a minimum of
nine shall be used for rectangular stacks having equivalent diameters
less than 0.61 m (24 in.), and a minimum of 12 traverse points shall be
used for all other cases. The traverse points shall be located according
to Method 1.
8.3.2 Follow the procedures outlined in sections 8.2.2 through
8.2.4, except for the following: Traverse all sampling points, and
sample at each point for an equal length of time. Record sampling data
as shown in Figure 3-3 of Method 3.

9.0 Quality Control

9.1 Data Validation Using Fuel Factor. Although in most instances,
only CO2 or O2 measurement is required, it is
recommended that both CO2 and O2 be measured to
provide a check on the quality of the data. The data validation
procedure of section 12.3 is suggested.

Note: Since this method for validating the CO2 and
O2 analyses is based on combustion of organic and fossil
fuels and dilution of the gas stream with air, this method does not
apply to sources that (1) remove CO2 or O2 through
processes other than combustion, (2) add O2 (e.g., oxygen
enrichment) and N2 in proportions different from that of air,
(3) add CO2 (e.g., cement or lime kilns), or (4) have no fuel
factor, FO, values obtainable (e.g., extremely variable waste
mixtures). This method validates the measured proportions of
CO2 and O2 for fuel type, but the method does not
detect sample dilution resulting from leaks during or after sample
collection. The method is applicable for samples collected downstream of
most lime or limestone flue-gas desulfurization units as the
CO2 added or removed from the gas stream is not significant
in relation to the total CO2 concentration. The
CO2 concentrations from other types of scrubbers using only
water or basic slurry can be significantly affected and would render the
fuel factor check minimally useful.

10.0 Calibration and Standardization

10.1 Analyzer. The analyzer and analyzer operator technique should
be audited periodically as follows: take a sample from a manifold
containing a known mixture of CO2 and O2, and
analyze according to the procedure in section 11.3. Repeat this
procedure until the measured concentration of three consecutive samples
agrees with the stated value 0.5 percent. If necessary, take corrective
action, as specified in the analyzer users manual.
10.2 Rotameter. The rotameter need not be calibrated, but should be
cleaned and maintained according to the manufacturer's instruction.

11.0 Analytical Procedure

11.1 Maintenance. The Orsat analyzer should be maintained according
to the manufacturers specifications.
11.2 Grab Sample Analysis. To ensure complete absorption of the
CO2, O2, or if applicable, CO, make repeated
passes through each absorbing solution until two consecutive readings
are the same. Several passes (three or four) should be made between
readings. (If constant readings cannot be obtained after three
consecutive readings, replace the absorbing solution.) Although in most
cases, only CO2 or O2 concentration is required,
it is recommended that both CO2 and O2 be
measured, and that the procedure in section 12.3 be used to validate the
analytical data.

Note: Since this single-point, grab sampling and analytical
procedure is normally conducted in conjunction with a single-point, grab
sampling and analytical procedure for a pollutant, only one analysis is
ordinarily conducted. Therefore, great care must be taken to obtain a
valid sample and analysis.

11.3 Integrated Sample Analysis. The Orsat analyzer must be leak-
checked (see section 11.5 of Method 3) before the analysis. If excess
air is desired, proceed as follows: (1) within 4 hours after the sample
is taken, analyze it (as in sections 11.3.1 through

[[Page 156]]

11.3.3) for percent CO2, O2, and CO; (2) determine
the percentage of the gas that is N2 by subtracting the sum
of the percent CO2, percent O2, and percent CO
from 100 percent; and (3) calculate percent excess air, as outlined in
section 12.2.
11.3.1 To ensure complete absorption of the CO2,
O2, or if applicable, CO, follow the procedure described in
section 11.2.

Note: Although in most instances only CO2 or
O2 is required, it is recommended that both CO2
and O2 be measured, and that the procedures in section 12.3
be used to validate the analytical data.

11.3.2 Repeat the analysis until the following criteria are met:
11.3.2.1 For percent CO2, repeat the analytical procedure
until the results of any three analyses differ by no more than (a) 0.3
percent by volume when CO2 is greater than 4.0 percent or (b)
0.2 percent by volume when CO2 is less than or equal to 4.0
percent. Average three acceptable values of percent CO2, and
report the results to the nearest 0.2 percent.
11.3.2.2 For percent O2, repeat the analytical procedure
until the results of any three analyses differ by no more than (a) 0.3
percent by volume when O2 is less than 15.0 percent or (b)
0.2 percent by volume when O2 is greater than or equal to
15.0 percent. Average the three acceptable values of percent
O2, and report the results to the nearest 0.1 percent.
11.3.2.3 For percent CO, repeat the analytical procedure until the
results of any three analyses differ by no more than 0.3 percent.
Average the three acceptable values of percent CO, and report the
results to the nearest 0.1 percent.
11.3.3 After the analysis is completed, leak-check (mandatory) the
Orsat analyzer once again, as described in section 11.5 of Method 3. For
the results of the analysis to be valid, the Orsat analyzer must pass
this leak-test before and after the analysis.
11.4 Standardization. A periodic check of the reagents and of
operator technique should be conducted at least once every three series
of test runs as indicated in section 10.1.

12.0 Calculations and Data Analysis

12.1 Nomenclature. Same as section 12.1 of Method 3 with the
addition of the following:
%EA = Percent excess air.
0.264 = Ratio of O2 to N2 in air, v/v.

12.2 Percent Excess Air. Determine the percentage of the gas that is
N2 by subtracting the sum of the percent CO2,
percent CO, and percent O2 from 100 percent. Calculate the
percent excess air (if applicable) by substituting the appropriate
values of percent O2, CO, and N2 into Equation 3B-
1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.093

Note: The equation above assumes that ambient air is used as the
source of O2 and that the fuel does not contain appreciable
amounts of N2 (as do coke oven or blast furnace gases). For
those cases when appreciable amounts of N2 are present (coal,
oil, and natural gas do not contain appreciable amounts of
N2) or when oxygen enrichment is used, alternative methods,
subject to approval of the Administrator, are required.

12.3 Data Validation When Both CO2 and O2 Are
Measured.
12.3.1 Fuel Factor, Fo. Calculate the fuel factor (if
applicable) using Equation 3B-2:
[GRAPHIC] [TIFF OMITTED] TR17OC00.094

Where:

%O2 = Percent O2 by volume, dry basis.
%CO2 = Percent CO2 by volume, dry basis.
20.9 = Percent O2 by volume in ambient air.

If CO is present in quantities measurable by this method, adjust the
O2 and CO2 values using Equations 3B-3 and 3B-4
before performing the calculation for Fo:
[GRAPHIC] [TIFF OMITTED] TR17OC00.095

[GRAPHIC] [TIFF OMITTED] TR17OC00.096

Where:
%CO = Percent CO by volume, dry basis.

12.3.2 Compare the calculated Fo factor with the expected
Fo values. Table 3B-1 in section 17.0 may be used in
establishing acceptable ranges for the expected Fo if the
fuel being burned is known. When fuels are burned in combinations,
calculate the combined fuel Fd and Fc factors (as
defined in Method 19, section 12.2) according to the procedure in Method
19, sections 12.2 and 12.3. Then calculate the Fo factor
according to Equation 3B-5.
[GRAPHIC] [TIFF OMITTED] TR17OC00.097

[[Page 157]]

12.3.3 Calculated Fo values, beyond the acceptable ranges
shown in this table, should be investigated before accepting the test
results. For example, the strength of the solutions in the gas analyzer
and the analyzing technique should be checked by sampling and analyzing
a known concentration, such as air; the fuel factor should be reviewed
and verified. An acceptability range of 12 percent is appropriate for
the Fo factor of mixed fuels with variable fuel ratios. The
level of the emission rate relative to the compliance level should be
considered in determining if a retest is appropriate; i.e., if the
measured emissions are much lower or much greater than the compliance
limit, repetition of the test would not significantly change the
compliance status of the source and would be unnecessarily time
consuming and costly.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as Method 3, section 16.0.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Table 3B-1--Fo Factors for Selected Fuels
------------------------------------------------------------------------
Fuel type Fo range
------------------------------------------------------------------------
Coal:
Anthracite and lignite.............................. 1.016-1.130
Bituminous.......................................... 1.083-1.230
Oil:
Distillate.......................................... 1.260-1.413
Residual............................................ 1.210-1.370
Gas:
Natural............................................. 1.600-1.836
Propane............................................. 1.434-1.586
Butane.............................................. 1.405-1.553
Wood.................................................... 1.000-1.120
Wood bark............................................... 1.003-1.130
------------------------------------------------------------------------

Method 3C--Determination of Carbon Dioxide, Methane, Nitrogen, and
Oxygen From Stationary Sources

1. Applicability and Principle

1.1 Applicability. This method applies to the analysis of carbon
dioxide (CO2), methane (CH4), nitrogen
(N2), and oxygen (O2) in samples from municipal
solid waste landfills and other sources when specified in an applicable
subpart.
1.2 Principle. A portion of the sample is injected into a gas
chromatograph (GC) and the CO2, CH4,
N2, and O2 concentrations are determined by using
a thermal conductivity detector (TCD) and integrator.

2. Range and Sensitivity

2.1 Range. The range of this method depends upon the concentration
of samples. The analytical range of TCD's is generally between
approximately 10 ppmv and the upper percent range.
2.2 Sensitivity. The sensitivity limit for a compound is defined as
the minimum detectable concentration of that compound, or the
concentration that produces a signal-to-noise ratio of three to one. For
CO2, CH4, N2, and O2, the
sensitivity limit is in the low ppmv range.

3. Interferences

Since the TCD exhibits universal response and detects all gas
components except the carrier, interferences may occur. Choosing the
appropriate GC or shifting the retention times by changing the column
flow rate may help to eliminate resolution interferences.
To assure consistent detector response, helium is used to prepare
calibration gases. Frequent exposure to samples or carrier gas
containing oxygen may gradually destroy filaments.

4. Apparatus

4.1 Gas Chromatograph. GC having at least the following components:
4.1.1 Separation Column. Appropriate column(s) to resolve
CO2, CH4, N2, O2, and other
gas components that may be present in the sample.
4.1.2 Sample Loop. Teflon or stainless steel tubing of the
appropriate diameter.

Note: Mention of trade names or specific products does not
constitute endorsement or recommendation by the U. S. Environmental
Protection Agency.

4.1.3 Conditioning System. To maintain the column and sample loop at
constant temperature.
4.1.4 Thermal Conductivity Detector.
4.2 Recorder. Recorder with linear strip chart. Electronic
integrator (optional) is recommended.
4.3 Teflon Tubing. Diameter and length determined by connection
requirements of cylinder regulators and the GC.
4.4 Regulators. To control gas cylinder pressures and flow rates.
4.5 Adsorption Tubes. Applicable traps to remove any O2
from the carrier gas.

5. Reagents

5.1 Calibration and Linearity Gases. Standard cylinder gas mixtures
for each compound of interest with at least three concentration levels
spanning the range of suspected sample concentrations. The calibration
gases shall be prepared in helium.
5.2 Carrier Gas. Helium, high-purity.

[[Page 158]]

6. Analysis

6.1 Sample Collection. Use the sample collection procedures
described in Methods 3 or 25C to collect a sample of landfill gas (LFG).
6.2 Preparation of GC. Before putting the GC analyzer into routine
operation, optimize the operational conditions according to the
manufacturer's specifications to provide good resolution and minimum
analysis time. Establish the appropriate carrier gas flow and set the
detector sample and reference cell flow rates at exactly the same
levels. Adjust the column and detector temperatures to the recommended
levels. Allow sufficient time for temperature stabilization. This may
typically require 1 hour for each change in temperature.
6.3 Analyzer Linearity Check and Calibration. Perform this test
before sample analysis. Using the gas mixtures in section 5.1, verify
the detector linearity over the range of suspected sample concentrations
with at least three points per compound of interest. This initial check
may also serve as the initial instrument calibration. All subsequent
calibrations may be performed using a single-point standard gas provided
the calibration point is within 20 percent of the sample component
concentration. For each instrument calibration, record the carrier and
detector flow rates, detector filament and block temperatures,
attenuation factor, injection time, chart speed, sample loop volume, and
component concentrations. Plot a linear regression of the standard
concentrations versus area values to obtain the response factor of each
compound. Alternatively, response factors of uncorrected component
concentrations (wet basis) may be generated using instrumental
integration.

Note: Peak height may be used instead of peak area throughout this
method.

6.4 Sample Analysis. Purge the sample loop with sample, and allow to
come to atmospheric pressure before each injection. Analyze each sample
in duplicate, and calculate the average sample area (A). The results are
acceptable when the peak areas for two consecutive injections agree
within 5 percent of their average. If they do not agree, run additional
samples until consistent area data are obtained. Determine the tank
sample concentrations according to section 7.2.

7. Calculations

Carry out calculations retaining at least one extra decimal figure
beyond that of the acquired data. Round off results only after the final
calculation.
7.1 Nomenclature.

Bw = Moisture content in the sample, fraction.
CN2 = Measured N2 concentration (by Method 3C),
fraction.
CN2Corr = Measured N2 concentration corrected only
for dilution, fraction.
Ct = Calculated NMOC concentration, ppmv C equivalent.
Ctm = Measured NMOC concentration, ppmv C equivalent.
Pb = Barometric pressure, mm Hg.
Pt = Gas sample tank pressure after sampling, but before
pressurizing, mm Hg absolute.
Ptf = Final gas sample tank pressure after pressurizing, mm
Hg absolute.
Pti = Gas sample tank pressure after evacuation, mm Hg
absolute.
Pw = Vapor pressure of H2O (from Table 25C-1), mm
Hg.
r = Total number of analyzer injections of sample tank during analysis
(where j = injection number, 1 . . . r).
R = Mean calibration response factor for specific sample component,
area/ppm.
Tt = Sample tank temperature at completion of sampling,
[deg]K.
Tti = Sample tank temperature before sampling, [deg]K.
Ttf = Sample tank temperature after pressurizing, [deg]K.
7.2 Concentration of Sample Components. Calculate C for each
compound using Equations 3C-1 and 3C-2. Use the temperature and
barometric pressure at the sampling site to calculate Bw. If the sample
was diluted with helium using the procedures in Method 25C, use Equation
3C-3 to calculate the concentration.
[GRAPHIC] [TIFF OMITTED] TR12MR96.031

7.3 Measured N2 Concentration Correction. Calculate the
reported N2 correction for Method 25-C using Eq. 3C-4. If
oxygen is determined in place of N2, substitute the oxygen
concentration for the nitrogen concentration in the equation.

[[Page 159]]

[GRAPHIC] [TIFF OMITTED] TR27FE14.010

8. Bibliography

1. McNair, H.M., and E.J. Bonnelli. Basic Gas Chromatography.
Consolidated Printers, Berkeley, CA. 1969.

[36 FR 24877, Dec. 23, 1971]

Editorial Note: For Federal Register citations affecting appendix A-
2 to part 60, see the List of CFR sections Affected, which appears in
the Finding Aids section of the printed volume and at www.fdsys.gov.

Sec. Appendix A-3 to Part 60--Test Methods 4 through 5I

Method 4--Determination of moisture content in stack gases
Method 5--Determination of particulate matter emissions from stationary
sources
Method 5A--Determination of particulate matter emissions from the
asphalt processing and asphalt roofing industry
Method 5B--Determination of nonsulfuric acid particulate matter
emissions from stationary sources
Method 5C [Reserved]
Method 5D--Determination of particulate matter emissions from positive
pressure fabric filters
Method 5E--Determination of particulate matter emissions from the wool
fiberglass insulation manufacturing industry
Method 5F--Determination of nonsulfate particulate matter emissions from
stationary sources
Method 5G--Determination of particulate matter emissions from wood
heaters (dilution tunnel sampling location)
Method 5H--Determination of particulate emissions from wood heaters from
a stack location
Method 5I--Determination of Low Level Particulate Matter Emissions From
Stationary Sources
The test methods in this appendix are referred to in Sec. 60.8
(Performance Tests) and Sec. 60.11 (Compliance With Standards and
Maintenance Requirements) of 40 CFR part 60, subpart A (General
Provisions). Specific uses of these test methods are described in the
standards of performance contained in the subparts, beginning with
Subpart D.
Within each standard of performance, a section title ``Test Methods
and Procedures'' is provided to: (1) Identify the test methods to be
used as reference methods to the facility subject to the respective
standard and (2) identify any special instructions or conditions to be
followed when applying a method to the respective facility. Such
instructions (for example, establish sampling rates, volumes, or
temperatures) are to be used either in addition to, or as a substitute
for procedures in a test method. Similarly, for sources subject to
emission monitoring requirements, specific instructions pertaining to
any use of a test method as a reference method are provided in the
subpart or in Appendix B.
Inclusion of methods in this appendix is not intended as an
endorsement or denial of their applicability to sources that are not
subject to standards of performance. The methods are potentially
applicable to other sources; however, applicability should be confirmed
by careful and appropriate evaluation of the conditions prevalent at
such sources.
The approach followed in the formulation of the test methods
involves specifications for equipment, procedures, and performance. In
concept, a performance specification approach would be preferable in all
methods because this allows the greatest flexibility to the user. In
practice, however, this approach is impractical in most cases because
performance specifications cannot be established. Most of the methods
described herein, therefore, involve specific equipment specifications
and procedures, and only a few methods in this appendix rely on
performance criteria.
Minor changes in the test methods should not necessarily affect the
validity of the results and it is recognized that alternative and
equivalent methods exist. section 60.8 provides authority for the
Administrator to specify or approve (1) equivalent methods, (2)
alternative methods, and (3) minor changes in the methodology of the
test methods. It should be clearly understood that unless otherwise
identified all such methods and changes must have prior approval of the
Administrator. An owner employing such methods or deviations from the
test methods without obtaining prior approval does so at

[[Page 160]]

the risk of subsequent disapproval and retesting with approved methods.
Within the test methods, certain specific equipment or procedures
are recognized as being acceptable or potentially acceptable and are
specifically identified in the methods. The items identified as
acceptable options may be used without approval but must be identified
in the test report. The potentially approvable options are cited as
``subject to the approval of the Administrator'' or as ``or
equivalent.'' Such potentially approvable techniques or alternatives may
be used at the discretion of the owner without prior approval. However,
detailed descriptions for applying these potentially approvable
techniques or alternatives are not provided in the test methods. Also,
the potentially approvable options are not necessarily acceptable in all
applications. Therefore, an owner electing to use such potentially
approvable techniques or alternatives is responsible for: (1) assuring
that the techniques or alternatives are in fact applicable and are
properly executed; (2) including a written description of the
alternative method in the test report (the written method must be clear
and must be capable of being performed without additional instruction,
and the degree of detail should be similar to the detail contained in
the test methods); and (3) providing any rationale or supporting data
necessary to show the validity of the alternative in the particular
application. Failure to meet these requirements can result in the
Administrator's disapproval of the alternative.

Method 4--Determination of Moisture Content in Stack Gases

Note: This method does not include all the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling) essential to its
performance. Some material is incorporated by reference from other
methods in this part. Therefore, to obtain reliable results, persons
using this method should have a thorough knowledge of at least the
following additional test methods: Method 1, Method 5, and Method 6.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Water vapor (H2O)................. 7732-18-5 N/A
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of the moisture content of stack gas.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted at a constant rate from the source;
moisture is removed from the sample stream and determined either
volumetrically or gravimetrically.
2.2 The method contains two possible procedures: a reference method
and an approximation method.
2.2.1 The reference method is used for accurate determinations of
moisture content (such as are needed to calculate emission data). The
approximation method, provides estimates of percent moisture to aid in
setting isokinetic sampling rates prior to a pollutant emission
measurement run. The approximation method described herein is only a
suggested approach; alternative means for approximating the moisture
content (e.g., drying tubes, wet bulb-dry bulb techniques, condensation
techniques, stoichiometric calculations, previous experience, etc.) are
also acceptable.
2.2.2 The reference method is often conducted simultaneously with a
pollutant emission measurement run. When it is, calculation of percent
isokinetic, pollutant emission rate, etc., for the run shall be based
upon the results of the reference method or its equivalent. These
calculations shall not be based upon the results of the approximation
method, unless the approximation method is shown, to the satisfaction of
the Administrator, to be capable of yielding results within one percent
H2O of the reference method.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 The moisture content of saturated gas streams or streams that
contain water droplets, as measured by the reference method, may be
positively biased. Therefore, when these conditions exist or are
suspected, a second determination of the moisture content shall be made
simultaneously with the reference method, as follows: Assume that the
gas stream is saturated. Attach a temperature sensor [capable of
measuring to 1 [deg]C (2 [deg]F)] to the reference method probe.
Measure the stack gas temperature at each traverse point (see section
8.1.1.1) during the reference method traverse, and calculate the average
stack gas temperature. Next, determine the moisture percentage, either
by: (1) Using a psychrometric chart and making appropriate corrections
if the stack pressure is different from that of the chart, or (2) using
saturation vapor pressure tables. In cases where the psychrometric chart
or the saturation vapor pressure tables are not applicable (based on
evaluation of the process), alternative methods, subject to the approval
of the Administrator, shall be used.

[[Page 161]]

5.0 Safety

6.0 Equipment and Supplies

6.1 Reference Method. A schematic of the sampling train used in this
reference method is shown in Figure 4-1.
6.1.1 Probe. Stainless steel or glass tubing, sufficiently heated to
prevent water condensation, and equipped with a filter, either in-stack
(e.g., a plug of glass wool inserted into the end of the probe) or
heated out-of-stack (e.g., as described in Method 5), to remove
particulate matter. When stack conditions permit, other metals or
plastic tubing may be used for the probe, subject to the approval of the
Administrator.
6.1.2 Condenser. Same as Method 5, section 6.1.1.8.
6.1.3 Cooling System. An ice bath container, crushed ice, and water
(or equivalent), to aid in condensing moisture.
6.1.4 Metering System. Same as in Method 5, section 6.1.1.9, except
do not use sampling systems designed for flow rates higher than 0.0283
m\3\/min (1.0 cfm). Other metering systems, capable of maintaining a
constant sampling rate to within 10 percent and determining sample gas
volume to within 2 percent, may be used, subject to the approval of the
Administrator.
6.1.5 Barometer and Graduated Cylinder and/or Balance. Same as
Method 5, sections 6.1.2 and 6.2.5, respectively.
6.2. Approximation Method. A schematic of the sampling train used in
this approximation method is shown in Figure 4-2.
6.2.1 Probe. Same as section 6.1.1.
6.2.2 Condenser. Two midget impingers, each with 30-ml capacity, or
equivalent.
6.2.3 Cooling System. Ice bath container, crushed ice, and water, to
aid in condensing moisture in impingers.
6.2.4 Drying Tube. Tube packed with new or regenerated 6- to 16-mesh
indicating-type silica gel (or equivalent desiccant), to dry the sample
gas and to protect the meter and pump.
6.2.5 Valve. Needle valve, to regulate the sample gas flow rate.
6.2.6 Pump. Leak-free, diaphragm type, or equivalent, to pull the
gas sample through the train.
6.2.7 Volume Meter. Dry gas meter, sufficiently accurate to measure
the sample volume to within 2 percent, and calibrated over the range of
flow rates and conditions actually encountered during sampling.
6.2.8 Rate Meter. Rotameter, or equivalent, to measure the flow
range from 0 to 3 liters/min (0 to 0.11 cfm).
6.2.9 Graduated Cylinder. 25-ml.
6.2.10 Barometer. Same as Method 5, section 6.1.2.
6.2.11 Vacuum Gauge. At least 760-mm (30-in.) Hg gauge, to be used
for the sampling leak check.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection, Preservation, Transport, and Storage

8.1 Reference Method. The following procedure is intended for a
condenser system (such as the impinger system described in section
6.1.1.8 of Method 5) incorporating volumetric analysis to measure the
condensed moisture, and silica gel and gravimetric analysis to measure
the moisture leaving the condenser.
8.1.1 Preliminary Determinations.
8.1.1.1 Unless otherwise specified by the Administrator, a minimum
of eight traverse points shall be used for circular stacks having
diameters less than 0.61 m (24 in.), a minimum of nine points shall be
used for rectangular stacks having equivalent diameters less than 0.61 m
(24 in.), and a minimum of twelve traverse points shall be used in all
other cases. The traverse points shall be located according to Method 1.
The use of fewer points is subject to the approval of the Administrator.
Select a suitable probe and probe length such that all traverse points
can be sampled. Consider sampling from opposite sides of the stack (four
total sampling ports) for large stacks, to permit use of shorter probe
lengths. Mark the probe with heat resistant tape or by some other method
to denote the proper distance into the stack or duct for each sampling
point.
8.1.1.2 Select a total sampling time such that a minimum total gas
volume of 0.60 scm (21 scf) will be collected, at a rate no greater than
0.021 m\3\/min (0.75 cfm). When both moisture content and pollutant
emission rate are to be determined, the moisture determination shall be
simultaneous with, and for the same total length of time as, the
pollutant emission rate run, unless otherwise specified in an applicable
subpart of the standards.
8.1.2 Preparation of Sampling Train.
8.1.2.1 Place known volumes of water in the first two impingers;
alternatively, transfer water into the first two impingers and record
the weight of each impinger (plus water) to the nearest 0.5 g. Weigh and
record the weight of the silica gel to the nearest 0.5 g, and transfer
the silica gel to the fourth impinger; alternatively, the silica gel may
first be transferred to the impinger, and the weight of the silica gel
plus impinger recorded.
8.1.2.2 Set up the sampling train as shown in Figure 4-1. Turn on
the probe heater and

[[Page 162]]

(if applicable) the filter heating system to temperatures of
approximately 120 [deg]C (248 [deg]F), to prevent water condensation
ahead of the condenser. Allow time for the temperatures to stabilize.
Place crushed ice and water in the ice bath container.
8.1.3 Leak Check Procedures. It is recommended, but not required,
that the volume metering system and sampling train be leak-checked as
follows:
8.1.3.1 Metering System. Same as Method 5, section 8.4.1.
8.1.3.2 Sampling Train. Disconnect the probe from the first impinger
or (if applicable) from the filter holder. Plug the inlet to the first
impinger (or filter holder), and pull a 380 mm (15 in.) Hg vacuum. A
lower vacuum may be used, provided that it is not exceeded during the
test. A leakage rate in excess of 4 percent of the average sampling rate
or 0.00057 m\3\/min (0.020 cfm), whichever is less, is unacceptable.
Following the leak check, reconnect the probe to the sampling train.
8.1.4 Sampling Train Operation. During the sampling run, maintain a
sampling rate within 10 percent of constant rate, or as specified by the
Administrator. For each run, record the data required on a data sheet
similar to that shown in Figure 4-3. Be sure to record the dry gas meter
reading at the beginning and end of each sampling time increment and
whenever sampling is halted. Take other appropriate readings at each
sample point at least once during each time increment.

Note: When Method 4 is used concurrently with an isokinetic method
(e.g., Method 5) the sampling rate should be maintained at isokinetic
conditions rather than 10 percent of constant rate.

8.1.4.1 To begin sampling, position the probe tip at the first
traverse point. Immediately start the pump, and adjust the flow to the
desired rate. Traverse the cross section, sampling at each traverse
point for an equal length of time. Add more ice and, if necessary, salt
to maintain a temperature of less than 20 [deg]C (68 [deg]F) at the
silica gel outlet.
8.1.4.2 After collecting the sample, disconnect the probe from the
first impinger (or from the filter holder), and conduct a leak check
(mandatory) of the sampling train as described in section 8.1.3.2.
Record the leak rate. If the leakage rate exceeds the allowable rate,
either reject the test results or correct the sample volume as in
section 12.3 of Method 5.
8.2 Approximation Method.

Note: The approximation method described below is presented only as
a suggested method (see section 2.0).

8.2.1 Place exactly 5 ml water in each impinger. Leak check the
sampling train as follows: Temporarily insert a vacuum gauge at or near
the probe inlet. Then, plug the probe inlet and pull a vacuum of at
least 250 mm (10 in.) Hg. Note the time rate of change of the dry gas
meter dial; alternatively, a rotameter (0 to 40 ml/min) may be
temporarily attached to the dry gas meter outlet to determine the
leakage rate. A leak rate not in excess of 2 percent of the average
sampling rate is acceptable.

Note: Release the probe inlet plug slowly before turning off the
pump.

8.2.2 Connect the probe, insert it into the stack, and sample at a
constant rate of 2 liters/min (0.071 cfm). Continue sampling until the
dry gas meter registers about 30 liters (1.1 ft\3\) or until visible
liquid droplets are carried over from the first impinger to the second.
Record temperature, pressure, and dry gas meter readings as indicated by
Figure 4-4.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
Section 8.1.1.4............. Leak rate of the Ensures the accuracy
sampling system of the volume of
cannot exceed four gas sampled.
percent of the (Reference Method).
average sampling
rate or 0.00057
m\3\/min (0.020
cfm).
Section 8.2.1............... Leak rate of the Ensures the accuracy
sampling system of the volume of
cannot exceed two gas sampled.
percent of the (Approximation
average sampling Method).
rate.
------------------------------------------------------------------------

9.2 Volume Metering System Checks. Same as Method 5, section 9.2.

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.

10.1 Reference Method. Calibrate the metering system, temperature
sensors, and barometer according to Method 5, sections 10.3, 10.5, and
10.6, respectively.
10.2 Approximation Method. Calibrate the metering system and the
barometer according to Method 6, section 10.1 and Method 5, section
10.6, respectively.

11.0 Analytical Procedure

11.1 Reference Method. Measure the volume of the moisture condensed
in each of the impingers to the nearest ml. Alternatively, if the
impingers were weighed prior to sampling, weigh the impingers after
sampling

[[Page 163]]

and record the difference in weight to the nearest 0.5 g. Determine the
increase in weight of the silica gel (or silica gel plus impinger) to
the nearest 0.5 g. Record this information (see example data sheet,
Figure 4-5), and calculate the moisture content, as described in section
12.0.
11.2 Approximation Method. Combine the contents of the two
impingers, and measure the volume to the nearest 0.5 ml.

12.0 Data Analysis and Calculations

Carry out the following calculations, retaining at least one extra
significant figure beyond that of the acquired data. Round off figures
after final calculation.
12.1 Reference Method.
12.1.1 Nomenclature.
Bws = Proportion of water vapor, by volume, in the gas
stream.
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 lb/lb-
mole).
Pm = Absolute pressure (for this method, same as barometric
pressure) at the dry gas meter, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
R = Ideal gas constant, 0.06236 (mm Hg)(m\3\)/(g-mole)([deg]K) for
metric units and 21.85 (in. Hg)(ft\3\)/(lb-mole)([deg]R) for
English units.
Tm = Absolute temperature at meter, [deg]K ([deg]R).
Tstd = Standard absolute temperature, 293 [deg]K (528
[deg]R).
Vf = Final volume of condenser water, ml.
Vi = Initial volume, if any, of condenser water, ml.
Vm = Dry gas volume measured by dry gas meter, dcm (dcf).
Vm(std) = Dry gas volume measured by the dry gas meter,
corrected to standard conditions, dscm (dscf).
Vwc(std) = Volume of water vapor condensed, corrected to
standard conditions, scm (scf).
Vwsg(std) = Volume of water vapor collected in silica gel,
corrected to standard conditions, scm (scf).
Wf = Final weight of silica gel or silica gel plus impinger,
g.
Wi = Initial weight of silica gel or silica gel plus
impinger, g.
Y = Dry gas meter calibration factor.
FVm = Incremental dry gas volume measured by dry gas meter at
each traverse point, dcm (dcf).
nw = Density of water, 0.9982 g/ml (0.002201 lb/ml).

12.1.2 Volume of Water Vapor Condensed.
[GRAPHIC] [TIFF OMITTED] TR17OC00.098

Where:

K1 = 0.001333 m\3\/ml for metric units,
= 0.04706 ft\3\/ml for English units.

12.1.3 Volume of Water Collected in Silica Gel.
[GRAPHIC] [TIFF OMITTED] TR17OC00.099

Where:

K2 = 1.0 g/g for metric units,
= 453.6 g/lb for English units.
K3 = 0.001335 m\3\/g for metric units,
= 0.04715 ft\3\/g for English units.

12.1.4 Sample Gas Volume.
[GRAPHIC] [TIFF OMITTED] TR17OC00.100

Where:

K4 = 0.3855 [deg]K/mm Hg for metric units,
= 17.64 [deg]R/in. Hg for English units.

Note: If the post-test leak rate (Section 8.1.4.2) exceeds the
allowable rate, correct the value of Vm in Equation 4-3, as described in
section 12.3 of Method 5.

12.1.5 Moisture Content.
[GRAPHIC] [TIFF OMITTED] TR17OC00.101

12.1.6 Verification of Constant Sampling Rate. For each time
increment, determine the FVm. Calculate the average. If the
value for any time increment differs from the average by more than 10
percent, reject the results, and repeat the run.
12.1.7 In saturated or moisture droplet-laden gas streams, two
calculations of the moisture content of the stack gas shall be made, one
using a value based upon the saturated conditions (see section 4.1), and
another based upon the results of the impinger

[[Page 164]]

analysis. The lower of these two values of Bws shall be
considered correct.
12.2 Approximation Method. The approximation method presented is
designed to estimate the moisture in the stack gas; therefore, other
data, which are only necessary for accurate moisture determinations, are
not collected. The following equations adequately estimate the moisture
content for the purpose of determining isokinetic sampling rate
settings.
12.2.1 Nomenclature.
Bwm = Approximate proportion by volume of water vapor in the
gas stream leaving the second impinger, 0.025.
Bws = Water vapor in the gas stream, proportion by volume.
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 lb/lb-
mole).
Pm = Absolute pressure (for this method, same as barometric
pressure) at the dry gas meter, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
R = Ideal gas constant, 0.06236 [(mm Hg)(m\3\)]/[(g-mole)(K)] for metric
units and 21.85 [(in. Hg)(ft\3\)]/[(lb-mole)([deg]R)] for
English units.
Tm = Absolute temperature at meter, [deg]K ([deg]R).
Tstd = Standard absolute temperature, 293 [deg]K (528
[deg]R).
Vf = Final volume of impinger contents, ml.
Vi = Initial volume of impinger contents, ml.
Vm = Dry gas volume measured by dry gas meter, dcm (dcf).
Vm(std) = Dry gas volume measured by dry gas meter, corrected
to standard conditions, dscm (dscf).
Vwc(std) = Volume of water vapor condensed, corrected to
standard conditions, scm (scf).
Y = Dry gas meter calibration factor.
nw = Density of water, 0.09982 g/ml (0.002201 lb/ml).

12.2.2 Volume of Water Vapor Collected.
[GRAPHIC] [TIFF OMITTED] TR17OC00.102

Where:

K5 = 0.001333 m\3\/ml for metric units,
= 0.04706 ft\3\/ml for English units.

12.2.3 Sample Gas Volume.
[GRAPHIC] [TIFF OMITTED] TR17OC00.103

Where:

K6 = 0.3855 [deg]K/mm Hg for metric units,
= 17.64 [deg]R/in. Hg for English units.

12.2.4 Approximate Moisture Content.
[GRAPHIC] [TIFF OMITTED] TR17OC00.104

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 The procedure described in Method 5 for determining moisture
content is an acceptable alternative to Method 4.
16.2 The procedures in Method 6A for determining moisture is an
acceptable alternative to Method 4.
16.3 Method 320 is an acceptable alternative to Method 4 for
determining moisture.
16.4 Using F-factors to determine moisture is an acceptable
alternative to Method 4 for a combustion stack not using a scrubber. If
this option is selected, calculate the moisture content as follows:

BWS - BH + BA + BF

Where:

[[Page 165]]

[GRAPHIC] [TIFF OMITTED] TR27FE14.011

Bws = Mole fraction of moisture in the stack gas.
Fd = Volume of dry combustion components per unit of heat
content at 0 percent oxygen, dscf/10\6\ Btu (scm/J). See Table
19-2 in Method 19.
FW = Volume of wet combustion components per unit of heat
content at 0 percent oxygen, wet scf/10\6\ Btu (scm/J). See
Table 19-2 in Method 19.
%RH = Percent relative humidity (calibrated hydrometer acceptable),
percent.
PBar = Barometric pressure, in. Hg.
T = Ambient temperature, [deg]F.
W = Percent free water by weight, percent.
O2 = Percent oxygen in stack gas, dry basis, percent.

17.0 References

1. Air Pollution Engineering Manual (Second Edition). Danielson,
J.A. (ed.). U.S. Environmental Protection Agency, Office of Air Quality
Planning and Standards. Research Triangle Park, NC. Publication No. AP-
40. 1973.
2. Devorkin, Howard, et al. Air Pollution Source Testing Manual. Air
Pollution Control District, Los Angeles, CA. November 1963.
3. Methods for Determination of Velocity, Volume, Dust and Mist
Content of Gases. Western Precipitation Division of Joy Manufacturing
Co. Los Angeles, CA. Bulletin WP-50. 1968.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

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[GRAPHIC] [TIFF OMITTED] TR17OC00.105

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[GRAPHIC] [TIFF OMITTED] TR17OC00.106

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Plant___________________________________________________________________
Location________________________________________________________________
Operator________________________________________________________________
Date____________________________________________________________________
Run No._________________________________________________________________
Ambient temperature_____________________________________________________
Barometric pressure_____________________________________________________
Probe Length____________________________________________________________

------------------------------------------------------------------------

-------------------------------------------------------------------------

------------------------------------------------------------------------

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--------------------------------------------------------------------------------------------------------------------------------------------------------
Gas sample temperature Temperature
Pressure at dry gas meter of gas
Sampling Stack differential Meter -------------------------- leaving
time (F), temperature across reading gas FVm m\3\ condenser
Traverse Pt. No. min [deg]C ( orifice sample (ft\3\) Inlet Tmin Outlet or last
[deg]F) meter FH mm volume m\3\ [deg]C ( Tmout impinger
(in.) H2O (ft\3\) [deg]F) [deg]C ( [deg]C (
[deg]F) [deg]F)
--------------------------------------------------------------------------------------------------------------------------------------------------------

--------------------------------------------------------------------------------------------------------------------------------------------------------

--------------------------------------------------------------------------------------------------------------------------------------------------------
Average
--------------------------------------------------------------------------------------------------------------------------------------------------------

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Location________________________________________________________________
Test____________________________________________________________________
Date____________________________________________________________________
Operator________________________________________________________________
Barometric pressure_____________________________________________________
Comments:_______________________________________________________________
________________________________________________________________________

Figure 4-3. Moisture Determination--Reference Method

----------------------------------------------------------------------------------------------------------------
Gas Volume through
Clock time meter, (Vm), m\3\ Rate meter setting m\3\/ Meter temperature
(ft\3\) min (ft\3\/min) [deg]C ( [deg]F)
----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------

Figure 4-4. Example Moisture Determination Field Data Sheet--
Approximation Method

------------------------------------------------------------------------
Impinger volume, Silica gel weight,
ml g
------------------------------------------------------------------------
Final
Initial
Difference
------------------------------------------------------------------------

Figure 4-5. Analytical Data--Reference Method

Method 5--Determination of Particulate Matter Emissions From Stationary
Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3.

1.0 Scope and Application

1.1 Analyte. Particulate matter (PM). No CAS number assigned.
1.2 Applicability. This method is applicable for the determination
of PM emissions from stationary sources.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

Particulate matter is withdrawn isokinetically from the source and
collected on a glass fiber filter maintained at a temperature of 120 14
[deg]C (248 25 [deg]F) or such other temperature as specified by an
applicable subpart of the standards or approved by the Administrator for
a particular application. The PM mass, which includes any material that
condenses at or above the filtration temperature, is determined
gravimetrically after the removal of uncombined water.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The following items are required for sample
collection:
6.1.1 Sampling Train. A schematic of the sampling train used in this
method is shown in Figure 5-1 in section 18.0. Complete construction
details are given in APTD-0581 (Reference 2 in section 17.0); commercial

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models of this train are also available. For changes from APTD-0581 and
for allowable modifications of the train shown in Figure 5-1, see the
following subsections.

Note: The operating and maintenance procedures for the sampling
train are described in APTD-0576 (Reference 3 in section 17.0). Since
correct usage is important in obtaining valid results, all users should
read APTD-0576 and adopt the operating and maintenance procedures
outlined in it, unless otherwise specified herein.

6.1.1.1 Probe Nozzle. Stainless steel (316) or glass with a sharp,
tapered leading edge. The angle of taper shall be 30[deg],
and the taper shall be on the outside to preserve a constant internal
diameter. The probe nozzle shall be of the button-hook or elbow design,
unless otherwise specified by the Administrator. If made of stainless
steel, the nozzle shall be constructed from seamless tubing. Other
materials of construction may be used, subject to the approval of the
Administrator. A range of nozzle sizes suitable for isokinetic sampling
should be available. Typical nozzle sizes range from 0.32 to 1.27 cm
(\1/8\ to \1/2\ in) inside diameter (ID) in increments of 0.16 cm (\1/
16\ in). Larger nozzles sizes are also available if higher volume
sampling trains are used. Each nozzle shall be calibrated, according to
the procedures outlined in section 10.1.
6.1.1.2 Probe Liner. Borosilicate or quartz glass tubing with a
heating system capable of maintaining a probe gas temperature during
sampling of 120 14 [deg]C (248 25 [deg]F), or such other temperature
as specified by an applicable subpart of the standards or as approved by
the Administrator for a particular application. Since the actual
temperature at the outlet of the probe is not usually monitored during
sampling, probes constructed according to APTD-0581 and utilizing the
calibration curves of APTD-0576 (or calibrated according to the
procedure outlined in APTD-0576) will be considered acceptable. Either
borosilicate or quartz glass probe liners may be used for stack
temperatures up to about 480 [deg]C (900 [deg]F); quartz glass liners
shall be used for temperatures between 480 and 900 [deg]C (900 and 1,650
[deg]F). Both types of liners may be used at higher temperatures than
specified for short periods of time, subject to the approval of the
Administrator. The softening temperature for borosilicate glass is 820
[deg]C (1500 [deg]F), and for quartz glass it is 1500 [deg]C (2700
[deg]F). Whenever practical, every effort should be made to use
borosilicate or quartz glass probe liners. Alternatively, metal liners
(e.g., 316 stainless steel, Incoloy 825 or other corrosion resistant
metals) made of seamless tubing may be used, subject to the approval of
the Administrator.
6.1.1.3 Pitot Tube. Type S, as described in section 6.1 of Method 2,
or other device approved by the Administrator. The pitot tube shall be
attached to the probe (as shown in Figure 5-1) to allow constant
monitoring of the stack gas velocity. The impact (high pressure) opening
plane of the pitot tube shall be even with or above the nozzle entry
plane (see Method 2, Figure 2-7) during sampling. The Type S pitot tube
assembly shall have a known coefficient, determined as outlined in
section 10.0 of Method 2.
6.1.1.4 Differential Pressure Gauge. Inclined manometer or
equivalent device (two), as described in section 6.2 of Method 2. One
manometer shall be used for velocity head (Fp) readings, and the other,
for orifice differential pressure readings.
6.1.1.5 Filter Holder. Borosilicate glass, with a glass or Teflon
frit filter support and a silicone rubber gasket. Other materials of
construction (e.g., stainless steel or Viton) may be used, subject to
the approval of the Administrator. The holder design shall provide a
positive seal against leakage from the outside or around the filter. The
holder shall be attached immediately at the outlet of the probe (or
cyclone, if used).
6.1.1.6 Filter Heating System. Any heating system capable of
monitoring and maintaining temperature around the filter shall be used
to ensure the sample gas temperature exiting the filter of 120 14
[deg]C (248 25 [deg]F) during sampling or such other temperature as
specified by an applicable subpart of the standards or approved by the
Administrator for a particular application. The monitoring and
regulation of the temperature around the filter may be done with the
filter temperature sensor or another temperature sensor.
6.1.1.7 Filter Temperature Sensor. A temperature sensor capable of
measuring temperature to within 3 [deg]C (5.4 [deg]F) shall be
installed so that the sensing tip of the temperature sensor is in direct
contact with the sample gas exiting the filter. The sensing tip of the
sensor may be encased in glass, Teflon, or metal and must protrude at
least \1/2\ in. into the sample gas exiting the filter. The filter
temperature sensor must be monitored and recorded during sampling to
ensure a sample gas temperature exiting the filter of 120 14 [deg]C
(248 25 [deg]F), or such other temperature as specified by an
applicable subpart of the standards or approved by the Administrator for
a particular application.
6.1.1.8 Condenser. The following system shall be used to determine
the stack gas moisture content: Four impingers connected in series with
leak-free ground glass fittings or any similar leak-free
noncontaminating fittings. The first, third, and fourth impingers shall
be of the Greenburg-Smith design, modified by replacing the tip with a
1.3 cm (\1/2\ in.) ID glass tube extending to about 1.3 cm (\1/2\ in.)
from the bottom of the flask. The second impinger shall be of the
Greenburg-Smith design with the standard

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tip. Modifications (e.g., using flexible connections between the
impingers, using materials other than glass, or using flexible vacuum
lines to connect the filter holder to the condenser) may be used,
subject to the approval of the Administrator. The first and second
impingers shall contain known quantities of water (Section 8.3.1), the
third shall be empty, and the fourth shall contain a known weight of
silica gel, or equivalent desiccant. A temperature sensor, capable of
measuring temperature to within 1 [deg]C (2 [deg]F) shall be placed at
the outlet of the fourth impinger for monitoring purposes.
Alternatively, any system that cools the sample gas stream and allows
measurement of the water condensed and moisture leaving the condenser,
each to within 1 ml or 1 g may be used, subject to the approval of the
Administrator. An acceptable technique involves the measurement of
condensed water either gravimetrically or volumetrically and the
determination of the moisture leaving the condenser by: (1) monitoring
the temperature and pressure at the exit of the condenser and using
Dalton's law of partial pressures; or (2) passing the sample gas stream
through a tared silica gel (or equivalent desiccant) trap with exit
gases kept below 20 [deg]C (68 [deg]F) and determining the weight gain.
If means other than silica gel are used to determine the amount of
moisture leaving the condenser, it is recommended that silica gel (or
equivalent) still be used between the condenser system and pump to
prevent moisture condensation in the pump and metering devices and to
avoid the need to make corrections for moisture in the metered volume.

Note: If a determination of the PM collected in the impingers is
desired in addition to moisture content, the impinger system described
above shall be used, without modification. Individual States or control
agencies requiring this information shall be contacted as to the sample
recovery and analysis of the impinger contents.

6.1.1.9 Metering System. Vacuum gauge, leak-free pump, calibrated
temperature sensors (rechecked at at least one point after each test),
dry gas meter (DGM) capable of measuring volume to within 2 percent, and
related equipment, as shown in Figure 5-1. Alternatively, an Isostack
metering system may be used if all Method 5 calibrations are performed,
with the exception of those related to FH@ in Section 9.2.1, wherein the
sample flow rate system shall be calibrated in lieu of FH@ and shall not
deviate by more than 5 percent. Other metering systems capable of
maintaining sampling rates within 10 percent of isokinetic and of
determining sample volumes to within 2 percent may be used, subject to
the approval of the Administrator. When the metering system is used in
conjunction with a pitot tube, the system shall allow periodic checks of
isokinetic rates.
6.1.1.10 Sampling trains utilizing metering systems designed for
higher flow rates than that described in APTD-0581 or APTD-0576 may be
used provided that the specifications of this method are met.
6.1.2 Barometer. Mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 2.5 mm Hg (0.1 in.).

Note: The barometric pressure reading may be obtained from a nearby
National Weather Service station. In this case, the station value (which
is the absolute barometric pressure) shall be requested and an
adjustment for elevation differences between the weather station and
sampling point shall be made at a rate of minus 2.5 mm Hg (0.1 in.) per
30 m (100 ft) elevation increase or plus 2.5 mm Hg (0.1 in) per 30 m
(100 ft) elevation decrease.

6.1.3 Gas Density Determination Equipment. Temperature sensor and
pressure gauge, as described in sections 6.3 and 6.4 of Method 2, and
gas analyzer, if necessary, as described in Method 3. The temperature
sensor shall, preferably, be permanently attached to the pitot tube or
sampling probe in a fixed configuration, such that the tip of the sensor
extends beyond the leading edge of the probe sheath and does not touch
any metal. Alternatively, the sensor may be attached just prior to use
in the field. Note, however, that if the temperature sensor is attached
in the field, the sensor must be placed in an interference-free
arrangement with respect to the Type S pitot tube openings (see Method
2, Figure 2-4). As a second alternative, if a difference of not more
than 1 percent in the average velocity measurement is to be introduced,
the temperature sensor need not be attached to the probe or pitot tube.
(This alternative is subject to the approval of the Administrator.)
6.2 Sample Recovery. The following items are required for sample
recovery:
6.2.1 Probe-Liner and Probe-Nozzle Brushes. Nylon bristle brushes
with stainless steel wire handles. The probe brush shall have extensions
(at least as long as the probe) constructed of stainless steel, Nylon,
Teflon, or similarly inert material. The brushes shall be properly sized
and shaped to brush out the probe liner and nozzle.
6.2.2 Wash Bottles. Two Glass wash bottles are recommended.
Alternatively, polyethylene wash bottles may be used. It is recommended
that acetone not be stored in polyethylene bottles for longer than a
month.
6.2.3 Glass Sample Storage Containers. Chemically resistant,
borosilicate glass bottles, for acetone washes, 500 ml or 1000 ml. Screw
cap liners shall either be rubber-backed Teflon or shall be constructed
so as

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to be leak-free and resistant to chemical attack by acetone. (Narrow
mouth glass bottles have been found to be less prone to leakage.)
Alternatively, polyethylene bottles may be used.
6.2.4 Petri Dishes. For filter samples; glass or polyethylene,
unless otherwise specified by the Administrator.
6.2.5 Graduated Cylinder and/or Balance. To measure condensed water
to within 1 ml or 0.5 g. Graduated cylinders shall have subdivisions no
greater than 2 ml.
6.2.6 Plastic Storage Containers. Air-tight containers to store
silica gel.
6.2.7 Funnel and Rubber Policeman. To aid in transfer of silica gel
to container; not necessary if silica gel is weighed in the field.
6.2.8 Funnel. Glass or polyethylene, to aid in sample recovery.
6.3 Sample Analysis. The following equipment is required for sample
analysis:
6.3.1 Glass Weighing Dishes.
6.3.2 Desiccator.
6.3.3 Analytical Balance. To measure to within 0.1 mg.
6.3.4 Balance. To measure to within 0.5 g.
6.3.5 Beakers. 250 ml.
6.3.6 Hygrometer. To measure the relative humidity of the laboratory
environment.
6.3.7 Temperature Sensor. To measure the temperature of the
laboratory environment.

7.0 Reagents and Standards

7.1 Sample Collection. The following reagents are required for
sample collection:
7.1.1 Filters. Glass fiber filters, without organic binder,
exhibiting at least 99.95 percent efficiency (<0.05 percent penetration)
on 0.3 micron dioctyl phthalate smoke particles. The filter efficiency
test shall be conducted in accordance with ASTM Method D 2986-71, 78, or
95a (incorporated by reference--see Sec. 60.17). Test data from the
supplier's quality control program are sufficient for this purpose. In
sources containing SO2 or SO3, the filter material
must be of a type that is unreactive to SO2 or
SO3. Reference 10 in section 17.0 may be used to select the
appropriate filter.
7.1.2 Silica Gel. Indicating type, 6 to 16 mesh. If previously used,
dry at 175 [deg]C (350 [deg]F) for 2 hours. New silica gel may be used
as received. Alternatively, other types of desiccants (equivalent or
better) may be used, subject to the approval of the Administrator.
7.1.3 Water. When analysis of the material caught in the impingers
is required, deionized distilled water [to conform to ASTM D1193-77 or
91 Type 3 (incorporated by reference--see Sec. 60.17)] with at least
<0.001 percent residue shall be used or as specified in the applicable
method requiring analysis of the water. Run reagent blanks prior to
field use to eliminate a high blank on test samples.
7.1.4 Crushed Ice.
7.2 Sample Recovery. Acetone, reagent grade, 0.001
percent residue, in glass bottles, is required. Acetone from metal
containers generally has a high residue blank and should not be used.
Sometimes, suppliers transfer acetone to glass bottles from metal
containers; thus, acetone blanks shall be run prior to field use and
only acetone with low blank values (0.001 percent) shall be
used. In no case shall a blank value of greater than 0.001 percent of
the weight of acetone used be subtracted from the sample weight.
7.3 Sample Analysis. The following reagents are required for sample
analysis:
7.3.1 Acetone. Same as in section 7.2.
7.3.2 Desiccant. Anhydrous calcium sulfate, indicating type.
Alternatively, other types of desiccants may be used, subject to the
approval of the Administrator.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Pretest Preparation. It is suggested that sampling equipment be
maintained according to the procedures described in APTD-0576.
Alternative mercury-free thermometers may be used if the thermometers
are at a minimum equivalent in terms of performance or suitably
effective for the specific temperature measurement application.
8.1.1 Place 200 to 300 g of silica gel in each of several air-tight
containers. Weigh each container, including silica gel, to the nearest
0.5 g, and record this weight. As an alternative, the silica gel need
not be preweighed, but may be weighed directly in its impinger or
sampling holder just prior to train assembly.
8.1.2 Check filters visually against light for irregularities,
flaws, or pinhole leaks. Label filters of the proper diameter on the
back side near the edge using numbering machine ink. As an alternative,
label the shipping containers (glass or polyethylene petri dishes), and
keep each filter in its identified container at all times except during
sampling.
8.1.3 Desiccate the filters at 20 5.6 [deg]C (68 10 [deg]F) and
ambient pressure for at least 24 hours. Weigh each filter (or filter and
shipping container) at intervals of at least 6 hours to a constant
weight (i.e., 0.5 mg change from previous weighing). Record
results to the nearest 0.1 mg. During each weighing, the period for
which the filter is exposed to the laboratory atmosphere shall be less
than 2 minutes. Alternatively (unless otherwise specified by the
Administrator), the filters may be oven dried at 105 [deg]C (220 [deg]F)
for 2 to 3 hours, desiccated for 2 hours, and weighed. Procedures other
than those described, which account for relative humidity effects, may
be used, subject to the approval of the Administrator.
8.2 Preliminary Determinations.
8.2.1 Select the sampling site and the minimum number of sampling
points according

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to Method 1 or as specified by the Administrator. Determine the stack
pressure, temperature, and the range of velocity heads using Method 2;
it is recommended that a leak check of the pitot lines (see Method 2,
section 8.1) be performed. Determine the moisture content using
Approximation Method 4 or its alternatives for the purpose of making
isokinetic sampling rate settings. Determine the stack gas dry molecular
weight, as described in Method 2, section 8.6; if integrated Method 3
sampling is used for molecular weight determination, the integrated bag
sample shall be taken simultaneously with, and for the same total length
of time as, the particulate sample run.
8.2.2 Select a nozzle size based on the range of velocity heads,
such that it is not necessary to change the nozzle size in order to
maintain isokinetic sampling rates. During the run, do not change the
nozzle size. Ensure that the proper differential pressure gauge is
chosen for the range of velocity heads encountered (see section 8.3 of
Method 2).
8.2.3 Select a suitable probe liner and probe length such that all
traverse points can be sampled. For large stacks, consider sampling from
opposite sides of the stack to reduce the required probe length.
8.2.4 Select a total sampling time greater than or equal to the
minimum total sampling time specified in the test procedures for the
specific industry such that (l) the sampling time per point is not less
than 2 minutes (or some greater time interval as specified by the
Administrator), and (2) the sample volume taken (corrected to standard
conditions) will exceed the required minimum total gas sample volume.
The latter is based on an approximate average sampling rate.
8.2.5 The sampling time at each point shall be the same. It is
recommended that the number of minutes sampled at each point be an
integer or an integer plus one-half minute, in order to avoid
timekeeping errors.
8.2.6 In some circumstances (e.g., batch cycles) it may be necessary
to sample for shorter times at the traverse points and to obtain smaller
gas sample volumes. In these cases, the Administrator's approval must
first be obtained.
8.3 Preparation of Sampling Train.
8.3.1 During preparation and assembly of the sampling train, keep
all openings where contamination can occur covered until just prior to
assembly or until sampling is about to begin. Place 100 ml of water in
each of the first two impingers, leave the third impinger empty, and
transfer approximately 200 to 300 g of preweighed silica gel from its
container to the fourth impinger. More silica gel may be used, but care
should be taken to ensure that it is not entrained and carried out from
the impinger during sampling. Place the container in a clean place for
later use in the sample recovery. Alternatively, the weight of the
silica gel plus impinger may be determined to the nearest 0.5 g and
recorded.
8.3.2 Using a tweezer or clean disposable surgical gloves, place a
labeled (identified) and weighed filter in the filter holder. Be sure
that the filter is properly centered and the gasket properly placed so
as to prevent the sample gas stream from circumventing the filter. Check
the filter for tears after assembly is completed.
8.3.3 When glass probe liners are used, install the selected nozzle
using a Viton A O-ring when stack temperatures are less than 260 [deg]C
(500 [deg]F) or a heat-resistant string gasket when temperatures are
higher. See APTD-0576 for details. Other connecting systems using either
316 stainless steel or Teflon ferrules may be used. When metal liners
are used, install the nozzle as discussed above or by a leak-free direct
mechanical connection. Mark the probe with heat resistant tape or by
some other method to denote the proper distance into the stack or duct
for each sampling point.
8.3.4 Set up the train as shown in Figure 5-1 ensuring that the
connections are leak-tight. Subject to the approval of the
Administrator, a glass cyclone may be used between the probe and filter
holder when the total particulate catch is expected to exceed 100 mg or
when water droplets are present in the stack gas.
8.3.5 Place crushed ice around the impingers.
8.4 Leak-Check Procedures.
8.4.1 Leak Check of Metering System Shown in Figure 5-1. That
portion of the sampling train from the pump to the orifice meter should
be leak-checked prior to initial use and after each shipment. Leakage
after the pump will result in less volume being recorded than is
actually sampled. The following procedure is suggested (see Figure 5-2):
Close the main valve on the meter box. Insert a one-hole rubber stopper
with rubber tubing attached into the orifice exhaust pipe. Disconnect
and vent the low side of the orifice manometer. Close off the low side
orifice tap. Pressurize the system to 13 to 18 cm (5 to 7 in.) water
column by blowing into the rubber tubing. Pinch off the tubing, and
observe the manometer for one minute. A loss of pressure on the
manometer indicates a leak in the meter box; leaks, if present, must be
corrected.
8.4.2 Pretest Leak Check. A pretest leak check of the sampling train
is recommended, but not required. If the pretest leak check is
conducted, the following procedure should be used.
8.4.2.1 After the sampling train has been assembled, turn on and set
the filter and probe heating systems to the desired operating
temperatures. Allow time for the temperatures to stabilize. If a Viton A
O-ring or

[[Page 175]]

other leak-free connection is used in assembling the probe nozzle to the
probe liner, leak-check the train at the sampling site by plugging the
nozzle and pulling a 380 mm (15 in.) Hg vacuum.

Note: A lower vacuum may be used, provided that it is not exceeded
during the test.

8.4.2.2 If a heat-resistant string is used, do not connect the probe
to the train during the leak check. Instead, leak-check the train by
first plugging the inlet to the filter holder (cyclone, if applicable)
and pulling a 380 mm (15 in.) Hg vacuum (see note in section 8.4.2.1).
Then connect the probe to the train, and leak-check at approximately 25
mm (1 in.) Hg vacuum; alternatively, the probe may be leak-checked with
the rest of the sampling train, in one step, at 380 mm (15 in.) Hg
vacuum. Leakage rates in excess of 4 percent of the average sampling
rate or 0.00057 m\3\/min (0.020 cfm), whichever is less, are
unacceptable.
8.4.2.3 The following leak-check instructions for the sampling train
described in APTD-0576 and APTD-0581 may be helpful. Start the pump with
the bypass valve fully open and the coarse adjust valve completely
closed. Partially open the coarse adjust valve, and slowly close the
bypass valve until the desired vacuum is reached. Do not reverse the
direction of the bypass valve, as this will cause water to back up into
the filter holder. If the desired vacuum is exceeded, either leak-check
at this higher vacuum, or end the leak check and start over.
8.4.2.4 When the leak check is completed, first slowly remove the
plug from the inlet to the probe, filter holder, or cyclone (if
applicable), and immediately turn off the vacuum pump. This prevents the
water in the impingers from being forced backward into the filter holder
and the silica gel from being entrained backward into the third
impinger.
8.4.3 Leak Checks During Sample Run. If, during the sampling run, a
component (e.g., filter assembly or impinger) change becomes necessary,
a leak check shall be conducted immediately before the change is made.
The leak check shall be done according to the procedure outlined in
section 8.4.2 above, except that it shall be done at a vacuum equal to
or greater than the maximum value recorded up to that point in the test.
If the leakage rate is found to be no greater than 0.00057 m\3\/min
(0.020 cfm) or 4 percent of the average sampling rate (whichever is
less), the results are acceptable, and no correction will need to be
applied to the total volume of dry gas metered; if, however, a higher
leakage rate is obtained, either record the leakage rate and plan to
correct the sample volume as shown in section 12.3 of this method, or
void the sample run.

Note: Immediately after component changes, leak checks are optional.
If such leak checks are done, the procedure outlined in section 8.4.2
above should be used.

8.4.4 Post-Test Leak Check. A leak check of the sampling train is
mandatory at the conclusion of each sampling run. The leak check shall
be performed in accordance with the procedures outlined in section
8.4.2, except that it shall be conducted at a vacuum equal to or greater
than the maximum value reached during the sampling run. If the leakage
rate is found to be no greater than 0.00057 m\3\ min (0.020 cfm) or 4
percent of the average sampling rate (whichever is less), the results
are acceptable, and no correction need be applied to the total volume of
dry gas metered. If, however, a higher leakage rate is obtained, either
record the leakage rate and correct the sample volume as shown in
section 12.3 of this method, or void the sampling run.
8.5 Sampling Train Operation. During the sampling run, maintain an
isokinetic sampling rate (within 10 percent of true isokinetic unless
otherwise specified by the Administrator) and a sample gas temperature
through the filter of 120 14 [deg]C (248 25 [deg]F) or such other
temperature as specified by an applicable subpart of the standards or
approved by the Administrator.
8.5.1 For each run, record the data required on a data sheet such as
the one shown in Figure 5-3. Be sure to record the initial DGM reading.
Record the DGM readings at the beginning and end of each sampling time
increment, when changes in flow rates are made, before and after each
leak check, and when sampling is halted. Take other readings indicated
by Figure 5-3 at least once at each sample point during each time
increment and additional readings when significant changes (20 percent
variation in velocity head readings) necessitate additional adjustments
in flow rate. Level and zero the manometer. Because the manometer level
and zero may drift due to vibrations and temperature changes, make
periodic checks during the traverse.
8.5.2 Clean the portholes prior to the test run to minimize the
chance of collecting deposited material. To begin sampling, verify that
the filter and probe heating systems are up to temperature, remove the
nozzle cap, verify that the pitot tube and probe are properly
positioned. Position the nozzle at the first traverse point with the tip
pointing directly into the gas stream. Immediately start the pump, and
adjust the flow to isokinetic conditions. Nomographs are available which
aid in the rapid adjustment of the isokinetic sampling rate without
excessive computations. These nomographs are designed for use when the
Type S pitot tube coefficient (Cp) is 0.85 0.02, and the
stack gas equivalent density [dry molecular weight (Md)] is
equal to 29 4. APTD-0576 details the procedure for using the
nomographs. If Cp and Md are outside the above
stated ranges,

[[Page 176]]

do not use the nomographs unless appropriate steps (see Reference 7 in
section 17.0) are taken to compensate for the deviations.
8.5.3 When the stack is under significant negative pressure (i.e.,
height of impinger stem), take care to close the coarse adjust valve
before inserting the probe into the stack to prevent water from backing
into the filter holder. If necessary, the pump may be turned on with the
coarse adjust valve closed.
8.5.4 When the probe is in position, block off the openings around
the probe and porthole to prevent unrepresentative dilution of the gas
stream.
8.5.5 Traverse the stack cross-section, as required by Method 1 or
as specified by the Administrator, being careful not to bump the probe
nozzle into the stack walls when sampling near the walls or when
removing or inserting the probe through the portholes; this minimizes
the chance of extracting deposited material.
8.5.6 During the test run, make periodic adjustments to keep the
temperature around the filter holder at the proper level to maintain the
sample gas temperature exiting the filter; add more ice and, if
necessary, salt to maintain a temperature of less than 20 [deg]C (68
[deg]F) at the condenser/silica gel outlet. Also, periodically check the
level and zero of the manometer.
8.5.7 If the pressure drop across the filter becomes too high,
making isokinetic sampling difficult to maintain, the filter may be
replaced in the midst of the sample run. It is recommended that another
complete filter assembly be used rather than attempting to change the
filter itself. Before a new filter assembly is installed, conduct a leak
check (see section 8.4.3). The total PM weight shall include the
summation of the filter assembly catches.
8.5.8 A single train shall be used for the entire sample run, except
in cases where simultaneous sampling is required in two or more separate
ducts or at two or more different locations within the same duct, or in
cases where equipment failure necessitates a change of trains. In all
other situations, the use of two or more trains will be subject to the
approval of the Administrator.

Note: When two or more trains are used, separate analyses of the
front-half and (if applicable) impinger catches from each train shall be
performed, unless identical nozzle sizes were used on all trains, in
which case, the front-half catches from the individual trains may be
combined (as may the impinger catches) and one analysis of front-half
catch and one analysis of impinger catch may be performed. Consult with
the Administrator for details concerning the calculation of results when
two or more trains are used.

8.5.9 At the end of the sample run, close the coarse adjust valve,
remove the probe and nozzle from the stack, turn off the pump, record
the final DGM meter reading, and conduct a post-test leak check, as
outlined in section 8.4.4. Also, leak-check the pitot lines as described
in Method 2, section 8.1. The lines must pass this leak check, in order
to validate the velocity head data.
8.6 Calculation of Percent Isokinetic. Calculate percent isokinetic
(see Calculations, section 12.11) to determine whether the run was valid
or another test run should be made. If there was difficulty in
maintaining isokinetic rates because of source conditions, consult with
the Administrator for possible variance on the isokinetic rates.
8.7 Sample Recovery.
8.7.1 Proper cleanup procedure begins as soon as the probe is
removed from the stack at the end of the sampling period. Allow the
probe to cool.
8.7.2 When the probe can be safely handled, wipe off all external PM
near the tip of the probe nozzle, and place a cap over it to prevent
losing or gaining PM. Do not cap off the probe tip tightly while the
sampling train is cooling down. This would create a vacuum in the filter
holder, thereby drawing water from the impingers into the filter holder.
8.7.3 Before moving the sample train to the cleanup site, remove the
probe from the sample train and cap the open outlet of the probe. Be
careful not to lose any condensate that might be present. Cap the filter
inlet where the probe was fastened. Remove the umbilical cord from the
last impinger, and cap the impinger. If a flexible line is used between
the first impinger or condenser and the filter holder, disconnect the
line at the filter holder, and let any condensed water or liquid drain
into the impingers or condenser. Cap off the filter holder outlet and
impinger inlet. Either ground-glass stoppers, plastic caps, or serum
caps may be used to close these openings.
8.7.4 Transfer the probe and filter-impinger assembly to the cleanup
area. This area should be clean and protected from the wind so that the
chances of contaminating or losing the sample will be minimized.
8.7.5 Save a portion of the acetone used for cleanup as a blank.
From each storage container of acetone used for cleanup, save 200 ml and
place in a glass sample container labeled ``acetone blank.'' To minimize
any particulate contamination, rinse the wash bottle prior to filling
from the tested container.
8.7.6 Inspect the train prior to and during disassembly, and note
any abnormal conditions. Treat the samples as follows:
8.7.6.1 Container No. 1. Carefully remove the filter from the filter
holder, and place it in its identified petri dish container. Use a pair
of tweezers and/or clean disposable surgical gloves to handle the
filter. If it is necessary to fold the filter, do so such that the

[[Page 177]]

PM cake is inside the fold. Using a dry Nylon bristle brush and/or a
sharp-edged blade, carefully transfer to the petri dish any PM and/or
filter fibers that adhere to the filter holder gasket. Seal the
container.
8.7.6.2 Container No. 2. Taking care to see that dust on the outside
of the probe or other exterior surfaces does not get into the sample,
quantitatively recover PM or any condensate from the probe nozzle, probe
fitting, probe liner, and front half of the filter holder by washing
these components with acetone and placing the wash in a glass container.
Deionized distilled water may be used instead of acetone when approved
by the Administrator and shall be used when specified by the
Administrator. In these cases, save a water blank, and follow the
Administrator's directions on analysis. Perform the acetone rinse as
follows:
8.7.6.2.1 Carefully remove the probe nozzle. Clean the inside
surface by rinsing with acetone from a wash bottle and brushing with a
Nylon bristle brush. Brush until the acetone rinse shows no visible
particles, after which make a final rinse of the inside surface with
acetone.
8.7.6.2.2 Brush and rinse the inside parts of the fitting with
acetone in a similar way until no visible particles remain.
8.7.6.2.3 Rinse the probe liner with acetone by tilting and rotating
the probe while squirting acetone into its upper end so that all inside
surfaces will be wetted with acetone. Let the acetone drain from the
lower end into the sample container. A funnel (glass or polyethylene)
may be used to aid in transferring liquid washes to the container.
Follow the acetone rinse with a probe brush. Hold the probe in an
inclined position, squirt acetone into the upper end as the probe brush
is being pushed with a twisting action through the probe; hold a sample
container underneath the lower end of the probe, and catch any acetone
and particulate matter that is brushed from the probe. Run the brush
through the probe three times or more until no visible PM is carried out
with the acetone or until none remains in the probe liner on visual
inspection. With stainless steel or other metal probes, run the brush
through in the above prescribed manner at least six times since metal
probes have small crevices in which particulate matter can be entrapped.
Rinse the brush with acetone, and quantitatively collect these washings
in the sample container. After the brushing, make a final acetone rinse
of the probe.
8.7.6.2.4 It is recommended that two people clean the probe to
minimize sample losses. Between sampling runs, keep brushes clean and
protected from contamination.
8.7.6.2.5 After ensuring that all joints have been wiped clean of
silicone grease, clean the inside of the front half of the filter holder
by rubbing the surfaces with a Nylon bristle brush and rinsing with
acetone. Rinse each surface three times or more if needed to remove
visible particulate. Make a final rinse of the brush and filter holder.
Carefully rinse out the glass cyclone, also (if applicable). After all
acetone washings and particulate matter have been collected in the
sample container, tighten the lid on the sample container so that
acetone will not leak out when it is shipped to the laboratory. Mark the
height of the fluid level to allow determination of whether leakage
occurred during transport. Label the container to identify clearly its
contents.
8.7.6.3 Container No. 3. Note the color of the indicating silica gel
to determine whether it has been completely spent, and make a notation
of its condition. Transfer the silica gel from the fourth impinger to
its original container, and seal. A funnel may make it easier to pour
the silica gel without spilling. A rubber policeman may be used as an
aid in removing the silica gel from the impinger. It is not necessary to
remove the small amount of dust particles that may adhere to the
impinger wall and are difficult to remove. Since the gain in weight is
to be used for moisture calculations, do not use any water or other
liquids to transfer the silica gel. If a balance is available in the
field, follow the procedure for Container No. 3 in section 11.2.3.
8.7.6.4 Impinger Water. Treat the impingers as follows: Make a
notation of any color or film in the liquid catch. Measure the liquid
that is in the first three impingers to within 1 ml by using a graduated
cylinder or by weighing it to within 0.5 g by using a balance. Record
the volume or weight of liquid present. This information is required to
calculate the moisture content of the effluent gas. Discard the liquid
after measuring and recording the volume or weight, unless analysis of
the impinger catch is required (see NOTE, section 6.1.1.8). If a
different type of condenser is used, measure the amount of moisture
condensed either volumetrically or gravimetrically.
8.8 Sample Transport. Whenever possible, containers should be
shipped in such a way that they remain upright at all times.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.4, 10.1-10.6................ Sampling Ensures accurate
equipment leak measurement of stack
check and gas flow rate,
calibration. sample volume.
------------------------------------------------------------------------

[[Page 178]]

9.2 Volume Metering System Checks. The following procedures are
suggested to check the volume metering system calibration values at the
field test site prior to sample collection. These procedures are
optional.
9.2.1 Meter Orifice Check. Using the calibration data obtained
during the calibration procedure described in section 10.3, determine
the FH@ for the metering system orifice. The FH@ is the orifice pressure
differential in units of in. H2O that correlates to 0.75 cfm
of air at 528 [deg]R and 29.92 in. Hg. The FH@ is calculated as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.107

Where:

FH = Average pressure differential across the orifice meter, in.
H2O.
Tm = Absolute average DGM temperature, [deg]R.
Pbar = Barometric pressure, in. Hg.
k = Total sampling time, min.
Y = DGM calibration factor, dimensionless.
Vm = Volume of gas sample as measured by DGM, dcf.
0.0319 = (0.0567 in. Hg/[deg]R) (0.75 cfm)\2\

9.2.1.1 Before beginning the field test (a set of three runs usually
constitutes a field test), operate the metering system (i.e., pump,
volume meter, and orifice) at the FH@ pressure differential for 10
minutes. Record the volume collected, the DGM temperature, and the
barometric pressure. Calculate a DGM calibration check value,
Yc, as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.108

where:

Yc = DGM calibration check value, dimensionless.
10 = Run time, min.
9.2.1.2 Compare the Yc value with the dry gas meter
calibration factor Y to determine that: 0.97Y c <1.03Y. If
the Yc value is not within this range, the volume metering
system should be investigated before beginning the test.
9.2.2 Calibrated Critical Orifice. A critical orifice, calibrated
against a wet test meter or spirometer and designed to be inserted at
the inlet of the sampling meter box, may be used as a check by following
the procedure of section 16.2.

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.

10.1 Probe Nozzle. Probe nozzles shall be calibrated before their
initial use in the field. Using a micrometer, measure the ID of the
nozzle to the nearest 0.025 mm (0.001 in.). Make three separate
measurements using different diameters each time, and obtain the average
of the measurements. The difference between the high and low numbers
shall not exceed 0.1 mm (0.004 in.). When nozzles become nicked, dented,
or corroded, they shall be reshaped, sharpened, and recalibrated before
use. Each nozzle shall be permanently and uniquely identified.
10.2 Pitot Tube Assembly. The Type S pitot tube assembly shall be
calibrated according to the procedure outlined in section 10.1 of Method
2.
10.3 Metering System.
10.3.1 Calibration Prior to Use. Before its initial use in the
field, the metering system shall be calibrated as follows: Connect the
metering system inlet to the outlet of a wet test meter that is accurate
to within 1 percent. Refer to Figure 5-4. The wet test meter should have
a capacity of 30 liters/rev (1 ft\3\/rev). A spirometer of 400 liters
(14 ft\3\) or more capacity, or equivalent, may be used for this
calibration, although a wet test meter is usually more practical. The
wet test meter should be periodically calibrated with a spirometer or a
liquid displacement meter to ensure the accuracy of the wet test meter.
Spirometers or wet test meters of other sizes may be used, provided that
the specified accuracies of the procedure are maintained. Run the
metering system pump for about 15 minutes with the orifice manometer
indicating a median reading as expected in field use to allow the pump
to warm up and to permit the interior surface of the wet test meter to
be thoroughly wetted. Then, at each of a minimum of three orifice
manometer settings, pass an exact quantity of gas through the wet test
meter and note the gas volume indicated by the DGM. Also note the
barometric pressure and the temperatures of the wet test meter, the
inlet of the DGM, and the outlet of the DGM. Select the highest and
lowest orifice settings to bracket the expected field operating range of
the orifice. Use a minimum volume of 0.14 m\3\ (5 ft\3\) at all orifice
settings. Record all the data on a form similar to Figure 5-5 and
calculate Y, the DGM calibration factor, and FH , the orifice
calibration factor, at each orifice setting as shown on Figure 5-5.
Allowable tolerances for individual Y and FH values are
given in Figure 5-5. Use the average of the Y values in the calculations
in section 12.0.
10.3.1.1 Before calibrating the metering system, it is suggested
that a leak check be conducted. For metering systems having diaphragm
pumps, the normal leak-check procedure will not detect leakages within
the pump. For these cases the following leak-check procedure is
suggested: make a 10-minute calibration run at 0.00057 m\3\/min (0.020
cfm). At the end of the run, take the difference of the measured wet
test meter and DGM volumes. Divide the difference by

[[Page 179]]

10 to get the leak rate. The leak rate should not exceed 0.00057 m\3\/
min (0.020 cfm).
10.3.2 Calibration After Use. After each field use, the calibration
of the metering system shall be checked by performing three calibration
runs at a single, intermediate orifice setting (based on the previous
field test), with the vacuum set at the maximum value reached during the
test series. To adjust the vacuum, insert a valve between the wet test
meter and the inlet of the metering system. Calculate the average value
of the DGM calibration factor. If the value has changed by more than 5
percent, recalibrate the meter over the full range of orifice settings,
as detailed in section 10.3.1.

Note: Alternative procedures (e.g., rechecking the orifice meter
coefficient) may be used, subject to the approval of the Administrator.

10.3.3 Acceptable Variation in Calibration Check. If the DGM
coefficient values obtained before and after a test series differ by
more than 5 percent, the test series shall either be voided, or
calculations for the test series shall be performed using whichever
meter coefficient value (i.e., before or after) gives the lower value of
total sample volume.
10.4 Probe Heater Calibration. Use a heat source to generate air
heated to selected temperatures that approximate those expected to occur
in the sources to be sampled. Pass this air through the probe at a
typical sample flow rate while measuring the probe inlet and outlet
temperatures at various probe heater settings. For each air temperature
generated, construct a graph of probe heating system setting versus
probe outlet temperature. The procedure outlined in APTD-0576 can also
be used. Probes constructed according to APTD-0581 need not be
calibrated if the calibration curves in APTD-0576 are used. Also, probes
with outlet temperature monitoring capabilities do not require
calibration.

Note: The probe heating system shall be calibrated before its
initial use in the field.

10.5 Temperature Sensors. Use the procedure in Section 10.3 of
Method 2 to calibrate in-stack temperature sensors. Dial thermometers,
such as are used for the DGM and condenser outlet, shall be calibrated
against mercury-in-glass thermometers. An alternative mercury-free NIST-
traceable thermometer may be used if the thermometer is, at a minimum,
equivalent in terms of performance or suitably effective for the
specific temperature measurement application. As an alternative, the
following single-point calibration procedure may be used. After each
test run series, check the accuracy (and, hence, the calibration) of
each thermocouple system at ambient temperature, or any other
temperature, within the range specified by the manufacturer, using a
reference thermometer (either ASTM reference thermometer or a
thermometer that has been calibrated against an ASTM reference
thermometer). The temperatures of the thermocouple and reference
thermometers shall agree to within 2 [deg]F.
10.6 Barometer. Calibrate against a mercury barometer or NIST-
traceable barometer prior to the field test. Alternatively, barometric
pressure may be obtained from a weather report that has been adjusted
for the test point (on the stack) elevation.

11.0 Analytical Procedure

11.1 Record the data required on a sheet such as the one shown in
Figure 5-6.
11.2 Handle each sample container as follows:
11.2.1 Container No. 1. Leave the contents in the shipping container
or transfer the filter and any loose PM from the sample container to a
tared glass weighing dish. Desiccate for 24 hours in a desiccator
containing anhydrous calcium sulfate. Weigh to a constant weight, and
report the results to the nearest 0.1 mg. For the purposes of this
section, the term ``constant weight'' means a difference of no more than
0.5 mg or 1 percent of total weight less tare weight, whichever is
greater, between two consecutive weighings, with no less than 6 hours of
desiccation time between weighings. Alternatively, the sample may be
oven dried at 104 [deg]C (220 [deg]F) for 2 to 3 hours, cooled in the
desiccator, and weighed to a constant weight, unless otherwise specified
by the Administrator. The sample may be oven dried at 104 [deg]C (220
[deg]F) for 2 to 3 hours. Once the sample has cooled, weigh the sample,
and use this weight as a final weight.
11.2.2 Container No. 2. Note the level of liquid in the container,
and confirm on the analysis sheet whether leakage occurred during
transport. If a noticeable amount of leakage has occurred, either void
the sample or use methods, subject to the approval of the Administrator,
to correct the final results. Measure the liquid in this container
either volumetrically to 1 ml or gravimetrically to 0.5 g. Transfer
the contents to a tared 250 ml beaker, and evaporate to dryness at
ambient temperature and pressure. Desiccate for 24 hours, and weigh to a
constant weight. Report the results to the nearest 0.1 mg.
11.2.3 Container No. 3. Weigh the spent silica gel (or silica gel
plus impinger) to the nearest 0.5 g using a balance. This step may be
conducted in the field.
11.2.4 Acetone Blank Container. Measure the acetone in this
container either volumetrically or gravimetrically. Transfer the acetone
to a tared 250 ml beaker, and evaporate to dryness at ambient
temperature and pressure. Desiccate for 24 hours, and weigh to a
constant weight. Report the results to the nearest 0.1 mg.

[[Page 180]]

Note: The contents of Container No. 2 as well as the acetone blank
container may be evaporated at temperatures higher than ambient. If
evaporation is done at an elevated temperature, the temperature must be
below the boiling point of the solvent; also, to prevent ``bumping,''
the evaporation process must be closely supervised, and the contents of
the beaker must be swirled occasionally to maintain an even temperature.
Use extreme care, as acetone is highly flammable and has a low flash
point.

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after the
final calculation. Other forms of the equations may be used, provided
that they give equivalent results.
12.1 Nomenclature.

An = Cross-sectional area of nozzle, m\2\ (ft\2\).
Bws = Water vapor in the gas stream, proportion by volume.
Ca = Acetone blank residue concentration, mg/mg.
cs = Concentration of particulate matter in stack gas, dry
basis, corrected to standard conditions, g/dscm (gr/dscf).
I = Percent of isokinetic sampling.
L1 = Individual leakage rate observed during the leak-check
conducted prior to the first component change, m\3\/min
(ft\3\/min)
La = Maximum acceptable leakage rate for either a pretest
leak-check or for a leak-check following a component change;
equal to 0.00057 m\3\/min (0.020 cfm) or 4 percent of the
average sampling rate, whichever is less.
Li = Individual leakage rate observed during the leak-check
conducted prior to the ``i\th\'' component change (i = 1, 2, 3
. . . n), m\3\/min (cfm).
Lp = Leakage rate observed during the post-test leak-check,
m\3\/min (cfm).
ma = Mass of residue of acetone after evaporation, mg.
mn = Total amount of particulate matter collected, mg.
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 lb/lb-
mole).
Pbar = Barometric pressure at the sampling site, mm Hg (in.
Hg).
Ps = Absolute stack gas pressure, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
R = Ideal gas constant, 0.06236 ((mm Hg)(m\3\))/((K)(g-mole)) {21.85
((in. Hg) (ft \3\))/(([deg]R) (lb-mole))}.
Tm = Absolute average DGM temperature (see Figure 5-3), K
([deg]R).
Ts = Absolute average stack gas temperature (see Figure 5-3),
K ([deg]R).
Tstd = Standard absolute temperature, 293 K (528 [deg]R).
Va = Volume of acetone blank, ml.
Vaw = Volume of acetone used in wash, ml.
V1c = Total volume of liquid collected in impingers and
silica gel (see Figure 5-6), ml.
Vm = Volume of gas sample as measured by dry gas meter, dcm
(dcf).
Vm(std) = Volume of gas sample measured by the dry gas meter,
corrected to standard conditions, dscm (dscf).
Vw(std) = Volume of water vapor in the gas sample, corrected
to standard conditions, scm (scf).
Vs = Stack gas velocity, calculated by Method 2, Equation 2-
7, using data obtained from Method 5, m/sec (ft/sec).
Wa = Weight of residue in acetone wash, mg.
Y = Dry gas meter calibration factor.
FH = Average pressure differential across the orifice meter (see Figure
5-4), mm H2O (in. H2O).
na = Density of acetone, mg/ml (see label on bottle).
nw = Density of water, 0.9982 g/ml. (0.002201 lb/ml).
k = Total sampling time, min.
k1 = Sampling time interval, from the beginning of a run
until the first component change, min.
ki = Sampling time interval, between two successive component
changes, beginning with the interval between the first and
second changes, min.
kp = Sampling time interval, from the final (n \th\)
component change until the end of the sampling run, min.
13.6 = Specific gravity of mercury.
60 = Sec/min.
100 = Conversion to percent.

12.2 Average Dry Gas Meter Temperature and Average Orifice Pressure
Drop. See data sheet (Figure 5-3).
12.3 Dry Gas Volume. Correct the sample volume measured by the dry
gas meter to standard conditions (20 [deg]C, 760 mm Hg or 68 [deg]F,
29.92 in. Hg) by using Equation 5-1.

[[Page 181]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.109

Where:

K1 = 0.3858 [deg]K/mm Hg for metric units, = 17.64 [deg]R/in.
Hg for English units.

Note: Equation 5-1 can be used as written unless the leakage rate
observed during any of the mandatory leak checks (i.e., the post-test
leak check or leak checks conducted prior to component changes) exceeds
La. If Lp or Li exceeds La,
Equation 5-1 must be modified as follows:

(a) Case I. No component changes made during sampling run. In this
case, replace Vm in Equation 5-1 with the expression:
[GRAPHIC] [TIFF OMITTED] TR17OC00.110

(b) Case II. One or more component changes made during the sampling
run. In this case, replace Vm in Equation 5-1 by the
expression:
[GRAPHIC] [TIFF OMITTED] TR17OC00.111

and substitute only for those leakage rates (Li or
Lp) which exceed La.
12.4 Volume of Water Vapor Condensed.
[GRAPHIC] [TIFF OMITTED] TR17OC00.112

Where:

K2 = 0.001333 m\3\/ml for metric units, = 0.04706 ft \3\/ml
for English units.

12.5 Moisture Content.
[GRAPHIC] [TIFF OMITTED] TR17OC00.113

Note: In saturated or water droplet-laden gas streams, two
calculations of the moisture content of the stack gas shall be made, one
from the impinger analysis (Equation 5-3), and a second from the
assumption of saturated conditions. The lower of the two values of
Bws shall be considered correct. The procedure for
determining the moisture content based upon the assumption of saturated
conditions is given in section 4.0 of Method 4. For the purposes of this
method, the average stack gas temperature from Figure 5-3 may be used to
make this determination, provided that the accuracy of the in-stack
temperature sensor is 1 [deg]C (2 [deg]F).

12.6 Acetone Blank Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.114

12.7 Acetone Wash Blank.
[GRAPHIC] [TIFF OMITTED] TR17OC00.115

12.8 Total Particulate Weight. Determine the total particulate
matter catch from the sum of the weights obtained from Containers 1 and
2 less the acetone blank (see Figure 5-6).

Note: In no case shall a blank value of greater than 0.001 percent
of the weight of acetone used be subtracted from the sample weight.
Refer to section 8.5.8 to assist in calculation of results involving two
or more filter assemblies or two or more sampling trains.
12.9 Particulate Concentration.

[[Page 182]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.116

Where:

K3 = 0.001 g/mg for metric units.
= 0.0154 gr/mg for English units.
12.10 Conversion Factors:

------------------------------------------------------------------------
From To Multiply by
------------------------------------------------------------------------
ft\3\............................... m\3\ 0.02832
gr.................................. mg 64.80004
gr/ft\3\............................ mg/m\3\ 2288.4
mg.................................. g 0.001
gr.................................. lb 1.429 x 10 4
------------------------------------------------------------------------

12.11 Isokinetic Variation.
12.11.1 Calculation from Raw Data.
[GRAPHIC] [TIFF OMITTED] TR17OC00.117

Where:

K4 = 0.003454 ((mm Hg)(m\3\))/((ml)([deg]K)) for metric
units,
= 0.002669 ((in. Hg)(ft\3\))/((ml)([deg]R)) for English units.

12.11.2 Calculation from Intermediate Values.
[GRAPHIC] [TIFF OMITTED] TR17OC00.118

Where:

K5 = 4.320 for metric units,
= 0.09450 for English units.

12.11.3 Acceptable Results. If 90 percent I
110 percent, the results are acceptable. If the PM results
are low in comparison to the standard, and ``I'' is over 110 percent or
less than 90 percent, the Administrator may opt to accept the results.
Reference 4 in section 17.0 may be used to make acceptability judgments.
If ``I'' is judged to be unacceptable, reject the results, and repeat
the sampling run.
12.12 Stack Gas Velocity and Volumetric Flow Rate. Calculate the
average stack gas velocity and volumetric flow rate, if needed, using
data obtained in this method and the equations in sections 12.3 and 12.4
of Method 2.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 Dry Gas Meter as a Calibration Standard. A DGM may be used as a
calibration standard for volume measurements in place of the wet test
meter specified in section 10.3, provided that it is calibrated
initially and recalibrated periodically as follows:
16.1.1 Standard Dry Gas Meter Calibration.
16.1.1.1. The DGM to be calibrated and used as a secondary reference
meter should be of high quality and have an appropriately sized capacity
(e.g., 3 liters/rev (0.1 ft\3\/rev)). A spirometer (400 liters (14
ft\3\) or more capacity), or equivalent, may be used for this
calibration, although a wet test meter is usually more practical. The
wet test meter should have a capacity of 30 liters/rev (1 ft\3\/rev) and
capable of measuring volume to within 1.0 percent. Wet test meters
should be checked against a spirometer or a liquid displacement meter to
ensure the accuracy of the wet test meter. Spirometers or wet test
meters of other sizes may be used, provided that the specified
accuracies of the procedure are maintained.
16.1.1.2 Set up the components as shown in Figure 5-7. A spirometer,
or equivalent, may be used in place of the wet test meter in the system.
Run the pump for at least 5 minutes at a flow rate of about 10 liters/
min (0.35 cfm) to condition the interior surface of the wet test meter.
The pressure drop indicated by the manometer at the inlet side of the
DGM should be minimized (no greater than 100 mm H2O (4 in.
H2O) at a flow rate of 30 liters/min (1 cfm)). This can be
accomplished by using

[[Page 183]]

large diameter tubing connections and straight pipe fittings.
16.1.1.3 Collect the data as shown in the example data sheet (see
Figure 5-8). Make triplicate runs at each of the flow rates and at no
less than five different flow rates. The range of flow rates should be
between 10 and 34 liters/min (0.35 and 1.2 cfm) or over the expected
operating range.
16.1.1.4 Calculate flow rate, Q, for each run using the wet test
meter volume, VW, and the run time, k. Calculate the DGM
coefficient, Yds, for each run. These calculations are as
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.119

[GRAPHIC] [TIFF OMITTED] TR17OC00.120

Where:

K1 = 0.3858 [deg]C/mm Hg for metric units = 17.64 [deg]F/in.
Hg for English units.
VW = Wet test meter volume, liter (ft\3\).
Vds = Dry gas meter volume, liter (ft\3\).
Tds = Average dry gas meter temperature, [deg]C ( [deg]F).
Tadj = 273 [deg]C for metric units = 460 [deg]F for English
units.
TW = Average wet test meter temperature, [deg]C ( [deg]F)
Pbar = Barometric pressure, mm Hg (in. Hg).
Fp = Dry gas meter inlet differential pressure, mm H2O (in.
H2O).
k = Run time, min.

16.1.1.5 Compare the three Yds values at each of the flow
rates and determine the maximum and minimum values. The difference
between the maximum and minimum values at each flow rate should be no
greater than 0.030. Extra sets of triplicate runs may be made in order
to complete this requirement. In addition, the meter coefficients should
be between 0.95 and 1.05. If these specifications cannot be met in three
sets of successive triplicate runs, the meter is not suitable as a
calibration standard and should not be used as such. If these
specifications are met, average the three Yds values at each
flow rate resulting in no less than five average meter coefficients,
Yds.
16.1.1.6 Prepare a curve of meter coefficient, Yds,
versus flow rate, Q, for the DGM. This curve shall be used as a
reference when the meter is used to calibrate other DGMs and to
determine whether recalibration is required.
16.1.2 Standard Dry Gas Meter Recalibration.
16.1.2.1 Recalibrate the standard DGM against a wet test meter or
spirometer annually or after every 200 hours of operation, whichever
comes first. This requirement is valid provided the standard DGM is kept
in a laboratory and, if transported, cared for as any other laboratory
instrument. Abuse to the standard meter may cause a change in the
calibration and will require more frequent recalibrations.
16.1.2.2 As an alternative to full recalibration, a two-point
calibration check may be made. Follow the same procedure and equipment
arrangement as for a full recalibration, but run the meter at only two
flow rates [suggested rates are 14 and 30 liters/min (0.5 and 1.0 cfm)].
Calculate the meter coefficients for these two points, and compare the
values with the meter calibration curve. If the two coefficients are
within 1.5 percent of the calibration curve values at the same flow
rates, the meter need not be recalibrated until the next date for a
recalibration check.
16.2 Critical Orifices As Calibration Standards. Critical orifices
may be used as calibration standards in place of the wet test meter
specified in section 16.1, provided that they are selected, calibrated,
and used as follows:
16.2.1 Selection of Critical Orifices.
16.2.1.1 The procedure that follows describes the use of hypodermic
needles or stainless steel needle tubings which have been found suitable
for use as critical orifices. Other materials and critical orifice
designs may be used provided the orifices act as true critical orifices
(i.e., a critical vacuum can be obtained, as described in section
16.2.2.2.3). Select five critical orifices that are appropriately sized
to cover the range of flow rates between 10 and 34 liters/min (0.35 and
1.2 cfm) or the expected operating range. Two of the critical orifices
should bracket the expected operating range. A minimum of three critical
orifices will be needed to calibrate a Method 5 DGM; the other two
critical orifices can serve as spares and provide better selection for
bracketing the range of operating flow rates. The needle sizes and
tubing lengths shown in Table 5-1 in section 18.0 give the approximate
flow rates.

[[Page 184]]

16.2.1.2 These needles can be adapted to a Method 5 type sampling
train as follows: Insert a serum bottle stopper, 13 by 20 mm sleeve
type, into a \1/2\-inch Swagelok (or equivalent) quick connect. Insert
the needle into the stopper as shown in Figure 5-9.
16.2.2 Critical Orifice Calibration. The procedure described in this
section uses the Method 5 meter box configuration with a DGM as
described in section 6.1.1.9 to calibrate the critical orifices. Other
schemes may be used, subject to the approval of the Administrator.
16.2.2.1 Calibration of Meter Box. The critical orifices must be
calibrated in the same configuration as they will be used (i.e., there
should be no connections to the inlet of the orifice).
16.2.2.1.1 Before calibrating the meter box, leak check the system
as follows: Fully open the coarse adjust valve, and completely close the
by-pass valve. Plug the inlet. Then turn on the pump, and determine
whether there is any leakage. The leakage rate shall be zero (i.e., no
detectable movement of the DGM dial shall be seen for 1 minute).
16.2.2.1.2 Check also for leakages in that portion of the sampling
train between the pump and the orifice meter. See section 8.4.1 for the
procedure; make any corrections, if necessary. If leakage is detected,
check for cracked gaskets, loose fittings, worn O-rings, etc., and make
the necessary repairs.
16.2.2.1.3 After determining that the meter box is leakless,
calibrate the meter box according to the procedure given in section
10.3. Make sure that the wet test meter meets the requirements stated in
section 16.1.1.1. Check the water level in the wet test meter. Record
the DGM calibration factor, Y.
16.2.2.2 Calibration of Critical Orifices. Set up the apparatus as
shown in Figure 5-10.
16.2.2.2.1 Allow a warm-up time of 15 minutes. This step is
important to equilibrate the temperature conditions through the DGM.
16.2.2.2.2 Leak check the system as in section 16.2.2.1.1. The
leakage rate shall be zero.
16.2.2.2.3 Before calibrating the critical orifice, determine its
suitability and the appropriate operating vacuum as follows: Turn on the
pump, fully open the coarse adjust valve, and adjust the by-pass valve
to give a vacuum reading corresponding to about half of atmospheric
pressure. Observe the meter box orifice manometer reading, FH. Slowly
increase the vacuum reading until a stable reading is obtained on the
meter box orifice manometer. Record the critical vacuum for each
orifice. Orifices that do not reach a critical value shall not be used.
16.2.2.2.4 Obtain the barometric pressure using a barometer as
described in section 6.1.2. Record the barometric pressure,
Pbar, in mm Hg (in. Hg).
16.2.2.2.5 Conduct duplicate runs at a vacuum of 25 to 50 mm Hg (1
to 2 in. Hg) above the critical vacuum. The runs shall be at least 5
minutes each. The DGM volume readings shall be in increments of complete
revolutions of the DGM. As a guideline, the times should not differ by
more than 3.0 seconds (this includes allowance for changes in the DGM
temperatures) to achieve 0.5 percent in K' (see Eq. 5-11). Record the
information listed in Figure 5-11.
16.2.2.2.6 Calculate K' using Equation 5-11.
[GRAPHIC] [TIFF OMITTED] TR17OC00.121

Where:

K' = Critical orifice coefficient,
[m\3\)([deg]K)\1/2\]/
[(mm Hg)(min)] {[(ft \3\)([deg]R)\1/2\)] [(in. Hg)(min)].
Tamb = Absolute ambient temperature, [deg]K ([deg]R).
Calculate the arithmetic mean of the K' values. The individual K'
values should not differ by more than 0.5 percent from the mean value.

16.2.3 Using the Critical Orifices as Calibration Standards.
16.2.3.1 Record the barometric pressure.
16.2.3.2 Calibrate the metering system according to the procedure
outlined in section 16.2.2. Record the information listed in Figure 5-
12.
16.2.3.3 Calculate the standard volumes of air passed through the
DGM and the critical orifices, and calculate the DGM calibration factor,
Y, using the equations below:

[[Page 185]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.122

[GRAPHIC] [TIFF OMITTED] TR27FE14.012

[GRAPHIC] [TIFF OMITTED] TR17OC00.124

Where:

Vcr(std) = Volume of gas sample passed through the critical
orifice, corrected to standard conditions, dscm (dscf).
K1 = 0.3858 K/mm Hg for metric units
= 17.64 [deg]R/in. Hg for English units.

16.2.3.4 Average the DGM calibration values for each of the flow
rates. The calibration factor, Y, at each of the flow rates should not
differ by more than 2 percent from the average.
16.2.3.5 To determine the need for recalibrating the critical
orifices, compare the DGM Y factors obtained from two adjacent orifices
each time a DGM is calibrated; for example, when checking orifice 13/
2.5, use orifices 12/10.2 and 13/5.1. If any critical orifice yields a
DGM Y factor differing by more than 2 percent from the others,
recalibrate the critical orifice according to section 16.2.2.
16.3 Alternative Post-Test Metering System Calibration. The
following procedure may be used as an alternative to the post-test
calibration described in Section 10.3.2. This alternative procedure does
not detect leakages between the inlet of the metering system and the dry
gas meter. Therefore, two steps must be included to make it an
equivalent alternative:
(1) The metering system must pass the post-test leak-check from
either the inlet of the sampling train or the inlet of the metering
system. Therefore, if the train fails the former leak-check, another
leak-check from the inlet of the metering system must be conducted;
(2) The metering system must pass the leak-check of that portion of
the train from the pump to the orifice meter as described in Section
8.4.1.
16.3.1 After each test run, do the following:
16.3.1.1 Ensure that the metering system has passed the post-test
leak-check. If not, conduct a leak-check of the metering system from its
inlet.
16.3.1.2 Conduct the leak-check of that portion of the train from
the pump to the orifice meter as described in Section 10.3.1.1.
16.3.1.3 Calculate Yqa for each test run using the
following equation:
[GRAPHIC] [TIFF OMITTED] TR27FE14.013

Where:

Yqa = Dry gas meter calibration check value, dimensionless.
0.0319 = (29.92/528) (0.75) \2\ (in. Hg/[deg]R) cfm\2\.
FH@ = Orifice meter calibration coefficient, in. H2O.
Md = Dry molecular weight of stack gas, lb/lb-mole.
29 = Dry molecular weight of air, lb/lb-mole.

16.3.2 After each test run series, do the following:
16.3.2.1 Average the three or more Yqa's obtained from
the test run series and compare this average Yqa with the dry
gas meter calibration factor Y. The average Yqa must be
within 5 percent of Y.
16.3.2.2 If the average Yqa does not meet the 5 percent
criterion, recalibrate the meter

[[Page 186]]

over the full range of orifice settings as detailed in Section 10.3.1.
Then follow the procedure in Section 10.3.3.

17.0 References.

1. Addendum to Specifications for Incinerator Testing at Federal
Facilities. PHS, NCAPC. December 6, 1967.
2. Martin, Robert M. Construction Details of Isokinetic Source-
Sampling Equipment. Environmental Protection Agency. Research Triangle
Park, NC. APTD-0581. April 1971.
3. Rom, Jerome J. Maintenance, Calibration, and Operation of
Isokinetic Source Sampling Equipment. Environmental Protection Agency.
Research Triangle Park, NC. APTD-0576. March 1972.
4. Smith, W.S., R.T. Shigehara, and W.F. Todd. A Method of
Interpreting Stack Sampling Data. Paper Presented at the 63rd Annual
Meeting of the Air Pollution Control Association, St. Louis, MO. June
14-19, 1970.
5. Smith, W.S., et al. Stack Gas Sampling Improved and Simplified
With New Equipment. APCA Paper No. 67-119. 1967.
6. Specifications for Incinerator Testing at Federal Facilities.
PHS, NCAPC. 1967.
7. Shigehara, R.T. Adjustment in the EPA Nomograph for Different
Pitot Tube Coefficients and Dry Molecular Weights. Stack Sampling News
2:4-11. October 1974.
8. Vollaro, R.F. A Survey of Commercially Available Instrumentation
for the Measurement of Low-Range Gas Velocities. U.S. Environmental
Protection Agency, Emission Measurement Branch. Research Triangle Park,
NC. November 1976 (unpublished paper).
9. Annual Book of ASTM Standards. Part 26. Gaseous Fuels; Coal and
Coke; Atmospheric Analysis. American Society for Testing and Materials.
Philadelphia, PA. 1974. pp. 617-622.
10. Felix, L.G., G.I. Clinard, G.E. Lacy, and J.D. McCain. Inertial
Cascade Impactor Substrate Media for Flue Gas Sampling. U.S.
Environmental Protection Agency. Research Triangle Park, NC 27711.
Publication No. EPA-600/7-77-060. June 1977. 83 pp.
11. Westlin, P.R. and R.T. Shigehara. Procedure for Calibrating and
Using Dry Gas Volume Meters as Calibration Standards. Source Evaluation
Society Newsletter. 3(1):17-30. February 1978.
12. Lodge, J.P., Jr., J.B. Pate, B.E. Ammons, and G.A. Swanson. The
Use of Hypodermic Needles as Critical Orifices in Air Sampling. J. Air
Pollution Control Association. 16:197-200. 1966.
13. Shigehara, Roger T., P.G. Royals, and E.W. Steward.
``Alternative Method 5 Post-Test Calibration.'' Entropy Incorporated,
Research Triangle Park, NC 27709.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

Table 5-1 Flor Rates for Various needle Sizes and Tube Lengths
----------------------------------------------------------------------------------------------------------------
Flow rate Flow rate
Gauge/cm liters/min. Gauge/cm liters/min.
----------------------------------------------------------------------------------------------------------------
12/7.6.......................................................... 32.56 14/2.5 19.54
12/10.2......................................................... 30.02 14/5.1 17.27
13/2.5.......................................................... 25.77 14/7.6 16.14
13/5.1.......................................................... 23.50 15/3.2 14.16
13/7.6.......................................................... 22.37 15/7.6 11.61
13/10.2......................................................... 20.67 15/10.2 10.48
----------------------------------------------------------------------------------------------------------------

[[Page 187]]

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[[Page 188]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.126

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[GRAPHIC] [TIFF OMITTED] TR17OC00.127

[[Page 190]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.128

[[Page 191]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.129

[[Page 192]]

________________________________________________________________________

----------------------------------------------------------------------------------------------------------------
Weight of particulate collected, mg
Container number --------------------------------------------------------------------------
Final weight Tare weight Weight gain
----------------------------------------------------------------------------------------------------------------
1.
----------------------------------------------------------------------------------------------------------------
2.
----------------------------------------------------------------------------------------------------------------
Total:
Less acetone blank...........
Weight of particulate matter.
----------------------------------------------------------------------------------------------------------------

------------------------------------------------------------------------
Volume of liquid water collected
---------------------------------------
Impinger volume, Silica gel weight,
ml g
------------------------------------------------------------------------
Final
Initial
Liquid collected
Total volume collected.... .................. g* ml
------------------------------------------------------------------------
* Convert weight of water to volume by dividing total weight increase by
density of water (1 g/ml).

Figure 5-6. Analytical Data Sheet
[GRAPHIC] [TIFF OMITTED] TR17OC00.147

[[Page 193]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.130

[[Page 194]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.131

[[Page 195]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.132

[[Page 196]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.133

Date____________________________________________________________________
Train ID________________________________________________________________
DGM cal. factor_________________________________________________________
Critical orifice ID_____________________________________________________

[[Page 197]]

Temperatures:............ [deg]C ( / /
[deg]F).
Initial.................. [deg]C ( / /
[deg]F).
Final.................... min/sec........ / /
Av. Temeperature, t m.... min............ ........... ...........
Time, k...................... ............... ........... ...........
Orifice man. rdg., FH........ mm (in.) H 2... ........... ...........
Bar. pressure, P \bar\....... mm (in.) Hg.... ........... ...........
Ambient temperature, tamb.... mm (in.) Hg.... ........... ...........
Pump vacuum.................. ............... ........... ...........
K' factor.................... ............... ........... ...........
Average.................. ............... ........... ...........
------------------------------------------------------------------------

Figure 5-11. Data sheet of determining K' factor.

Date____________________________________________________________________
Train ID________________________________________________________________
Critical orifice ID_____________________________________________________
Critical orifice K' factor______________________________________________

------------------------------------------------------------------------
Run No.
Dry gas meter -------------------------
1 2
------------------------------------------------------------------------
Final reading................ m\3\ (ft\3\)... ........... ...........
Initial reading.............. m\3\ (ft\3\)... ........... ...........
Difference, Vm............... m\3\ (ft\3\)... ........... ...........
Inlet/outlet temperatures.... [deg]C ( / /
[deg]F).
Initial.................. [deg]C ( / /
[deg]F).
Final.................... [deg]C ( ........... ...........
[deg]F).
Avg. Temperature, tm..... min/sec........ / /
Time, k...................... min............ ........... ...........
Orifice man. rdg., FH........ min............ ........... ...........
Bar. pressure, Pbar.......... mm (in.) H2O... ........... ...........
Ambient temperature, tamb.... mm (in.) Hg.... ........... ...........
Pump vacuum.................. [deg]C ( ........... ...........
[deg]F).
Vm(std)...................... mm (in.) Hg.... ........... ...........
Vcr(std)..................... m\3\ (ft\3\)... ........... ...........
DGM cal. factor, Y........... m\3\ (ft\3\)... ........... ...........
------------------------------------------------------------------------

Figure 5-12. Data Sheet for Determining DGM Y Factor

Method 5A--Determination of Particulate Matter Emissions From the
Asphalt Processing and Asphalt Roofing Industry

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3, and
Method 5.

1.0 Scope and Applications

1.1 Analyte. Particulate matter (PM). No CAS number assigned.
1.2 Applicability. This method is applicable for the determination
of PM emissions from asphalt roofing industry process saturators,
blowing stills, and other sources as specified in the regulations.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

Particulate matter is withdrawn isokinetically from the source and
collected on a glass fiber filter maintained at a temperature of 42 10
[deg]C (108 18 [deg]F). The PM mass, which includes any material that
condenses at or above the filtration temperature, is determined
gravimetrically after the removal of uncombined water.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

[[Page 198]]

applicability of regulatory limitations prior to performing this test
method.

6.0 Equipment and Supplies

6.1 Sample Collection. Same as Method 5, section 6.1, with the
following exceptions and additions:
6.1.1 Probe Liner. Same as Method 5, section 6.1.1.2, with the note
that at high stack gas temperatures greater than 250 [deg]C (480
[deg]F), water-cooled probes may be required to control the probe exit
temperature to 42 10 [deg]C (108 18 [deg]F).
6.1.2 Precollector Cyclone. Borosilicate glass following the
construction details shown in Air Pollution Technical Document (APTD)-
0581, ``Construction Details of Isokinetic Source-Sampling Equipment''
(Reference 2 in Method 5, section 17.0).

Note: The cyclone shall be used when the stack gas moisture is
greater than 10 percent, and shall not be used otherwise.

6.1.3 Filter Heating System. Any heating (or cooling) system capable
of maintaining a sample gas temperature at the exit end of the filter
holder during sampling at 42 10 [deg]C (108 18 [deg]F).
6.2 Sample Recovery. The following items are required for sample
recovery:
6.2.1 Probe-Liner and Probe-Nozzle Brushes, Graduated Cylinder and/
or Balance, Plastic Storage Containers, and Funnel and Rubber Policeman.
Same as in Method 5, sections 6.2.1, 6.2.5, 6.2.6, and 6.2.7,
respectively.
6.2.2 Wash Bottles. Glass.
6.2.3 Sample Storage Containers. Chemically resistant 500-ml or
1,000-ml borosilicate glass bottles, with rubber-backed Teflon screw cap
liners or caps that are constructed so as to be leak-free, and resistant
to chemical attack by 1,1,1-trichloroethane (TCE). (Narrow-mouth glass
bottles have been found to be less prone to leakage.)
6.2.4 Petri Dishes. Glass, unless otherwise specified by the
Administrator.
6.2.5 Funnel. Glass.
6.3 Sample Analysis. Same as Method 5, section 6.3, with the
following additions:
6.3.1 Beakers. Glass, 250-ml and 500-ml.
6.3.2 Separatory Funnel. 100-ml or greater.

7.0. Reagents and Standards

7.1 Sample Collection. The following reagents are required for
sample collection:
7.1.1 Filters, Silica Gel, Water, and Crushed Ice. Same as in Method
5, sections 7.1.1, 7.1.2, 7.1.3, and 7.1.4, respectively.
7.1.2 Stopcock Grease. TCE-insoluble, heat-stable grease (if
needed). This is not necessary if screw-on connectors with Teflon
sleeves, or similar, are used.
7.2 Sample Recovery. Reagent grade TCE, 0.001 percent
residue and stored in glass bottles. Run TCE blanks before field use,
and use only TCE with low blank values (0.001 percent). In no
case shall a blank value of greater than 0.001 percent of the weight of
TCE used be subtracted from the sample weight.
7.3 Analysis. Two reagents are required for the analysis:
7.3.1 TCE. Same as in section 7.2.
7.3.2 Desiccant. Same as in Method 5, section 7.3.2.

8.0. Sample Collection, Preservation, Storage, and Transport

8.1 Pretest Preparation. Unless otherwise specified, maintain and
calibrate all components according to the procedure described in APTD-
0576, ``Maintenance, Calibration, and Operation of Isokinetic Source-
Sampling Equipment'' (Reference 3 in Method 5, Section 17.0).
Alternative mercury-free thermometers may be used if the thermometers
are, at a minimum, equivalent in terms of performance or suitably
effective for the specific temperature measurement application.
8.1.1 Prepare probe liners and sampling nozzles as needed for use.
Thoroughly clean each component with soap and water followed by a
minimum of three TCE rinses. Use the probe and nozzle brushes during at
least one of the TCE rinses (refer to section 8.7 for rinsing
techniques). Cap or seal the open ends of the probe liners and nozzles
to prevent contamination during shipping.
8.1.2 Prepare silica gel portions and glass filters as specified in
Method 5, section 8.1.
8.2 Preliminary Determinations. Select the sampling site, probe
nozzle, and probe length as specified in Method 5, section 8.2. Select a
total sampling time greater than or equal to the minimum total sampling
time specified in the ``Test Methods and Procedures'' section of the
applicable subpart of the regulations. Follow the guidelines outlined in
Method 5, section 8.2 for sampling time per point and total sample
volume collected.
8.3 Preparation of Sampling Train. Prepare the sampling train as
specified in Method 5, section 8.3, with the addition of the
precollector cyclone, if used, between the probe and filter holder. The
temperature of the precollector cyclone, if used, should be maintained
in the same range as that of the filter, i.e., 42 10 [deg]C (108 18
[deg]F). Use no stopcock grease on ground glass joints unless grease is
insoluble in TCE.
8.4 Leak-Check Procedures. Same as Method 5, section 8.4.
8.5 Sampling Train Operation. Operate the sampling train as
described in Method 5, section 8.5, except maintain the temperature of
the gas exiting the filter holder at 42 10 [deg]C (108 18 [deg]F).
8.6 Calculation of Percent Isokinetic. Same as Method 5, section
8.6.
8.7 Sample Recovery. Same as Method 5, section 8.7.1 through
8.7.6.1, with the addition of the following:
8.7.1 Container No. 2 (Probe to Filter Holder).

[[Page 199]]

8.7.1.1 Taking care to see that material on the outside of the probe
or other exterior surfaces does not get into the sample, quantitatively
recover PM or any condensate from the probe nozzle, probe fitting, probe
liner, precollector cyclone and collector flask (if used), and front
half of the filter holder by washing these components with TCE and
placing the wash in a glass container. Carefully measure the total
amount of TCE used in the rinses. Perform the TCE rinses as described in
Method 5, section 8.7.6.2, using TCE instead of acetone.
8.7.1.2 Brush and rinse the inside of the cyclone, cyclone
collection flask, and the front half of the filter holder. Brush and
rinse each surface three times or more, if necessary, to remove visible
PM.
8.7.2 Container No. 3 (Silica Gel). Same as in Method 5, section
8.7.6.3.
8.7.3 Impinger Water. Same as Method 5, section 8.7.6.4.
8.8 Blank. Save a portion of the TCE used for cleanup as a blank.
Take 200 ml of this TCE directly from the wash bottle being used, and
place it in a glass sample container labeled ``TCE Blank.''

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

9.2 A quality control (QC) check of the volume metering system at
the field site is suggested before collecting the sample. Use the
procedure outlined in Method 5, section 9.2.

10.0 Calibration and Standardization

Same as Method 5, section 10.0.

11.0 Analytical Procedures

11.1 Analysis. Record the data required on a sheet such as the one
shown in Figure 5A-1. Handle each sample container as follows:
11.1.1 Container No. 1 (Filter). Transfer the filter from the sample
container to a tared glass weighing dish, and desiccate for 24 hours in
a desiccator containing anhydrous calcium sulfate. Rinse Container No. 1
with a measured amount of TCE, and analyze this rinse with the contents
of Container No. 2. Weigh the filter to a constant weight. For the
purpose of this analysis, the term ``constant weight'' means a
difference of no more than 10 percent of the net filter weight or 2 mg
(whichever is greater) between two consecutive weighings made 24 hours
apart. Report the ``final weight'' to the nearest 0.1 mg as the average
of these two values.
11.1.2 Container No. 2 (Probe to Filter Holder).
11.1.2.1 Before adding the rinse from Container No. 1 to Container
No. 2, note the level of liquid in Container No. 2, and confirm on the
analysis sheet whether leakage occurred during transport. If noticeable
leakage occurred, either void the sample or take steps, subject to the
approval of the Administrator, to correct the final results.
11.1.2.2 Add the rinse from Container No. 1 to Container No. 2 and
measure the liquid in this container either volumetrically to 1 ml or
gravimetrically to 0.5 g. Check to see whether there is any appreciable
quantity of condensed water present in the TCE rinse (look for a
boundary layer or phase separation). If the volume of condensed water
appears larger than 5 ml, separate the oil-TCE fraction from the water
fraction using a separatory funnel. Measure the volume of the water
phase to the nearest ml; adjust the stack gas moisture content, if
necessary (see sections 12.3 and 12.4). Next, extract the water phase
with several 25-ml portions of TCE until, by visual observation, the TCE
does not remove any additional organic material. Transfer the remaining
water fraction to a tared beaker and evaporate to dryness at 93 [deg]C
(200 [deg]F), desiccate for 24 hours, and weigh to the nearest 0.1 mg.
11.1.2.3 Treat the total TCE fraction (including TCE from the filter
container rinse and water phase extractions) as follows: Transfer the
TCE and oil to a tared beaker, and evaporate at ambient temperature and
pressure. The evaporation of TCE from the solution may take several
days. Do not desiccate the sample until the solution reaches an apparent
constant volume or until the odor of TCE is not detected. When it
appears that the TCE has evaporated, desiccate the sample, and weigh it
at 24-hour intervals to obtain a ``constant weight'' (as defined for
Container No. 1 above). The ``total weight'' for Container No. 2 is the
sum of the evaporated PM weight of the TCE-oil and water phase
fractions. Report the results to the nearest 0.1 mg.
11.1.3 Container No. 3 (Silica Gel). This step may be conducted in
the field. Weigh the spent silica gel (or silica gel plus impinger) to
the nearest 0.5 g using a balance.
11.1.4 ``TCE Blank'' Container. Measure TCE in this container either
volumetrically or gravimetrically. Transfer the TCE to a tared 250-ml
beaker, and evaporate to dryness at ambient temperature and pressure.

[[Page 200]]

Desiccate for 24 hours, and weigh to a constant weight. Report the
results to the nearest 0.1 mg.

Note: In order to facilitate the evaporation of TCE liquid samples,
these samples may be dried in a controlled temperature oven at
temperatures up to 38 [deg]C (100 [deg]F) until the liquid is
evaporated.

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after the
final calculation. Other forms of the equations may be used as long as
they give equivalent results.
12.1 Nomenclature. Same as Method 5, section 12.1, with the
following additions:

Ct = TCE blank residue concentration, mg/g.
mt = Mass of residue of TCE blank after evaporation, mg.
Vpc = Volume of water collected in precollector, ml.
Vt = Volume of TCE blank, ml.
Vtw = Volume of TCE used in wash, ml.
Wt = Weight of residue in TCE wash, mg.
nt = Density of TCE (see label on bottle), g/ml.

12.2 Dry Gas Meter Temperature, Orifice Pressure Drop, and Dry Gas
Volume. Same as Method 5, sections 12.2 and 12.3, except use data
obtained in performing this test.
12.3 Volume of Water Vapor.
[GRAPHIC] [TIFF OMITTED] TR17OC00.134

Where:

K2 = 0.001333 m\3\/ml for metric units.
= 0.04706 ft\3\/ml for English units.

12.4 Moisture Content.
[GRAPHIC] [TIFF OMITTED] TR17OC00.135

Note: In saturated or water droplet-laden gas streams, two
calculations of the moisture content of the stack gas shall be made, one
from the impinger and precollector analysis (Equations 5A-1 and 5A-2)
and a second from the assumption of saturated conditions. The lower of
the two values of moisture content shall be considered correct. The
procedure for determining the moisture content based upon assumption of
saturated conditions is given in section 4.0 of Method 4. For the
purpose of this method, the average stack gas temperature from Figure 5-
3 of Method 5 may be used to make this determination, provided that the
accuracy of the in-stack temperature sensor is within 1 [deg]C (2
[deg]F).

12.5 TCE Blank Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.136

Note: In no case shall a blank value of greater than 0.001 percent
of the weight of TCE used be subtracted from the sample weight.

12.6 TCE Wash Blank.
[GRAPHIC] [TIFF OMITTED] TR17OC00.137

12.7 Total PM Weight. Determine the total PM catch from the sum of
the weights obtained from Containers 1 and 2, less the TCE blank.
12.8 PM Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.138

Where:

K3 = 0.001 g/mg for metric units
= 0.0154 gr/mg for English units

12.9 Isokinetic Variation. Same as in Method 5, section 12.11.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as Method 5, section 17.0.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Plant___________________________________________________________________
Date____________________________________________________________________
Run No._________________________________________________________________
Filter No.______________________________________________________________
Amount liquid lost during transport_____________________________________
Acetone blank volume, m1________________________________________________
Acetone blank concentration, mg/mg (Equation 5-4)_______________________
Acetone wash blank, mg (Equation 5-5)___________________________________

[[Page 201]]

Weight of particulate matter.
----------------------------------------------------------------------------------------------------------------

[GRAPHIC] [TIFF OMITTED] TR17OC00.139

Method 5B--Determination of Nonsulfuric Acid Particulate Matter
Emissions From Stationary Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 5.

1.0 Scope and Application

1.1 Analyte. Nonsulfuric acid particulate matter. No CAS number
assigned.
1.2 Applicability. This method is determining applicable for the
determination of nonsulfuric acid particulate matter from stationary
sources, only where specified by an applicable subpart of the
regulations or where approved by the Administrator for a particular
application.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

Particulate matter is withdrawn isokinetically from the source and
collected on a glass fiber filter maintained at a temperature of 160 14
[deg]C (320 25 [deg]F). The collected sample is then heated in an oven
at 160 [deg]C (320 [deg]F) for 6 hours to volatilize any condensed
sulfuric acid that may have been collected, and the nonsulfuric acid
particulate mass is determined gravimetrically.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Same as Method 5, section 6.0, with the following addition and
exceptions:
6.1 Sample Collection. The probe liner heating system and filter
heating system must be capable of maintaining a sample gas temperature
of 160 14 [deg]C (320 25 [deg]F).
6.2 Sample Preparation. An oven is required for drying the sample.

7.0 Reagents and Standards

Same as Method 5, section 7.0.

8.0 Sample Collection, Preservation, Storage, and Transport.

Same as Method 5, with the exception of the following:
8.1 Initial Filter Tare. Oven dry the filter at 160 5 [deg]C (320
10 [deg]F) for 2 to 3 hours, cool in a desiccator for 2 hours, and
weigh. Desiccate to constant weight to obtain the initial tare weight.
Use the applicable specifications and techniques of section 8.1.3 of
Method 5 for this determination.
8.2 Probe and Filter Temperatures. Maintain the probe outlet and
filter temperatures at 160 14 [deg]C (320 25 [deg]F).

9.0 Quality Control

Same as Method 5, section 9.0.

10.0 Calibration and Standardization

Same as Method 5, section 10.0.

[[Page 202]]

11.0 Analytical Procedure

Same as Method 5, section 11.0, except replace section
11.2.2 With the following:
11.1 Container No. 2. Note the level of liquid in the container, and
confirm on the analysis sheet whether leakage occurred during transport.
If a noticeable amount of leakage has occurred, either void the sample
or use methods, subject to the approval of the Administrator, to correct
the final results. Measure the liquid in this container either
volumetrically to 1 ml or gravimetrically to 0.5 g. Transfer the
contents to a tared 250 ml beaker, and evaporate to dryness at ambient
temperature and pressure. Then oven dry the probe and filter samples at
a temperature of 160 5 [deg]C (320 10 [deg]F) for 6 hours. Cool in a
desiccator for 2 hours, and weigh to constant weight. Report the results
to the nearest 0.1 mg.

12.0 Data Analysis and Calculations

Same as in Method 5, section 12.0.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as Method 5, section 17.0.

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 5C [Reserved]

Method 5D--Determination of Particulate Matter Emissions from Positive
Pressure Fabric Filters

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 5, Method 17.

1.0 Scope and Application

1.1 Analyte. Particulate matter (PM). No CAS number assigned.
1.2 Applicability.
1.2.1 This method is applicable for the determination of PM
emissions from positive pressure fabric filters. Emissions are
determined in terms of concentration (mg/m\3\ or gr/ft\3\) and emission
rate (kg/hr or lb/hr).
1.2.2 The General Provisions of 40 CFR part 60, Sec. 60.8(e),
require that the owner or operator of an affected facility shall provide
performance testing facilities. Such performance testing facilities
include sampling ports, safe sampling platforms, safe access to sampling
sites, and utilities for testing. It is intended that affected
facilities also provide sampling locations that meet the specification
for adequate stack length and minimal flow disturbances as described in
Method 1. Provisions for testing are often overlooked factors in
designing fabric filters or are extremely costly. The purpose of this
procedure is to identify appropriate alternative locations and
procedures for sampling the emissions from positive pressure fabric
filters. The requirements that the affected facility owner or operator
provide adequate access to performance testing facilities remain in
effect.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Particulate matter is withdrawn isokinetically from the source
and collected on a glass fiber filter maintained at a temperature at or
above the exhaust gas temperature up to a nominal 120 [deg]C (248 25
[deg]F). The particulate mass, which includes any material that
condenses at or above the filtration temperature, is determined
gravimetrically after the removal of uncombined water.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Same as section 6.0 of either Method 5 or Method 17.

7.0 Reagents and Standards

Same as section 7.0 of either Method 5 or Method 17.

8.0 Sample Collection, Preservation, Storage, and Transport

Same section 8.0 of either Method 5 or Method 17, except replace
section 8.2.1 of Method 5 with the following:
8.1 Determination of Measurement Site. The configuration of positive
pressure fabric filter structures frequently are not amenable

[[Page 203]]

to emission testing according to the requirements of Method 1. Following
are several alternatives for determining measurement sites for positive
pressure fabric filters.
8.1.1 Stacks Meeting Method 1 Criteria. Use a measurement site as
specified in Method 1, section 11.1.
8.1.2 Short Stacks Not Meeting Method 1 Criteria. Use stack
extensions and the procedures in Method 1. Alternatively, use flow
straightening vanes of the ``egg-crate'' type (see Figure 5D-1). Locate
the measurement site downstream of the straightening vanes at a distance
equal to or greater than two times the average equivalent diameter of
the vane openings and at least one-half of the overall stack diameter
upstream of the stack outlet.
8.1.3 Roof Monitor or Monovent. (See Figure 5D-2). For a positive
pressure fabric filter equipped with a peaked roof monitor, ridge vent,
or other type of monovent, use a measurement site at the base of the
monovent. Examples of such locations are shown in Figure 5D-2. The
measurement site must be upstream of any exhaust point (e.g., louvered
vent).
8.1.4 Compartment Housing. Sample immediately downstream of the
filter bags directly above the tops of the bags as shown in the examples
in Figure 5D-2. Depending on the housing design, use sampling ports in
the housing walls or locate the sampling equipment within the
compartment housing.
8.2 Determination of Number and Location of Traverse Points. Locate
the traverse points according to Method 1, section 11.3. Because a
performance test consists of at least three test runs and because of the
varied configurations of positive pressure fabric filters, there are
several schemes by which the number of traverse points can be determined
and the three test runs can be conducted.
8.2.1 Single Stacks Meeting Method 1 Criteria. Select the number of
traverse points according to Method 1. Sample all traverse points for
each test run.
8.2.2 Other Single Measurement Sites. For a roof monitor or
monovent, single compartment housing, or other stack not meeting Method
1 criteria, use at least 24 traverse points. For example, for a
rectangular measurement site, such as a monovent, use a balanced 5 x 5
traverse point matrix. Sample all traverse points for each test run.
8.2.3 Multiple Measurement Sites. Sampling from two or more stacks
or measurement sites may be combined for a test run, provided the
following guidelines are met:
8.2.3.1 All measurement sites up to 12 must be sampled. For more
than 12 measurement sites, conduct sampling on at least 12 sites or 50
percent of the sites, whichever is greater. The measurement sites
sampled should be evenly, or nearly evenly, distributed among the
available sites; if not, all sites are to be sampled.
8.2.3.2 The same number of measurement sites must be sampled for
each test run.
8.2.3.3 The minimum number of traverse points per test run is 24. An
exception to the 24-point minimum would be a test combining the sampling
from two stacks meeting Method 1 criteria for acceptable stack length,
and Method 1 specifies fewer than 12 points per site.
8.2.3.4 As long as the 24 traverse points per test run criterion is
met, the number of traverse points per measurement site may be reduced
to eight.
8.2.3.5 Alternatively, conduct a test run for each measurement site
individually using the criteria in section 8.2.1 or 8.2.2 to determine
the number of traverse points. Each test run shall count toward the
total of three required for a performance test. If more than three
measurement sites are sampled, the number of traverse points per
measurement site may be reduced to eight as long as at least 72 traverse
points are sampled for all the tests.
8.2.3.6 The following examples demonstrate the procedures for
sampling multiple measurement sites.
8.2.3.6.1 Example 1: A source with nine circular measurement sites
of equal areas may be tested as follows: For each test run, traverse
three measurement sites using four points per diameter (eight points per
measurement site). In this manner, test run number 1 will include
sampling from sites 1,2, and 3; run 2 will include samples from sites 4,
5, and 6; and run 3 will include sites 7, 8, and 9. Each test area may
consist of a separate test of each measurement site using eight points.
Use the results from all nine tests in determining the emission average.
8.2.3.6.2 Example 2: A source with 30 rectangular measurement sites
of equal areas may be tested as follows: For each of the three test
runs, traverse five measurement sites using a 3 x 3 matrix of traverse
points for each site. In order to distribute the sampling evenly over
all the available measurement sites while sampling only 50 percent of
the sites, number the sites consecutively from 1 to 30 and sample all
the even numbered (or odd numbered) sites. Alternatively, conduct a
separate test of each of 15 measurement sites using section 8.2.1 or
8.2.2 to determine the number and location of traverse points, as
appropriate.
8.2.3.6.3 Example 3: A source with two measurement sites of equal
areas may be tested as follows: For each test of three test runs,
traverse both measurement sites, using section 8.2.3 in determining the
number of traverse points. Alternatively, conduct two full emission test
runs for each measurement site using the criteria in section 8.2.1 or
8.2.2 to determine the number of traverse points.

[[Page 204]]

8.2.3.7 Other test schemes, such as random determination of traverse
points for a large number of measurement sites, may be used with prior
approval from the Administrator.
8.3 Velocity Determination.
8.3.1 The velocities of exhaust gases from positive pressure
baghouses are often too low to measure accurately with the type S pitot
tube specified in Method 2 (i.e., velocity head <1.3 mm H2O
(0.05 in. H2O)). For these conditions, measure the gas flow
rate at the fabric filter inlet following the procedures outlined in
Method 2. Calculate the average gas velocity at the measurement site as
shown in section 12.2 and use this average velocity in determining and
maintaining isokinetic sampling rates.
8.3.2 Velocity determinations to determine and maintain isokinetic
rates at measurement sites with gas velocities within the range
measurable with the type S pitot tube (i.e., velocity head greater than
1.3 mm H2O (0.05 in. H2O)) shall be conducted
according to the procedures outlined in Method 2.
8.4 Sampling. Follow the procedures specified in sections 8.1
through 8.6 of Method 5 or sections 8.1 through 8.25 in Method 17 with
the exceptions as noted above.
8.5 Sample Recovery. Follow the procedures specified in section 8.7
of Method 5 or section 8.2 of Method 17.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

9.2 Volume Metering System Checks. Same as Method 5, section 9.2.

10.0 Calibration and Standardization

Same as section 10.0 of either Method 5 or Method 17.

11.0 Analytical Procedure

Same as section 11.0 of either Method 5 or Method 17.

12.0 Data Analysis and Calculations

Same as section 12.0 of either Method 5 or Method 17 with the
following exceptions:
12.1 Nomenclature.
Ao = Measurement site(s) total cross-sectional area, m\2\
(ft\2\).
C or Cavg = Average concentration of PM for all n runs, mg/
scm (gr/scf).
Qi = Inlet gas volume flow rate, m\3\/sec (ft\3\/sec).
mi = Mass collected for run i of n, mg (gr).
To = Average temperature of gas at measurement site, [deg]K
([deg]R).
Ti = Average temperature of gas at inlet, [deg]K ([deg]R).
Voli = Sample volume collected for run i of n, scm (scf).
v = Average gas velocity at the measurement site(s), m/s (ft/s)
Qo = Total baghouse exhaust volumetric flow rate, m\3\/sec
(ft\3\/sec).
Qd = Dilution air flow rate, m\3\/sec (ft\3\/sec).
Tamb = Ambient Temperature, ([deg]K).

12.2 Average Gas Velocity. When following section 8.3.1, calculate
the average gas velocity at the measurement site as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.140

12.3 Volumetric Flow Rate. Total volumetric flow rate may be
determined as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.141

12.4 Dilution Air Flow Rate.
[GRAPHIC] [TIFF OMITTED] TR17OC00.142

12.5 Average PM Concentration. For multiple measurement sites,
calculate the average PM concentration as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.143

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as Method 5, section 17.0.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 205]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.144

[[Page 206]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.145

Method 5E--Determination of Particulate Matter Emissions From the Wool
Fiberglass Insulation Manufacturing Industry

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3, and
Method 5.

1.0 Scope and Applications

1.1 Analyte. Particulate matter (PM). No CAS number assigned.

[[Page 207]]

1.2 Applicability. This method is applicable for the determination
of PM emissions from wool fiberglass insulation manufacturing sources.

2.0 Summary of Method

Particulate matter is withdrawn isokinetically from the source and
is collected either on a glass fiber filter maintained at a temperature
in the range of 120 14 [deg]C (248 25 [deg]F) and in impingers in
solutions of 0.1 N sodium hydroxide (NaOH). The filtered particulate
mass, which includes any material that condenses at or above the
filtration temperature, is determined gravimetrically after the removal
of uncombined water. The condensed PM collected in the impinger
solutions is determined as total organic carbon (TOC) using a
nondispersive infrared type of analyzer. The sum of the filtered PM mass
and the condensed PM is reported as the total PM mass.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. Same as Method 5, section 6.1, with the
exception of the following:
6.1.1 Probe Liner. Same as described in section 6.1.1.2 of Method 5
except use only borosilicate or quartz glass liners.
6.1.2 Filter Holder. Same as described in section 6.1.1.5 of Method
5 with the addition of a leak-tight connection in the rear half of the
filter holder designed for insertion of a temperature sensor used for
measuring the sample gas exit temperature.
6.2 Sample Recovery. Same as Method 5, section 6.2, except three
wash bottles are needed instead of two and only glass storage bottles
and funnels may be used.
6.3 Sample Analysis. Same as Method 5, section 6.3, with the
additional equipment for TOC analysis as described below:
6.3.1 Sample Blender or Homogenizer. Waring type or ultrasonic.
6.3.2 Magnetic Stirrer.
6.3.3 Hypodermic Syringe. 0- to 100-l capacity.
6.3.4 Total Organic Carbon Analyzer. Rosemount Model 2100A analyzer
or equivalent and a recorder.
6.3.5 Beaker. 30-ml.
6.3.6 Water Bath. Temperature controlled.
6.3.7 Volumetric Flasks. 1000-ml and 500-ml.

7.0 Reagents and Standards

[[Page 208]]

(Na2CO3.) in about 500 ml of CO2-free
water in a 1-liter volumetric flask. Add 3.497 g anhydrous sodium
bicarbonate (NaHCO3) to the flask, and dilute to 1 liter with
CO2 -free water. This solution contains 1000 mg/L inorganic
carbon.
7.3.5 Oxygen Gas. CO2 -free.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Pretest Preparation and Preliminary Determinations. Same as
Method 5, sections 8.1 and 8.2, respectively.
8.2 Preparation of Sampling Train. Same as Method 5, section 8.3,
except that 0.1 N NaOH is used in place of water in the impingers. The
volumes of the solutions are the same as in Method 5.
8.3 Leak-Check Procedures, Sampling Train Operation, Calculation of
Percent Isokinetic. Same as Method 5, sections 8.4 through 8.6,
respectively.
8.4 Sample Recovery. Same as Method 5, sections 8.7.1 through 8.7.4,
with the addition of the following:
8.4.1 Save portions of the water, acetone, and 0.1 N NaOH used for
cleanup as blanks. Take 200 ml of each liquid directly from the wash
bottles being used, and place in glass sample containers labeled ``water
blank,'' ``acetone blank,'' and ``NaOH blank,'' respectively.
8.4.2 Inspect the train prior to and during disassembly, and note
any abnormal conditions. Treat the samples as follows:
8.4.2.1 Container No. 1. Same as Method 5, section 8.7.6.1.
8.4.2.2 Container No. 2. Use water to rinse the sample nozzle,
probe, and front half of the filter holder three times in the manner
described in section 8.7.6.2 of Method 5 except that no brushing is
done. Put all the water wash in one container, seal, and label.
8.4.2.3 Container No. 3. Rinse and brush the sample nozzle, probe,
and front half of the filter holder with acetone as described for
Container No. 2 in section 8.7.6.2 of Method 5.
8.4.2.4 Container No. 4. Place the contents of the silica gel
impinger in its original container as described for Container No. 3 in
section 8.7.6.3 of Method 5.
8.4.2.5 Container No. 5. Measure the liquid in the first three
impingers and record the volume or weight as described for the Impinger
Water in section 8.7.6.4 of Method 5. Do not discard this liquid, but
place it in a sample container using a glass funnel to aid in the
transfer from the impingers or graduated cylinder (if used) to the
sample container. Rinse each impinger thoroughly with 0.1 N NaOH three
times, as well as the graduated cylinder (if used) and the funnel, and
put these rinsings in the same sample container. Seal the container and
label to clearly identify its contents.
8.5 Sample Transport. Whenever possible, containers should be
shipped in such a way that they remain upright at all times.

9.0 Quality Control.

9.1 Miscellaneous Quality Control Measures.

9.2 Volume Metering System Checks. Same as Method 5, section 9.2.

10.0 Calibration and Standardization

Same as Method 5, section 10.0, with the addition of the following
procedures for calibrating the total organic carbon analyzer:
10.1 Preparation of Organic Carbon Standard Curve.
10.1.1 Add 10 ml, 20 ml, 30 ml, 40 ml, and 50 ml of the organic
carbon stock solution to a series of five 1000-ml volumetric flasks. Add
30 ml, 40 ml, and 50 ml of the same solution to a series of three 500-ml
volumetric flasks. Dilute the contents of each flask to the mark using
CO2-free water. These flasks contain 10, 20, 30, 40, 50, 60,
80, and 100 mg/L organic carbon, respectively.
10.1.2 Use a hypodermic syringe to withdraw a 20- to 50-l
aliquot from the 10 mg/L standard solution and inject it into the total
carbon port of the analyzer. Measure the peak height. Repeat the
injections until three consecutive peaks are obtained within 10 percent
of their arithmetic mean. Repeat this procedure for the remaining
organic carbon standard solutions.
10.1.3 Calculate the corrected peak height for each standard by
deducting the blank correction (see section 11.2.5.3) as follows:

[[Page 209]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.146

Where:

A = Peak height of standard or sample, mm or other appropriate unit.
B = Peak height of blank, mm or other appropriate unit.

10.1.4 Prepare a linear regression plot of the arithmetic mean of
the three consecutive peak heights obtained for each standard solution
against the concentration of that solution. Calculate the calibration
factor as the inverse of the slope of this curve. If the product of the
arithmetic mean peak height for any standard solution and the
calibration factor differs from the actual concentration by more than 5
percent, remake and reanalyze that standard.
10.2 Preparation of Inorganic Carbon Standard Curve. Repeat the
procedures outlined in sections 10.1.1 through 10.1.4, substituting the
inorganic carbon stock solution for the organic carbon stock solution,
and the inorganic carbon port of the analyzer for the total carbon port.

11.0 Analytical Procedure

11.1 Record the data required on a sheet such as the one shown in
Figure 5-6 of Method 5.
11.2 Handle each sample container as follows:
11.2.1 Container No. 1. Same as Method 5, section 11.2.1, except
that the filters must be dried at 20 6 [deg]C (68 10 [deg]F) and
ambient pressure.
11.2.2 Containers No. 2 and No. 3. Same as Method 5, section 11.2.2,
except that evaporation of the samples must be at 20 6 [deg]C (68 10
[deg]F) and ambient pressure.
11.2.3 Container No. 4. Same as Method 5, section 11.2.3.
11.2.4 ``Water Blank'' and ``Acetone Blank'' Containers. Determine
the water and acetone blank values following the procedures for the
``Acetone Blank'' container in section 11.2.4 of Method 5. Evaporate the
samples at ambient temperature (20 6 [deg]C (68 10 [deg]F)) and
pressure.
11.2.5 Container No. 5. For the determination of total organic
carbon, perform two analyses on successive identical samples, i.e.,
total carbon and inorganic carbon. The desired quantity is the
difference between the two values obtained. Both analyses are based on
conversion of sample carbon into carbon dioxide for measurement by a
nondispersive infrared analyzer. Results of analyses register as peaks
on a strip chart recorder.
11.2.5.1 The principal differences between the operating parameters
for the two channels involve the combustion tube packing material and
temperature. In the total carbon channel, a high temperature (950 [deg]C
(1740 [deg]F)) furnace heats a Hastelloy combustion tube packed with
cobalt oxide-impregnated asbestos fiber. The oxygen in the carrier gas,
the elevated temperature, and the catalytic effect of the packing result
in oxidation of both organic and inorganic carbonaceous material to
CO2, and steam. In the inorganic carbon channel, a low
temperature (150 [deg]C (300 [deg]F)) furnace heats a glass tube
containing quartz chips wetted with 85 percent phosphoric acid. The acid
liberates CO2 and steam from inorganic carbonates. The
operating temperature is below that required to oxidize organic matter.
Follow the manufacturer's instructions for assembly, testing,
calibration, and operation of the analyzer.
11.2.5.2 As samples collected in 0.1 N NaOH often contain a high
measure of inorganic carbon that inhibits repeatable determinations of
TOC, sample pretreatment is necessary. Measure and record the liquid
volume of each sample (or impinger contents). If the sample contains
solids or immiscible liquid matter, homogenize the sample with a blender
or ultrasonics until satisfactory repeatability is obtained. Transfer a
representative portion of 10 to 15 ml to a 30-ml beaker, and acidify
with about 2 drops of concentrated HCl to a pH of 2 or less. Warm the
acidified sample at 50 [deg]C (120 [deg]F) in a water bath for 15
minutes.
11.2.5.3 While stirring the sample with a magnetic stirrer, use a
hypodermic syringe to withdraw a 20-to 50-1 aliquot from the
beaker. Analyze the sample for total carbon and calculate its corrected
mean peak height according to the procedures outlined in sections 10.1.2
and 10.1.3. Similarly analyze an aliquot of the sample for inorganic
carbon. Repeat the analyses for all the samples and for the 0.1 N NaOH
blank.
11.2.5.4 Ascertain the total carbon and inorganic carbon
concentrations (CTC and CIC, respectively) of each
sample and blank by comparing the corrected mean peak heights for each
sample and blank to the appropriate standard curve.

Note: If samples must be diluted for analysis, apply an appropriate
dilution factor.

12.0 Data Analysis and Calculations

Same as Method 5, section 12.0, with the addition of the following:
12.1 Nomenclature.

Cc = Concentration of condensed particulate matter in stack
gas, gas dry basis, corrected to standard conditions, g/dscm
(gr/dscf).
CIC = Concentration of condensed TOC in the liquid sample,
from section 11.2.5, mg/L.

[[Page 210]]

Ct = Total particulate concentration, dry basis, corrected to
standard conditions, g/dscm (gr/dscf).
CTC = Concentration of condensed TOC in the liquid sample,
from section 11.2.5, mg/L.
CTOC = Concentration of condensed TOC in the liquid sample,
mg/L.
mTOC = Mass of condensed TOC collected in the impingers, mg.
Vm(std) = Volume of gas sample measured by the dry gas meter,
corrected to standard conditions, from section 12.3 of Method
5, dscm (dscf).
Vs = Total volume of liquid sample, ml.

12.2 Concentration of Condensed TOC in Liquid Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.148

12.3 Mass of Condensed TOC Collected.
[GRAPHIC] [TIFF OMITTED] TR17OC00.149

Where:

0.001 = Liters per milliliter.

12.4 Concentration of Condensed Particulate Material.
[GRAPHIC] [TIFF OMITTED] TR17OC00.150

Where:

K4 = 0.001 g/mg for metric units.
= 0.0154 gr/mg for English units.

12.5 Total Particulate Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.151

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 Total Organic Carbon Analyzer. Tekmar-Dohrmann analyzers using
the single injection technique may be used as an alternative to
Rosemount Model 2100A analyzers.

17.0 References.

Same as section 17.0 of Method 5, with the addition of the
following:

1. American Public Health Association, American Water Works
Association, Water Pollution Control Federation. Standard Methods for
the Examination of Water and Wastewater. Fifteenth Edition. Washington,
D.C. 1980.

18.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 5F--Determination of Nonsulfate Particulate Matter Emissions From
Stationary Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3, and
Method 5.

1.0 Scope and Applications

1.1 Analyte. Nonsulfate particulate matter (PM). No CAS number
assigned.
1.2 Applicability. This method is applicable for the determination
of nonsulfate PM emissions from stationary sources. Use of this method
must be specified by an applicable subpart of the standards, or approved
by the Administrator for a particular application.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

Particulate matter is withdrawn isokinetically from the source and
collected on a filter maintained at a temperature in the range 160 14
[deg]C (320 25 [deg]F). The collected sample is extracted with water. A
portion of the extract is analyzed for sulfate content by ion
chromatography. The remainder is neutralized with ammonium hydroxide
(NH4OH), dried, and weighed. The weight of sulfate in the
sample is calculated as ammonium sulfate
((NH4)2SO4), and is subtracted from the
total particulate weight; the result is reported as nonsulfate
particulate matter.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

[[Page 211]]

6.0 Equipment and Supplies

6.1 Sample Collection and Recovery. Same as Method 5, sections 6.1
and 6.2, respectively.
6.2 Sample Analysis. Same as Method 5, section 6.3, with the
addition of the following:
6.2.1 Erlenmeyer Flasks. 125-ml, with ground glass joints.
6.2.2 Air Condenser. With ground glass joint compatible with the
Erlenmeyer flasks.
6.2.3 Beakers. 600-ml.
6.2.4 Volumetric Flasks. 1-liter, 500-ml (one for each sample), 200-
ml, and 50-ml (one for each sample and standard).
6.2.5 Pipet. 5-ml (one for each sample and standard).
6.2.6 Ion Chromatograph. The ion chromatograph should have at least
the following components.
6.2.6.1 Columns. An anion separation column or other column capable
of resolving the sulfate ion from other species present and a standard
anion suppressor column. Suppressor columns are produced as proprietary
items; however, one can be produced in the laboratory using the resin
available from BioRad Company, 32nd and Griffin Streets, Richmond,
California. Other systems which do not use suppressor columns may also
be used.
6.2.6.2 Pump. Capable of maintaining a steady flow as required by
the system.
6.2.6.3 Flow Gauges. Capable of measuring the specified system flow
rate.
6.2.6.4 Conductivity Detector.
6.2.6.5 Recorder. Compatible with the output voltage range of the
detector.

7.0 Reagents and Standards

Unless otherwise indicated, it is intended that all reagents conform
to the specifications established by the Committee on Analytical
Reagents of the American Chemical Society, where such specifications are
available; otherwise, use the best available grade.
7.1 Sample Collection. Same as Method 5, section 7.1.
7.2 Sample Recovery. Same as Method 5, section 7.2, with the
addition of the following:
7.2.1 Water. Deionized distilled, to conform to ASTM D 1193-77 or 91
Type 3 (incorporated by reference--see Sec. 60.17). The potassium
permanganate (KMnO4) test for oxidizable organic matter may
be omitted when high concentrations of organic matter are not expected
to be present.
7.3 Analysis. Same as Method 5, section 7.3, with the addition of
the following:
7.3.1 Water. Same as in section 7.2.1.
7.3.2 Stock Standard Solution, 1 mg
(NH4)2SO4/ml. Dry an adequate amount of
primary standard grade ammonium sulfate
((NH4)2SO4) at 105 to 110 [deg]C (220
to 230 [deg]F) for a minimum of 2 hours before preparing the standard
solution. Then dissolve exactly 1.000 g of dried
(NH4)2SO4 in water in a 1-liter
volumetric flask, and dilute to 1 liter. Mix well.
7.3.3 Working Standard Solution, 25 g
(NH4)2SO4/ml. Pipet 5 ml of the stock
standard solution into a 200-ml volumetric flask. Dilute to 200 ml with
water.
7.3.4 Eluent Solution. Weigh 1.018 g of sodium carbonate
(Na2CO3) and 1.008 g of sodium bicarbonate
(NaHCO3), and dissolve in 4 liters of water. This solution is
0.0024 M Na2CO3/0.003 M NaHCO3. Other
eluents appropriate to the column type and capable of resolving sulfate
ion from other species present may be used.
7.3.5 Ammonium Hydroxide. Concentrated, 14.8 M.
7.3.6 Phenolphthalein Indicator. 3,3-Bis(4-hydroxyphenyl)-1-(3H)-
isobenzo-furanone. Dissolve 0.05 g in 50 ml of ethanol and 50 ml of
water.

8.0 Sample Collection, Preservation, Storage, and Transport

Same as Method 5, section 8.0, with the exception of the following:
8.1 Sampling Train Operation. Same as Method 5, section 8.5, except
that the probe outlet and filter temperatures shall be maintained at 160
14 [deg]C (320 25 [deg]F).
8.2 Sample Recovery. Same as Method 5, section 8.7, except that the
recovery solvent shall be water instead of acetone, and a clean filter
from the same lot as those used during testing shall be saved for
analysis as a blank.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures

[[Page 212]]

9.2 Volume Metering System Checks. Same as Method 5, section 9.2.

10.0 Calibration and Standardization

Same as Method 5, section 10.0, with the addition of the following:
10.1 Determination of Ion Chromatograph Calibration Factor S.
Prepare a series of five standards by adding 1.0, 2.0, 4.0, 6.0, and
10.0 ml of working standard solution (25 g/ml) to a series of
five 50-ml volumetric flasks. (The standard masses will equal 25, 50,
100, 150, and 250 g.) Dilute each flask to the mark with water,
and mix well. Analyze each standard according to the chromatograph
manufacturer's instructions. Take peak height measurements with
symmetrical peaks; in all other cases, calculate peak areas. Prepare or
calculate a linear regression plot of the standard masses in g
(x-axis) versus their responses (y-axis). From this line, or equation,
determine the slope and calculate its reciprocal which is the
calibration factor, S. If any point deviates from the line by more than
7 percent of the concentration at that point, remake and reanalyze that
standard. This deviation can be determined by multiplying S times the
response for each standard. The resultant concentrations must not differ
by more than 7 percent from each known standard mass (i.e., 25, 50, 100,
150, and 250 g).
10.2 Conductivity Detector. Calibrate according to manufacturer's
specifications prior to initial use.

11.0 Analytical Procedure

11.1 Sample Extraction.
11.1.1 Note on the analytical data sheet, the level of the liquid in
the container, and whether any sample was lost during shipment. If a
noticeable amount of leakage has occurred, either void the sample or use
methods, subject to the approval of the Administrator, to correct the
final results.
11.1.2 Cut the filter into small pieces, and place it in a 125-ml
Erlenmeyer flask with a ground glass joint equipped with an air
condenser. Rinse the shipping container with water, and pour the rinse
into the flask. Add additional water to the flask until it contains
about 75 ml, and place the flask on a hot plate. Gently reflux the
contents for 6 to 8 hours. Cool the solution, and transfer it to a 500-
ml volumetric flask. Rinse the Erlenmeyer flask with water, and transfer
the rinsings to the volumetric flask including the pieces of filter.
11.1.3 Transfer the probe rinse to the same 500-ml volumetric flask
with the filter sample. Rinse the sample bottle with water, and add the
rinsings to the volumetric flask. Dilute the contents of the flask to
the mark with water.
11.1.4 Allow the contents of the flask to settle until all solid
material is at the bottom of the flask. If necessary, remove and
centrifuge a portion of the sample.
11.1.5 Repeat the procedures outlined in sections 11.1.1 through
11.1.4 for each sample and for the filter blank.
11.2 Sulfate (SO4) Analysis.
11.2.1 Prepare a standard calibration curve according to the
procedures outlined in section 10.1.
11.2.2 Pipet 5 ml of the sample into a 50-ml volumetric flask, and
dilute to 50 ml with water. (Alternatively, eluent solution may be used
instead of water in all sample, standard, and blank dilutions.) Analyze
the set of standards followed by the set of samples, including the
filter blank, using the same injection volume used for the standards.
11.2.3 Repeat the analyses of the standards and the samples, with
the standard set being done last. The two peak height or peak area
responses for each sample must agree within 5 percent of their
arithmetic mean for the analysis to be valid. Perform this analysis
sequence on the same day. Dilute any sample and the blank with equal
volumes of water if the concentration exceeds that of the highest
standard.
11.2.4 Document each sample chromatogram by listing the following
analytical parameters: injection point, injection volume, sulfate
retention time, flow rate, detector sensitivity setting, and recorder
chart speed.
11.3 Sample Residue.
11.3.1 Transfer the remaining contents of the volumetric flask to a
tared 600-ml beaker or similar container. Rinse the volumetric flask
with water, and add the rinsings to the tared beaker. Make certain that
all particulate matter is transferred to the beaker. Evaporate the water
in an oven at 105 [deg]C (220 [deg]F) until only about 100 ml of water
remains. Remove the beakers from the oven, and allow them to cool.
11.3.2 After the beakers have cooled, add five drops of
phenolphthalein indicator, and then add concentrated ammonium hydroxide
until the solution turns pink. Return the samples to the oven at 105
[deg]C (220 [deg]F), and evaporate the samples to dryness. Cool the
samples in a desiccator, and weigh the samples to constant weight.

12.0 Data Analysis and Calculations

Same as Method 5, section 12.0, with the addition of the following:
12.1 Nomenclature.

CW = Water blank residue concentration, mg/ml.
F = Dilution factor (required only if sample dilution was needed to
reduce the concentration into the range of calibration).
HS = Arithmetic mean response of duplicate sample analyses,
mm for height or mm2 for area.

[[Page 213]]

Hb = Arithmetic mean response of duplicate filter blank
analyses, mm for height or mm2 for area.
mb = Mass of beaker used to dry sample, mg.
mf = Mass of sample filter, mg.
mn = Mass of nonsulfate particulate matter in the sample as
collected, mg.
ms = Mass of ammonium sulfate in the sample as collected, mg.
mt = Mass of beaker, filter, and dried sample, mg.
mw = Mass of residue after evaporation of water blank, mg.
S = Calibration factor, g/mm.
Vb = Volume of water blank, ml.
VS = Volume of sample collected, 500 ml.

12.2 Water Blank Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.152

12.3 Mass of Ammonium Sulfate.
[GRAPHIC] [TIFF OMITTED] TR17OC00.153

Where:

100 = Aliquot factor, 495 ml/5 ml
1000 = Constant, g/mg

12.4 Mass of Nonsulfate Particulate Matter.
[GRAPHIC] [TIFF OMITTED] TR17OC00.154

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 The following procedure may be used as an alternative to the
procedure in section 11.0
16.1.1 Apparatus. Same as for Method 6, sections 6.3.3 to 6.3.6 with
the following additions.
16.1.1.1 Beakers. 250-ml, one for each sample, and 600-ml.
16.1.1.2 Oven. Capable of maintaining temperatures of 75 5 [deg]C
(167 9 [deg]F) and 105 5 [deg]C (221 9 [deg]F).
16.1.1.3 Buchner Funnel.
16.1.1.4 Glass Columns. 25-mm x 305-mm (1-in. x 12-in.) with Teflon
stopcock.
16.1.1.5 Volumetric Flasks. 50-ml and 500-ml, one set for each
sample, and 100-ml, 200-ml, and 1000-ml.
16.1.1.6 Pipettes. Two 20-ml and one 200-ml, one set for each
sample, and 5-ml.
16.1.1.7 Filter Flasks. 500-ml.
16.1.1.8 Polyethylene Bottle. 500-ml, one for each sample.
16.1.2 Reagents. Same as Method 6, sections 7.3.2 to 7.3.5 with the
following additions:
16.1.2.1 Water, Ammonium Hydroxide, and Phenolphthalein. Same as
sections 7.2.1, 7.3.5, and 7.3.6 of this method, respectively.
16.1.2.2 Filter. Glass fiber to fit Buchner funnel.
16.1.2.3 Hydrochloric Acid (HCl), 1 m. Add 8.3 ml of concentrated
HCl (12 M) to 50 ml of water in a 100-ml volumetric flask. Dilute to 100
ml with water.
16.1.2.4 Glass Wool.
16.1.2.5 Ion Exchange Resin. Strong cation exchange resin, hydrogen
form, analytical grade.
16.1.2.6 pH Paper. Range of 1 to 7.
16.1.3 Analysis.
16.1.3.1 Ion Exchange Column Preparation. Slurry the resin with 1 M
HCl in a 250-ml beaker, and allow to stand overnight. Place 2.5 cm (1
in.) of glass wool in the bottom of the glass column. Rinse the slurried
resin twice with water. Resuspend the resin in water, and pour
sufficient resin into the column to make a bed 5.1 cm (2 in.) deep. Do
not allow air bubbles to become entrapped in the resin or glass wool to
avoid channeling, which may produce erratic results. If necessary, stir
the resin with a glass rod to remove air bubbles, after the column has
been prepared, never let the liquid level fall below the top of the
upper glass wool plug. Place a 2.5-cm (1-in.) plug of glass wool on top
of the resin. Rinse the column with water until the eluate gives a pH of
5 or greater as measured with pH paper.
16.1.3.2 Sample Extraction. Followup the procedure given in section
11.1.3 except do not dilute the sample to 500 ml.
16.1.3.3 Sample Residue.
16.1.3.3.1 Place at least one clean glass filter for each sample in
a Buchner funnel, and rinse the filters with water. Remove the filters
from the funnel, and dry them in an oven at 105 5 [deg]C (221 9
[deg]F); then cool in a desiccator. Weigh each filter to constant weight
according to the procedure in Method 5, section 11.0. Record the weight
of each filter to the nearest 0.1 mg.
16.1.3.3.2 Assemble the vacuum filter apparatus, and place one of
the clean, tared glass fiber filters in the Buchner funnel. Decant the
liquid portion of the extracted sample (Section 16.1.3.2) through the
tared glass fiber filter into a clean, dry, 500-ml filter flask. Rinse
all the particulate matter remaining in the volumetric flask onto the
glass fiber filter with water. Rinse the particulate matter with
additional water.

[[Page 214]]

Transfer the filtrate to a 500-ml volumetric flask, and dilute to 500 ml
with water. Dry the filter overnight at 105 5 [deg]C (221 9 [deg]F),
cool in a desiccator, and weigh to the nearest 0.1 mg.
16.1.3.3.3 Dry a 250-ml beaker at 75 5 [deg]C (167 9 [deg]F), and
cool in a desiccator; then weigh to constant weight to the nearest 0.1
mg. Pipette 200 ml of the filtrate that was saved into a tared 250-ml
beaker; add five drops of phenolphthalein indicator and sufficient
concentrated ammonium hydroxide to turn the solution pink. Carefully
evaporate the contents of the beaker to dryness at 75 5 [deg]C (167 9
[deg]F). Check for dryness every 30 minutes. Do not continue to bake the
sample once it has dried. Cool the sample in a desiccator, and weigh to
constant weight to the nearest 0.1 mg.
16.1.3.4 Sulfate Analysis. Adjust the flow rate through the ion
exchange column to 3 ml/min. Pipette a 20-ml aliquot of the filtrate
onto the top of the ion exchange column, and collect the eluate in a 50-
ml volumetric flask. Rinse the column with two 15-ml portions of water.
Stop collection of the eluate when the volume in the flask reaches 50-
ml. Pipette a 20-ml aliquot of the eluate into a 250-ml Erlenmeyer
flask, add 80 ml of 100 percent isopropanol and two to four drops of
thorin indicator, and titrate to a pink end point using 0.0100 N barium
perchlorate. Repeat and average the titration volumes. Run a blank with
each series of samples. Replicate titrations must agree within 1 percent
or 0.2 ml, whichever is larger. Perform the ion exchange and titration
procedures on duplicate portions of the filtrate. Results should agree
within 5 percent. Regenerate or replace the ion exchange resin after 20
sample aliquots have been analyzed or if the end point of the titration
becomes unclear.

Note: Protect the 0.0100 N barium perchlorate solution from
evaporation at all times.

16.1.3.5 Blank Determination. Begin with a sample of water of the
same volume as the samples being processed and carry it through the
analysis steps described in sections 16.1.3.3 and 16.1.3.4. A blank
value larger than 5 mg should not be subtracted from the final
particulate matter mass. Causes for large blank values should be
investigated and any problems resolved before proceeding with further
analyses.
16.1.4 Calibration. Calibrate the barium perchlorate solutions as in
Method 6, section 10.5.
16.1.5 Calculations.
16.1.5.1 Nomenclature. Same as section 12.1 with the following
additions:

ma = Mass of clean analytical filter, mg.
md = Mass of dissolved particulate matter, mg.
me = Mass of beaker and dissolved particulate matter after
evaporation of filtrate, mg.
mp = Mass of insoluble particulate matter, mg.
mr = Mass of analytical filter, sample filter, and insoluble
particulate matter, mg.
mbk = Mass of nonsulfate particulate matter in blank sample,
mg.
mn = Mass of nonsulfate particulate matter, mg.
ms = Mass of Ammonium sulfate, mg.
N = Normality of Ba(ClO4) titrant, meq/ml.
Va = Volume of aliquot taken for titration, 20 ml.
Vc = Volume of titrant used for titration blank, ml.
Vd = Volume of filtrate evaporated, 200 ml.
Ve = Volume of eluate collected, 50 ml.
Vf = Volume of extracted sample, 500 ml.
Vi = Volume of filtrate added to ion exchange column, 20 ml.
Vt = Volume of Ba(C104)2 titrant, ml.
W = Equivalent weight of ammonium sulfate, 66.07 mg/meq.
16.1.5.2 Mass of Insoluble Particulate Matter.
[GRAPHIC] [TIFF OMITTED] TR17OC00.155

16.1.5.3 Mass of Dissolved Particulate Matter.
[GRAPHIC] [TIFF OMITTED] TR17OC00.156

16.1.5.4 Mass of Ammonium Sulfate.
[GRAPHIC] [TIFF OMITTED] TR17OC00.157

16.1.5.5 Mass of Nonsulfate Particulate Matter.
[GRAPHIC] [TIFF OMITTED] TR17OC00.158

17.0 References

Same as Method 5, section 17.0, with the addition of the following:

1. Mulik, J.D. and E. Sawicki. Ion Chromatographic Analysis of
Environmental Pollutants. Ann Arbor, Ann Arbor Science Publishers, Inc.
Vol. 2, 1979.
2. Sawicki, E., J.D. Mulik, and E. Wittgenstein. Ion Chromatographic
Analysis of Environmental Pollutants. Ann Arbor, Ann Arbor Science
Publishers, Inc. Vol. 1. 1978.
3. Siemer, D.D. Separation of Chloride and Bromide from Complex
Matrices Prior to Ion Chromatographic Determination. Analytical
Chemistry 52(12): 1874-1877. October 1980.
4. Small, H., T.S. Stevens, and W.C. Bauman. Novel Ion Exchange
Chromatographic Method Using

[[Page 215]]

Conductimetric Determination. Analytical Chemistry. 47(11):1801. 1975.

18.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 5G--Determination of Particulate Matter Emissions From Wood
Heaters (Dilution Tunnel Sampling Location)

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 4, Method 5, Method 5H, and Method 28.

1.0 Scope and Application

1.1 Analyte. Particulate matter (PM). No CAS number assigned.
1.2 Applicability. This method is applicable for the determination
of PM emissions from wood heaters.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 The exhaust from a wood heater is collected with a total
collection hood, and is combined with ambient dilution air. Particulate
matter is withdrawn proportionally from a single point in a sampling
tunnel, and is collected on two glass fiber filters in series. The
filters are maintained at a temperature of no greater than 32 [deg]C (90
[deg]F). The particulate mass is determined gravimetrically after the
removal of uncombined water.
2.2 There are three sampling train approaches described in this
method: (1) One dual-filter dry sampling train operated at about 0.015
m\3\/min (0.5 cfm), (2) One dual-filter plus impingers sampling train
operated at about 0.015 m\3\/min (0.5 cfm), and (3) two dual-filter dry
sampling trains operated simultaneously at any flow rate. Options (2)
and (3) are referenced in section 16.0 of this method. The dual-filter
dry sampling train equipment and operation, option (1), are described in
detail in this method.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The following items are required for sample
collection:
6.1.1 Sampling Train. The sampling train configuration is shown in
Figure 5G-1 and consists of the following components:
6.1.1.1 Probe. Stainless steel (e.g., 316 or grade more corrosion
resistant) or glass about 9.5 mm (\3/8\ in.) I.D., 0.6 m (24 in.) in
length. If made of stainless steel, the probe shall be constructed from
seamless tubing.
6.1.1.2 Pitot Tube. Type S, as described in section 6.1 of Method 2.
The Type S pitot tube assembly shall have a known coefficient,
determined as outlined in Method 2, section 10. Alternatively, a
standard pitot may be used as described in Method 2, section 6.1.2.
6.1.1.3 Differential Pressure Gauge. Inclined manometer or
equivalent device, as described in Method 2, section 6.2. One manometer
shall be used for velocity head (Fp) readings and another (optional) for
orifice differential pressure readings (FH).
6.1.1.4 Filter Holders. Two each made of borosilicate glass,
stainless steel, or Teflon, with a glass frit or stainless steel filter
support and a silicone rubber, Teflon, or Viton gasket. The holder
design shall provide a positive seal against leakage from the outside or
around the filters. The filter holders shall be placed in series with
the backup filter holder located 25 to 100 mm (1 to 4 in.) downstream
from the primary filter holder. The filter holder shall be capable of
holding a filter with a 100 mm (4 in.) diameter, except as noted in
section 16.
6.1.1.5 Filter Temperature Monitoring System. A temperature sensor
capable of measuring temperature to within 3 [deg]C (5 [deg]F). The
sensor shall be installed at the exit side of the front filter holder so
that the sensing tip of the temperature sensor is in direct contact with
the sample gas or in a thermowell as shown in Figure 5G-1. The
temperature sensor shall comply with the calibration specifications in
Method 2, section 10.3. Alternatively, the sensing tip of the
temperature sensor may be installed at the inlet side of the front
filter holder.
6.1.1.6 Dryer. Any system capable of removing water from the sample
gas to less than 1.5 percent moisture (volume percent) prior to the
metering system. The system shall include a temperature sensor for
demonstrating that sample gas temperature exiting the dryer is less than
20 [deg]C (68 [deg]F).
6.1.1.7 Metering System. Same as Method 5, section 6.1.1.9.
6.1.2 Barometer. Same as Method 5, section 6.1.2.
6.1.3 Dilution Tunnel Gas Temperature Measurement. A temperature
sensor capable

[[Page 216]]

of measuring temperature to within 3 [deg]C (5 [deg]F).
6.1.4 Dilution Tunnel. The dilution tunnel apparatus is shown in
Figure 5G-2 and consists of the following components:
6.1.4.1 Hood. Constructed of steel with a minimum diameter of 0.3 m
(1 ft) on the large end and a standard 0.15 to 0.3 m (0.5 to 1 ft)
coupling capable of connecting to standard 0.15 to 0.3 m (0.5 to 1 ft)
stove pipe on the small end.
6.1.4.2 90[deg] Elbows. Steel 90[deg] elbows, 0.15 to 0.3 m (0.5 to
1 ft) in diameter for connecting mixing duct, straight duct and optional
damper assembly. There shall be at least two 90[deg] elbows upstream of
the sampling section (see Figure 5G-2).
6.1.4.3 Straight Duct. Steel, 0.15 to 0.3 m (0.5 to 1 ft) in
diameter to provide the ducting for the dilution apparatus upstream of
the sampling section. Steel duct, 0.15 m (0.5 ft) in diameter shall be
used for the sampling section. In the sampling section, at least 1.2 m
(4 ft) downstream of the elbow, shall be two holes (velocity traverse
ports) at 90[deg] to each other of sufficient size to allow entry of the
pitot for traverse measurements. At least 1.2 m (4 ft) downstream of the
velocity traverse ports, shall be one hole (sampling port) of sufficient
size to allow entry of the sampling probe. Ducts of larger diameter may
be used for the sampling section, provided the specifications for
minimum gas velocity and the dilution rate range shown in section 8 are
maintained. The length of duct from the hood inlet to the sampling ports
shall not exceed 9.1 m (30 ft).
6.1.4.4 Mixing Baffles. Steel semicircles (two) attached at 90[deg]
to the duct axis on opposite sides of the duct midway between the two
elbows upstream of sampling section. The space between the baffles shall
be about 0.3 m (1 ft).
6.1.4.5 Blower. Squirrel cage or other fan capable of extracting gas
from the dilution tunnel of sufficient flow to maintain the velocity and
dilution rate specifications in section 8 and exhausting the gas to the
atmosphere.
6.2 Sample Recovery. The following items are required for sample
recovery: probe brushes, wash bottles, sample storage containers, petri
dishes, and funnel. Same as Method 5, sections 6.2.1 through 6.2.4, and
6.2.8, respectively.
6.3 Sample Analysis. The following items are required for sample
analysis: glass weighing dishes, desiccator, analytical balance, beakers
(250-ml or smaller), hygrometer, and temperature sensor. Same as Method
5, sections 6.3.1 through 6.3.3 and 6.3.5 through 6.3.7, respectively.

7.0 Reagents and Standards

7.1 Sample Collection. The following reagents are required for
sample collection:
7.1.1 Filters. Glass fiber filters with a minimum diameter of 100 mm
(4 in.), without organic binder, exhibiting at least 99.95 percent
efficiency (<0.05 percent penetration) on 0.3-micron dioctyl phthalate
smoke particles. Gelman A/E 61631 has been found acceptable for this
purpose.
7.1.2 Stopcock Grease. Same as Method 5, section 7.1.5. 7.2 Sample
Recovery. Acetone-reagent grade, same as Method 5, section 7.2.
7.3 Sample Analysis. Two reagents are required for the sample
analysis:
7.3.1 Acetone. Same as in section 7.2.
7.3.2 Desiccant. Anhydrous calcium sulfate, calcium chloride, or
silica gel, indicating type.

8.0 Sample Collection, Preservation, Transport, and Storage

8.1 Dilution Tunnel Assembly and Cleaning. A schematic of a dilution
tunnel is shown in Figure 5G-2. The dilution tunnel dimensions and other
features are described in section 6.1.4. Assemble the dilution tunnel,
sealing joints and seams to prevent air leakage. Clean the dilution
tunnel with an appropriately sized wire chimney brush before each
certification test.
8.2 Draft Determination. Prepare the wood heater as in Method 28,
section 6.2.1. Locate the dilution tunnel hood centrally over the wood
heater stack exhaust. Operate the dilution tunnel blower at the flow
rate to be used during the test run. Measure the draft imposed on the
wood heater by the dilution tunnel (i.e., the difference in draft
measured with and without the dilution tunnel operating) as described in
Method 28, section 6.2.3. Adjust the distance between the top of the
wood heater stack exhaust and the dilution tunnel hood so that the
dilution tunnel induced draft is less than 1.25 Pa (0.005 in.
H2O). Have no fire in the wood heater, close the wood heater
doors, and open fully the air supply controls during this check and
adjustment.
8.3 Pretest Ignition. Same as Method 28, section 8.7.
8.4 Smoke Capture. During the pretest ignition period, operate the
dilution tunnel and visually monitor the wood heater stack exhaust.
Operate the wood heater with the doors closed and determine that 100
percent of the exhaust gas is collected by the dilution tunnel hood. If
less than 100 percent of the wood heater exhaust gas is collected,
adjust the distance between the wood heater stack and the dilution
tunnel hood until no visible exhaust gas is escaping. Stop the pretest
ignition period, and repeat the draft determination procedure described
in section 8.2.
8.5 Velocity Measurements. During the pretest ignition period,
conduct a velocity traverse to identify the point of average velocity.
This single point shall be used for measuring velocity during the test
run.

[[Page 217]]

8.5.1 Velocity Traverse. Measure the diameter of the duct at the
velocity traverse port location through both ports. Calculate the duct
area using the average of the two diameters. A pretest leak-check of
pitot lines as in Method 2, section 8.1, is recommended. Place the
calibrated pitot tube at the centroid of the stack in either of the
velocity traverse ports. Adjust the damper or similar device on the
blower inlet until the velocity indicated by the pitot is approximately
220 m/min (720 ft/min). Continue to read the Fp and temperature until
the velocity has remained constant (less than 5 percent change) for 1
minute. Once a constant velocity is obtained at the centroid of the
duct, perform a velocity traverse as outlined in Method 2, section 8.3
using four points per traverse as outlined in Method 1. Measure the Fp
and tunnel temperature at each traverse point and record the readings.
Calculate the total gas flow rate using calculations contained in Method
2, section 12. Verify that the flow rate is 4 0.40 dscm/min (140 14
dscf/min); if not, readjust the damper, and repeat the velocity
traverse. The moisture may be assumed to be 4 percent (100 percent
relative humidity at 85 [deg]F). Direct moisture measurements (e.g.,
according to Method 4) are also permissible.

Note: If burn rates exceed 3 kg/hr (6.6 lb/hr), dilution tunnel duct
flow rates greater than 4 dscm/min (140 dscfm) and sampling section duct
diameters larger than 150 mm (6 in.) are allowed. If larger ducts or
flow rates are used, the sampling section velocity shall be at least 220
m/min (720 fpm). In order to ensure measurable particulate mass catch,
it is recommended that the ratio of the average mass flow rate in the
dilution tunnel to the average fuel burn rate be less than 150:1 if
larger duct sizes or flow rates are used.

8.5.2 Testing Velocity Measurements. After obtaining velocity
traverse results that meet the flow rate requirements, choose a point of
average velocity and place the pitot and temperature sensor at that
location in the duct. Alternatively, locate the pitot and the
temperature sensor at the duct centroid and calculate a velocity
correction factor for the centroidal position. Mount the pitot to ensure
no movement during the test run and seal the port holes to prevent any
air leakage. Align the pitot opening to be parallel with the duct axis
at the measurement point. Check that this condition is maintained during
the test run (about 30-minute intervals). Monitor the temperature and
velocity during the pretest ignition period to ensure that the proper
flow rate is maintained. Make adjustments to the dilution tunnel flow
rate as necessary.
8.6 Pretest Preparation. Same as Method 5, section 8.1.
8.7 Preparation of Sampling Train. During preparation and assembly
of the sampling train, keep all openings where contamination can occur
covered until just prior to assembly or until sampling is about to
begin.
Using a tweezer or clean disposable surgical gloves, place one
labeled (identified) and weighed filter in each of the filter holders.
Be sure that each filter is properly centered and that the gasket is
properly placed so as to prevent the sample gas stream from
circumventing the filter. Check each filter for tears after assembly is
completed.
Mark the probe with heat resistant tape or by some other method to
denote the proper distance into the stack or duct. Set up the train as
shown in Figure 5G-1.
8.8 Leak-Check Procedures.
8.8.1 Leak-Check of Metering System Shown in Figure 5G-1. That
portion of the sampling train from the pump to the orifice meter shall
be leak-checked prior to initial use and after each certification or
audit test. Leakage after the pump will result in less volume being
recorded than is actually sampled. Use the procedure described in Method
5, section 8.4.1. Similar leak-checks shall be conducted for other types
of metering systems (i.e., without orifice meters).
8.8.2 Pretest Leak-Check. A pretest leak-check of the sampling train
is recommended, but not required. If the pretest leak check is
conducted, the procedures outlined in Method 5, section 8.4.2 should be
used. A vacuum of 130 mm Hg (5 in. Hg) may be used instead of 380 mm Hg
(15 in. Hg).
8.8.3 Post-Test Leak-Check. A leak-check of the sampling train is
mandatory at the conclusion of each test run. The leak-check shall be
performed in accordance with the procedures outlined in Method 5,
section 8.4.2. A vacuum of 130 mm Hg (5 in. Hg) or the highest vacuum
measured during the test run, whichever is greater, may be used instead
of 380 mm Hg (15 in. Hg).
8.9 Preliminary Determinations. Determine the pressure, temperature
and the average velocity of the tunnel gases as in section 8.5. Moisture
content of diluted tunnel gases is assumed to be 4 percent for making
flow rate calculations; the moisture content may be measured directly as
in Method 4.
8.10 Sampling Train Operation. Position the probe inlet at the stack
centroid, and block off the openings around the probe and porthole to
prevent unrepresentative dilution of the gas stream. Be careful not to
bump the probe into the stack wall when removing or inserting the probe
through the porthole; this minimizes the chance of extracting deposited
material.
8.10.1 Begin sampling at the start of the test run as defined in
Method 28, section 8.8.1. During the test run, maintain a sample flow
rate proportional to the dilution tunnel flow rate (within 10 percent of
the initial proportionality ratio) and a filter holder temperature of no
greater than 32 [deg]C (90 [deg]F).

[[Page 218]]

The initial sample flow rate shall be approximately 0.015 m\3\/min (0.5
cfm).
8.10.2 For each test run, record the data required on a data sheet
such as the one shown in Figure 5G-3. Be sure to record the initial dry
gas meter reading. Record the dry gas meter readings at the beginning
and end of each sampling time increment and when sampling is halted.
Take other readings as indicated on Figure 5G-3 at least once each 10
minutes during the test run. Since the manometer level and zero may
drift because of vibrations and temperature changes, make periodic
checks during the test run.
8.10.3 For the purposes of proportional sampling rate
determinations, data from calibrated flow rate devices, such as glass
rotameters, may be used in lieu of incremental dry gas meter readings.
Proportional rate calculation procedures must be revised, but
acceptability limits remain the same.
8.10.4 During the test run, make periodic adjustments to keep the
temperature between (or upstream of) the filters at the proper level. Do
not change sampling trains during the test run.
8.10.5 At the end of the test run (see Method 28, section 6.4.6),
turn off the coarse adjust valve, remove the probe from the stack, turn
off the pump, record the final dry gas meter reading, and conduct a
post-test leak-check, as outlined in section 8.8.2. Also, leak-check the
pitot lines as described in Method 2, section 8.1; the lines must pass
this leak-check in order to validate the velocity head data.
8.11 Calculation of Proportional Sampling Rate. Calculate percent
proportionality (see section 12.7) to determine whether the run was
valid or another test run should be made.
8.12 Sample Recovery. Same as Method 5, section 8.7, with the
exception of the following:
8.12.1 An acetone blank volume of about 50-ml or more may be used.
8.12.2 Treat the samples as follows:
8.12.2.1 Container Nos. 1 and 1A. Treat the two filters according to
the procedures outlined in Method 5, section 8.7.6.1. The filters may be
stored either in a single container or in separate containers. Use the
sum of the filter tare weights to determine the sample mass collected.
8.12.2.3 Container No. 2.
8.12.2.3.1 Taking care to see that dust on the outside of the probe
or other exterior surfaces does not get into the sample, quantitatively
recover particulate matter or any condensate from the probe and filter
holders by washing and brushing these components with acetone and
placing the wash in a labeled glass container. At least three cycles of
brushing and rinsing are required.
8.12.2.3.2 Between sampling runs, keep brushes clean and protected
from contamination.
8.12.2.3.3 After all acetone washings and particulate matter have
been collected in the sample containers, tighten the lids on the sample
containers so that the acetone will not leak out when transferred to the
laboratory weighing area. Mark the height of the fluid levels to
determine whether leakage occurs during transport. Label the containers
clearly to identify contents.
8.13 Sample Transport. Whenever possible, containers should be
shipped in such a way that they remain upright at all times.

Note: Requirements for capping and transport of sample containers
are not applicable if sample recovery and analysis occur in the same
room.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.8, 10.1-10.4................ Sampling Ensures accurate
equipment leak measurement of stack
check and gas flow rate,
calibration. sample volume.
10.5.......................... Analytical Ensure accurate and
balance precise measurement
calibration. of collected
particulate.
16.2.5........................ Simultaneous, Ensure precision of
dual-train measured particulate
sample concentration.
collection.
------------------------------------------------------------------------

9.2 Volume Metering System Checks. Same as Method 5, section 9.2.

10.0 Calibration and Standardization

Note: Maintain a laboratory record of all calibrations.

10.1 Pitot Tube. The Type S pitot tube assembly shall be calibrated
according to the procedure outlined in Method 2, section 10.1, prior to
the first certification test and checked semiannually, thereafter. A
standard pitot need not be calibrated but shall be inspected and
cleaned, if necessary, prior to each certification test.
10.2 Volume Metering System.
10.2.1 Initial and Periodic Calibration. Before its initial use and
at least semiannually thereafter, calibrate the volume metering system
as described in Method 5, section 10.3.1, except that the wet test meter
with a capacity of 3.0 liters/rev (0.1 ft\3\/rev) may be used. Other
liquid displacement systems accurate to within 1 percent, may be used
as calibration standards.

[[Page 219]]

Note: Procedures and equipment specified in Method 5, section 16.0,
for alternative calibration standards, including calibrated dry gas
meters and critical orifices, are allowed for calibrating the dry gas
meter in the sampling train. A dry gas meter used as a calibration
standard shall be recalibrated at least once annually.

10.2.2 Calibration After Use. After each certification or audit test
(four or more test runs conducted on a wood heater at the four burn
rates specified in Method 28), check calibration of the metering system
by performing three calibration runs at a single, intermediate flow rate
as described in Method 5, section 10.3.2.

Note: Procedures and equipment specified in Method 5, section 16.0,
for alternative calibration standards are allowed for the post-test dry
gas meter calibration check.

10.2.3 Acceptable Variation in Calibration. If the dry gas meter
coefficient values obtained before and after a certification test differ
by more than 5 percent, the certification test shall either be voided
and repeated, or calculations for the certification test shall be
performed using whichever meter coefficient value (i.e., before or
after) gives the lower value of total sample volume.
10.3 Temperature Sensors. Use the procedure in Method 2, section
10.3, to calibrate temperature sensors before the first certification or
audit test and at least semiannually, thereafter.
10.4 Barometer. Calibrate against a mercury barometer before the
first certification test and at least semiannually, thereafter. If a
mercury barometer is used, no calibration is necessary. Follow the
manufacturer's instructions for operation.
10.5 Analytical Balance. Perform a multipoint calibration (at least
five points spanning the operational range) of the analytical balance
before the first certification test and semiannually, thereafter. Before
each certification test, audit the balance by weighing at least one
calibration weight (class F) that corresponds to 50 to 150 percent of
the weight of one filter. If the scale cannot reproduce the value of the
calibration weight to within 0.1 mg, conduct the multipoint calibration
before use.

11.0 Analytical Procedure

11.1 Record the data required on a sheet such as the one shown in
Figure 5G-4. Use the same analytical balance for determining tare
weights and final sample weights.
11.2 Handle each sample container as follows:
11.2.1 Container Nos. 1 and 1A. Treat the two filters according to
the procedures outlined in Method 5, section 11.2.1.
11.2.2 Container No. 2. Same as Method 5, section 11.2.2, except
that the beaker may be smaller than 250 ml.
11.2.3 Acetone Blank Container. Same as Method 5, section 11.2.4,
except that the beaker may be smaller than 250 ml.

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after the
final calculation. Other forms of the equations may be used as long as
they give equivalent results.
12.1 Nomenclature.

Bws = Water vapor in the gas stream, proportion by volume
(assumed to be 0.04).
cs = Concentration of particulate matter in stack gas, dry
basis, corrected to standard conditions, g/dscm (gr/dscf).
E = Particulate emission rate, g/hr (lb/hr).
Eadj = Adjusted particulate emission rate, g/hr (lb/hr).
La = Maximum acceptable leakage rate for either a pretest or
post-test leak-check, equal to 0.00057 m\3\/min (0.020 cfm) or
4 percent of the average sampling rate, whichever is less.
Lp = Leakage rate observed during the post-test leak-check,
m\3\/min (cfm).
ma = Mass of residue of acetone blank after evaporation, mg.
maw = Mass of residue from acetone wash after evaporation,
mg.
mn = Total amount of particulate matter collected, mg.
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 lb/lb-
mole).
Pbar = Barometric pressure at the sampling site, mm Hg (in.
Hg).
PR = Percent of proportional sampling rate.
Ps = Absolute gas pressure in dilution tunnel, mm Hg (in.
Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
Qsd = Average gas flow rate in dilution tunnel, calculated as
in Method 2, Equation 2-8, dscm/hr (dscf/hr).
Tm = Absolute average dry gas meter temperature (see Figure
5G-3), [deg]K ([deg]R).
Tmi = Absolute average dry gas meter temperature during each
10-minute interval, i, of the test run, [deg]K ([deg]R).
Ts = Absolute average gas temperature in the dilution tunnel
(see Figure 5G-3), [deg]K ([deg]R).
Tsi = Absolute average gas temperature in the dilution tunnel
during each 10 minute interval, i, of the test run, [deg]K
([deg]R).
Tstd = Standard absolute temperature, 293 [deg]K (528
[deg]R).
Va = Volume of acetone blank, ml.
Vaw = Volume of acetone used in wash, ml.
Vm = Volume of gas sample as measured by dry gas meter, dcm
(dcf).

[[Page 220]]

Vmi = Volume of gas sample as measured by dry gas meter
during each 10-minute interval, i, of the test run, dcm.
Vm(std) = Volume of gas sample measured by the dry gas meter,
corrected to standard conditions, dscm (dscf).
Vs = Average gas velocity in the dilution tunnel, calculated
by Method 2, Equation 2-7, m/sec (ft/sec). The dilution tunnel
dry gas molecular weight may be assumed to be 29 g/g mole (lb/
lb mole).
Vsi = Average gas velocity in dilution tunnel during each 10-
minute interval, i, of the test run, calculated by Method 2,
Equation 2-7, m/sec (ft/sec).
Y = Dry gas meter calibration factor.
FH = Average pressure differential across the orifice meter, if used
(see Figure 5G-2), mm H\2\O (in. H\2\O).
U = Total sampling time, min.
10 = 10 minutes, length of first sampling period.
13.6 = Specific gravity of mercury.
100 = Conversion to percent.
12.2 Dry Gas Volume. Same as Method 5, section 12.2, except that
component changes are not allowable.
12.3 Solvent Wash Blank.
[GRAPHIC] [TIFF OMITTED] TR17OC00.159

12.4 Total Particulate Weight. Determine the total particulate
catch, mn, from the sum of the weights obtained from Container Nos. 1,
1A, and 2, less the acetone blank (see Figure 5G-4).
12.5 Particulate Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.160

Where:
K2 = 0.001 g/mg for metric units.
= 0.0154 gr/mg for English units.
12.6 Particulate Emission Rate.
[GRAPHIC] [TIFF OMITTED] TR17OC00.161

Note: Particulate emission rate results produced using the sampling
train described in section 6 and shown in Figure 5G-1 shall be adjusted
for reporting purposes by the following method adjustment factor:
[GRAPHIC] [TIFF OMITTED] TR17OC00.162

Where:

K3 = constant, 1.82 for metric units.
= constant, 0.643 for English units.

12.7 Proportional Rate Variation. Calculate PR for each 10-minute
interval, i, of the test run.
[GRAPHIC] [TIFF OMITTED] TR17OC00.163

Alternate calculation procedures for proportional rate variation may
be used if other sample flow rate data (e.g., orifice flow meters or
rotameters) are monitored to maintain proportional sampling rates. The
proportional rate variations shall be calculated for each 10-minute
interval by comparing the stack to nozzle velocity ratio for each 10-
minute interval to the average stack to nozzle velocity ratio for the
test run. Proportional rate variation may be calculated for intervals
shorter than 10 minutes with appropriate revisions to Equation 5G-5. If
no more than 10 percent of the PR values for all the intervals exceed 90
percent PR 110 percent, and if no PR value for any
interval exceeds 80 percent PR 120 percent, the
results are acceptable. If the PR values for the test run are judged to
be unacceptable, report the test run emission results, but do not
include the results in calculating the weighted average emission rate,
and repeat the test run.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 Method 5H Sampling Train. The sampling train and sample
collection, recovery, and analysis procedures described in Method 5H,
sections 6.1.1, 7.1, 7.2, 8.1, 8.10, 8.11, and 11.0, respectively, may
be used in lieu of similar sections in Method 5G. Operation of the
Method 5H sampling train in the dilution tunnel is as described in
section 8.10 of this method. Filter temperatures and condenser
conditions are as described in Method 5H. No adjustment to the measured
particulate matter emission rate (Equation 5G-4, section 12.6) is to be
applied to the particulate emission rate measured by this alternative
method.
16.2 Dual Sampling Trains. Two sampling trains may be operated
simultaneously at sample flow rates other than that specified

[[Page 221]]

in section 8.10, provided that the following specifications are met.
16.2.1 Sampling Train. The sampling train configuration shall be the
same as specified in section 6.1.1, except the probe, filter, and filter
holder need not be the same sizes as specified in the applicable
sections. Filter holders of plastic materials such as Nalgene or
polycarbonate materials may be used (the Gelman 1119 filter holder has
been found suitable for this purpose). With such materials, it is
recommended that solvents not be used in sample recovery. The filter
face velocity shall not exceed 150 mm/sec (30 ft/min) during the test
run. The dry gas meter shall be calibrated for the same flow rate range
as encountered during the test runs. Two separate, complete sampling
trains are required for each test run.
16.2.2 Probe Location. Locate the two probes in the dilution tunnel
at the same level (see section 6.1.4.3). Two sample ports are necessary.
Locate the probe inlets within the 50 mm (2 in.) diameter centroidal
area of the dilution tunnel no closer than 25 mm (1 in.) apart.
16.2.3 Sampling Train Operation. Operate the sampling trains as
specified in section 8.10, maintaining proportional sampling rates and
starting and stopping the two sampling trains simultaneously. The pitot
values as described in section 8.5.2 shall be used to adjust sampling
rates in both sampling trains.
16.2.4 Recovery and Analysis of Sample. Recover and analyze the
samples from the two sampling trains separately, as specified in
sections 8.12 and 11.0, respectively.
16.2.4.1 For this alternative procedure, the probe and filter holder
assembly may be weighed without sample recovery (use no solvents)
described above in order to determine the sample weight gains. For this
approach, weigh the clean, dry probe and filter holder assembly upstream
of the front filter (without filters) to the nearest 0.1 mg to establish
the tare weights. The filter holder section between the front and second
filter need not be weighed. At the end of the test run, carefully clean
the outside of the probe, cap the ends, and identify the sample (label).
Remove the filters from the filter holder assemblies as described for
container Nos. 1 and 1A in section 8.12.2.1. Reassemble the filter
holder assembly, cap the ends, identify the sample (label), and transfer
all the samples to the laboratory weighing area for final weighing.
Requirements for capping and transport of sample containers are not
applicable if sample recovery and analysis occur in the same room.
16.2.4.2 For this alternative procedure, filters may be weighed
directly without a petri dish. If the probe and filter holder assembly
are to be weighed to determine the sample weight, rinse the probe with
acetone to remove moisture before desiccating prior to the test run.
Following the test run, transport the probe and filter holder to the
desiccator, and uncap the openings of the probe and the filter holder
assembly. Desiccate for 24 hours and weigh to a constant weight. Report
the results to the nearest 0.1 mg.
16.2.5 Calculations. Calculate an emission rate (Section 12.6) for
the sample from each sampling train separately and determine the average
emission rate for the two values. The two emission rates shall not
differ by more than 7.5 percent from the average emission rate, or 7.5
percent of the weighted average emission rate limit in the applicable
subpart of the regulations, whichever is greater. If this specification
is not met, the results are unacceptable. Report the results, but do not
include the results in calculating the weighted average emission rate.
Repeat the test run until acceptable results are achieved, report the
average emission rate for the acceptable test run, and use the average
in calculating the weighted average emission rate.

17.0 References

Same as Method 5, section 17.0, References 1 through 11, with the
addition of the following:

1. Oregon Department of Environmental Quality. Standard Method for
Measuring the Emissions and Efficiencies of Woodstoves. June 8, 1984.
Pursuant to Oregon Administrative Rules Chapter 340, Division 21.
2. American Society for Testing and Materials. Proposed Test Methods
for Heating Performance and Emissions of Residential Wood-fired Closed
Combustion-Chamber Heating Appliances. E-6 Proposal P 180. August 1986.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

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Method 5H--Determination of Particulate Matter Emissions From Wood
Heaters From a Stack Location

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 2, Method 3, Method 5,
Method 5G, Method 6, Method 6C, Method 16A, and Method 28.

1.0 Scope and Application

1.1 Analyte. Particulate matter (PM). No CAS number assigned.

[[Page 226]]

1.2 Applicability. This method is applicable for the determination
of PM and condensible emissions from wood heaters.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Particulate matter is withdrawn proportionally from the wood
heater exhaust and is collected on two glass fiber filters separated by
impingers immersed in an ice water bath. The first filter is maintained
at a temperature of no greater than 120 [deg]C (248 [deg]F). The second
filter and the impinger system are cooled such that the temperature of
the gas exiting the second filter is no greater than 20 [deg]C (68
[deg]F). The particulate mass collected in the probe, on the filters,
and in the impingers is determined gravimetrically after the removal of
uncombined water.

3.0 Definitions

Same as in Method 6C, section 3.0.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The following items are required for sample
collection:
6.1.1 Sampling Train. The sampling train configuration is shown in
Figure 5H-1. Same as Method 5, section 6.1.1, with the exception of the
following:
6.1.1.1 Probe Nozzle. The nozzle is optional; a straight sampling
probe without a nozzle is an acceptable alternative.
6.1.1.2 Probe Liner. Same as Method 5, section 6.1.1.2, except that
the maximum length of the sample probe shall be 0.6 m (2 ft) and probe
heating is optional.
6.1.1.3 Filter Holders. Two each of borosilicate glass, with a glass
frit or stainless steel filter support and a silicone rubber, Teflon, or
Viton gasket. The holder design shall provide a positive seal against
leakage from the outside or around the filter. The front filter holder
shall be attached immediately at the outlet of the probe and prior to
the first impinger. The second filter holder shall be attached on the
outlet of the third impinger and prior to the inlet of the fourth
(silica gel) impinger.
6.1.2 Barometer. Same as Method 5, section 6.2.
6.1.3 Stack Gas Flow Rate Measurement System. A schematic of an
example test system is shown in Figure 5H-2. The flow rate measurement
system consists of the following components:
6.1.3.1 Sample Probe. A glass or stainless steel sampling probe.
6.1.3.2 Gas Conditioning System. A high density filter to remove
particulate matter and a condenser capable of lowering the dew point of
the gas to less than 5 [deg]C (40 [deg]F). Desiccant, such as Drierite,
may be used to dry the sample gas. Do not use silica gel.
6.1.3.3 Pump. An inert (e.g., Teflon or stainless steel heads)
sampling pump capable of delivering more than the total amount of sample
required in the manufacturer's instructions for the individual
instruments. A means of controlling the analyzer flow rate and a device
for determining proper sample flow rate (e.g., precision rotameter,
pressure gauge downstream of all flow controls) shall be provided at the
analyzer. The requirements for measuring and controlling the analyzer
flow rate are not applicable if data are presented that demonstrate that
the analyzer is insensitive to flow variations over the range
encountered during the test.
6.1.3.4 Carbon Monoxide (CO) Analyzer. Any analyzer capable of
providing a measure of CO in the range of 0 to 10 percent by volume at
least once every 10 minutes.
6.1.3.5 Carbon Dioxide (CO2) Analyzer. Any analyzer
capable of providing a measure of CO2 in the range of 0 to 25
percent by volume at least once every 10 minutes.

Note: Analyzers with ranges less than those specified above may be
used provided actual concentrations do not exceed the range of the
analyzer.

6.1.3.6 Manifold. A sampling tube capable of delivering the sample
gas to two analyzers and handling an excess of the total amount used by
the analyzers. The excess gas is exhausted through a separate port.
6.1.3.7 Recorders (optional). To provide a permanent record of the
analyzer outputs.
6.1.4 Proportional Gas Flow Rate System. To monitor stack flow rate
changes and provide a measurement that can be used to adjust and
maintain particulate sampling flow rates proportional to the stack gas
flow rate. A schematic of the proportional flow rate system is shown in
Figure 5H-2 and consists of the following components:
6.1.4.1 Tracer Gas Injection System. To inject a known concentration
of sulfur dioxide (SO2) into the flue. The tracer gas
injection system consists of a cylinder of SO2, a gas
cylinder regulator, a stainless steel needle valve or flow controller, a
nonreactive (stainless steel and glass) rotameter, and an injection loop
to disperse the SO2 evenly in the flue.

[[Page 227]]

6.1.4.2 Sample Probe. A glass or stainless steel sampling probe.
6.1.4.3 Gas Conditioning System. A combustor as described in Method
16A, sections 6.1.5 and 6.1.6, followed by a high density filter to
remove particulate matter, and a condenser capable of lowering the dew
point of the gas to less than 5 [deg]C (40 [deg]F). Desiccant, such as
Drierite, may be used to dry the sample gas. Do not use silica gel.
6.1.4.4 Pump. Same as described in section 6.1.3.3.
6.1.4.5 SO2 Analyzer. Any analyzer capable of providing a
measure of the SO2 concentration in the range of 0 to 1,000
ppm by volume (or other range necessary to measure the SO2
concentration) at least once every 10 minutes.
6.1.4.6 Recorder (optional). To provide a permanent record of the
analyzer outputs.

Note: Other tracer gas systems, including helium gas systems, are
acceptable for determination of instantaneous proportional sampling
rates.

6.2 Sample Recovery. Same as Method 5, section 6.2.
6.3 Sample Analysis. Same as Method 5, section 6.3, with the
addition of the following:
6.3.1 Separatory Funnel. Glass or Teflon, 500-ml or greater.

7.0 Reagents and Standards

7.1 Sample Collection. Same as Method 5, section 7.1, including
deionized distilled water.
7.2 Sample Recovery. Same as Method 5, section 7.2.
7.3 Sample Analysis. The following reagents and standards are
required for sample analysis:
7.3.1 Acetone. Same as Method 5 section 7.2.
7.3.2 Dichloromethane (Methylene Chloride). Reagent grade, <0.001
percent residue in glass bottles.
7.3.3 Desiccant. Anhydrous calcium sulfate, calcium chloride, or
silica gel, indicating type.
7.3.4 Cylinder Gases. For the purposes of this procedure, span value
is defined as the upper limit of the range specified for each analyzer
as described in section 6.1.3.4 or 6.1.3.5. If an analyzer with a range
different from that specified in this method is used, the span value
shall be equal to the upper limit of the range for the analyzer used
(see note in section 6.1.3.5).
7.3.4.1 Calibration Gases. The calibration gases for the
CO2, CO, and SO2 analyzers shall be CO2
in nitrogen (N2), CO in N2, and SO2 in
N2, respectively. CO2 and CO calibration gases may
be combined in a single cylinder. Use three calibration gases as
specified in Method 6C, sections 7.2.1 through 7.2.3.
7.3.4.2 SO2 Injection Gas. A known concentration of
SO2 in N2. The concentration must be at least 2
percent SO2 with a maximum of 100 percent SO2.

8.0 Sample Collection, Preservation, Transport, and Storage

8.1 Pretest Preparation. Same as Method 5, section 8.1.
8.2 Calibration Gas and SO2 Injection Gas Concentration
Verification, Sampling System Bias Check, Response Time Test, and Zero
and Calibration Drift Tests. Same as Method 6C, sections 8.2.1, 8.2.3,
8.2.4, and 8.5, respectively, except that for verification of CO and
CO2 gas concentrations, substitute Method 3 for Method 6.
8.3 Preliminary Determinations.
8.3.1 Sampling Location. The sampling location for the particulate
sampling probe shall be 2.45 0.15 m (8 0.5 ft) above the platform upon
which the wood heater is placed (i.e., the top of the scale).
8.3.2 Sampling Probe and Nozzle. Select a nozzle, if used, sized for
the range of velocity heads, such that it is not necessary to change the
nozzle size in order to maintain proportional sampling rates. During the
run, do not change the nozzle size. Select a suitable probe liner and
probe length to effect minimum blockage.
8.4 Preparation of Particulate Sampling Train. Same as Method 5,
section 8.3, with the exception of the following:
8.4.1 The train should be assembled as shown in Figure 5H-1.
8.4.2 A glass cyclone may not be used between the probe and filter
holder.
8.5 Leak-Check Procedures.
8.5.1 Leak-Check of Metering System Shown in Figure 5H-1. That
portion of the sampling train from the pump to the orifice meter shall
be leak-checked after each certification or audit test. Use the
procedure described in Method 5, section 8.4.1.
8.5.2 Pretest Leak-Check. A pretest leak-check of the sampling train
is recommended, but not required. If the pretest leak-check is
conducted, the procedures outlined in Method 5, section 8.5.2 should be
used. A vacuum of 130 mm Hg (5 in. Hg) may be used instead of 380 mm Hg
(15 in. Hg).
8.5.2 Leak-Checks During Sample Run. If, during the sampling run, a
component (e.g., filter assembly or impinger) change becomes necessary,
conduct a leak-check as described in Method 5, section 8.4.3.
8.5.3 Post-Test Leak-Check. A leak-check is mandatory at the
conclusion of each sampling run. The leak-check shall be performed in
accordance with the procedures outlined in Method 5, section 8.4.4,
except that a vacuum of 130 mm Hg (5 in. Hg) or the greatest vacuum
measured during the test run, whichever is greater, may be used instead
of 380 mm Hg (15 in. Hg).

[[Page 228]]

8.6 Tracer Gas Procedure. A schematic of the tracer gas injection
and sampling systems is shown in Figure 5H-2.
8.6.1 SO2 Injection Probe. Install the SO2
injection probe and dispersion loop in the stack at a location 2.9 0.15
m (9.5 0.5 ft) above the sampling platform.
8.6.2 SO2 Sampling Probe. Install the SO2
sampling probe at the centroid of the stack at a location 4.1 0.15 m
(13.5 0.5 ft) above the sampling platform.
8.7 Flow Rate Measurement System. A schematic of the flow rate
measurement system is shown in Figure 5H-2. Locate the flow rate
measurement sampling probe at the centroid of the stack at a location
2.3 0.3 m (7.5 1 ft) above the sampling platform.
8.8 Tracer Gas Procedure. Within 1 minute after closing the wood
heater door at the start of the test run (as defined in Method 28,
section 8.8.1), meter a known concentration of SO2 tracer gas
at a constant flow rate into the wood heater stack. Monitor the
SO2 concentration in the stack, and record the SO2
concentrations at 10-minute intervals or more often. Adjust the
particulate sampling flow rate proportionally to the SO2
concentration changes using Equation 5H-6 (e.g., the SO2
concentration at the first 10-minute reading is measured to be 100 ppm;
the next 10 minute SO2 concentration is measured to be 75
ppm: the particulate sample flow rate is adjusted from the initial 0.15
cfm to 0.20 cfm). A check for proportional rate variation shall be made
at the completion of the test run using Equation 5H-10.
8.9 Volumetric Flow Rate Procedure. Apply stoichiometric
relationships to the wood combustion process in determining the exhaust
gas flow rate as follows:
8.9.1 Test Fuel Charge Weight. Record the test fuel charge weight
(wet) as specified in Method 28, section 8.8.2. The wood is assumed to
have the following weight percent composition: 51 percent carbon, 7.3
percent hydrogen, 41 percent oxygen. Record the wood moisture for each
fuel charge as described in Method 28, section 8.6.5. The ash is assumed
to have negligible effect on associated C, H, and O concentrations after
the test burn.
8.9.2 Measured Values. Record the CO and CO2
concentrations in the stack on a dry basis every 10 minutes during the
test run or more often. Average these values for the test run. Use as a
mole fraction (e.g., 10 percent CO2 is recorded as 0.10) in
the calculations to express total flow (see Equation 5H-6).
8.10 Sampling Train Operation.
8.10.1 For each run, record the data required on a data sheet such
as the one shown in Figure 5H-3. Be sure to record the initial dry gas
meter reading. Record the dry gas meter readings at the beginning and
end of each sampling time increment, when changes in flow rates are
made, before and after each leak-check, and when sampling is halted.
Take other readings as indicated on Figure 5H-3 at least once each 10
minutes during the test run.
8.10.2 Remove the nozzle cap, verify that the filter and probe
heating systems are up to temperature, and that the probe is properly
positioned. Position the nozzle, if used, facing into gas stream, or the
probe tip in the 50 mm (2 in.) centroidal area of the stack.
8.10.3 Be careful not to bump the probe tip into the stack wall when
removing or inserting the probe through the porthole; this minimizes the
chance of extracting deposited material.
8.10.4 When the probe is in position, block off the openings around
the probe and porthole to prevent unrepresentative dilution of the gas
stream.
8.10.5 Begin sampling at the start of the test run as defined in
Method 28, section 8.8.1, start the sample pump, and adjust the sample
flow rate to between 0.003 and 0.014 m\3\/min (0.1 and 0.5 cfm). Adjust
the sample flow rate proportionally to the stack gas flow during the
test run according to the procedures outlined in section 8. Maintain a
proportional sampling rate (within 10 percent of the desired value) and
a filter holder temperature no greater than 120 [deg]C (248 [deg]F).
8.10.6 During the test run, make periodic adjustments to keep the
temperature around the filter holder at the proper level. Add more ice
to the impinger box and, if necessary, salt to maintain a temperature of
less than 20 [deg]C (68 [deg]F) at the condenser/silica gel outlet.
8.10.7 If the pressure drop across the filter becomes too high,
making proportional sampling difficult to maintain, either filter may be
replaced during a sample run. It is recommended that another complete
filter assembly be used rather than attempting to change the filter
itself. Before a new filter assembly is installed, conduct a leak-check
(see section 8.5.2). The total particulate weight shall include the
summation of all filter assembly catches. The total time for changing
sample train components shall not exceed 10 minutes. No more than one
component change is allowed for any test run.
8.10.8 At the end of the test run, turn off the coarse adjust valve,
remove the probe and nozzle from the stack, turn off the pump, record
the final dry gas meter reading, and conduct a post-test leak-check, as
outlined in section 8.5.3.
8.11 Sample Recovery. Same as Method 5, section 8.7, with the
exception of the following:
8.11.1 Blanks. The volume of the acetone blank may be about 50-ml,
rather than 200-ml; a 200-ml water blank shall also be saved for
analysis.
8.11.2 Samples.
8.11.2.1 Container Nos. 1 and 1A. Treat the two filters according to
the procedures outlined in Method 5, section 8.7.6.1. The filters

[[Page 229]]

may be stored either in a single container or in separate containers.
8.11.2.2 Container No. 2. Same as Method 5, section 8.7.6.2, except
that the container should not be sealed until the impinger rinse
solution is added (see section 8.10.2.4).
8.11.2.3 Container No. 3. Treat the impingers as follows: Measure
the liquid which is in the first three impingers to within 1-ml by using
a graduated cylinder or by weighing it to within 0.5 g by using a
balance (if one is available). Record the volume or weight of liquid
present. This information is required to calculate the moisture content
of the effluent gas. Transfer the water from the first, second, and
third impingers to a glass container. Tighten the lid on the sample
container so that water will not leak out.
8.11.2.4 Rinse impingers and graduated cylinder, if used, with
acetone three times or more. Avoid direct contact between the acetone
and any stopcock grease or collection of any stopcock grease in the
rinse solutions. Add these rinse solutions to sample Container No. 2.
8.11.2.5 Container No. 4. Same as Method 5, section 8.7.6.3
8.12 Sample Transport. Whenever possible, containers should be
transferred in such a way that they remain upright at all times.

Note: Requirements for capping and transport of sample containers
are not applicable if sample recovery and analysis occur in the same
room.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.2........................... Sampling system Ensures that bias
bias check. introduced by
measurement system,
minus analyzer, is
no greater than 3
percent of span.
8.2........................... Analyzer zero and Ensures that bias
calibration introduced by drift
drift tests. in the measurement
system output during
the run is no
greater than 3
percent of span.
8.5, 10.1, 12.13.............. Sampling Ensures accurate
equipment leak- measurement of stack
check and gas flow rate,
calibration; sample volume.
proportional
sampling rate
verification.
10.1.......................... Analytical Ensure accurate and
balance precise measurement
calibration. of collected
particulate.
10.3.......................... Analyzer Ensures that bias
calibration introduced by
error check. analyzer calibration
error is no greater
than 2 percent of
span.
------------------------------------------------------------------------

9.2 Volume Metering System Checks. Same as Method 5, section 9.2.

10.0 Calibration and Standardization

Note: Maintain a laboratory record of all calibrations.

10.1 Volume Metering System, Temperature Sensors, Barometer, and
Analytical Balance. Same as Method 5G, sections 10.2 through 10.5,
respectively.
10.2 SO2 Injection Rotameter. Calibrate the
SO2 injection rotameter system with a soap film flowmeter or
similar direct volume measuring device with an accuracy of 2 percent.
Operate the rotameter at a single reading for at least three calibration
runs for 10 minutes each. When three consecutive calibration flow rates
agree within 5 percent, average the three flow rates, mark the rotameter
at the calibrated setting, and use the calibration flow rate as the
SO2 injection flow rate during the test run. Repeat the
rotameter calibration before the first certification test and
semiannually thereafter.
10.3. Gas Analyzers. Same as Method 6C, section 10.0.

11.0 Analytical Procedure

11.1 Record the data required on a sheet such as the one shown in
Figure 5H-4.
11.2 Handle each sample container as follows:
11.2.1 Container Nos. 1 and 1A. Treat the two filters according to
the procedures outlined in Method 5, section 11.2.1.
11.2.2 Container No. 2. Same as Method 5, section 11.2.2, except
that the beaker may be smaller than 250-ml.
11.2.3 Container No. 3. Note the level of liquid in the container
and confirm on the analysis sheet whether leakage occurred during
transport. If a noticeable amount of leakage has occurred, either void
the sample or use methods, subject to the approval of the Administrator,
to correct the final results. Determination of sample leakage is not
applicable if sample recovery and analysis occur in the same room.
Measure the liquid in this container either volumetrically to within 1-
ml or gravimetrically to within 0.5 g. Transfer the contents to a 500-ml
or larger separatory funnel. Rinse the container with water, and add to
the separatory funnel. Add 25-ml of dichloromethane to the separatory
funnel, stopper and vigorously shake 1 minute, let separate and transfer
the dichloromethane (lower layer) into a tared beaker or evaporating
dish. Repeat twice more. It is necessary to rinse Container No. 3 with
dichloromethane. This rinse is added to the impinger extract container.
Transfer the remaining water from the separatory

[[Page 230]]

funnel to a tared beaker or evaporating dish and evaporate to dryness at
104 [deg]C (220 [deg]F). Desiccate and weigh to a constant weight.
Evaporate the combined impinger water extracts at ambient temperature
and pressure. Desiccate and weigh to a constant weight. Report both
results to the nearest 0.1 mg.
11.2.4 Container No. 4. Weigh the spent silica gel (or silica gel
plus impinger) to the nearest 0.5 g using a balance.
11.2.5 Acetone Blank Container. Same as Method 5, section 11.2.4,
except that the beaker may be smaller than 250 ml.
11.2.6 Dichloromethane Blank Container. Treat the same as the
acetone blank.
11.2.7 Water Blank Container. Transfer the water to a tared 250 ml
beaker and evaporate to dryness at 104 [deg]C (220 [deg]F). Desiccate
and weigh to a constant weight.

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after the
final calculation. Other forms of the equations may be used as long as
they give equivalent results.
12.1 Nomenclature.

A = Sample flow rate adjustment factor.
BR = Dry wood burn rate, kg/hr (lb/hr), from Method 28, Section 8.3.
Bws = Water vapor in the gas stream, proportion by volume.
Ci = Tracer gas concentration at inlet, ppmv.
Co = Tracer gas concentration at outlet, ppmv.
Cs = Concentration of particulate matter in stack gas, dry
basis, corrected to standard conditions, g/dscm (g/dscf).
E = Particulate emission rate, g/hr (lb/hr).
FH = Average pressure differential across the orifice meter (see Figure
5H-1), mm H2O (in. H2O).
La = Maximum acceptable leakage rate for either a post-test
leak-check or for a leak-check following a component change;
equal to 0.00057 cmm (0.020 cfm) or 4 percent of the average
sampling rate, whichever is less.
L1 = Individual leakage rate observed during the leak-check
conducted before a component change, cmm (cfm).
Lp = Leakage rate observed during the post-test leak-check,
cmm (cfm).
mn = Total amount of particulate matter collected, mg.
Ma = Mass of residue of solvent after evaporation, mg.
NC = Grams of carbon/gram of dry fuel (lb/lb), equal to
0.0425.
NT = Total dry moles of exhaust gas/kg of dry wood burned, g-
moles/kg (lb-moles/lb).
PR = Percent of proportional sampling rate.
Pbar = Barometric pressure at the sampling site, mm Hg
(in.Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in.Hg).
Qi = Gas volumetric flow rate at inlet, cfm (l/min).
Qo = Gas volumetric flow rate at outlet, cfm (l/min).
12.2 Average Dry Gas Meter Temperature and Average Orifice Pressure
Drop. See data sheet (Figure 5H-3).
12.3 Dry Gas Volume. Same as Method 5, section 12.3.
12.4 Volume of Water Vapor.
[GRAPHIC] [TIFF OMITTED] TR17OC00.168

Where:

K2 = 0.001333 m\3\/ml for metric units.
K2 = 0.04707 ft\3\/ml for English units.

12.5 Moisture Content.
[GRAPHIC] [TIFF OMITTED] TR17OC00.169

12.6 Solvent Wash Blank.
[GRAPHIC] [TIFF OMITTED] TR17OC00.170

12.7 Total Particulate Weight. Determine the total particulate catch
from the sum of the weights obtained from containers 1, 2, 3, and 4 less
the appropriate solvent blanks (see Figure 5H-4).

Note: Refer to Method 5, section 8.5 to assist in calculation of
results involving two filter assemblies.

12.8 Particulate Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.171

12.9 Sample Flow Rate Adjustment.
[GRAPHIC] [TIFF OMITTED] TR17OC00.172

12.10 Carbon Balance for Total Moles of Exhaust Gas (dry)/kg of Wood
Burned in the Exhaust Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.173

Where:

K3 = 1000 g/kg for metric units.
K3 = 1.0 lb/lb for English units.

Note: The NOX/SOX portion of the gas is
assumed to be negligible.

12.11 Total Stack Gas Flow Rate.
[GRAPHIC] [TIFF OMITTED] TR17OC00.174

Where:

K4 = 0.02406 dscm/g-mole for metric units.

[[Page 231]]

K4 = 384.8 dscf/lb-mole for English units.

12.12 Particulate Emission Rate.
[GRAPHIC] [TIFF OMITTED] TR17OC00.175

12.13 Proportional Rate Variation. Calculate PR for each 10-minute
interval, i, of the test run.
[GRAPHIC] [TIFF OMITTED] TR17OC00.176

12.14 Acceptable Results. If no more than 15 percent of the PR
values for all the intervals fall outside the range 90 percent
PR 110 percent, and if no PR value for any
interval falls outside the range 75 PR 125
percent, the results are acceptable. If the PR values for the test runs
are judged to be unacceptable, report the test run emission results, but
do not include the test run results in calculating the weighted average
emission rate, and repeat the test.
12.15 Alternative Tracer Gas Flow Rate Determination.
[GRAPHIC] [TIFF OMITTED] TR27FE14.014

Note: This gives Q for a single instance only. Repeated multiple
determinations are needed to track temporal variations. Very small
variations in Qi, Ci, or Co may give
very large variations in Qo.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 Alternative Stack Gas Volumetric Flow Rate Determination
(Tracer Gas).
16.1.1 Apparatus.
16.1.1.1 Tracer Gas Injector System. This is to inject a known
concentration of tracer gas into the stack. This system consists of a
cylinder of tracer gas, a gas cylinder regulator, a stainless steel
needle valve or a flow controller, a nonreactive (stainless steel or
glass) rotameter, and an injection loop to disperse the tracer gas
evenly in the stack.
16.1.1.2 Tracer Gas Probe. A glass or stainless steel sampling
probe.
16.1.1.3 Gas Conditioning System. A gas conditioning system is
suitable for delivering a cleaned sample to the analyzer consisting of a
filter to remove particulate and a condenser capable of lowering the dew
point of the sample gas to less than 5 [deg]C (40 [deg]F). A desiccant
such as anhydrous calcium sulfate may be used to dry the sample gas.
Desiccants which react or absorb tracer gas or stack gas may not be
used, e.g. silica gel absorbs CO2.
16.1.1.4 Pump. An inert (i.e., stainless steel or Teflon head) pump
to deliver more than the total sample required by the manufacturer's
specifications for the analyzer used to measure the downstream tracer
gas concentration.
16.1.1.5 Gas Analyzer. A gas analyzer is any analyzer capable of
measuring the tracer gas concentration in the range necessary at least
every 10 minutes. A means of controlling the analyzer flow rate and a
device for determining proper sample flow rate shall be provided unless
data is provided to show that the analyzer is insensitive to flow
variations over the range encountered during the test. The gas analyzer
needs to meet or exceed the following performance specifications:

------------------------------------------------------------------------

------------------------------------------------------------------------
Linearity....................... 1 percent of full scale.
Calibration Error............... 2 percent of span.
Response Time................... 10 seconds.
Zero Drift (24 hour)............ 2 percent of full scale.
Span Drift (24 hour)............ 2 percent of full scale.
Resolution...................... 0.5 percent of span.
------------------------------------------------------------------------

16.1.1.6 Recorder (optional). To provide a permanent record of the
analyzer output.
16.1.2 Reagents.
16.1.2.1 Tracer Gas. The tracer gas is sulfur hexafluoride in an
appropriate concentration for accurate analyzer measurement or pure
sulfur dioxide. The gas used must be nonreactive with the stack effluent
and give minimal (<3 percent) interference to measurement by the gas
analyzer.
16.1.3 Procedure. Select upstream and downstream locations in the
stack or duct for introducing the tracer gas and delivering the sampled
gas to the analyzer. The inlet location should be 8 or more duct
diameters beyond any upstream flow disturbance. The outlet should be 8
or more undisturbed duct diameters from the inlet and 2 or more duct
diameters from the duct exit. After installing the apparatus, meter a
known concentration of the tracer gas into the stack at the inlet
location. Use the gas sample probe and analyzer to show that no
stratification of the tracer gas is found in the stack at the
measurement locations. Monitor the tracer gas concentration from the
outlet location and record the concentration at 10-minute intervals or
more often at the option of the

[[Page 232]]

tester. A minimum of three measured intervals is recommended to
determine the stack gas volumetric flow rate. Other statistical
procedures may be applied for complete flow characterization and
additional QA/QC.

17.0 References

Same as Method 5G, section 17.0.

18.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.177

[[Page 233]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.178

[[Page 234]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.179

[[Page 235]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.180

Method 5I--Determination of Low Level Particulate Matter Emissions From
Stationary Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Certain information is contained in other
EPA procedures found in this part. Therefore, to obtain reliable
results, persons using this method should have experience with and a
thorough knowledge of the following Methods: Methods 1, 2, 3, 4 and 5.

1. Scope and Application.

1.1 Analyte. Particulate matter (PM). No CAS number assigned.

[[Page 236]]

1.2 Applicability. This method is applicable for the determination
of low level particulate matter (PM) emissions from stationary sources.
The method is most effective for total PM catches of 50 mg or less. This
method was initially developed for performing correlation of manual PM
measurements to PM continuous emission monitoring systems (CEMS),
however it is also useful for other low particulate concentration
applications.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods. Method 5I requires the use of paired trains.
Acceptance criteria for the identification of data quality outliers from
the paired trains are provided in section 12.2 of this Method.

2. Summary of Method.

2.1. Description. The system setup and operation is essentially
identical to Method 5. Particulate is withdrawn isokinetically from the
source and collected on a 47 mm glass fiber filter maintained at a
temperature of 120 14 [deg]C (248 25 [deg]F). The PM mass is
determined by gravimetric analysis after the removal of uncombined
water. Specific measures in this procedure designed to improve system
performance at low particulate levels include:
1. Improved sample handling procedures
2 Light weight sample filter assembly
3. Use of low residue grade acetone
Accuracy is improved through the minimization of systemic errors
associated with sample handling and weighing procedures. High purity
reagents, all glass, grease free, sample train components, and light
weight filter assemblies and beakers, each contribute to the overall
objective of improved precision and accuracy at low particulate
concentrations.
2.2 Paired Trains. This method must be performed using a paired
train configuration. These trains may be operated as co-located trains
(to trains operating collecting from one port) or as simultaneous trains
(separate trains operating from different ports at the same time).
Procedures for calculating precision of the paired trains are provided
in section 12.
2.3 Detection Limit. a. Typical detection limit for manual
particulate testing is 0.5 mg. This mass is also cited as the accepted
weight variability limit in determination of ``constant weight'' as
cited in section 8.1.2 of this Method. EPA has performed studies to
provide guidance on minimum PM catch. The minimum detection limit (MDL)
is the minimum concentration or amount of an analyte that can be
determined with a specified degree of confidence to be different from
zero. We have defined the minimum or target catch as a concentration or
amount sufficiently larger than the MDL to ensure that the results are
reliable and repeatable. The particulate matter catch is the product of
the average particulate matter concentration on a mass per volume basis
and the volume of gas collected by the sample train. The tester can
generally control the volume of gas collected by increasing the sampling
time or to a lesser extent by increasing the rate at which sample is
collected. If the tester has a reasonable estimate of the PM
concentration from the source, the tester can ensure that the target
catch is collected by sampling the appropriate gas volume.
b. However, if the source has a very low particulate matter
concentration in the stack, the volume of gas sampled may need to be
very large which leads to unacceptably long sampling times. When
determining compliance with an emission limit, EPA guidance has been
that the tester does not always have to collect the target catch.
Instead, we have suggested that the tester sample enough stack gas, that
if the source were exactly at the level of the emission standard, the
sample catch would equal the target catch. Thus, if at the end of the
test the catch were smaller than the target, we could still conclude
that the source is in compliance though we might not know the exact
emission level. This volume of gas becomes a target volume that can be
translated into a target sampling time by assuming an average sampling
rate. Because the MDL forms the basis for our guidance on target
sampling times, EPA has conducted a systematic laboratory study to
define what is the MDL for Method 5 and determined the Method to have a
calculated practical quantitation limit (PQL) of 3 mg of PM and an MDL
of 1 mg.
c. Based on these results, the EPA has concluded that for PM
testing, the target catch must be no less than 3 mg. Those sample
catches between 1 mg and 3 mg are between the detection limit and the
limit of quantitation. If a tester uses the target catch to estimate a
target sampling time that results in sample catches that are less than 3
mg, you should not automatically reject the results. If the tester
calculated the target sampling time as described above by assuming that
the source was at the level of the emission limit, the results would
still be valid for determining that the source was in compliance. For
purposes other than determining compliance, results should be divided
into two categories--those that fall between 3 mg and 1 mg and those
that are below 1 mg. A sample catch between 1 and 3 mg may be used for
such purposes as calculating emission rates with the understanding that
the resulting emission rates can have a high degree of uncertainty.
Results of less than 1 mg should not be used for calculating emission
rates or pollutant concentrations.
d. When collecting small catches such as 3 mg, bias becomes an
important issue. Source testers must use extreme caution to reach the
PQL of 3 mg by assuring that sampling

[[Page 237]]

probes are very clean (perhaps confirmed by low blank weights) before
use in the field. They should also use low tare weight sample
containers, and establish a well-controlled balance room to weigh the
samples.

3. Definitions.

3.1 Light Weight Filter Housing. A smaller housing that allows the
entire filtering system to be weighed before and after sample
collection. (See. 6.1.3)
3.2 Paired Train. Sample systems trains may be operated as co-
located trains (two sample probes attached to each other in the same
port) or as simultaneous trains (two separate trains operating from
different ports at the same time).

4. Interferences.

a. There are numerous potential interferents that may be encountered
during performance of Method 5I sampling and analyses. This Method
should be considered more sensitive to the normal interferents typically
encountered during particulate testing because of the low level
concentrations of the flue gas stream being sampled.
b. Care must be taken to minimize field contamination, especially to
the filter housing since the entire unit is weighed (not just the filter
media). Care must also be taken to ensure that no sample is lost during
the sampling process (such as during port changes, removal of the filter
assemblies from the probes, etc.).
c. Balance room conditions are a source of concern for analysis of
the low level samples. Relative humidity, ambient temperatures
variations, air draft, vibrations and even barometric pressure can
affect consistent reproducible measurements of the sample media.
Ideally, the same analyst who performs the tare weights should perform
the final weights to minimize the effects of procedural differences
specific to the analysts.
d. Attention must also be provided to weighing artifacts caused by
electrostatic charges which may have to be discharged or neutralized
prior to sample analysis. Static charge can affect consistent and
reliable gravimetric readings in low humidity environments. Method 5I
recommends a relative humidity of less than 50 percent in the weighing
room environment used for sample analyses. However, lower humidity may
be encountered or required to address sample precision problems. Low
humidity conditions can increase the effects of static charge.
e. Other interferences associated with typical Method 5 testing
(sulfates, acid gases, etc.) are also applicable to Method 5I.

5. Safety.

Disclaimer. This method may involve hazardous materials, operations,
and equipment. This test method may not address all of the safety
concerns associated with its use. It is the responsibility of the user
to establish appropriate safety and health practices and to determine
the applicability and observe all regulatory limitations before using
this method.

6. Equipment and Supplies.

6.1 Sample Collection Equipment and Supplies. The sample train is
nearly identical in configuration to the train depicted in Figure 5-1 of
Method 5. The primary difference in the sample trains is the lightweight
Method 5I filter assembly that attaches directly to the exit to the
probe. Other exceptions and additions specific to Method 5I include:
6.1.1 Probe Nozzle. Same as Method 5, with the exception that it
must be constructed of borosilicate or quartz glass tubing.
6.1.2 Probe Liner. Same as Method 5, with the exception that it must
be constructed of borosilicate or quartz glass tubing.
6.1.3 Filter Holder. The filter holder is constructed of
borosilicate or quartz glass front cover designed to hold a 47-mm glass
fiber filter, with a wafer thin stainless steel (SS) filter support, a
silicone rubber or Viton O-ring, and Teflon tape seal. This holder
design will provide a positive seal against leakage from the outside or
around the filter. The filter holder assembly fits into a SS filter
holder and attaches directly to the outlet of the probe. The tare weight
of the filter, borosilicate or quartz glass holder, SS filter support,
O-ring and Teflon tape seal generally will not exceed approximately 35
grams. The filter holder is designed to use a 47-mm glass fiber filter
meeting the quality criteria in of Method 5. These units are
commercially available from several source testing equipment vendors.
Once the filter holder has been assembled, desiccated and tared, protect
it from external sources of contamination by covering the front socket
with a ground glass plug. Secure the plug with an impinger clamp or
other item that will ensure a leak-free fitting.
6.2 Sample Recovery Equipment and Supplies. Same as Method 5, with
the following exceptions:
6.2.1 Probe-Liner and Probe-Nozzle Brushes. Teflon or nylon bristle
brushes with stainless steel wire handles, should be used to clean the
probe. The probe brush must have extensions (at least as long as the
probe) of Teflon, nylon or similarly inert material. The brushes must be
properly sized and shaped for brushing out the probe liner and nozzle.
6.2.2 Wash Bottles. Two Teflon wash bottles are recommended however,
polyethylene wash bottles may be used at the option of the tester.
Acetone should not be stored in polyethylene bottles for longer than one
month.

[[Page 238]]

6.2.3 Filter Assembly Transport. A system should be employed to
minimize contamination of the filter assemblies during transport to and
from the field test location. A carrying case or packet with clean
compartments of sufficient size to accommodate each filter assembly can
be used. This system should have an air tight seal to further minimize
contamination during transport to and from the field.
6.3 Analysis Equipment and Supplies. Same as Method 5, with the
following exception:
6.3.1 Lightweight Beaker Liner. Teflon or other lightweight beaker
liners are used for the analysis of the probe and nozzle rinses. These
light weight liners are used in place of the borosilicate glass beakers
typically used for the Method 5 weighings in order to improve sample
analytical precision.
6.3.2 Anti-static Treatment. Commercially available gaseous anti-
static rinses are recommended for low humidity situations that
contribute to static charge problems.

7. Reagents and Standards.

7.1 Sampling Reagents. The reagents used in sampling are the same as
Method 5 with the following exceptions:
7.1.1 Filters. The quality specifications for the filters are
identical to those cited for Method 5. The only difference is the filter
diameter of 47 millimeters.
7.1.2 Stopcock Grease. Stopcock grease cannot be used with this
sampling train. We recommend that the sampling train be assembled with
glass joints containing O-ring seals or screw-on connectors, or similar.
7.1.3 Acetone. Low residue type acetone, 0.001 percent
residue, purchased in glass bottles is used for the recovery of
particulate matter from the probe and nozzle. Acetone from metal
containers generally has a high residue blank and should not be used.
Sometimes, suppliers transfer acetone to glass bottles from metal
containers; thus, acetone blanks must be run prior to field use and only
acetone with low blank values (0.001 percent residue, as
specified by the manufacturer) must be used. Acetone blank correction is
not allowed for this method; therefore, it is critical that high purity
reagents be purchased and verified prior to use.
7.1.4 Gloves. Disposable, powder-free, latex surgical gloves, or
their equivalent are used at all times when handling the filter housings
or performing sample recovery.
7.2 Standards. There are no applicable standards commercially
available for Method 5I analyses.

8. Sample Collection, Preservation, Storage, and Transport.

8.1 Pretest Preparation. Same as Method 5 with several exceptions
specific to filter assembly and weighing.
8.1.1 Filter Assembly. Uniquely identify each filter support before
loading filters into the holder assembly. This can be done with an
engraving tool or a permanent marker. Use powder free latex surgical
gloves whenever handling the filter holder assemblies. Place the O-ring
on the back of the filter housing in the O-ring groove. Place a 47 mm
glass fiber filter on the O-ring with the face down. Place a stainless
steel filter holder against the back of the filter. Carefully wrap 5 mm
(\1/4\ inch) wide Teflon'' tape one timearound the outside of the filter
holder overlapping the stainless steel filter support by approximately
2.5 mm (\1/8\ inch). Gently brush the Teflon tape down on the back of
the stainless steel filter support. Store the filter assemblies in their
transport case until time for weighing or field use.
8.1.2 Filter Weighing Procedures. a. Desiccate the entire filter
holder assemblies at 20 5.6 [deg]C (68 10 [deg]F) and ambient pressure
for at least 24 hours. Weigh at intervals of at least 6 hours to a
constant weight, i.e., 0.5 mg change from previous weighing. Record the
results to the nearest 0.1 mg. During each weighing, the filter holder
assemblies must not be exposed to the laboratory atmosphere for a period
greater than 2 minutes and a relative humidity above 50 percent. Lower
relative humidity may be required in order to improve analytical
precision. However, low humidity conditions increase static charge to
the sample media.
b. Alternatively (unless otherwise specified by the Administrator),
the filters holder assemblies may be oven dried at 105 [deg]C (220
[deg]F) for a minimum of 2 hours, desiccated for 2 hours, and weighed.
The procedure used for the tare weigh must also be used for the final
weight determination.
c. Experience has shown that weighing uncertainties are not only
related to the balance performance but to the entire weighing procedure.
Therefore, before performing any measurement, establish and follow
standard operating procedures, taking into account the sampling
equipment and filters to be used.
8.2 Preliminary Determinations. Select the sampling site, traverse
points, probe nozzle, and probe length as specified in Method 5.
8.3 Preparation of Sampling Train. Same as Method 5, section 8.3,
with the following exception: During preparation and assembly of the
sampling train, keep all openings where contamination can occur covered
until justbefore assembly or until sampling is about to begin. Using
gloves, place a labeled (identified) and weighed filter holder assembly
into the stainless steel holder. Then place this whole unit in the
Method 5 hot box, and attach it to the probe. Do not use stopcock
grease.
8.4 Leak-Check Procedures. Same as Method 5.
8.5 Sampling Train Operation.

[[Page 239]]

8.5.1. Operation. Operate the sampling train in a manner consistent
with those described in Methods 1, 2, 4 and 5 in terms of the number of
sample points and minimum time per point. The sample rate and total gas
volume should be adjusted based on estimated grain loading of the source
being characterized. The total sampling time must be a function of the
estimated mass of particulate to be collected for the run. Targeted mass
to be collected in a typical Method 5I sample train should be on the
order of 10 to 20 mg. Method 5I is most appropriate for total collected
masses of less than 50 milligrams, however, there is not an exact
particulate loading cutoff, and it is likely that some runs may exceed
50 mg. Exceeding 50 mg (or less than 10 mg) for the sample mass does not
necessarily justify invalidating a sample run if all other Method
criteria are met.
8.5.2 Paired Train. This Method requires PM samples be collected
with paired trains.
8.5.2.1 It is important that the systems be operated truly
simultaneously. This implies that both sample systems start and stop at
the same times. This also means that if one sample system is stopped
during the run, the other sample systems must also be stopped until the
cause has been corrected.
8.5.2.2 Care should be taken to maintain the filter box temperature
of the paired trains as close as possible to the Method required
temperature of 120 14 [deg]C (248 25 [deg]F). If separate ovens are
being used for simultaneously operated trains, it is recommended that
the oven temperature of each train be maintained within 14 [deg]C (25
[deg]F) of each other.
8.5.2.3 The nozzles for paired trains need not be identically sized.
8.5.2.4 Co-located sample nozzles must be within the same plane
perpendicular to the gas flow. Co-located nozzles and pitot assemblies
should be within a 6.0 cm x 6.0 cm square (as cited for a quadruple
train in Reference Method 301).
8.5.3 Duplicate gas samples for molecular weight determination need
not be collected.
8.6 Sample Recovery. Same as Method 5 with several exceptions
specific to the filter housing.
8.6.1 Before moving the sampling train to the cleanup site, remove
the probe from the train and seal the nozzle inlet and outlet of the
probe. Be careful not to lose any condensate that might be present. Cap
the filter inlet using a standard ground glass plug and secure the cap
with an impinger clamp. Remove the umbilical cord from the last impinger
and cap the impinger. If a flexible line is used between the first
impinger condenser and the filter holder, disconnect the line at the
filter holder and let any condensed water or liquid drain into the
impingers or condenser.
8.6.2 Transfer the probe and filter-impinger assembly to the cleanup
area. This area must be clean and protected from the wind so that the
possibility of losing any of the sample will be minimized.
8.6.3 Inspect the train prior to and during disassembly and note any
abnormal conditions such as particulate color, filter loading, impinger
liquid color, etc.
8.6.4 Container No. 1, Filter Assembly. Carefully remove the cooled
filter holder assembly from the Method 5 hot box and place it in the
transport case. Use a pair of clean gloves to handle the filter holder
assembly.
8.6.5 Container No. 2, Probe Nozzle and Probe Liner Rinse. Rinse the
probe and nozzle components with acetone. Be certain that the probe and
nozzle brushes have been thoroughly rinsed prior to use as they can be a
source of contamination.
8.6.6 All Other Train Components. (Impingers) Same as Method 5.
8.7 Sample Storage and Transport. Whenever possible, containers
should be shipped in such a way that they remain upright at all times.
All appropriate dangerous goods shipping requirements must be observed
since acetone is a flammable liquid.

9. Quality Control.

9.1 Miscellaneous Field Quality Control Measures.
9.1.1 A quality control (QC) check of the volume metering system at
the field site is suggested before collecting the sample using the
procedures in Method 5, section 4.4.1.
9.1.2 All other quality control checks outlined in Methods 1, 2, 4
and 5 also apply to Method 5I. This includes procedures such as leak-
checks, equipment calibration checks, and independent checks of field
data sheets for reasonableness and completeness.
9.2 Quality Control Samples.
9.2.1 Required QC Sample. A laboratory reagent blank must be
collected and analyzed for each lot of acetone used for a field program
to confirm that it is of suitable purity. The particulate samples cannot
be blank corrected.
9.2.2 Recommended QC Samples. These samples may be collected and
archived for future analyses.
9.2.2.1 A field reagent blank is a recommended QC sample collected
from a portion of the acetone used for cleanup of the probe and nozzle.
Take 100 ml of this acetone directly from the wash bottle being used and
place it in a glass sample container labeled ``field acetone reagent
blank.'' At least one field reagent blank is recommended for every five
runs completed. The field reagent blank samples demonstrate the purity
of the acetone was maintained throughout the program.

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9.2.2.2 A field bias blank train is a recommended QC sample. This
sample is collected by recovering a probe and filter assembly that has
been assembled, taken to the sample location, leak checked, heated,
allowed to sit at the sample location for a similar duration of time as
a regular sample run, leak-checked again, and then recovered in the same
manner as a regular sample. Field bias blanks are not a Method
requirement, however, they are recommended and are very useful for
identifying sources of contamination in emission testing samples. Field
bias blank train results greater than 5 times the method detection limit
may be considered problematic.

10. Calibration and Standardization Same as Method 5, section 5.

11. Analytical Procedures.

11.1 Analysis. Same as Method 5, sections 11.1-11.2.4, with the
following exceptions:
11.1.1 Container No. 1. Same as Method 5, section 11.2.1, with the
following exception: Use disposable gloves to remove each of the filter
holder assemblies from the desiccator, transport container, or sample
oven (after appropriate cooling).
11.1.2 Container No. 2. Same as Method 5, section 11.2.2, with the
following exception: It is recommended that the contents of Container
No. 2 be transferred to a 250 ml beaker with a Teflon liner or similar
container that has a minimal tare weight before bringing to dryness.

12. Data Analysis and Calculations.

12.1 Particulate Emissions. The analytical results cannot be blank
corrected for residual acetone found in any of the blanks. All other
sample calculations are identical to Method 5.
12.2 Paired Trains Outliers. a. Outliers are identified through the
determination of precision and any systemic bias of the paired trains.
Data that do not meet this criteria should be flagged as a data quality
problem. The primary reason for performing dual train sampling is to
generate information to quantify the precision of the Reference Method
data. The relative standard deviation (RSD) of paired data is the
parameter used to quantify data precision. RSD for two simultaneously
gathered data points is determined according to:
[GRAPHIC] [TIFF OMITTED] TR30SE99.008

where, Ca and Cb are concentration values determined from trains A and B
respectively. For RSD calculation, the concentration units are
unimportant so long as they are consistent.
b. A minimum precision criteria for Reference Method PM data is that
RSD for any data pair must be less than 10% as long as the mean PM
concentration is greater than 10 mg/dscm. If the mean PM concentration
is less than 10 mg/dscm higher RSD values are acceptable. At mean PM
concentration of 1 mg/dscm acceptable RSD for paired trains is 25%.
Between 1 and 10 mg/dscm acceptable RSD criteria should be linearly
scaled from 25% to 10%. Pairs of manual method data exceeding these RSD
criteria should be eliminated from the data set used to develop a PM
CEMS correlation or to assess RCA. If the mean PM concentration is less
than 1 mg/dscm, RSD does not apply and the mean result is acceptable.

13. Method Performance [Reserved]

14. Pollution Prevention [Reserved]

15. Waste Management [Reserved]

16. Alternative Procedures. Same as Method 5.
17. Bibliography. Same as Method 5.
18. Tables, Diagrams, Flowcharts and Validation Data. Figure 5I-1 is
a schematic of the sample train.

[[Page 241]]

[GRAPHIC] [TIFF OMITTED] TR30SE99.009

[36 FR 24877, Dec. 23, 1971]

Editorial Note: For Federal Register citations affecting appendix A-
3 to part 60, see the List of CFR sections Affected, which appears in
the Finding Aids section of the printed volume and at www.fdsys.gov.

[[Page 242]]

Sec. Appendix A-4 to Part 60--Test Methods 6 through 10B

Method 6--Determination of sulfur dioxide emissions from stationary
sources
Method 6A--Determination of sulfur dioxide, moisture, and carbon dioxide
emissions from fossil fuel combustion sources
Method 6B--Determination of sulfur dioxide and carbon dioxide daily
average emissions from fossil fuel combustion sources
Method 6C--Determination of Sulfur Dioxide Emissions From Stationary
Sources (Instrumental Analyzer Procedure)
Method 7--Determination of nitrogen oxide emissions from stationary
sources
Method 7A--Determination of nitrogen oxide emissions from stationary
sources--Ion chromatographic method
Method 7B--Determination of nitrogen oxide emissions from stationary
sources (Ultraviolet spectrophotometry)
Method 7C--Determination of nitrogen oxide emissions from stationary
sources--Alkaline-permanganate/colorimetric method
Method 7D--Determination of nitrogen oxide emissions from stationary
sources--Alkaline-permanganate/ion chromatographic method
Method 7E--Determination of Nitrogen Oxides Emissions From Stationary
Sources (Instrumental Analyzer Procedure)
Method 8--Determination of sulfuric acid mist and sulfur dioxide
emissions from stationary sources
Method 9--Visual determination of the opacity of emissions from
stationary sources
Alternate method 1--Determination of the opacity of emissions from
stationary sources remotely by lidar
Method 10--Determination of carbon monoxide emissions from stationary
sources
Method 10A--Determination of carbon monoxide emissions in certifying
continuous emission monitoring systems at petroleum refineries
Method 10B--Determination of carbon monoxide emissions from stationary
sources
The test methods in this appendix are referred to in Sec. 60.8
(Performance Tests) and Sec. 60.11 (Compliance With Standards and
Maintenance Requirements) of 40 CFR part 60, subpart A (General
Provisions). Specific uses of these test methods are described in the
standards of performance contained in the subparts, beginning with
Subpart D.
Within each standard of performance, a section title ``Test Methods
and Procedures'' is provided to: (1) Identify the test methods to be
used as reference methods to the facility subject to the respective
standard and (2) identify any special instructions or conditions to be
followed when applying a method to the respective facility. Such
instructions (for example, establish sampling rates, volumes, or
temperatures) are to be used either in addition to, or as a substitute
for procedures in a test method. Similarly, for sources subject to
emission monitoring requirements, specific instructions pertaining to
any use of a test method as a reference method are provided in the
subpart or in Appendix B.
Inclusion of methods in this appendix is not intended as an
endorsement or denial of their applicability to sources that are not
subject to standards of performance. The methods are potentially
applicable to other sources; however, applicability should be confirmed
by careful and appropriate evaluation of the conditions prevalent at
such sources.
The approach followed in the formulation of the test methods
involves specifications for equipment, procedures, and performance. In
concept, a performance specification approach would be preferable in all
methods because this allows the greatest flexibility to the user. In
practice, however, this approach is impractical in most cases because
performance specifications cannot be established. Most of the methods
described herein, therefore, involve specific equipment specifications
and procedures, and only a few methods in this appendix rely on
performance criteria.
Minor changes in the test methods should not necessarily affect the
validity of the results and it is recognized that alternative and
equivalent methods exist. section 60.8 provides authority for the
Administrator to specify or approve (1) equivalent methods, (2)
alternative methods, and (3) minor changes in the methodology of the
test methods. It should be clearly understood that unless otherwise
identified all such methods and changes must have prior approval of the
Administrator. An owner employing such methods or deviations from the
test methods without obtaining prior approval does so at the risk of
subsequent disapproval and retesting with approved methods.
Within the test methods, certain specific equipment or procedures
are recognized as being acceptable or potentially acceptable and are
specifically identified in the methods. The items identified as
acceptable options may be used without approval but must be identified
in the test report. The potentially approvable options are cited as
``subject to the approval of the Administrator'' or as ``or
equivalent.'' Such potentially approvable techniques or alternatives may
be used at the discretion of the owner without prior approval. However,
detailed descriptions for applying these potentially approvable
techniques or alternatives are not provided in the test methods. Also,
the potentially approvable options are not necessarily acceptable in all
applications. Therefore, an owner electing to use such potentially
approvable techniques or alternatives is responsible for: (1) assuring
that

[[Page 243]]

the techniques or alternatives are in fact applicable and are properly
executed; (2) including a written description of the alternative method
in the test report (the written method must be clear and must be capable
of being performed without additional instruction, and the degree of
detail should be similar to the detail contained in the test methods);
and (3) providing any rationale or supporting data necessary to show the
validity of the alternative in the particular application. Failure to
meet these requirements can result in the Administrator's disapproval of
the alternative.

Method 6--Determination of Sulfur Dioxide Emissions From Stationary
Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 5, and Method 8.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
SO2............................... 7449-09-5 3.4 mg SO2/m\3\
(2.12 x 10)-7 lb/
ft\3\
------------------------------------------------------------------------

1.2 Applicability. This method applies to the measurement of sulfur
dioxide (SO2) emissions from stationary sources.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted from the sampling point in the stack.
The SO2 and the sulfur trioxide, including those fractions in
any sulfur acid mist, are separated. The SO2 fraction is
measured by the barium-thorin titration method.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Free Ammonia. Free ammonia interferes with this method by
reacting with SO2 to form particulate sulfite and by reacting
with the indicator. If free ammonia is present (this can be determined
by knowledge of the process and/or noticing white particulate matter in
the probe and isopropanol bubbler), alternative methods, subject to the
approval of the Administrator are required. One approved alternative is
listed in Reference 13 of section 17.0.
4.2 Water-Soluble Cations and Fluorides. The cations and fluorides
are removed by a glass wool filter and an isopropanol bubbler;
therefore, they do not affect the SO2 analysis. When samples
are collected from a gas stream with high concentrations of metallic
fumes (i.e., very fine cation aerosols) a high-efficiency glass fiber
filter must be used in place of the glass wool plug (i.e., the one in
the probe) to remove the cation interferent.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The following items are required for sample
collection:
6.1.1 Sampling Train. A schematic of the sampling train is shown in
Figure 6-1. The sampling equipment described in Method 8 may be
substituted in place of the midget impinger equipment of Method 6.
However, the Method 8 train must be modified to include a heated filter
between the probe and isopropanol impinger, and the operation of the
sampling train and sample analysis must be at the flow rates and
solution volumes defined in Method 8. Alternatively, SO2 may
be determined simultaneously with particulate

[[Page 244]]

matter and moisture determinations by either (1) replacing the water in
a Method 5 impinger system with a 3 percent H2O2
solution, or (2) replacing the Method 5 water impinger system with a
Method 8 isopropanol-filter-H2O2 system. The
analysis for SO2 must be consistent with the procedure of
Method 8. The Method 6 sampling train consists of the following
components:
6.1.1.1 Probe. Borosilicate glass or stainless steel (other
materials of construction may be used, subject to the approval of the
Administrator), approximately 6 mm (0.25 in.) inside diameter, with a
heating system to prevent water condensation and a filter (either in-
stack or heated out-of-stack) to remove particulate matter, including
sulfuric acid mist. A plug of glass wool is a satisfactory filter.
6.1.1.2 Bubbler and Impingers. One midget bubbler with medium-coarse
glass frit and borosilicate or quartz glass wool packed in top (see
Figure 6-1) to prevent sulfuric acid mist carryover, and three 30-ml
midget impingers. The midget bubbler and midget impingers must be
connected in series with leak-free glass connectors. Silicone grease may
be used, if necessary, to prevent leakage. A midget impinger may be used
in place of the midget bubbler.

Note: Other collection absorbers and flow rates may be used, subject
to the approval of the Administrator, but the collection efficiency must
be shown to be at least 99 percent for each test run and must be
documented in the report. If the efficiency is found to be acceptable
after a series of three tests, further documentation is not required. To
conduct the efficiency test, an extra absorber must be added and
analyzed separately. This extra absorber must not contain more than 1
percent of the total SO2.

6.1.1.3 Glass Wool. Borosilicate or quartz.
6.1.1.4 Stopcock Grease. Acetone-insoluble, heat-stable silicone
grease may be used, if necessary.
6.1.1.5 Temperature Sensor. Dial thermometer, or equivalent, to
measure temperature of gas leaving impinger train to within 1 [deg]C (2
[deg]F).
6.1.1.6 Drying Tube. Tube packed with 6- to 16- mesh indicating-type
silica gel, or equivalent, to dry the gas sample and to protect the
meter and pump. If silica gel is previously used, dry at 177 [deg]C (350
[deg]F) for 2 hours. New silica gel may be used as received.
Alternatively, other types of desiccants (equivalent or better) may be
used, subject to the approval of the Administrator.
6.1.1.7 Valve. Needle valve, to regulate sample gas flow rate.
6.1.1.8 Pump. Leak-free diaphragm pump, or equivalent, to pull gas
through the train. Install a small surge tank between the pump and rate
meter to negate the pulsation effect of the diaphragm pump on the rate
meter.
6.1.1.9 Rate Meter. Rotameter, or equivalent, capable of measuring
flow rate to within 2 percent of the selected flow rate of about 1
liter/min (0.035 cfm).
6.1.1.10 Volume Meter. Dry gas meter (DGM), sufficiently accurate to
measure the sample volume to within 2 percent, calibrated at the
selected flow rate and conditions actually encountered during sampling,
and equipped with a temperature sensor (dial thermometer, or equivalent)
capable of measuring temperature accurately to within 3 [deg]C (5.4
[deg]F). A critical orifice may be used in place of the DGM specified in
this section provided that it is selected, calibrated, and used as
specified in section 16.0.
6.1.2 Barometer. Mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 2.5 mm Hg (0.1 in. Hg). See the
note in Method 5, section 6.1.2.
6.1.3 Vacuum Gauge and Rotameter. At least 760-mm Hg (30-in. Hg)
gauge and 0- to 40-ml/min rotameter, to be used for leak-check of the
sampling train.
6.2 Sample Recovery. The following items are needed for sample
recovery:
6.2.1 Wash Bottles. Two polyethylene or glass bottles, 500-ml.
6.2.2 Storage Bottles. Polyethylene bottles, 100-ml, to store
impinger samples (one per sample).
6.3 Sample Analysis. The following equipment is needed for sample
analysis:
6.3.1 Pipettes. Volumetric type, 5-ml, 20-ml (one needed per
sample), and 25-ml sizes.
6.3.2 Volumetric Flasks. 100-ml size (one per sample) and 1000-ml
size.
6.3.3 Burettes. 5- and 50-ml sizes.
6.3.4 Erlenmeyer Flasks. 250-ml size (one for each sample, blank,
and standard).
6.3.5 Dropping Bottle. 125-ml size, to add indicator.
6.3.6 Graduated Cylinder. 100-ml size.
6.3.7 Spectrophotometer. To measure absorbance at 352 nm.

7.0 Reagents and Standards

Note: Unless otherwise indicated, all reagents must conform to the
specifications established by the Committee on Analytical Reagents of
the American Chemical Society. Where such specifications are not
available, use the best available grade.

7.1 Sample Collection. The following reagents are required for
sample collection:
7.1.1 Water. Deionized distilled to conform to ASTM Specification D
1193-77 or 91 Type 3 (incorporated by reference--see Sec. 60.17). The
KMnO4 test for oxidizable organic matter may be omitted when
high concentrations of organic matter are not expected to be present.
7.1.2 Isopropanol, 80 Percent by Volume. Mix 80 ml of isopropanol
with 20 ml of water.

[[Page 245]]

7.1.2.1 Check each lot of isopropanol for peroxide impurities as
follows: Shake 10 ml of isopropanol with 10 ml of freshly prepared 10
percent potassium iodide solution. Prepare a blank by similarly treating
10 ml of water. After 1 minute, read the absorbance at 352 nm on a
spectrophotometer using a 1-cm path length. If absorbance exceeds 0.1,
reject alcohol for use.
7.1.2.2 Peroxides may be removed from isopropanol by redistilling or
by passage through a column of activated alumina; however, reagent grade
isopropanol with suitably low peroxide levels may be obtained from
commercial sources. Rejection of contaminated lots may, therefore, be a
more efficient procedure.
7.1.3 Hydrogen Peroxide (H2O2), 3 Percent by
Volume. Add 10 ml of 30 percent H2O2 to 90 ml of
water. Prepare fresh daily.
7.1.4 Potassium Iodide Solution, 10 Percent Weight by Volume (w/v).
Dissolve 10.0 g of KI in water, and dilute to 100 ml. Prepare when
needed.
7.2 Sample Recovery. The following reagents are required for sample
recovery:
7.2.1 Water. Same as in section 7.1.1.
7.2.2 Isopropanol, 80 Percent by Volume. Same as in section 7.1.2.
7.3 Sample Analysis. The following reagents and standards are
required for sample analysis:
7.3.1 Water. Same as in section 7.1.1.
7.3.2 Isopropanol, 100 Percent.
7.3.3 Thorin Indicator. 1-(o-arsonophenylazo)-2-naphthol-3,6-
disulfonic acid, disodium salt, or equivalent. Dissolve 0.20 g in 100 ml
of water.
7.3.4 Barium Standard Solution, 0.0100 N. Dissolve 1.95 g of barium
perchlorate trihydrate [Ba(ClO4)2 3H2O]
in 200 ml water, and dilute to 1 liter with isopropanol. Alternatively,
1.22 g of barium chloride dihydrate [BaCl2 2H2O]
may be used instead of the barium perchlorate trihydrate. Standardize as
in section 10.5.
7.3.5 Sulfuric Acid Standard, 0.0100 N. Purchase or standardize to
0.0002 N against 0.0100 N NaOH which has previously been standardized
against potassium acid phthalate (primary standard grade).

8.0 Sample Collection, Preservation, Storage and Transport

8.1 Preparation of Sampling Train. Measure 15 ml of 80 percent
isopropanol into the midget bubbler and 15 ml of 3 percent
H2O2 into each of the first two midget impingers.
Leave the final midget impinger dry. Assemble the train as shown in
Figure 6-1. Adjust the probe heater to a temperature sufficient to
prevent water condensation. Place crushed ice and water around the
impingers.
8.2 Sampling Train Leak-Check Procedure. A leak-check prior to the
sampling run is recommended, but not required. A leak-check after the
sampling run is mandatory. The leak-check procedure is as follows:
8.2.1 Temporarily attach a suitable (e.g., 0- to 40- ml/min)
rotameter to the outlet of the DGM, and place a vacuum gauge at or near
the probe inlet. Plug the probe inlet, pull a vacuum of at least 250 mm
Hg (10 in. Hg), and note the flow rate as indicated by the rotameter. A
leakage rate in excess of 2 percent of the average sampling rate is not
acceptable.

Note: Carefully (i.e., slowly) release the probe inlet plug before
turning off the pump.

8.2.2 It is suggested (not mandatory) that the pump be leak-checked
separately, either prior to or after the sampling run. To leak-check the
pump, proceed as follows: Disconnect the drying tube from the probe-
impinger assembly. Place a vacuum gauge at the inlet to either the
drying tube or the pump, pull a vacuum of 250 mm Hg (10 in. Hg), plug or
pinch off the outlet of the flow meter, and then turn off the pump. The
vacuum should remain stable for at least 30 seconds.
If performed prior to the sampling run, the pump leak-check shall
precede the leak-check of the sampling train described immediately
above; if performed after the sampling run, the pump leak-check shall
follow the sampling train leak-check.
8.2.3 Other leak-check procedures may be used, subject to the
approval of the Administrator.
8.3 Sample Collection.
8.3.1 Record the initial DGM reading and barometric pressure. To
begin sampling, position the tip of the probe at the sampling point,
connect the probe to the bubbler, and start the pump. Adjust the sample
flow to a constant rate of approximately 1.0 liter/min as indicated by
the rate meter. Maintain this constant rate (10 percent) during the
entire sampling run.
8.3.2 Take readings (DGM volume, temperatures at DGM and at impinger
outlet, and rate meter flow rate) at least every 5 minutes. Add more ice
during the run to keep the temperature of the gases leaving the last
impinger at 20 [deg]C (68 [deg]F) or less.
8.3.3 At the conclusion of each run, turn off the pump, remove the
probe from the stack, and record the final readings. Conduct a leak-
check as described in section 8.2. (This leak-check is mandatory.) If a
leak is detected, void the test run or use procedures acceptable to the
Administrator to adjust the sample volume for the leakage.
8.3.4 Drain the ice bath, and purge the remaining part of the train
by drawing clean ambient air through the system for 15 minutes at the
sampling rate. Clean ambient air can be provided by passing air through
a charcoal filter or through an extra midget impinger containing 15 ml
of 3 percent H2O2. Alternatively, ambient air
without purification may be used.

[[Page 246]]

8.4 Sample Recovery. Disconnect the impingers after purging. Discard
the contents of the midget bubbler. Pour the contents of the midget
impingers into a leak-free polyethylene bottle for shipment. Rinse the
three midget impingers and the connecting tubes with water, and add the
rinse to the same storage container. Mark the fluid level. Seal and
identify the sample container.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
7.1.2.................... Isopropanol check.. Ensure acceptable level
of peroxide impurities
in isopropanol.
8.2, 10.1-10.4........... Sampling equipment Ensure accurate
leak-check and measurement of stack
calibration. gas flow rate, sample
volume.
10.5..................... Barium standard Ensure precision of
solution normality determination
standardization.
11.2.3................... Replicate Ensure precision of
titrations. titration
determinations.
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 Volume Metering System.
10.1.1 Initial Calibration.
10.1.1.1 Before its initial use in the field, leak-check the
metering system (drying tube, needle valve, pump, rate meter, and DGM)
as follows: Place a vacuum gauge at the inlet to the drying tube and
pull a vacuum of 250 mm Hg (10 in. Hg). Plug or pinch off the outlet of
the flow meter, and then turn off the pump. The vacuum must remain
stable for at least 30 seconds. Carefully release the vacuum gauge
before releasing the flow meter end.
10.1.1.2 Remove the drying tube, and calibrate the metering system
(at the sampling flow rate specified by the method) as follows: Connect
an appropriately sized wet-test meter (e.g., 1 liter per revolution) to
the inlet of the needle valve. Make three independent calibration runs,
using at least five revolutions of the DGM per run. Calculate the
calibration factor Y (wet-test meter calibration volume divided by the
DGM volume, both volumes adjusted to the same reference temperature and
pressure) for each run, and average the results (Yi). If any
Y-value deviates by more than 2 percent from (Yi), the
metering system is unacceptable for use. If the metering system is
acceptable, use (Yi) as the calibration factor for subsequent
test runs.
10.1.2 Post-Test Calibration Check. After each field test series,
conduct a calibration check using the procedures outlined in section
10.1.1.2, except that three or more revolutions of the DGM may be used,
and only two independent runs need be made. If the average of the two
post-test calibration factors does not deviate by more than 5 percent
from Yi, then Yi is accepted as the DGM
calibration factor (Y), which is used in Equation 6-1 to calculate
collected sample volume (see section 12.2). If the deviation is more
than 5 percent, recalibrate the metering system as in section 10.1.1,
and determine a post-test calibration factor (Yf). Compare
Yi and Yf; the smaller of the two factors is
accepted as the DGM calibration factor. If recalibration indicates that
the metering system is unacceptable for use, either void the test run or
use methods, subject to the approval of the Administrator, to determine
an acceptable value for the collected sample volume.
10.1.3 DGM as a Calibration Standard. A DGM may be used as a
calibration standard for volume measurements in place of the wet-test
meter specified in section 10.1.1.2, provided that it is calibrated
initially and recalibrated periodically according to the same procedures
outlined in Method 5, section 10.3 with the following exceptions: (a)
the DGM is calibrated against a wet-test meter having a capacity of 1
liter/rev (0.035 ft\3\/rev) or 3 liters/rev (0.1 ft\3\/rev) and having
the capability of measuring volume to within 1 percent; (b) the DGM is
calibrated at 1 liter/min (0.035 cfm); and (c) the meter box of the
Method 6 sampling train is calibrated at the same flow rate.
10.2 Temperature Sensors. Calibrate against mercury-in-glass
thermometers. An alternative mercury-free thermometer may be used if the
thermometer is, at a minimum, equivalent in terms of performance or
suitably effective for the specific temperature measurement application.
10.3 Rate Meter. The rate meter need not be calibrated, but should
be cleaned and maintained according to the manufacturer's instructions.
10.4 Barometer. Calibrate against a mercury barometer or NIST-
traceable barometer prior to the field test.
10.5 Barium Standard Solution. Standardize the barium perchlorate or
chloride solution against 25 ml of standard sulfuric acid to which 100
ml of 100 percent isopropanol has been added. Run duplicate analyses.
Calculate the normality using the average of duplicate analyses where
the titrations agree within 1 percent or 0.2 ml, whichever is larger.

11.0 Analytical Procedure

11.1 Sample Loss Check. Note level of liquid in container and
confirm whether any sample was lost during shipment; note this

[[Page 247]]

finding on the analytical data sheet. If a noticeable amount of leakage
has occurred, either void the sample or use methods, subject to the
approval of the Administrator, to correct the final results.
11.2 Sample Analysis.
11.2.1 Transfer the contents of the storage container to a 100-ml
volumetric flask, dilute to exactly 100 ml with water, and mix the
diluted sample.
11.2.2 Pipette a 20-ml aliquot of the diluted sample into a 250-ml
Erlenmeyer flask and add 80 ml of 100 percent isopropanol plus two to
four drops of thorin indicator. While stirring the solution, titrate to
a pink endpoint using 0.0100 N barium standard solution.
11.2.3 Repeat the procedures in section 11.2.2, and average the
titration volumes. Run a blank with each series of samples. Replicate
titrations must agree within 1 percent or 0.2 ml, whichever is larger.

Note: Protect the 0.0100 N barium standard solution from evaporation
at all times.

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after final
calculation.

12.1 Nomenclature

CSO2 = Concentration of SO2, dry basis, corrected
to standard conditions, mg/dscm (lb/dscf).
N = Normality of barium standard titrant, meq/ml.
Pbar = Barometric pressure, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
Tm = Average DGM absolute temperature, [deg]K ([deg]R).
Tstd = Standard absolute temperature, 293 [deg]K (528
[deg]R).
Va = Volume of sample aliquot titrated, ml.
Vm = Dry gas volume as measured by the DGM, dcm (dcf).
Vm(std) = Dry gas volume measured by the DGM, corrected to
standard conditions, dscm (dscf).
Vsoln = Total volume of solution in which the SO2
sample is contained, 100 ml.
Vt = Volume of barium standard titrant used for the sample
(average of replicate titration), ml.
Vtb = Volume of barium standard titrant used for the blank,
ml.
Y = DGM calibration factor.
12.2 Dry Sample Gas Volume, Corrected to Standard Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.181

Where:

K1 = 0.3855 [deg]K/mm Hg for metric units,
K1 = 17.65 [deg]R/in. Hg for English units.

12.3 SO2 Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.182

Where:

K2 = 32.03 mg SO2/meq for metric units,
K2 = 7.061 x 10^-5 lb SO2/meq for
English units.

13.0 Method Performance

13.1 Range. The minimum detectable limit of the method has been
determined to be 3.4 mg SO2/m\3\ (2.12 x 10^-7
lb/ft\3\). Although no upper limit has been established, tests have
shown that concentrations as high as 80,000 mg/m\3\ (0.005 lb/ft\3\) of
SO2 can be collected efficiently at a rate of 1.0 liter/min
(0.035 cfm) for 20 minutes in two midget impingers, each containing 15
ml of 3 percent H2O2. Based on theoretical
calculations, the upper concentration limit in a 20 liter (0.7 ft\3\)
sample is about 93,300 mg/m\3\ (0.00583 lb/ft\3\).

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 Nomenclature. Same as section 12.1, with the following
additions:

Bwa = Water vapor in ambient air, proportion by volume.
Ma = Molecular weight of the ambient air saturated at
impinger temperature, g/g-mole (lb/lb-mole).
Ms = Molecular weight of the sample gas saturated at impinger
temperature, g/g-mole (lb/lb-mole).
Pc = Inlet vacuum reading obtained during the calibration
run, mm Hg (in. Hg).
Psr = Inlet vacuum reading obtained during the sampling run,
mm Hg (in. Hg).

[[Page 248]]

Qstd = Volumetric flow rate through critical orifice, scm/min
(scf/min).
Qstd = Average flow rate of pre-test and post-test
calibration runs, scm/min (scf/min).
Tamb = Ambient absolute temperature of air, [deg]K ([deg]R).
Vsb = Volume of gas as measured by the soap bubble meter,
m\3\ (ft\3\).
Vsb(std) = Volume of gas as measured by the soap bubble
meter, corrected to standard conditions, scm (scf).
k = Soap bubble travel time, min.
ks = Time, min.

16.2 Critical Orifices for Volume and Rate Measurements. A critical
orifice may be used in place of the DGM specified in section 6.1.1.10,
provided that it is selected, calibrated, and used as follows:
16.2.1 Preparation of Sampling Train. Assemble the sampling train as
shown in Figure 6-2. The rate meter and surge tank are optional but are
recommended in order to detect changes in the flow rate.

Note: The critical orifices can be adapted to a Method 6 type
sampling train as follows: Insert sleeve type, serum bottle stoppers
into two reducing unions. Insert the needle into the stoppers as shown
in Figure 6-3.

16.2.2 Selection of Critical Orifices.
16.2.2.1 The procedure that follows describes the use of hypodermic
needles and stainless steel needle tubings, which have been found
suitable for use as critical orifices. Other materials and critical
orifice designs may be used provided the orifices act as true critical
orifices, (i.e., a critical vacuum can be obtained) as described in this
section. Select a critical orifice that is sized to operate at the
desired flow rate. The needle sizes and tubing lengths shown in Table 6-
1 give the following approximate flow rates.
16.2.2.2 Determine the suitability and the appropriate operating
vacuum of the critical orifice as follows: If applicable, temporarily
attach a rate meter and surge tank to the outlet of the sampling train,
if said equipment is not present (see section 16.2.1). Turn on the pump
and adjust the valve to give an outlet vacuum reading corresponding to
about half of the atmospheric pressure. Observe the rate meter reading.
Slowly increase the vacuum until a stable reading is obtained on the
rate meter. Record the critical vacuum, which is the outlet vacuum when
the rate meter first reaches a stable value. Orifices that do not reach
a critical value must not be used.
16.2.3 Field Procedures.
16.2.3.1 Leak-Check Procedure. A leak-check before the sampling run
is recommended, but not required. The leak-check procedure is as
follows: Temporarily attach a suitable (e.g., 0-40 ml/min) rotameter and
surge tank, or a soap bubble meter and surge tank to the outlet of the
pump. Plug the probe inlet, pull an outlet vacuum of at least 250 mm Hg
(10 in. Hg), and note the flow rate as indicated by the rotameter or
bubble meter. A leakage rate in excess of 2 percent of the average
sampling rate (Qstd) is not acceptable. Carefully release the
probe inlet plug before turning off the pump.
16.2.3.2 Moisture Determination. At the sampling location, prior to
testing, determine the percent moisture of the ambient air using the wet
and dry bulb temperatures or, if appropriate, a relative humidity meter.
16.2.3.3 Critical Orifice Calibration. At the sampling location,
prior to testing, calibrate the entire sampling train (i.e., determine
the flow rate of the sampling train when operated at critical
conditions). Attach a 500-ml soap bubble meter to the inlet of the
probe, and operate the sampling train at an outlet vacuum of 25 to 50 mm
Hg (1 to 2 in. Hg) above the critical vacuum. Record the information
listed in Figure 6-4. Calculate the standard volume of air measured by
the soap bubble meter and the volumetric flow rate using the equations
below:
[GRAPHIC] [TIFF OMITTED] TR17OC00.184

[GRAPHIC] [TIFF OMITTED] TR17OC00.185

16.2.3.4 Sampling.
16.2.3.4.1 Operate the sampling train for sample collection at the
same vacuum used during the calibration run. Start the watch and pump
simultaneously. Take readings (temperature, rate meter, inlet vacuum,
and outlet vacuum) at least every 5 minutes. At the end of the sampling
run, stop the watch and pump simultaneously.
16.2.3.4.2 Conduct a post-test calibration run using the calibration
procedure outlined in section 16.2.3.3. If the Qstd obtained
before and after the test differ by more than 5 percent, void the test
run; if not, calculate the volume of the gas measured with the critical
orifice using Equation 6-6 as follows:

[[Page 249]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.186

16.2.3.4.3 If the percent difference between the molecular weight of
the ambient air at saturated conditions and the sample gas is more that
3 percent, then the molecular weight of the gas sample must be
considered in the calculations using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.187

Note: A post-test leak-check is not necessary because the post-test
calibration run results will indicate whether there is any leakage.

16.2.3.4.4 Drain the ice bath, and purge the sampling train using
the procedure described in section 8.3.4.
16.3 Elimination of Ammonia Interference. The following alternative
procedures must be used in addition to those specified in the method
when sampling at sources having ammonia emissions.
16.3.1 Sampling. The probe shall be maintained at 275 [deg]C (527
[deg]F) and equipped with a high-efficiency in-stack filter (glass
fiber) to remove particulate matter. The filter material shall be
unreactive to SO2. Whatman 934AH (formerly Reeve Angel 934AH)
filters treated as described in Reference 10 in section 17.0 of Method 5
is an example of a filter that has been shown to work. Where alkaline
particulate matter and condensed moisture are present in the gas stream,
the filter shall be heated above the moisture dew point but below 225
[deg]C (437 [deg]F).
16.3.2 Sample Recovery. Recover the sample according to section 8.4
except for discarding the contents of the midget bubbler. Add the
bubbler contents, including the rinsings of the bubbler with water, to a
separate polyethylene bottle from the rest of the sample. Under normal
testing conditions where sulfur trioxide will not be present
significantly, the tester may opt to delete the midget bubbler from the
sampling train. If an approximation of the sulfur trioxide concentration
is desired, transfer the contents of the midget bubbler to a separate
polyethylene bottle.
16.3.3 Sample Analysis. Follow the procedures in sections 11.1 and
11.2, except add 0.5 ml of 0.1 N HCl to the Erlenmeyer flask and mix
before adding the indicator. The following analysis procedure may be
used for an approximation of the sulfur trioxide concentration. The
accuracy of the calculated concentration will depend upon the ammonia to
SO2 ratio and the level of oxygen present in the gas stream.
A fraction of the SO2 will be counted as sulfur trioxide as
the ammonia to SO2 ratio and the sample oxygen content
increases. Generally, when this ratio is 1 or less and the oxygen
content is in the range of 5 percent, less than 10 percent of the
SO2 will be counted as sulfur trioxide. Analyze the peroxide
and isopropanol sample portions separately. Analyze the peroxide portion
as described above. Sulfur trioxide is determined by difference using
sequential titration of the isopropanol portion of the sample. Transfer
the contents of the isopropanol storage container to a 100-ml volumetric
flask, and dilute to exactly 100 ml with water. Pipette a 20-ml aliquot
of this solution into a 250-ml Erlenmeyer flask, add 0.5 ml of 0.1 N
HCl, 80 ml of 100 percent isopropanol, and two to four drops of thorin
indicator. Titrate to a pink endpoint using 0.0100 N barium perchlorate.
Repeat and average the titration volumes that agree within 1 percent or
0.2 ml, whichever is larger. Use this volume in Equation 6-2 to
determine the sulfur trioxide concentration. From the flask containing
the remainder of the isopropanol sample, determine the fraction of
SO2 collected in the bubbler by pipetting 20-ml aliquots into
250-ml Erlenmeyer flasks. Add 5 ml of 3 percent
H2O2, 100 ml of 100 percent isopropanol, and two
to four drips of thorin indicator, and titrate as before. From this
titration volume, subtract the titrant volume determined for sulfur
trioxide, and add the titrant volume determined for the peroxide
portion. This final volume constitutes Vt, the volume of
barium perchlorate used for the SO2 sample.

17.0 References

1. Atmospheric Emissions from Sulfuric Acid Manufacturing Processes.
U.S. DHEW, PHS, Division of Air Pollution. Public

[[Page 250]]

Health Service Publication No. 999-AP-13. Cincinnati, OH. 1965.
2. Corbett, P.F. The Determination of SO2 and
SO3 in Flue Gases. Journal of the Institute of Fuel. 24:237-
243. 1961.
3. Matty, R.E., and E.K. Diehl. Measuring Flue-Gas SO2
and SO3. Power. 101:94-97. November 1957.
4. Patton, W.F., and J.A. Brink, Jr. New Equipment and Techniques
for Sampling Chemical Process Gases. J. Air Pollution Control
Association. 13:162. 1963.
5. Rom, J.J. Maintenance, Calibration, and Operation of Isokinetic
Source Sampling Equipment. Office of Air Programs, U.S. Environmental
Protection Agency. Research Triangle Park, NC. APTD-0576. March 1972.
6. Hamil, H.F., and D.E. Camann. Collaborative Study of Method for
the Determination of Sulfur Dioxide Emissions from Stationary Sources
(Fossil-Fuel Fired Steam Generators). U.S. Environmental Protection
Agency, Research Triangle Park, NC. EPA-650/4-74-024. December 1973.
7. Annual Book of ASTM Standards. Part 31; Water, Atmospheric
Analysis. American Society for Testing and Materials. Philadelphia, PA.
1974. pp. 40-42.
8. Knoll, J.E., and M.R. Midgett. The Application of EPA Method 6 to
High Sulfur Dioxide Concentrations. U.S. Environmental Protection
Agency. Research Triangle Park, NC. EPA-600/4-76-038. July 1976.
9. Westlin, P.R., and R.T. Shigehara. Procedure for Calibrating and
Using Dry Gas Volume Meters as Calibration Standards. Source Evaluation
Society Newsletter. 3(1):17-30. February 1978.
10. Yu, K.K. Evaluation of Moisture Effect on Dry Gas Meter
Calibration. Source Evaluation Society Newsletter. 5(1):24-28. February
1980.
11. Lodge, J.P., Jr., et al. The Use of Hypodermic Needles as
Critical Orifices in Air Sampling. J. Air Pollution Control Association.
16:197-200. 1966.
12. Shigehara, R.T., and C.B. Sorrell. Using Critical Orifices as
Method 5 CalibrationStandards. Source Evaluation Society Newsletter.
10:4-15. August 1985.
13. Curtis, F., Analysis of Method 6 Samples in the Presence of
Ammonia. Source Evaluation Society Newsletter. 13(1):9-15 February 1988.

18.0 Tables, Diagrams, Flowcharts and Validation Data

Table 6-1--Approximate Flow Rates for Various Needle Sizes
------------------------------------------------------------------------
Needle Flow rate
Needle size (gauge) length (cm) (ml/min)
------------------------------------------------------------------------
21............................................ 7.6 1,100
22............................................ 2.9 1,000
22............................................ 3.8 900
23............................................ 3.8 500
23............................................ 5.1 450
24............................................ 3.2 400
------------------------------------------------------------------------

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Method 6A--Determination of Sulfur Dioxide, Moisture, and Carbon Dioxide
From Fossil Fuel Combustion Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 5, Method 6, and Method 19.

1.0 Scope and Application

1.1 Analytes.

[[Page 255]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
SO2............................... 7449-09-05 3.4 mg SO2/m\3\
(2.12 x 10-7 lb/
ft\3\)
CO2............................... 124-38-9 N/A
H2O............................... 7732-18-5 N/A
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of sulfur dioxide (SO2) emissions from fossil fuel combustion
sources in terms of concentration (mg/dscm or lb/dscf) and in terms of
emission rate (ng/J or lb/10\6\ Btu) and for the determination of carbon
dioxide (CO2) concentration (percent). Moisture content
(percent), if desired, may also be determined by this method.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted from a sampling point in the stack.
The SO2 and the sulfur trioxide, including those fractions in
any sulfur acid mist, are separated. The SO2 fraction is
measured by the barium-thorin titration method. Moisture and
CO2 fractions are collected in the same sampling train, and
are determined gravimetrically.

3.0 Definitions [Reserved]

4.0 Interferences

Same as Method 6, section 4.0.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. Same as Method 6, section 6.1, with the
exception of the following:
6.1.1 Sampling Train. A schematic of the sampling train used in this
method is shown in Figure 6A-1.
6.1.1.1 Impingers and Bubblers. Two 30 = ml midget impingers with a
1 = mm restricted tip and two 30 = ml midget bubblers with unrestricted
tips. Other types of impingers and bubblers (e.g., Mae West for
SO2 collection and rigid cylinders containing Drierite for
moisture absorbers), may be used with proper attention to reagent
volumes and levels, subject to the approval of the Administrator.
6.1.1.2 CO2 Absorber. A sealable rigid cylinder or bottle
with an inside diameter between 30 and 90 mm , a length between 125 and
250 mm, and appropriate connections at both ends. The filter may be a
separate heated unit or may be within the heated portion of the probe.
If the filter is within the sampling probe, the filter should not be
within 15 cm of the probe inlet or any unheated section of the probe,
such as the connection to the first bubbler. The probe and filter should
be heated to at least 20 [deg]C (68 [deg]F) above the source
temperature, but not greater than 120 [deg]C (248 [deg]F). The filter
temperature (i.e., the sample gas temperature) should be monitored to
assure the desired temperature is maintained. A heated Teflon connector
may be used to connect the filter holder or probe to the first impinger.

Note: For applications downstream of wet scrubbers, a heated out-of-
stack filter (either borosilicate glass wool or glass fiber mat) is
necessary.

6.2 Sample Recovery. Same as Method 6, section 6.2.
6.3 Sample Analysis. Same as Method 6, section 6.3, with the
addition of a balance to measure within 0.05 g.

7.0 Reagents and Standards

7.1 Sample Collection. Same as Method 6, section 7.1, with the
addition of the following:
7.1.1 Drierite. Anhydrous calcium sulfate (CaSO4)
desiccant, 8 mesh, indicating type is recommended.

Note: Do not use silica gel or similar desiccant in this
application.

7.1.2 CO2 Absorbing Material. Ascarite II. Sodium
hydroxide-coated silica, 8- to 20-mesh.
7.2 Sample Recovery and Analysis. Same as Method 6, sections 7.2 and
7.3, respectively.

8.0 Sample Collection, Preservation, Transport, and Storage

8.1 Preparation of Sampling Train.
8.1.1 Measure 15 ml of 80 percent isopropanol into the first midget
bubbler and 15 ml of 3 percent hydrogen peroxide into each of the two
midget impingers (the second

[[Page 256]]

and third vessels in the train) as described in Method 6, section 8.1.
Insert the glass wool into the top of the isopropanol bubbler as shown
in Figure 6A-1. Place about 25 g of Drierite into the second midget
bubbler (the fourth vessel in the train). Clean the outside of the
bubblers and impingers and allow the vessels to reach room temperature.
Weigh the four vessels simultaneously to the nearest 0.1 g, and record
this initial weight (mwi).
8.1.2 With one end of the CO2 absorber sealed, place
glass wool into the cylinder to a depth of about 1 cm (0.5 in.). Place
about 150 g of CO2 absorbing material in the cylinder on top
of the glass wool, and fill the remaining space in the cylinder with
glass wool. Assemble the cylinder as shown in figure 6A-2. With the
cylinder in a horizontal position, rotate it around the horizontal axis.
The CO2 absorbing material should remain in position during
the rotation, and no open spaces or channels should be formed. If
necessary, pack more glass wool into the cylinder to make the
CO2 absorbing material stable. Clean the outside of the
cylinder of loose dirt and moisture and allow the cylinder to reach room
temperature. Weigh the cylinder to the nearest 0.1 g, and record this
initial weight (mai).
8.1.3 Assemble the train as shown in figure 6A-1. Adjust the probe
heater to a temperature sufficient to prevent condensation (see note in
section 6.1). Place crushed ice and water around the impingers and
bubblers. Mount the CO2 absorber outside the water bath in a
vertical flow position with the sample gas inlet at the bottom. Flexible
tubing (e.g., Tygon) may be used to connect the last SO2
absorbing impinger to the moisture absorber and to connect the moisture
absorber to the CO2 absorber. A second, smaller
CO2 absorber containing Ascarite II may be added in-line
downstream of the primary CO2 absorber as a breakthrough
indicator. Ascarite II turns white when CO2 is absorbed.
8.2 Sampling Train Leak-Check Procedure and Sample Collection. Same
as Method 6, sections 8.2 and 8.3, respectively.
8.3 Sample Recovery.
8.3.1 Moisture Measurement. Disconnect the isopropanol bubbler, the
SO2 impingers, and the moisture absorber from the sample
train. Allow about 10 minutes for them to reach room temperature, clean
the outside of loose dirt and moisture, and weigh them simultaneously in
the same manner as in section 8.1. Record this final weight
(mwf).
8.3.2 Peroxide Solution. Discard the contents of the isopropanol
bubbler and pour the contents of the midget impingers into a leak-free
polyethylene bottle for shipping. Rinse the two midget impingers and
connecting tubes with water, and add the washing to the same storage
container.
8.3.3 CO2 Absorber. Allow the CO2 absorber to
warm to room temperature (about 10 minutes), clean the outside of loose
dirt and moisture, and weigh to the nearest 0.1 g in the same manner as
in section 8.1. Record this final weight (maf). Discard used
Ascarite II material.

9.0 Quality Control

Same as Method 6, section 9.0.

10.0 Calibration and Standardization

Same as Method 6, section 10.0.

11.0 Analytical Procedure

11.1 Sample Analysis. The sample analysis procedure for
SO2 is the same as that specified in Method 6, section 11.0.

12.0 Data Analysis and Calculations

Same as Method 6, section 12.0, with the addition of the following:
12.1 Nomenclature.

Cw = Concentration of moisture, percent.
CCO2 = Concentration of CO2, dry basis, percent.
ESO2 = Emission rate of SO2, ng/J (lb/10\6\ Btu).
FC = Carbon F-factor from Method 19 for the fuel burned,
dscm/J (dscf/10\6\ Btu).
mwi = Initial weight of impingers, bubblers, and moisture
absorber, g.
mwf = Final weight of impingers, bubblers, and moisture
absorber, g.
mai = Initial weight of CO2 absorber, g.
maf = Final weight of CO2 absorber, g.
mSO2 = Mass of SO2 collected, mg.
VCO2(std) = Equivalent volume of CO2 collected at
standard conditions, dscm (dscf).
Vw(std) = Equivalent volume of moisture collected at standard
conditions, scm (scf).

12.2 CO2 Volume Collected, Corrected to Standard
Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.192

Where:

K3 = Equivalent volume of gaseous CO2 at standard
conditions, 5.467 x 10^-4 dscm/g (1.930 x
10^-2 dscf/g).

12.3 Moisture Volume Collected, Corrected to Standard Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.193

Where:

K4 = Equivalent volume of water vapor at standard conditions,
1.336 x 10^-3 scm/g (4.717 x 10^-2 scf/
g).

12.4 SO2 Concentration.

[[Page 257]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.194

Where:

K2 = 32.03 mg SO2/meq. SO2 (7.061 x
10^-5 lb SO2/meq. SO2)

12.5 CO2 Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.195

12.6 Moisture Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.196

13.0 Method Performance

13.1 Range and Precision. The minimum detectable limit and the upper
limit for the measurement of SO2 are the same as for Method
6. For a 20-liter sample, this method has a precision of 0.5 percent
CO2 for concentrations between 2.5 and 25 percent
CO2 and 1.0 percent moisture for moisture concentrations
greater than 5 percent.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Methods

If the only emission measurement desired is in terms of emission
rate of SO2 (ng/J or lb/10\6\ Btu), an abbreviated procedure
may be used. The differences between the above procedure and the
abbreviated procedure are described below.
16.1 Sampling Train. The sampling train is the same as that shown in
Figure 6A-1 and as described in section 6.1, except that the dry gas
meter is not needed.
16.2 Preparation of the Sampling Train. Follow the same procedure as
in section 8.1, except do not weigh the isopropanol bubbler, the
SO2 absorbing impingers, or the moisture absorber.
16.3 Sampling Train Leak-Check Procedure and Sample Collection.
Leak-check and operate the sampling train as described in section 8.2,
except that dry gas meter readings, barometric pressure, and dry gas
meter temperatures need not be recorded during sampling.
16.4 Sample Recovery. Follow the procedure in section 8.3, except do
not weigh the isopropanol bubbler, the SO2 absorbing
impingers, or the moisture absorber.
16.5 Sample Analysis. Analysis of the peroxide solution is the same
as that described in section 11.1.
16.6 Calculations.
16.6.1 SO2 Collected.
[GRAPHIC] [TIFF OMITTED] TR17OC00.197

Where:

K2 = 32.03 mg SO2/meq. SO2
K2 = 7.061 x 10^-5 lb SO2/meq.
SO2

16.6.2 Sulfur Dioxide Emission Rate.

[[Page 258]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.198

Where:

K5 = 1.829 x 10\9\ mg/dscm
K2 = 0.1142 lb/dscf

17.0 References

Same as Method 6, section 17.0, References 1 through 8, with the
addition of the following:

1. Stanley, Jon and P.R. Westlin. An Alternate Method for Stack Gas
Moisture Determination. Source Evaluation Society Newsletter. 3(4).
November 1978.
2. Whittle, Richard N. and P.R. Westlin. Air Pollution Test Report:
Development and Evaluation of an Intermittent Integrated SO2/
CO2 Emission Sampling Procedure. Environmental Protection
Agency, Emission Standard and Engineering Division, Emission Measurement
Branch. Research Triangle Park, NC. December 1979. 14 pp.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 259]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.199

[[Page 260]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.410

Method 6B--Determination of Sulfur Dioxide and Carbon Dioxide Daily
Average Emissions From Fossil Fuel Combustion Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 5, Method 6, and Method 6A.

1.0 Scope and Application

1.1 Analytes.

[[Page 261]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Sulfur dioxide (SO2).............. 7449-09-05 3.4 mg SO2/m\3\
(2.12 x 10 7 lb/
ft\3\)
Carbon dioxide (CO2).............. 124-38-9 N/A
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of SO2 emissions from combustion sources in terms of
concentration (ng/dscm or lb/dscf) and emission rate (ng/J or lb/10\6\
Btu), and for the determination of CO2 concentration
(percent) on a daily (24 hours) basis.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted from the sampling point in the stack
intermittently over a 24-hour or other specified time period. The
SO2 fraction is measured by the barium-thorin titration
method. Moisture and CO2 fractions are collected in the same
sampling train, and are determined gravimetrically.

3.0 Definitions [Reserved]

4.0 Interferences

Same as Method 6, section 4.0.

5.0 Safety

6.0 Equipment and Supplies

Same as Method 6A, section 6.0, with the following exceptions and
additions:
6.1 The isopropanol bubbler is not used. An empty bubbler for the
collection of liquid droplets, that does not allow direct contact
between the collected liquid and the gas sample, may be included in the
sampling train.
6.2 For intermittent operation, include an industrial timer-switch
designed to operate in the ``on'' position at least 2 minutes
continuously and ``off'' the remaining period over a repeating cycle.
The cycle of operation is designated in the applicable regulation. At a
minimum, the sampling operation should include at least 12, equal,
evenly-spaced periods per 24 hours.
6.3 Stainless steel sampling probes, type 316, are not recommended
for use with Method 6B because of potential sample contamination due to
corrosion. Glass probes or other types of stainless steel, e.g.,
Hasteloy or Carpenter 20, are recommended for long-term use.

Note: For applications downstream of wet scrubbers, a heated out-of-
stack filter (either borosilicate glass wool or glass fiber mat) is
necessary. Probe and filter heating systems capable of maintaining a
sample gas temperature of between 20 and 120 [deg]C (68 and 248 [deg]F)
at the filter are also required in these cases. The electric supply for
these heating systems should be continuous and separate from the timed
operation of the sample pump.

7.0 Reagents and Standards

Same as Method 6A, section 7.0, with the following exceptions:
7.1 Isopropanol is not used for sampling.
7.2 The hydrogen peroxide absorbing solution shall be diluted to no
less than 6 percent by volume, instead of 3 percent as specified in
Methods 6 and 6A.
7.3 If the Method 6B sampling train is to be operated in a low
sample flow condition (less than 100 ml/min or 0.21 ft\3\/hr), molecular
sieve material may be substituted for Ascarite II as the CO2
absorbing material. The recommended molecular sieve material is Union
Carbide \1/16\ inch pellets, 5 A[deg], or equivalent. Molecular sieve
material need not be discarded following the sampling run, provided that
it is regenerated as per the manufacturer's instruction. Use of
molecular sieve material at flow rates higher than 100 ml/min (0.21
ft\3\/hr) may cause erroneous CO2 results.

8.0 Sample Collection, Preservation, Transport, and Storage

8.1 Preparation of Sampling Train. Same as Method 6A, section 8.1,
with the addition of the following:
8.1.1 The sampling train is assembled as shown in Figure 6A-1 of
Method 6A, except that the isopropanol bubbler is not included.
8.1.2 Adjust the timer-switch to operate in the ``on'' position from
2 to 4 minutes on a 2-hour repeating cycle or other cycle specified in
the applicable regulation. Other timer sequences may be used with the
restriction that the total sample volume collected is between 25 and 60
liters (0.9 and 2.1 ft\3\) for the amounts of sampling reagents
prescribed in this method.
8.1.3 Add cold water to the tank until the impingers and bubblers
are covered at least two-thirds of their length. The impingers and
bubbler tank must be covered and protected from intense heat and direct
sunlight. If freezing conditions exist, the impinger solution and the
water bath must be protected.

Note: Sampling may be conducted continuously if a low flow-rate
sample pump [20

[[Page 262]]

to 40 ml/min (0.04 to 0.08 ft\3\/hr) for the reagent volumes described
in this method] is used. If sampling is continuous, the timer-switch is
not necessary. In addition, if the sample pump is designed for constant
rate sampling, the rate meter may be deleted. The total gas volume
collected should be between 25 and 60 liters (0.9 and 2.1 ft\3\) for the
amounts of sampling reagents prescribed in this method.

8.2 Sampling Train Leak-Check Procedure. Same as Method 6, section
8.2.
8.3 Sample Collection.
8.3.1 The probe and filter (either in-stack, out-of-stack, or both)
must be heated to a temperature sufficient to prevent water
condensation.
8.3.2 Record the initial dry gas meter reading. To begin sampling,
position the tip of the probe at the sampling point, connect the probe
to the first impinger (or filter), and start the timer and the sample
pump. Adjust the sample flow to a constant rate of approximately 1.0
liter/min (0.035 cfm) as indicated by the rotameter. Observe the
operation of the timer, and determine that it is operating as intended
(i.e., the timer is in the ``on'' position for the desired period, and
the cycle repeats as required).
8.3.3 One time between 9 a.m. and 11 a.m. during the 24-hour
sampling period, record the dry gas meter temperature (Tm)
and the barometric pressure (P(bar)).
8.3.4 At the conclusion of the run, turn off the timer and the
sample pump, remove the probe from the stack, and record the final gas
meter volume reading. Conduct a leak-check as described in section 8.2.
If a leak is found, void the test run or use procedures acceptable to
the Administrator to adjust the sample volume for leakage. Repeat the
steps in sections 8.3.1 to 8.3.4 for successive runs.
8.4 Sample Recovery. The procedures for sample recovery (moisture
measurement, peroxide solution, and CO2 absorber) are the
same as those in Method 6A, section 8.3.

9.0 Quality Control

Same as Method 6, section 9.0., with the exception of the
isopropanol-check.

10.0 Calibration and Standardization

Same as Method 6, section 10.0, with the addition of the following:
10.1 Periodic Calibration Check. After 30 days of operation of the
test train, conduct a calibration check according to the same procedures
as the post-test calibration check (Method 6, section 10.1.2). If the
deviation between initial and periodic calibration factors exceeds 5
percent, use the smaller of the two factors in calculations for the
preceding 30 days of data, but use the most recent calibration factor
for succeeding test runs.

11.0 Analytical Procedures

11.1 Sample Loss Check and Analysis. Same as Method 6, sections 11.1
and 11.2, respectively.

12.0 Data Analysis and Calculations

Same as Method 6A, section 12.0, except that Pbar and
Tm correspond to the values recorded in section 8.3.3 of this
method. The values are as follows:

Pbar = Initial barometric pressure for the test period, mm
Hg.
Tm = Absolute meter temperature for the test period, [deg]K.

13.0 Method Performance

13.1 Range.
13.1.1 Sulfur Dioxide. Same as Method 6.
13.1.2 Carbon Dioxide. Not determined.
13.2 Repeatability and Reproducibility. EPA-sponsored collaborative
studies were undertaken to determine the magnitude of repeatability and
reproducibility achievable by qualified testers following the procedures
in this method. The results of the studies evolve from 145 field tests
including comparisons with Methods 3 and 6. For measurements of emission
rates from wet, flue gas desulfurization units in (ng/J), the
repeatability (intra-laboratory precision) is 8.0 percent and the
reproducibility (inter-laboratory precision) is 11.1 percent.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Methods

Same as Method 6A, section 16.0, except that the timer is needed and
is operated as outlined in this method.

17.0 References

Same as Method 6A, section 17.0, with the addition of the following:

1. Butler, Frank E., et. al. The Collaborative Test of Method 6B:
Twenty-Four-Hour Analysis of SO2 and CO2. JAPCA.
Vol. 33, No. 10. October 1983.

18.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 6C--Determination of Sulfur Dioxide Emissions From Stationary
Sources (Instrumental Analyzer Procedure)

1.0 Scope and Application

What is Method 6C?

Method 6C is a procedure for measuring sulfur dioxide
(SO2) in stationary source emissions using a continuous
instrumental analyzer. Quality assurance and quality control
requirements are included to assure that

[[Page 263]]

you, the tester, collect data of known quality. You must document your
adherence to these specific requirements for equipment, supplies, sample
collection and analysis, calculations, and data analysis.
This method does not completely describe all equipment, supplies,
and sampling and analytical procedures you will need but refers to other
methods for some of the details. Therefore, to obtain reliable results,
you should also have a thorough knowledge of these additional test
methods which are found in appendix A to this part:
(a) Method 1--Sample and Velocity Traverses for Stationary Sources.
(b) Method 4--Determination of Moisture Content in Stack Gases.
(c) Method 6--Determination of Sulfur Dioxide Emissions from
Stationary Sources.
(d) Method 7E--Determination of Nitrogen Oxides Emissions from
Stationary Sources (Instrumental Analyzer Procedure).
1.1 Analytes. What does this method determine? This method measures
the concentration of sulfur dioxide.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
SO2............................ 7446-09-5 Typically <2% of
Calibration Span.
------------------------------------------------------------------------

1.2 Applicability. When is this method required? The use of Method
6C may be required by specific New Source Performance Standards, Clean
Air Marketing rules, State Implementation Plans, and permits where
SO2 concentrations in stationary source emissions must be
measured, either to determine compliance with an applicable emission
standard or to conduct performance testing of a continuous emission
monitoring system (CEMS). Other regulations may also require the use of
Method 6C.
1.3 Data Quality Objectives. How good must my collected data be?
Refer to section 1.3 of Method 7E.

2.0 Summary of Method

In this method, you continuously sample the effluent gas and convey
the sample to an analyzer that measures the concentration of
SO2. You must meet the performance requirements of this
method to validate your data.

3.0 Definitions

Refer to section 3.0 of Method 7E for the applicable definitions.

4.0 Interferences

Refer to Section 4.0 of Method 7E.

5.0 Safety

Refer to section 5.0 of Method 7E.

6.0 Equipment and Supplies

Figure 7E-1 of Method 7E is a schematic diagram of an acceptable
measurement system.
6.1 What do I need for the measurement system? The essential
components of the measurement system are the same as those in sections
6.1 and 6.2 of Method 7E, except that the SO2 analyzer
described in section 6.2 of this method must be used instead of the
analyzer described in section 6.2 of Method 7E. You must follow the
noted specifications in section 6.1 of Method 7E.
6.2 What analyzer must I use? You may use an instrument that uses an
ultraviolet, non-dispersive infrared, fluorescence, or other detection
principle to continuously measure SO2 in the gas stream and
meets the performance specifications in section 13.0. The low-range and
dual-range analyzer provisions in sections 6.2.8.1 and 6.2.8.2 of Method
7E apply.

7.0 Reagents and Standards

7.1 Calibration Gas. What calibration gases do I need? Refer to
section 7.1 of Method 7E for the calibration gas requirements. Example
calibration gas mixtures are listed below.
(a) SO2 in nitrogen (N2).
(b) SO2 in air.
(c) SO2 and CO2 in N2.
(d) SO2 andO2 in N2.
(e) SO2/CO2/O2 gas mixture in
N2.
(f) CO2/NOX gas mixture in N2.
(g) CO2/SO2/NOX gas mixture in
N2.
7.2 Interference Check. What additional reagents do I need for the
interference check? The test gases for the interference check are listed
in Table 7E-3 of Method 7E. For the alternative interference check, you
must use the reagents described in section 7.0 of Method 6.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sampling Site and Sampling Points. You must follow the
procedures of section 8.1 of Method 7E.
8.2 Initial Measurement System Performance Tests. You must follow
the procedures in section 8.2 of Method 7E. If a dilution-type
measurement system is used, the special considerations in section 8.3 of
Method 7E also apply.
8.3 Interference Check. You must follow the procedures of Section
8.2.7 of Method 7E to conduct an interference check, substituting
SO2 for NOX as the method pollutant. For dilution-
type measurement systems, you must

[[Page 264]]

use the alternative interference check procedure in Section 16 and a co-
located, unmodified Method 6 sampling train. Quenching in fluorescence
analyzers must be evaluated and remedied unless a dilution system and
ambient-level analyzer is used. This may be done by preparing the
calibration gas to contain within 1 percent of the absolute oxygen and
carbon dioxide content of the measured gas, preparing the calibration
gas in air and using vendor nomographs, or by other acceptable means.
8.4 Sample Collection. You must follow the procedures of section 8.4
of Method 7E.
8.5 Post-Run System Bias Check and Drift Assessment. You must follow
the procedures of section 8.5 of Method 7E.

9.0 Quality Control

Follow quality control procedures in section 9.0 of Method 7E.

10.0 Calibration and Standardization

Follow the procedures for calibration and standardization in section
10.0 of Method 7E.

11.0 Analytical Procedures

Because sample collection and analysis are performed together (see
section 8), additional discussion of the analytical procedure is not
necessary.

12.0 Calculations and Data Analysis

You must follow the applicable procedures for calculations and data
analysis in section 12.0 of Method 7E as applicable, substituting
SO2 for NOX as appropriate.

13.0 Method Performance

13.1 The specifications for the applicable performance checks are
the same as in section 13.0 of Method 7E.
13.2 Alternative Interference Check. The results are acceptable if
the difference between the Method 6C result and the modified Method 6
result is less than 7.0 percent of the Method 6 result for each of the
three test runs. For the purposes of comparison, the Method 6 and 6C
results must be expressed in the same units of measure.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 Alternative Interference Check. You may perform an alternative
interference check consisting of at least three comparison runs between
Method 6C and Method 6. This check validates the Method 6C results at
each particular source category (type of facility) where the check is
performed. When testing under conditions of low concentrations (<15
ppm), this alternative interference check is not allowed.
Note: The procedure described below applies to non-dilution sampling
systems only. If this alternative interference check is used for a
dilution sampling system, use a standard Method 6 sampling train and
extract the sample directly from the exhaust stream at points collocated
with the Method 6C sample probe.
a. Build the modified Method 6 sampling train (flow control valve,
two midget impingers containing 3 percent hydrogen peroxide, and dry gas
meter) shown in Figure 6C-1. Connect the sampling train to the sample
bypass discharge vent. Record the dry gas meter reading before you begin
sampling. Simultaneously collect modified Method 6 and Method 6C
samples. Open the flow control valve in the modified Method 6 train as
you begin to sample with Method 6C. Adjust the Method 6 sampling rate to
1 liter per minute (.10 percent). The sampling time per run must be the
same as for Method 6 plus twice the average measurement system response
time. If your modified Method 6 train does not include a pump, you risk
biasing the results high if you over-pressurize the midget impingers and
cause a leak. You can reduce this risk by cautiously increasing the flow
rate as sampling begins.
b. After completing a run, record the final dry gas meter reading,
meter temperature, and barometric pressure. Recover and analyze the
contents of the midget impingers using the procedures in Method 6.
Determine the average gas concentration reported by Method 6C for the
run.

17.0 References

1. ``EPA Traceability Protocol for Assay and Certification of
Gaseous Calibration Standards'' September 1997 as amended, EPA-600/R-97/
121

18.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 265]]

[GRAPHIC] [TIFF OMITTED] TR15MY06.000

Method 7--Determination of Nitrogen Oxide Emissions From Stationary
Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1 and Method 5.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Nitrogen oxides (NOX), as NO2,
including:
Nitric oxide (NO)............. 10102-43-9
Nitrogen dioxide (NO2)........ 10102-44-0 2-400 mg/dscm
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the measurement of
nitrogen oxides (NOX) emitted from stationary sources.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sample methods.

2.0 Summary of Method

A grab sample is collected in an evacuated flask containing a dilute
sulfuric acid-hydrogen peroxide absorbing solution, and the nitrogen
oxides, except nitrous oxide, are measured colorimetrically using the
phenoldisulfonic acid (PDS) procedure.

3.0 Definitions [Reserved]

4.0 Interferences

Biased results have been observed when sampling under conditions of
high sulfur dioxide concentrations. At or above 2100 ppm SO2,
use five times the H2O2 concentration of the
Method 7 absorbing solution. Laboratory tests have shown that high
concentrations of SO2 (about 2100 ppm) cause low results in
Method 7 and 7A. Increasing the H2O2 concentration
to five times the original concentration eliminates this bias. However,
when no SO2 is present, increasing the concentration by five
times results in a low bias.

[[Page 266]]

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. A schematic of the sampling train used in
performing this method is shown in Figure 7-1. Other grab sampling
systems or equipment, capable of measuring sample volume to within 2.0
percent and collecting a sufficient sample volume to allow analytical
reproducibility to within 5 percent, will be considered acceptable
alternatives, subject to the approval of the Administrator. The
following items are required for sample collection:
6.1.1 Probe. Borosilicate glass tubing, sufficiently heated to
prevent water condensation and equipped with an in-stack or heated out-
of-stack filter to remove particulate matter (a plug of glass wool is
satisfactory for this purpose). Stainless steel or Teflon tubing may
also be used for the probe. Heating is not necessary if the probe
remains dry during the purging period.
6.1.2 Collection Flask. Two-liter borosilicate, round bottom flask,
with short neck and 24/40 standard taper opening, protected against
implosion or breakage.
6.1.3 Flask Valve. T-bore stopcock connected to a 24/40 standard
taper joint.
6.1.4 Temperature Gauge. Dial-type thermometer, or other temperature
gauge, capable of measuring 1 [deg]C (2 [deg]F) intervals from -5 to 50
[deg]C (23 to 122 [deg]F).
6.1.5 Vacuum Line. Tubing capable of withstanding a vacuum of 75 mm
(3 in.) Hg absolute pressure, with ``T'' connection and T-bore stopcock.
6.1.6 Vacuum Gauge. U-tube manometer, 1 meter (39 in.), with 1 mm
(0.04 in.) divisions, or other gauge capable of measuring pressure to
within 2.5 mm (0.10 in.) Hg.
6.1.7 Pump. Capable of evacuating the collection flask to a pressure
equal to or less than 75 mm (3 in.) Hg absolute.
6.1.8 Squeeze Bulb. One-way.
6.1.9 Volumetric Pipette. 25-ml.
6.1.10 Stopcock and Ground Joint Grease. A high-vacuum, high-
temperature chlorofluorocarbon grease is required. Halocarbon 25-5S has
been found to be effective.
6.1.11 Barometer. Mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 2.5 mm (0.1 in.) Hg. See note
in Method 5, section 6.1.2.
6.2 Sample Recovery. The following items are required for sample
recovery:
6.2.1 Graduated Cylinder. 50-ml with 1 ml divisions.
6.2.2 Storage Containers. Leak-free polyethylene bottles.
6.2.3 Wash Bottle. Polyethylene or glass.
6.2.4 Glass Stirring Rod.
6.2.5 Test Paper for Indicating pH. To cover the pH range of 7 to
14.
6.3 Analysis. The following items are required for analysis:
6.3.1 Volumetric Pipettes. Two 1-ml, two 2-ml, one 3-ml, one 4-ml,
two 10-ml, and one 25-ml for each sample and standard.
6.3.2 Porcelain Evaporating Dishes. 175- to 250-ml capacity with lip
for pouring, one for each sample and each standard. The Coors No. 45006
(shallowform, 195-ml) has been found to be satisfactory. Alternatively,
polymethyl pentene beakers (Nalge No. 1203, 150-ml), or glass beakers
(150-ml) may be used. When glass beakers are used, etching of the
beakers may cause solid matter to be present in the analytical step; the
solids should be removed by filtration.
6.3.3 Steam Bath. Low-temperature ovens or thermostatically
controlled hot plates kept below 70 [deg]C (160 [deg]F) are acceptable
alternatives.
6.3.4 Dropping Pipette or Dropper. Three required.
6.3.5 Polyethylene Policeman. One for each sample and each standard.
6.3.6 Graduated Cylinder. 100-ml with 1-ml divisions.

[[Page 267]]

6.3.7 Volumetric Flasks. 50-ml (one for each sample and each
standard), 100-ml (one for each sample and each standard, and one for
the working standard KNO3 solution), and 1000-ml (one).
6.3.8 Spectrophotometer. To measure at 410 nm.
6.3.9 Graduated Pipette. 10-ml with 0.1-ml divisions.
6.3.10 Test Paper for Indicating pH. To cover the pH range of 7 to
14.
6.3.11 Analytical Balance. To measure to within 0.1 mg.

7.0 Reagents and Standards

Unless otherwise indicated, it is intended that all reagents conform
to the specifications established by the Committee on Analytical
Reagents of the American Chemical Society, where such specifications are
available; otherwise, use the best available grade.
7.1 Sample Collection. The following reagents are required for
sampling:
7.1.1 Water. Deionized distilled to conform to ASTM D 1193-77 or 91
Type 3 (incorporated by reference--see Sec. 60.17). The
KMnO4 test for oxidizable organic matter may be omitted when
high concentrations of organic matter are not expected to be present.
7.1.2 Absorbing Solution. Cautiously add 2.8 ml concentrated
H2SO4 to a 1-liter flask partially filled with
water. Mix well, and add 6 ml of 3 percent hydrogen peroxide, freshly
prepared from 30 percent hydrogen peroxide solution. Dilute to 1 liter
of water and mix well. The absorbing solution should be used within 1
week of its preparation. Do not expose to extreme heat or direct
sunlight.
7.2 Sample Recovery. The following reagents are required for sample
recovery:
7.2.1 Water. Same as in 7.1.1.
7.2.2 Sodium Hydroxide, 1 N. Dissolve 40 g NaOH in water, and dilute
to 1 liter.
7.3 Analysis. The following reagents and standards are required for
analysis:
7.3.1 Water. Same as in 7.1.1.
7.3.2 Fuming Sulfuric Acid. 15 to 18 percent by weight free sulfur
trioxide. HANDLE WITH CAUTION.
7.3.3 Phenol. White solid.
7.3.4 Sulfuric Acid. Concentrated, 95 percent minimum assay.
7.3.5 Potassium Nitrate (KNO3). Dried at 105 to 110
[deg]C (221 to 230 [deg]F) for a minimum of 2 hours just prior to
preparation of standard solution.
7.3.6 Standard KNO3 Solution. Dissolve exactly 2.198 g of
dried KNO3 in water, and dilute to 1 liter with water in a
1000-ml volumetric flask.
7.3.7 Working Standard KNO3 Solution. Dilute 10 ml of the
standard solution to 100 ml with water. One ml of the working standard
solution is equivalent to 100 g nitrogen dioxide
(NO2).
7.3.8 Phenoldisulfonic Acid Solution. Dissolve 25 g of pure white
phenol solid in 150 ml concentrated sulfuric acid on a steam bath. Cool,
add 75 ml fuming sulfuric acid (15 to 18 percent by weight free sulfur
trioxide--HANDLE WITH CAUTION), and heat at 100 [deg]C (212 [deg]F) for
2 hours. Store in a dark, stoppered bottle.
7.3.9 Concentrated Ammonium Hydroxide.

8.0 Sample Collection, Preservation, Storage and Transport

8.1 Sample Collection.
8.1.1 Flask Volume. The volume of the collection flask and flask
valve combination must be known prior to sampling. Assemble the flask
and flask valve, and fill with water to the stopcock. Measure the volume
of water to 10 ml. Record this volume on the flask.
8.1.2 Pipette 25 ml of absorbing solution into a sample flask,
retaining a sufficient quantity for use in preparing the calibration
standards. Insert the flask valve stopper into the flask with the valve
in the ``purge'' position. Assemble the sampling train as shown in
Figure 7-1, and place the probe at the sampling point. Make sure that
all fittings are tight and leak-free, and that all ground glass joints
have been greased properly with a high-vacuum, high temperature
chlorofluorocarbon-based stopcock grease. Turn the flask valve and the
pump valve to their ``evacuate'' positions. Evacuate the flask to 75 mm
(3 in.) Hg absolute pressure, or less. Evacuation to a pressure
approaching the vapor pressure of water at the existing temperature is
desirable. Turn the pump valve to its ``vent'' position, and turn off
the pump. Check for leakage by observing the manometer for any pressure
fluctuation. (Any variation greater than 10 mm (0.4 in.) Hg over a
period of 1 minute is not acceptable, and the flask is not to be used
until the leakage problem is corrected. Pressure in the flask is not to
exceed 75 mm (3 in.) Hg absolute at the time sampling is commenced.)
Record the volume of the flask and valve (Vf), the flask
temperature (Ti), and the barometric pressure. Turn the flask
valve counterclockwise to its ``purge'' position, and do the same with
the pump valve. Purge the probe and the vacuum tube using the squeeze
bulb. If condensation occurs in the probe and the flask valve area, heat
the probe, and purge until the condensation disappears. Next, turn the
pump valve to its ``vent'' position. Turn the flask valve clockwise to
its ``evacuate'' position, and record the difference in the mercury
levels in the manometer. The absolute internal pressure in the flask
(Pi) is equal to the barometric pressure less the manometer
reading. Immediately turn the flask valve to the ``sample'' position,
and permit the gas to enter the flask until pressures in the flask and
sample line (i.e., duct, stack) are equal. This will usually require
about 15 seconds; a longer period indicates a plug in the probe, which
must be

[[Page 268]]

corrected before sampling is continued. After collecting the sample,
turn the flask valve to its ``purge'' position, and disconnect the flask
from the sampling train.
8.1.3 Shake the flask for at least 5 minutes.
8.1.4 If the gas being sampled contains insufficient oxygen for the
conversion of NO to NO2 (e.g., an applicable subpart of the
standards may require taking a sample of a calibration gas mixture of NO
in N2), then introduce oxygen into the flask to permit this
conversion. Oxygen may be introduced into the flask by one of three
methods: (1) Before evacuating the sampling flask, flush with pure
cylinder oxygen, then evacuate flask to 75 mm (3 in.) Hg absolute
pressure or less; or (2) inject oxygen into the flask after sampling; or
(3) terminate sampling with a minimum of 50 mm (2 in.) Hg vacuum
remaining in the flask, record this final pressure, and then vent the
flask to the atmosphere until the flask pressure is almost equal to
atmospheric pressure.
8.2 Sample Recovery. Let the flask sit for a minimum of 16 hours,
and then shake the contents for 2 minutes.
8.2.1 Connect the flask to a mercury filled U-tube manometer. Open
the valve from the flask to the manometer, and record the flask
temperature (Tf), the barometric pressure, and the difference
between the mercury levels in the manometer. The absolute internal
pressure in the flask (Pf) is the barometric pressure less
the manometer reading. Transfer the contents of the flask to a leak-free
polyethylene bottle. Rinse the flask twice with 5 ml portions of water,
and add the rinse water to the bottle. Adjust the pH to between 9 and 12
by adding 1 N NaOH, dropwise (about 25 to 35 drops). Check the pH by
dipping a stirring rod into the solution and then touching the rod to
the pH test paper. Remove as little material as possible during this
step. Mark the height of the liquid level so that the container can be
checked for leakage after transport. Label the container to identify
clearly its contents. Seal the container for shipping.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.1.......................... Spectrophotometer Ensure linearity of
calibration. spectrophotometer
response to
standards.
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 Spectrophotometer.
10.1.1 Optimum Wavelength Determination.
10.1.1.1 Calibrate the wavelength scale of the spectrophotometer
every 6 months. The calibration may be accomplished by using an energy
source with an intense line emission such as a mercury lamp, or by using
a series of glass filters spanning the measuring range of the
spectrophotometer. Calibration materials are available commercially and
from the National Institute of Standards and Technology. Specific
details on the use of such materials should be supplied by the vendor;
general information about calibration techniques can be obtained from
general reference books on analytical chemistry. The wavelength scale of
the spectrophotometer must read correctly within 5 nm at all calibration
points; otherwise, repair and recalibrate the spectrophotometer. Once
the wavelength scale of the spectrophotometer is in proper calibration,
use 410 nm as the optimum wavelength for the measurement of the
absorbance of the standards and samples.
10.1.1.2 Alternatively, a scanning procedure may be employed to
determine the proper measuring wavelength. If the instrument is a
double-beam spectrophotometer, scan the spectrum between 400 and 415 nm
using a 200 g NO2 standard solution in the sample
cell and a blank solution in the reference cell. If a peak does not
occur, the spectrophotometer is probably malfunctioning and should be
repaired. When a peak is obtained within the 400 to 415 nm range, the
wavelength at which this peak occurs shall be the optimum wavelength for
the measurement of absorbance of both the standards and the samples. For
a single-beam spectrophotometer, follow the scanning procedure described
above, except scan separately the blank and standard solutions. The
optimum wavelength shall be the wavelength at which the maximum
difference in absorbance between the standard and the blank occurs.
10.1.2 Determination of Spectrophotometer Calibration Factor
Kc. Add 0 ml, 2.0 ml, 4.0 ml, 6.0 ml, and 8.0 ml of the
KNO3 working standard solution (1 ml = 100 g
NO2) to a series of five 50-ml volumetric flasks. To each
flask, add 25 ml of absorbing solution and 10 ml water. Add 1 N NaOH to
each flask until the pH is between 9 and 12 (about 25 to 35 drops).
Dilute to the mark with water. Mix thoroughly, and pipette a 25-ml
aliquot of each solution into a separate porcelain evaporating dish.
Beginning with the evaporation step, follow the analysis procedure of
section 11.2 until the solution has been transferred to the 100-ml
volumetric flask and diluted to the mark. Measure the absorbance of each
solution at the optimum wavelength as determined in section 10.2.1. This
calibration procedure must be repeated on each day that samples are
analyzed. Calculate the spectrophotometer calibration factor as shown in
section 12.2.

[[Page 269]]

10.1.3 Spectrophotometer Calibration Quality Control. Multiply the
absorbance value obtained for each standard by the Kc factor
(reciprocal of the least squares slope) to determine the distance each
calibration point lies from the theoretical calibration line. The
difference between the calculated concentration values and the actual
concentrations (i.e., 100, 200, 300, and 400 g NO2)
should be less than 7 percent for all standards.
10.2 Barometer. Calibrate against a mercury barometer or NIST-
traceable barometer prior to the field test.
10.3 Temperature Gauge. Calibrate dial thermometers against mercury-
in-glass thermometers. An alternative mercury-free thermometer may be
used if the thermometer is, at a minimum, equivalent in terms of
performance or suitably effective for the specific temperature
measurement application.
10.4 Vacuum Gauge. Calibrate mechanical gauges, if used, against a
mercury manometer such as that specified in section 6.1.6.
10.5 Analytical Balance. Calibrate against standard weights.

11.0 Analytical Procedures

11.1 Sample Loss Check. Note the level of the liquid in the
container, and confirm whether any sample was lost during shipment. Note
this on the analytical data sheet. If a noticeable amount of leakage has
occurred, either void the sample or use methods, subject to the approval
of the Administrator, to correct the final results.
11.2 Sample Preparation. Immediately prior to analysis, transfer the
contents of the shipping container to a 50 ml volumetric flask, and
rinse the container twice with 5 ml portions of water. Add the rinse
water to the flask, and dilute to mark with water; mix thoroughly.
Pipette a 25-ml aliquot into the porcelain evaporating dish. Return any
unused portion of the sample to the polyethylene storage bottle.
Evaporate the 25-ml aliquot to dryness on a steam bath, and allow to
cool. Add 2 ml phenoldisulfonic acid solution to the dried residue, and
triturate thoroughly with a polyethylene policeman. Make sure the
solution contacts all the residue. Add 1 ml water and 4 drops of
concentrated sulfuric acid. Heat the solution on a steam bath for 3
minutes with occasional stirring. Allow the solution to cool, add 20 ml
water, mix well by stirring, and add concentrated ammonium hydroxide,
dropwise, with constant stirring, until the pH is 10 (as determined by
pH paper). If the sample contains solids, these must be removed by
filtration (centrifugation is an acceptable alternative, subject to the
approval of the Administrator) as follows: Filter through Whatman No. 41
filter paper into a 100-ml volumetric flask. Rinse the evaporating dish
with three 5-ml portions of water. Filter these three rinses. Wash the
filter with at least three 15-ml portions of water. Add the filter
washings to the contents of the volumetric flask, and dilute to the mark
with water. If solids are absent, the solution can be transferred
directly to the 100-ml volumetric flask and diluted to the mark with
water.
11.3 Sample Analysis. Mix the contents of the flask thoroughly, and
measure the absorbance at the optimum wavelength used for the standards
(Section 10.2.1), using the blank solution as a zero reference. Dilute
the sample and the blank with equal volumes of water if the absorbance
exceeds A4, the absorbance of the 400-g
NO2 standard (see section 10.2.2).

12.0 Data Analysis and Calculations

Carry out the calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after final
calculations.
12.1 12.1 Nomenclature
A = Absorbance of sample.
A1 = Absorbance of the 100-g NO2
standard.
A2 = Absorbance of the 200-g NO2
standard.
A3 = Absorbance of the 300-g NO2
standard.
A4 = Absorbance of the 400-g NO2
standard.
C = Concentration of NOX as NO2, dry basis,
corrected to standard conditions, mg/dsm\3\ (lb/dscf).
F = Dilution factor (i.e., 25/5, 25/10, etc., required only if sample
dilution was needed to reduce the absorbance into the range of
the calibration).
Kc = Spectrophotometer calibration factor.
M = Mass of NOX as NO2 in gas sample, g.
Pf = Final absolute pressure of flask, mm Hg (in. Hg).
Pi = Initial absolute pressure of flask, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
Tf = Final absolute temperature of flask, [deg]K ([deg]R).
Ti = Initial absolute temperature of flask, [deg]K ([deg]R).
Tstd = Standard absolute temperature, 293 [deg]K (528[deg]R).
Vsc = Sample volume at standard conditions (dry basis), ml.
Vf = Volume of flask and valve, ml.
Va = Volume of absorbing solution, 25 ml.
12.2 Spectrophotometer Calibration Factor.
[GRAPHIC] [TIFF OMITTED] TR17OC00.200

[[Page 270]]

12.3 Sample Volume, Dry Basis, Corrected to Standard Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.201

Where:

K1 = 0.3858 [deg]K/mm Hg for metric units,
K1 = 17.65 [deg]R/in. Hg for English units.

12.4 Total g NO2 per sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.202

Where:
2 = 50/25, the aliquot factor.

Note: If other than a 25-ml aliquot is used for analysis, the factor
2 must be replaced by a corresponding factor.

12.5 Sample Concentration, Dry Basis, Corrected to Standard
Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.203

Where:

K2 = 10\3\ (mg/m\3\)/(g/ml) for metric units,
K2 = 6.242 x 10^-5 (lb/scf)/(g/ml) for
English units.

13.0 Method Performance

13.1 Range. The analytical range of the method has been determined
to be 2 to 400 milligrams NOX (as NO2) per dry
standard cubic meter, without having to dilute the sample.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Standard Methods of Chemical Analysis. 6th ed. New York, D. Van
Nostrand Co., Inc. 1962. Vol. 1, pp. 329-330.
2. Standard Method of Test for Oxides of Nitrogen in Gaseous
Combustion Products (Phenoldisulfonic Acid Procedure). In: 1968 Book of
ASTM Standards, Part 26. Philadelphia, PA. 1968. ASTM Designation D
1608-60, pp. 725-729.
3. Jacob, M.B. The Chemical Analysis of Air Pollutants. New York.
Interscience Publishers, Inc. 1960. Vol. 10, pp. 351-356.
4. Beatty, R.L., L.B. Berger, and H.H. Schrenk. Determination of
Oxides of Nitrogen by the Phenoldisulfonic Acid Method. Bureau of Mines,
U.S. Dept. of Interior. R.I. 3687. February 1943.
5. Hamil, H.F. and D.E. Camann. Collaborative Study of Method for
the Determination of Nitrogen Oxide Emissions from Stationary Sources
(Fossil Fuel-Fired Steam Generators). Southwest Research Institute
Report for Environmental Protection Agency. Research Triangle Park, NC.
October 5, 1973.
6. Hamil, H.F. and R.E. Thomas. Collaborative Study of Method for
the Determination of Nitrogen Oxide Emissions from Stationary Sources
(Nitric Acid Plants). Southwest Research Institute Report for
Environmental Protection Agency. Research Triangle Park, NC. May 8,
1974.
7. Stack Sampling Safety Manual (Draft). U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standards,
Research Triangle Park, NC. September 1978.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 271]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.205

Method 7A--Determination of Nitrogen Oxide Emissions From Stationary
Sources (Ion Chromatographic Method)

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 3, Method 5, and
Method 7.

1.0 Scope and Application

1.1 Analytes.

[[Page 272]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Nitrogen oxides (NOX), as NO2,
including:
Nitric oxide (NO)............. 10102-43-9 ....................
Nitrogen dioxide (NO2)........ 10102-44-0 65-655 ppmv
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of NOX emissions from stationary sources.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

A grab sample is collected in an evacuated flask containing a dilute
sulfuric acid-hydrogen peroxide absorbing solution. The nitrogen oxides,
excluding nitrous oxide (N2O), are oxidized to nitrate and
measured by ion chromatography.

3.0 Definitions [Reserved]

4.0 Interferences

5.0 Safety

5.1 This method may involve hazardous materials, operations, and
equipment. This test method may not address all of the safety problems
associated with its use. It is the responsibility of the user of this
test method to establish appropriate safety and health practices and to
determine the applicability of regulatory limitations prior to
performing this test method.
5.2 Corrosive reagents. The following reagents are hazardous.
Personal protective equipment and safe procedures are useful in
preventing chemical splashes. If contact occurs, immediately flush with
copious amounts of water at least 15 minutes. Remove clothing under
shower and decontaminate. Treat residual chemical burns as thermal
burns.
5.2.1 Hydrogen Peroxide (H2O2). Irritating to
eyes, skin, nose, and lungs.
5.2.2 Sulfuric Acid (H2SO4). Rapidly
destructive to body tissue. Will cause third degree burns. Eye damage
may result in blindness. Inhalation may be fatal from spasm of the
larynx, usually within 30 minutes. May cause lung tissue damage with
edema. 3 mg/m\3\ will cause lung damage in uninitiated. 1 mg/m\3\ for 8
hours will cause lung damage or, in higher concentrations, death.
Provide ventilation to limit inhalation. Reacts violently with metals
and organics.

6.0 Equipment and Supplies

6.1 Sample Collection. Same as in Method 7, section 6.1.
6.2 Sample Recovery. Same as in Method 7, section 6.2, except the
stirring rod and pH paper are not needed.
6.3 Analysis. For the analysis, the following equipment and supplies
are required. Alternative instrumentation and procedures will be allowed
provided the calibration precision requirement in section 10.1.2 can be
met.
6.3.1 Volumetric Pipets. Class A;1-, 2-, 4-, 5-ml (two for the set
of standards and one per sample), 6-, 10-, and graduated 5-ml sizes.
6.3.2 Volumetric Flasks. 50-ml (two per sample and one per
standard), 200-ml, and 1-liter sizes.
6.3.3 Analytical Balance. To measure to within 0.1 mg.
6.3.4 Ion Chromatograph. The ion chromatograph should have at least
the following components:
6.3.4.1 Columns. An anion separation or other column capable of
resolving the nitrate ion from sulfate and other species present and a
standard anion suppressor column (optional). Suppressor columns are
produced as proprietary items; however, one can be produced in the
laboratory using the resin available from BioRad Company, 32nd and
Griffin Streets, Richmond, California. Peak resolution can be optimized
by varying the eluent strength or column flow rate, or by experimenting
with alternative columns that may offer more efficient separation. When
using guard columns with the stronger reagent to protect the separation
column, the analyst should allow rest periods between injection
intervals to purge possible sulfate buildup in the guard column.
6.3.4.2 Pump. Capable of maintaining a steady flow as required by
the system.
6.3.4.3 Flow Gauges. Capable of measuring the specified system flow
rate.
6.3.4.4 Conductivity Detector.
6.3.4.5 Recorder. Compatible with the output voltage range of the
detector.

[[Page 273]]

7.0 Reagents and Standards

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sampling. Same as in Method 7, section 8.1.
8.2 Sample Recovery. Same as in Method 7, section 8.2, except delete
the steps on adjusting and checking the pH of the sample. Do not store
the samples more than 4 days between collection and analysis.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.1.......................... Ion Ensure linearity of
chromatographn ion chromatograph
calibration. response to
standards.
------------------------------------------------------------------------

10.0 Calibration and Standardizations

10.1 Ion Chromatograph.
10.1.1 Determination of Ion Chromatograph Calibration Factor S.
Prepare a series of five standards by adding 1.0, 2.0, 4.0, 6.0, and
10.0 ml of working standard solution (25 g/ml) to a series of
five 50-ml volumetric flasks. (The standard masses will equal 25, 50,
100, 150, and 250 g.) Dilute each flask to the mark with water,
and mix well. Analyze with the samples as described in section 11.2, and
subtract the blank from each value. Prepare or calculate a linear
regression plot of the standard masses in g (x-axis) versus
their peak height responses in millimeters (y-axis). (Take peak height
measurements with symmetrical peaks; in all other cases, calculate peak
areas.) From this curve, or equation, determine the slope, and calculate
its reciprocal to denote as the calibration factor, S.
10.1.2 Ion Chromatograph Calibration Quality Control. If any point
on the calibration curve deviates from the line by more than 7 percent
of the concentration at that point, remake and reanalyze that standard.
This deviation can be determined by multiplying S times the peak height
response for each standard. The resultant concentrations must not differ
by more than 7 percent from each known standard mass (i.e., 25, 50, 100,
150, and 250 g).
10.2 Conductivity Detector. Calibrate according to manufacturer's
specifications prior to initial use.
10.3 Barometer. Calibrate against a mercury barometer.
10.4 Temperature Gauge. Calibrate dial thermometers against mercury-
in-glass thermometers. An alternative mercury-free thermometer may be
used if the thermometer is, at a minimum, equivalent in terms of
performance or suitably effective for the specific temperature
measurement application.
10.5 Vacuum Gauge. Calibrate mechanical gauges, if used, against a
mercury manometer such as that specified in section 6.1.6 of Method 7.
10.6 Analytical Balance. Calibrate against standard weights.

11.0 Analytical Procedures

11.1 Sample Preparation.
11.1.1 Note on the analytical data sheet, the level of the liquid in
the container, and whether any sample was lost during shipment. If a
noticeable amount of leakage has occurred, either void the sample or use
methods, subject to the approval of the Administrator, to correct the
final results. Immediately before analysis, transfer the contents of the
shipping container to a 50-ml volumetric flask, and rinse the container
twice with 5 ml portions of water. Add the rinse water to the flask, and
dilute to the mark with water. Mix thoroughly.
11.1.2 Pipet a 5-ml aliquot of the sample into a 50-ml volumetric
flask, and dilute to the mark with water. Mix thoroughly. For each set
of determinations, prepare a reagent

[[Page 274]]

blank by diluting 5 ml of absorbing solution to 50 ml with water.
(Alternatively, eluent solution may be used instead of water in all
sample, standard, and blank dilutions.)
11.2 Analysis.
11.2.1 Prepare a standard calibration curve according to section
10.1.1. Analyze the set of standards followed by the set of samples
using the same injection volume for both standards and samples. Repeat
this analysis sequence followed by a final analysis of the standard set.
Average the results. The two sample values must agree within 5 percent
of their mean for the analysis to be valid. Perform this duplicate
analysis sequence on the same day. Dilute any sample and the blank with
equal volumes of water if the concentration exceeds that of the highest
standard.
11.2.2 Document each sample chromatogram by listing the following
analytical parameters: injection point, injection volume, nitrate and
sulfate retention times, flow rate, detector sensitivity setting, and
recorder chart speed.

12.0 Data Analysis and Calculations

Carry out the calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after final
calculations.
12.1 Sample Volume. Calculate the sample volume Vsc (in ml), on a
dry basis, corrected to standard conditions, using Equation 7-2 of
Method 7.
12.2 Sample Concentration of NOX as NO2.
12.2.1 Calculate the sample concentration C (in mg/dscm) as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.206

Where:

H = Sample peak height, mm.
S = Calibration factor, g/mm.
F = Dilution factor (required only if sample dilution was needed to
reduce the concentration into the range of calibration),
dimensionless.
10\4\ = 1:10 dilution times conversion factor of: (mg/10\3\
g)(10\6\ ml/m\3\).

12.2.2 If desired, the concentration of NO2 may be
calculated as ppm NO2 at standard conditions as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.207

Where:

0.5228 = ml/mg NO2.

13.0 Method Performance

13.1 Range. The analytical range of the method is from 125 to 1250
mg NOX/m\3\ as NO2 (65 to 655 ppmv), and higher
concentrations may be analyzed by diluting the sample. The lower
detection limit is approximately 19 mg/m\3\ (10 ppmv), but may vary
among instruments.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Mulik, J.D., and E. Sawicki. Ion Chromatographic Analysis of
Environmental Pollutants. Ann Arbor, Ann Arbor Science Publishers, Inc.
Vol. 2, 1979.
2. Sawicki, E., J.D. Mulik, and E. Wittgenstein. Ion Chromatographic
Analysis of Environmental Pollutants. Ann Arbor, Ann Arbor Science
Publishers, Inc. Vol. 1. 1978.
3. Siemer, D.D. Separation of Chloride and Bromide from Complex
Matrices Prior to Ion Chromatographic Determination. Anal. Chem.
52(12):1874-1877. October 1980.
4. Small, H., T.S. Stevens, and W.C. Bauman. Novel Ion Exchange
Chromatographic Method Using Conductimetric Determination. Anal. Chem.
47(11):1801. 1975.
5. Yu, K.K., and P.R. Westlin. Evaluation of Reference Method 7
Flask Reaction Time. Source Evaluation Society Newsletter. 4(4).
November 1979. 10 pp.
6. Stack Sampling Safety Manual (Draft). U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standard, Research
Triangle Park, NC. September 1978.

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 7B--Determination of Nitrogen Oxide Emissions From Stationary
Sources (Ultraviolet Spectrophotometric Method)

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 5, and Method 7.

1.0 Scope and Application

1.1 Analytes.

[[Page 275]]

Nitric oxide (NO)............. 10102-43-9
Nitrogen dioxide (NO2)........ 10102-44-0 30-786 ppmv
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of NOX emissions from nitric acid plants.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A grab sample is collected in an evacuated flask containing a
dilute sulfuric acid-hydrogen peroxide absorbing solution; the
NOX, excluding nitrous oxide (N2O), are measured
by ultraviolet spectrophotometry.

3.0 Definition [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

5.1 This method may involve hazardous materials, operations, and
equipment. This test method may not address all of the safety problems
associated with its use. It is the responsibility of the user of this
test method to establish appropriate safety and health practices and to
determine the applicability of regulatory limitations prior to
performing this test method.
5.2 Corrosive reagents. The following reagents are hazardous.
Personal protective equipment and safe procedures are useful in
preventing chemical splashes. If contact occurs, immediately flush with
copious amounts of water at least 15 minutes. Remove clothing under
shower and decontaminate. Treat residual chemical burn as thermal burn.
5.2.1 Hydrogen Peroxide (H2O2). Irritating to
eyes, skin, nose, and lungs.
5.2.2 Sodium Hydroxide (NaOH). Causes severe damage to eyes and
skin. Inhalation causes irritation to nose, throat, and lungs. Reacts
exothermically with limited amounts of water.
5.2.3 Sulfuric Acid (H2SO4). Rapidly
destructive to body tissue. Will cause third degree burns. Eye damage
may result in blindness. Inhalation may be fatal from spasm of the
larynx, usually within 30 minutes. May cause lung tissue damage with
edema. 3 mg/m\3\ will cause lung damage in uninitiated. 1 mg/m\3\ for 8
hours will cause lung damage or, in higher concentrations, death.
Provide ventilation to limit inhalation. Reacts violently with metals
and organics.

6.0 Equipment and Supplies

6.1 Sample Collection. Same as Method 7, section 6.1.
6.2 Sample Recovery. The following items are required for sample
recovery:
6.2.1 Wash Bottle. Polyethylene or glass.
6.2.2 Volumetric Flasks. 100-ml (one for each sample).
6.3 Analysis. The following items are required for analysis:
6.3.1 Volumetric Pipettes. 5-, 10-, 15-, and 20-ml to make standards
and sample dilutions.
6.3.2 Volumetric Flasks. 1000- and 100-ml for preparing standards
and dilution of samples.
6.3.3 Spectrophotometer. To measure ultraviolet absorbance at 210
nm.
6.3.4 Analytical Balance. To measure to within 0.1 mg.

7.0 Reagents and Standards

Note: Unless otherwise indicated, all reagents are to conform to the
specifications established by the Committee on Analytical Reagents of
the American Chemical Society, where such specifications are available.
Otherwise, use the best available grade.

7.1 Sample Collection. Same as Method 7, section 7.1. It is
important that the amount of hydrogen peroxide in the absorbing solution
not be increased. Higher concentrations of peroxide may interfere with
sample analysis.
7.2 Sample Recovery. Same as Method 7, section 7.2.
7.3 Analysis. Same as Method 7, sections 7.3.1, 7.3.3, and 7.3.4,
with the addition of the following:
7.3.1 Working Standard KNO3 Solution. Dilute 10 ml of the
standard solution to 1000 ml with water. One milliliter of the working
standard is equivalent to 10 g NO2.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sample Collection. Same as Method 7, section 8.1.
8.2 Sample Recovery.
8.2.1 Let the flask sit for a minimum of 16 hours, and then shake
the contents for 2 minutes.
8.2.2 Connect the flask to a mercury filled U-tube manometer. Open
the valve from the flask to the manometer, and record the flask
temperature (Tf), the barometric pressure, and the difference
between the mercury levels in the manometer. The absolute internal
pressure in the flask (Pf) is the barometric pressure less
the manometer reading.
8.2.3 Transfer the contents of the flask to a leak-free wash bottle.
Rinse the flask three times with 10-ml portions of water, and add

[[Page 276]]

to the bottle. Mark the height of the liquid level so that the container
can be checked for leakage after transport. Label the container to
identify clearly its contents. Seal the container for shipping.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.1.......................... Spectrophotometer Ensures linearity of
calibration. spectrophotometer
response to
standards.
------------------------------------------------------------------------

10.0 Calibration and Standardizations

Same as Method 7, sections 10.2 through 10.5, with the addition of
the following:
10.1 Determination of Spectrophotometer Standard Curve. Add 0 ml, 5
ml, 10 ml, 15 ml, and 20 ml of the KNO3 working standard
solution (1 ml = 10 g NO2) to a series of five 100-
ml volumetric flasks. To each flask, add 5 ml of absorbing solution.
Dilute to the mark with water. The resulting solutions contain 0.0, 50,
100, 150, and 200 g NO2, respectively. Measure the
absorbance by ultraviolet spectrophotometry at 210 nm, using the blank
as a zero reference. Prepare a standard curve plotting absorbance vs.
g NO2.

Note: If other than a 20-ml aliquot of sample is used for analysis,
then the amount of absorbing solution in the blank and standards must be
adjusted such that the same amount of absorbing solution is in the blank
and standards as is in the aliquot of sample used.

10.1.1 Calculate the spectrophotometer calibration factor as
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.208

Where:

Mi = Mass of NO2 in standard i, g.
Ai = Absorbance of NO2 standard i.
n = Total number of calibration standards.

10.1.2 For the set of calibration standards specified here, Equation
7B-1 simplifies to the following:
[GRAPHIC] [TIFF OMITTED] TR17OC00.209

10.2 Spectrophotometer Calibration Quality Control. Multiply the
absorbance value obtained for each standard by the Kc factor
(reciprocal of the least squares slope) to determine the distance each
calibration point lies from the theoretical calibration line. The
difference between the calculated concentration values and the actual
concentrations (i.e., 50, 100, 150, and 200 g NO2)
should be less than 7 percent for all standards.

11.0 Analytical Procedures

12.0 Data Analysis and Calculations

Same as Method 7, section 12.0, except replace section 12.3 with the
following:
12.1 Total g NO2 Per Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.211

Where:

5 = 100/20, the aliquot factor.

[[Page 277]]

Note: If other than a 20-ml aliquot is used for analysis, the factor
5 must be replaced by a corresponding factor.

13.0 Method Performance

13.1 Range. The analytical range of the method as outlined has been
determined to be 57 to 1500 milligrams NOX (as
NO2) per dry standard cubic meter, or 30 to 786 parts per
million by volume (ppmv) NOX.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. National Institute for Occupational Safety and Health.
Recommendations for Occupational Exposure to Nitric Acid. In:
Occupational Safety and Health Reporter. Washington, D.C. Bureau of
National Affairs, Inc. 1976. p. 149.
2. Rennie, P.J., A.M. Sumner, and F.B. Basketter. Determination of
Nitrate in Raw, Potable, and Waste Waters by Ultraviolet
Spectrophotometry. Analyst. 104:837. September 1979.

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 7C--Determination of Nitrogen Oxide Emissions From Stationary
Sources (Alkaline Permanganate/Colorimetric Method)

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 3, Method 6 and
Method 7.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS no. Sensitivity
------------------------------------------------------------------------
Nitrogen oxides (NOX), as NO2,
including:
Nitric oxide (NO)............. 10102-43-9 ....................
Nitrogen dioxide (NO2)........ 10102-44-07 ppmv
------------------------------------------------------------------------

1.2 Applicability. This method applies to the measurement of
NOX emissions from fossil-fuel fired steam generators,
electric utility plants, nitric acid plants, or other sources as
specified in the regulations.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

An integrated gas sample is extracted from the stack and passed
through impingers containing an alkaline potassium permanganate
solution; NOX (NO + NO2) emissions are oxidized to
NO2 and NO3. Then NO3^-is
reduced to NO2^-with cadmium, and the
NO2^-is analyzed colorimetrically.

3.0 Definitions [Reserved]

4.0 Interferences

Possible interferents are sulfur dioxides (SO2) and
ammonia (NH3).
4.1 High concentrations of SO2 could interfere because
SO2 consumes MnO4 (as does NOX) and,
therefore, could reduce the NOX collection efficiency.
However, when sampling emissions from a coal-fired electric utility
plant burning 2.1 percent sulfur coal with no control of SO2
emissions, collection efficiency was not reduced. In fact, calculations
show that sampling 3000 ppm SO2 will reduce the
MnO4 concentration by only 5 percent if all the
SO2 is consumed in the first impinger.
4.2 Ammonia (NH3) is slowly oxidized to
NO3^- by the absorbing solution. At 100 ppm
NH3 in the gas stream, an interference of 6 ppm
NOX (11 mg NO2/m\3\) was observed when the sample
was analyzed 10 days after collection. Therefore, the method may not be
applicable to plants using NH3 injection to control
NOX emissions unless means are taken to correct the results.
An equation has been developed to allow quantification of the
interference and is discussed in Reference 5 of section 16.0.

5.0 Safety

[[Page 278]]

5.2.1 Hydrochloric Acid (HCl). Highly toxic and corrosive. Causes
severe damage to skin. Vapors are highly irritating to eyes, skin, nose,
and lungs, causing severe damage. May cause bronchitis, pneumonia, or
edema of lungs. Exposure to vapor concentrations of 0.13 to 0.2 percent
can be lethal in minutes. Will react with metals, producing hydrogen.
5.2.2 Oxalic Acid (COOH)2. Poisonous. Irritating to eyes,
skin, nose, and throat.
5.2.3 Sodium Hydroxide (NaOH). Causes severe damage to eye tissues
and to skin. Inhalation causes irritation to nose, throat, and lungs.
Reacts exothermically with small amounts of water.
5.2.4 Potassium Permanganate (KMnO4). Caustic, strong
oxidizer. Avoid bodily contact with.

6.0 Equipment and Supplies

6.1 Sample Collection and Sample Recovery. A schematic of the Method
7C sampling train is shown in Figure 7C-1, and component parts are
discussed below. Alternative apparatus and procedures are allowed
provided acceptable accuracy and precision can be demonstrated to the
satisfaction of the Administrator.
6.1.1 Probe. Borosilicate glass tubing, sufficiently heated to
prevent water condensation and equipped with an in-stack or heated out-
of-stack filter to remove particulate matter (a plug of glass wool is
satisfactory for this purpose). Stainless steel or Teflon tubing may
also be used for the probe.
6.1.2 Impingers. Three restricted-orifice glass impingers, having
the specifications given in Figure 7C-2, are required for each sampling
train. The impingers must be connected in series with leak-free glass
connectors. Stopcock grease may be used, if necessary, to prevent
leakage. (The impingers can be fabricated by a glass blower if not
available commercially.)
6.1.3 Glass Wool, Stopcock Grease, Drying Tube, Valve, Pump,
Barometer, and Vacuum Gauge and Rotameter. Same as in Method 6, sections
6.1.1.3, 6.1.1.4, 6.1.1.6, 6.1.1.7, 6.1.1.8, 6.1.2, and 6.1.3,
respectively.
6.1.4 Rate Meter. Rotameter, or equivalent, accurate to within 2
percent at the selected flow rate of between 400 and 500 ml/min (0.014
to 0.018 cfm). For rotameters, a range of 0 to 1 liter/min (0 to 0.035
cfm) is recommended.
6.1.5 Volume Meter. Dry gas meter (DGM) capable of measuring the
sample volume under the sampling conditions of 400 to 500 ml/min (0.014
to 0.018 cfm) for 60 minutes within an accuracy of 2 percent.
6.1.6 Filter. To remove NOX from ambient air, prepared by
adding 20 g of 5-angstrom molecular sieve to a cylindrical tube (e.g., a
polyethylene drying tube).
6.1.7 Polyethylene Bottles. 1-liter, for sample recovery.
6.1.8 Funnel and Stirring Rods. For sample recovery.
6.2 Sample Preparation and Analysis.
6.2.1 Hot Plate. Stirring type with 50- by 10-mm Teflon-coated
stirring bars.
6.2.2 Beakers. 400-, 600-, and 1000-ml capacities.
6.2.3 Filtering Flask. 500-ml capacity with side arm.
6.2.4 Buchner Funnel. 75-mm ID, with spout equipped with a 13-mm ID
by 90-mm long piece of Teflon tubing to minimize possibility of
aspirating sample solution during filtration.
6.2.5 Filter Paper. Whatman GF/C, 7.0-cm diameter.
6.2.6 Stirring Rods.
6.2.7 Volumetric Flasks. 100-, 200- or 250-, 500-, and 1000-ml
capacity.
6.2.8 Watch Glasses. To cover 600- and 1000-ml beakers.
6.2.9 Graduated Cylinders. 50- and 250-ml capacities.
6.2.10 Pipettes. Class A.
6.2.11 pH Meter. To measure pH from 0.5 to 12.0.
6.2.12 Burette. 50-ml with a micrometer type stopcock. (The stopcock
is Catalog No. 8225-t-05, Ace Glass, Inc., Post Office Box 996,
Louisville, Kentucky 50201.) Place a glass wool plug in bottom of
burette. Cut off burette at a height of 43 cm (17 in.) from the top of
plug, and have a blower attach a glass funnel to top of burette such
that the diameter of the burette remains essentially unchanged. Other
means of attaching the funnel are acceptable.
6.2.13 Glass Funnel. 75-mm ID at the top.
6.2.14 Spectrophotometer. Capable of measuring absorbance at 540 nm;
1-cm cells are adequate.
6.2.15 Metal Thermometers. Bimetallic thermometers, range 0 to 150
[deg]C (32 to 300 [deg]F).
6.2.16 Culture Tubes. 20-by 150-mm, Kimax No. 45048.
6.2.17 Parafilm ``M.'' Obtained from American Can Company,
Greenwich, Connecticut 06830.
6.2.18 CO2 Measurement Equipment. Same as in Method 3,
section 6.0.

7.0 Reagents and Standards

[[Page 279]]

7.2.2 Oxalic Acid Solution. Dissolve 48 g of oxalic acid
[(COOH)22H2O] in water, and dilute to 500 ml. Do
not heat the solution.
7.2.3 Sodium Hydroxide, 0.5 N. Dissolve 20 g of NaOH in water, and
dilute to 1 liter.
7.2.4 Sodium Hydroxide, 10 N. Dissolve 40 g of NaOH in water, and
dilute to 100 ml.
7.2.5 Ethylenediamine Tetraacetic Acid (EDTA) Solution, 6.5 percent
(w/v). Dissolve 6.5 g of EDTA (disodium salt) in water, and dilute to
100 ml. Dissolution is best accomplished by using a magnetic stirrer.
7.2.6 Column Rinse Solution. Add 20 ml of 6.5 percent EDTA solution
to 960 ml of water, and adjust the pH to between 11.7 and 12.0 with 0.5
N NaOH.
7.2.7 Hydrochloric Acid (HCl), 2 N. Add 86 ml of concentrated HCl to
a 500 ml-volumetric flask containing water, dilute to volume, and mix
well. Store in a glass-stoppered bottle.
7.2.8 Sulfanilamide Solution. Add 20 g of sulfanilamide (melting
point 165 to 167 [deg]C (329 to 333 [deg]F)) to 700 ml of water. Add,
with mixing, 50 ml concentrated phosphoric acid (85 percent), and dilute
to 1000 ml. This solution is stable for at least 1 month, if
refrigerated.
7.2.9 N-(1-Naphthyl)-Ethylenediamine Dihydrochloride (NEDA)
Solution. Dissolve 0.5 g of NEDA in 500 ml of water. An aqueous solution
should have one absorption peak at 320 nm over the range of 260 to 400
nm. NEDA that shows more than one absorption peak over this range is
impure and should not be used. This solution is stable for at least 1
month if protected from light and refrigerated.
7.2.10 Cadmium. Obtained from Matheson Coleman and Bell, 2909
Highland Avenue, Norwood, Ohio 45212, as EM Laboratories Catalog No.
2001. Prepare by rinsing in 2 N HCl for 5 minutes until the color is
silver-grey. Then rinse the cadmium with water until the rinsings are
neutral when tested with pH paper. CAUTION: H2 is liberated
during preparation. Prepare in an exhaust hood away from any flame or
combustion source.
7.2.11 Sodium Sulfite (NaNO2) Standard Solution, Nominal
Concentration, 1000 g NO2^-/ml. Desiccate
NaNO2 overnight. Accurately weigh 1.4 to 1.6 g of NaNO2
(assay of 97 percent NaNO2 or greater), dissolve in water,
and dilute to 1 liter. Calculate the exact NO2-concentration
using Equation 7C-1 in section 12.2. This solution is stable for at
least 6 months under laboratory conditions.
7.2.12 Potassium Nitrate (KNO3) Standard Solution. Dry
KNO3 at 110 [deg]C (230 [deg]F) for 2 hours, and cool in a
desiccator. Accurately weigh 9 to 10 g of KNO3 to within 0.1
mg, dissolve in water, and dilute to 1 liter. Calculate the exact
NO3^- concentration using Equation 7C-2 in section
12.3. This solution is stable for 2 months without preservative under
laboratory conditions.
7.2.13 Spiking Solution. Pipette 7 ml of the KNO3
standard into a 100-ml volumetric flask, and dilute to volume.
7.2.14 Blank Solution. Dissolve 2.4 g of KMnO4 and 1.2 g
of NaOH in 96 ml of water. Alternatively, dilute 60 ml of
KMnO4/NaOH solution to 100 ml.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Preparation of Sampling Train. Add 200 ml of KMnO4/
NaOH solution (Section 7.1.2) to each of three impingers, and assemble
the train as shown in Figure 7C-1. Adjust the probe heater to a
temperature sufficient to prevent water condensation.
8.2 Leak-Checks. Same as in Method 6, section 8.2.
8.3 Sample Collection.
8.3.1 Record the initial DGM reading and barometric pressure.
Determine the sampling point or points according to the appropriate
regulations (e.g., Sec. 60.46(b)(5) of 40 CFR Part 60). Position the
tip of the probe at the sampling point, connect the probe to the first
impinger, and start the pump. Adjust the sample flow to a value between
400 and 500 ml/min (0.014 and 0.018 cfm). CAUTION: DO NOT EXCEED THESE
FLOW RATES. Once adjusted, maintain a constant flow rate during the
entire sampling run. Sample for 60 minutes. For relative accuracy (RA)
testing of continuous emission monitors, the minimum sampling time is 1
hour, sampling 20 minutes at each traverse point.

Note: When the SO2 concentration is greater than 1200
ppm, the sampling time may have to be reduced to 30 minutes to eliminate
plugging of the impinger orifice with MnO2. For RA tests with
SO2 greater than 1200 ppm, sample for 30 minutes (10 minutes
at each point).

8.3.2 Record the DGM temperature, and check the flow rate at least
every 5 minutes. At the conclusion of each run, turn off the pump,
remove the probe from the stack, and record the final readings. Divide
the sample volume by the sampling time to determine the average flow
rate. Conduct the mandatory post-test leak-check. If a leak is found,
void the test run, or use procedures acceptable to the Administrator to
adjust the sample volume for the leakage.
8.4 CO2 Measurement. During sampling, measure the
CO2 content of the stack gas near the sampling point using
Method 3. The single-point grab sampling procedure is adequate, provided
the measurements are made at least three times (near the start, midway,
and before the end of a run), and the average CO2
concentration is computed. The Orsat or Fyrite analyzer may be used for
this analysis.
8.5 Sample Recovery. Disconnect the impingers. Pour the contents of
the impingers into a 1-liter polyethylene bottle

[[Page 280]]

using a funnel and a stirring rod (or other means) to prevent spillage.
Complete the quantitative transfer by rinsing the impingers and
connecting tubes with water until the rinsings are clear to light pink,
and add the rinsings to the bottle. Mix the sample, and mark the
solution level. Seal and identify the sample container.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.2, 10.1-10.3................ Sampling Ensure accurate
equipment leak- measurement of
check and sample volume.
calibration.
10.4.......................... Spectrophotometer Ensure linearity of
calibration. spectrophotometer
response to
standards
11.3.......................... Spiked sample Ensure reduction
analysis.. efficiency of
column.
------------------------------------------------------------------------

10.0 Calibration and Standardizations

10.1 Volume Metering System. Same as Method 6, section 10.1. For
detailed instructions on carrying out these calibrations, it is
suggested that section 3.5.2 of Reference 4 of section 16.0 be
consulted.
10.2 Temperature Sensors and Barometer. Same as in Method 6,
sections 10.2 and 10.4, respectively.
10.3 Check of Rate Meter Calibration Accuracy (Optional). Disconnect
the probe from the first impinger, and connect the filter. Start the
pump, and adjust the rate meter to read between 400 and 500 ml/min
(0.014 and 0.018 cfm). After the flow rate has stabilized, start
measuring the volume sampled, as recorded by the dry gas meter and the
sampling time. Collect enough volume to measure accurately the flow
rate. Then calculate the flow rate. This average flow rate must be less
than 500 ml/min (0.018 cfm) for the sample to be valid; therefore, it is
recommended that the flow rate be checked as above prior to each test.
10.4 Spectrophotometer.
10.4.1 Dilute 5.0 ml of the NaNO2 standard solution to
200 ml with water. This solution nominally contains 25 g
NO2^-/ml. Use this solution to prepare calibration
standards to cover the range of 0.25 to 3.00 g
NO2^-/ml. Prepare a minimum of three standards each
for the linear and slightly nonlinear (described below) range of the
curve. Use pipettes for all additions.
10.4.2 Measure the absorbance of the standards and a water blank as
instructed in section 11.5. Plot the net absorbance vs. g
NO2^-/ml. Draw a smooth curve through the points.
The curve should be linear up to an absorbance of approximately 1.2 with
a slope of approximately 0.53 absorbance units/g
NO2^-/ml. The curve should pass through the origin.
The curve is slightly nonlinear from an absorbance of 1.2 to 1.6.

11.0 Analytical Procedures

11.1 Sample Stability. Collected samples are stable for at least
four weeks; thus, analysis must occur within 4 weeks of collection.
11.2 Sample Preparation.
11.2.1 Prepare a cadmium reduction column as follows: Fill the
burette with water. Add freshly prepared cadmium slowly, with tapping,
until no further settling occurs. The height of the cadmium column
should be 39 cm (15 in). When not in use, store the column under rinse
solution.

Note: The column should not contain any bands of cadmium fines. This
may occur if regenerated cadmium is used and will greatly reduce the
column lifetime.

11.2.2 Note the level of liquid in the sample container, and
determine whether any sample was lost during shipment. If a noticeable
amount of leakage has occurred, the volume lost can be determined from
the difference between initial and final solution levels, and this value
can then be used to correct the analytical result. Quantitatively
transfer the contents to a 1-liter volumetric flask, and dilute to
volume.
11.2.3 Take a 100-ml aliquot of the sample and blank (unexposed
KMnO4/NaOH) solutions, and transfer to 400-ml beakers
containing magnetic stirring bars. Using a pH meter, add concentrated
H2SO4 with stirring until a pH of 0.7 is obtained.
Allow the solutions to stand for 15 minutes. Cover the beakers with
watch glasses, and bring the temperature of the solutions to 50 [deg]C
(122 [deg]F). Keep the temperature below 60 [deg]C (140 [deg]F).
Dissolve 4.8 g of oxalic acid in a minimum volume of water,
approximately 50 ml, at room temperature. Do not heat the solution. Add
this solution slowly, in increments, until the KMnO4 solution
becomes colorless. If the color is not completely removed, prepare some
more of the above oxalic acid solution, and add until a colorless
solution is obtained. Add an excess of oxalic acid by dissolving 1.6 g
of oxalic acid in 50 ml of water, and add 6 ml of this solution to the
colorless solution. If suspended matter is present, add concentrated
H2SO4 until a clear solution is obtained.
11.2.4 Allow the samples to cool to near room temperature, being
sure that the samples are still clear. Adjust the pH to between 11.7 and
12.0 with 10 N NaOH. Quantitatively transfer the mixture to a Buchner
funnel containing GF/C filter paper, and filter the

[[Page 281]]

precipitate. Filter the mixture into a 500-ml filtering flask. Wash the
solid material four times with water. When filtration is complete, wash
the Teflon tubing, quantitatively transfer the filtrate to a 500-ml
volumetric flask, and dilute to volume. The samples are now ready for
cadmium reduction. Pipette a 50-ml aliquot of the sample into a 150-ml
beaker, and add a magnetic stirring bar. Pipette in 1.0 ml of 6.5
percent EDTA solution, and mix.
11.3 Determine the correct stopcock setting to establish a flow rate
of 7 to 9 ml/min of column rinse solution through the cadmium reduction
column. Use a 50-ml graduated cylinder to collect and measure the
solution volume. After the last of the rinse solution has passed from
the funnel into the burette, but before air entrapment can occur, start
adding the sample, and collect it in a 250-ml graduated cylinder.
Complete the quantitative transfer of the sample to the column as the
sample passes through the column. After the last of the sample has
passed from the funnel into the burette, start adding 60 ml of column
rinse solution, and collect the rinse solution until the solution just
disappears from the funnel. Quantitatively transfer the sample to a 200-
ml volumetric flask (a 250-ml flask may be required), and dilute to
volume. The samples are now ready for NO2-analysis.

Note: Two spiked samples should be run with every group of samples
passed through the column. To do this, prepare two additional 50-ml
aliquots of the sample suspected to have the highest NO2-
concentration, and add 1 ml of the spiking solution to these aliquots.
If the spike recovery or column efficiency (see section 12.2) is below
95 percent, prepare a new column, and repeat the cadmium reduction.

11.5 Sample Analysis. Pipette 10 ml of sample into a culture tube.
Pipette in 10 ml of sulfanilamide solution and 1.4 ml of NEDA solution.
Cover the culture tube with parafilm, and mix the solution. Prepare a
blank in the same manner using the sample from treatment of the
unexposed KMnO4/NaOH solution. Also, prepare a calibration
standard to check the slope of the calibration curve. After a 10-minute
color development interval, measure the absorbance at 540 nm against
water. Read g NO2^-/ml from the
calibration curve. If the absorbance is greater than that of the highest
calibration standard, use less than 10 ml of sample, and repeat the
analysis. Determine the NO2^-concentration using
the calibration curve obtained in section 10.4.

Note: Some test tubes give a high blank NO2^-
value but culture tubes do not.

11.6 Audit Sample Analysis. Same as in Method 7, section 11.4.

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after final
calculation.
12.1 Nomenclature.
B = Analysis of blank, g NO2^-/ml.
C = Concentration of NOX as NO2, dry basis, mg/
dsm\3\.
E = Column efficiency, dimensionless
K2 = 10^-3 mg/g.
m = Mass of NOX, as NO2, in sample, g.
Pbar = Barometric pressure, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
s = Concentration of spiking solution, g NO3/ml.
S = Analysis of sample, g NO2^-/ml.
Tm = Average dry gas meter absolute temperature, [deg]K.
Tstd = Standard absolute temperature, 293 [deg]K (528
[deg]R).
Vm(std) = Dry gas volume measured by the dry gas meter,
corrected to standard conditions, dscm (dscf).
Vm = Dry gas volume as measured by the dry gas meter, scm
(scf).
x = Analysis of spiked sample, g NO2^-/ml.
X = Correction factor for CO2 collection = 100/(100 -
%CO2(V/V)).
y = Analysis of unspiked sample, g NO2^-/
ml.
Y = Dry gas meter calibration factor.
1.0 ppm NO = 1.247 mg NO/m\3\ at STP.
1.0 ppm NO2 = 1.912 mg NO2/m\3\ at STP.
1 ft\3\ = 2.832 x 10^-2 m\3\.

12.2 NO2 Concentration. Calculate the NO2
concentration of the solution (see section 7.2.11) using the following
equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.212

12.3 NO3 Concentration. Calculate the NO3
concentration of the KNO3 solution (see section 7.2.12) using
the following equation:

[[Page 282]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.213

12.4 Sample Volume, Dry Basis, Corrected to Standard Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.214

Where:

K1 = 0.3855 [deg]K/mm Hg for metric units.
K1 = 17.65 [deg]R/in. Hg for English units.

12.5 Efficiency of Cadmium Reduction Column. Calculate this value as
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.215

Where:

200 = Final volume of sample and blank after passing through the column,
ml.
1.0 = Volume of spiking solution added, ml.
46.01=g NO2^-/mole.
62.01=g NO3^-/mole.

12.6 Total g NO2.
[GRAPHIC] [TIFF OMITTED] TR17OC00.216

Where:

500 = Total volume of prepared sample, ml.
50 = Aliquot of prepared sample processed through cadmium column, ml.
100 = Aliquot of KMnO4/NaOH solution, ml.
1000 = Total volume of KMnO4/NaOH solution, ml.

12.7 Sample Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.217

13.0 Method Performance

13.1 Precision. The intra-laboratory relative standard deviation for
a single measurement is 2.8 and 2.9 percent at 201 and 268 ppm
NOX, respectively.
13.2 Bias. The method does not exhibit any bias relative to Method
7.
13.3 Range. The lower detectable limit is 13 mg NOX/m\3\,
as NO2 (7 ppm NOX) when sampling at 500 ml/min for
1 hour. No upper limit has been established; however, when using the
recommended sampling conditions, the method has been found to collect
NOX emissions quantitatively up to 1782 mg NOX/
m\3\, as NO2 (932 ppm NOX).

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Margeson, J.H., W.J. Mitchell, J.C. Suggs, and M.R. Midgett.
Integrated Sampling and Analysis Methods for Determining NOX
Emissions at Electric Utility Plants. U.S. Environmental Protection
Agency, Research Triangle Park, NC. Journal of the Air Pollution Control
Association. 32:1210-1215. 1982.
2. Memorandum and attachment from J.H. Margeson, Source Branch,
Quality Assurance Division, Environmental Monitoring Systems Laboratory,
to The Record, EPA. March 30, 1983. NH3 Interference in
Methods 7C and 7D.
3. Margeson, J.H., J.C. Suggs, and M.R. Midgett. Reduction of
Nitrate to Nitrite with Cadmium. Anal. Chem. 52:1955-57. 1980.
4. Quality Assurance Handbook for Air Pollution Measurement Systems.
Volume III--Stationary Source Specific Methods. U.S.

[[Page 283]]

Environmental Protection Agency. Research Triangle Park, NC. Publication
No. EPA-600/4-77-027b. August 1977.
5. Margeson, J.H., et al. An Integrated Method for Determining
NOX Emissions at Nitric Acid Plants. Analytical Chemistry. 47
(11):1801. 1975.

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.218

[[Page 284]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.219

Method 7D--Determination of Nitrogen Oxide Emissions From Stationary
Sources (Alkaline-Permanganate/Ion Chromatographic Method)

Note: This method is not inclusive with respect to specifications
(e.g., equipment and supplies) and procedures (e.g., sampling and
analytical) essential to its performance. Some material is incorporated
by reference from other methods in this part. Therefore, to obtain
reliable results, persons using this method should have a thorough
knowledge of at least the following additional test methods: Method 1,
Method 3, Method 6, Method 7, and Method 7C.

1.0 Scope and Application

1.1 Analytes.

[[Page 285]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Nitrogen oxides (NOX), as NO2,
including:
Nitric oxide (NO)............. 10102-43-9
Nitrogen dioxide (NO2)........ 10102-44-0 7 ppmv
------------------------------------------------------------------------

2.0 Summary of Method

An integrated gas sample is extracted from the stack and passed
through impingers containing an alkaline-potassium permanganate
solution; NOX (NO + NO2) emissions are oxidized to
NO3^-. Then NO3^- is analyzed
by ion chromatography.

3.0 Definitions [Reserved]

4.0 Interferences

Same as in Method 7C, section 4.0.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection and Sample Recovery. Same as Method 7C,
section 6.1. A schematic of the sampling train used in performing this
method is shown in Figure 7C-1 of Method 7C.
6.2 Sample Preparation and Analysis.
6.2.1 Magnetic Stirrer. With 25- by 10-mm Teflon-coated stirring
bars.
6.2.2 Filtering Flask. 500-ml capacity with sidearm.
6.2.3 Buchner Funnel. 75-mm ID, with spout equipped with a 13-mm ID
by 90-mm long piece of Teflon tubing to minimize possibility of
aspirating sample solution during filtration.
6.2.4 Filter Paper. Whatman GF/C, 7.0-cm diameter.
6.2.5 Stirring Rods.
6.2.6 Volumetric Flask. 250-ml.
6.2.7 Pipettes. Class A.
6.2.8 Erlenmeyer Flasks. 250-ml.
6.2.9 Ion Chromatograph. Equipped with an anion separator column to
separate NO3^-, H3\ + \ suppressor, and
necessary auxiliary equipment. Nonsuppressed and other forms of ion
chromatography may also be used provided that adequate resolution of
NO3^- is obtained. The system must also be able to
resolve and detect NO2^-.

7.0 Reagents and Standards

Note: Unless otherwise indicated, it is intended that all reagents
conform to the specifications established by the Committee on Analytical
Reagents of the American Chemical Society, where such specifications are
available; otherwise, use the best available grade.

7.1 Sample Collection.
7.1.1 Water. Deionized distilled to conform to ASTM specification D
1193-77 or 91 Type 3 (incorporated by reference--see Sec. 60.17).
7.1.2 Potassium Permanganate, 4.0 Percent (w/w), Sodium Hydroxide,
2.0 Percent (w/w). Dissolve 40.0 g of KMnO4 and 20.0 g of
NaOH in 940 ml of water.
7.2 Sample Preparation and Analysis.
7.2.1 Water. Same as in section 7.1.1.
7.2.2 Hydrogen Peroxide (H2O2), 5 Percent.
Dilute 30 percent H2O2 1:5 (v/v) with water.
7.2.3 Blank Solution. Dissolve 2.4 g of KMnO4 and 1.2 g
of NaOH in 96 ml of water. Alternatively, dilute 60 ml of
KMnO4/NaOH solution to 100 ml.
7.2.4 KNO3 Standard Solution. Dry KNO3 at 110
[deg]C for 2 hours, and cool in a desiccator. Accurately weigh 9 to 10 g
of KNO3 to within 0.1 mg, dissolve in water, and dilute to 1
liter. Calculate the exact NO3^- concentration
using Equation 7D-1 in section 12.2. This

[[Page 286]]

solution is stable for 2 months without preservative under laboratory
conditions.
7.2.5 Eluent, 0.003 M NaHCO3/0.0024 M
Na2CO3. Dissolve 1.008 g NaHCO3 and
1.018 g Na2CO3 in water, and dilute to 4 liters.
Other eluents capable of resolving nitrate ion from sulfate and other
species present may be used.

8.0 Sample Collection, Preservation, Transport, and Storage.

8.1 Sampling. Same as in Method 7C, section 8.1.
8.2 Sample Recovery. Same as in Method 7C, section 8.2.
8.3 Sample Preparation for Analysis.

Note: Samples must be analyzed within 28 days of collection.

8.3.1 Note the level of liquid in the sample container, and
determine whether any sample was lost during shipment. If a noticeable
amount of leakage has occurred, the volume lost can be determined from
the difference between initial and final solution levels, and this value
can then be used to correct the analytical result. Quantitatively
transfer the contents to a 1-liter volumetric flask, and dilute to
volume.
8.3.2 Sample preparation can be started 36 hours after collection.
This time is necessary to ensure that all NO2^- is
converted to NO3^- in the collection solution. Take
a 50-ml aliquot of the sample and blank, and transfer to 250-ml
Erlenmeyer flasks. Add a magnetic stirring bar. Adjust the stirring rate
to as fast a rate as possible without loss of solution. Add 5 percent
H2O2 in increments of approximately 5 ml using a
5-ml pipette. When the KMnO4 color appears to have been
removed, allow the precipitate to settle, and examine the supernatant
liquid. If the liquid is clear, the H2O2 addition
is complete. If the KMnO4 color persists, add more
H2O2, with stirring, until the supernatant liquid
is clear.

Note: The faster the stirring rate, the less volume of
H2O2 that will be required to remove the
KMnO4.) Quantitatively transfer the mixture to a Buchner
funnel containing GF/C filter paper, and filter the precipitate. The
spout of the Buchner funnel should be equipped with a 13-mm ID by 90-mm
long piece of Teflon tubing. This modification minimizes the possibility
of aspirating sample solution during filtration. Filter the mixture into
a 500-ml filtering flask. Wash the solid material four times with water.
When filtration is complete, wash the Teflon tubing, quantitatively
transfer the filtrate to a 250-ml volumetric flask, and dilute to
volume. The sample and blank are now ready for
NO3^-analysis.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.2, 10.1-10.3................ Sampling Ensure accurate
equipment leak- measurement of
check and sample volume.
calibration.
10.4.......................... Spectrophotometer Ensure linearity of
calibration. spectrophotometer
response to
standards.
11.3.......................... Spiked sample Ensure reduction
analysis. efficiency of
column.
------------------------------------------------------------------------

10.0 Calibration and Standardizations

10.1 Dry Gas Meter (DGM) System.
10.1.1 Initial Calibration. Same as in Method 6, section 10.1.1. For
detailed instructions on carrying out this calibration, it is suggested
that section 3.5.2 of Citation 4 in section 16.0 of Method 7C be
consulted.
10.1.2 Post-Test Calibration Check. Same as in Method 6, section
10.1.2.
10.2 Thermometers for DGM and Barometer. Same as in Method 6,
sections 10.2 and 10.4, respectively.
10.3 Ion Chromatograph.
10.3.1 Dilute a given volume (1.0 ml or greater) of the
KNO3 standard solution to a convenient volume with water, and
use this solution to prepare calibration standards. Prepare at least
four standards to cover the range of the samples being analyzed. Use
pipettes for all additions. Run standards as instructed in section 11.2.
Determine peak height or area, and plot the individual values versus
concentration in g NO3^-/ml.
10.3.2 Do not force the curve through zero. Draw a smooth curve
through the points. The curve should be linear. With the linear curve,
use linear regression to determine the calibration equation.

11.0 Analytical Procedures

11.1 The following chromatographic conditions are recommended: 0.003
M NaHCO3/0.0024 Na2CO3 eluent solution
(Section 7.2.5), full scale range, 3 MHO; sample loop, 0.5 ml;
flow rate, 2.5 ml/min. These conditions should give a
NO3^- retention time of approximately 15 minutes
(Figure 7D-1).
11.2 Establish a stable baseline. Inject a sample of water, and
determine whether any NO3^- appears in the
chromatogram. If NO3^- is present, repeat the water
load/injection procedure approximately five times; then re-inject a
water sample and observe the chromatogram. When no
NO3^- is present, the instrument is ready for use.
Inject calibration standards. Then inject samples and a blank. Repeat
the injection of the calibration

[[Page 287]]

standards (to compensate for any drift in response of the instrument).
Measure the NO3^- peak height or peak area, and
determine the sample concentration from the calibration curve.

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after final
calculation.
12.1 Nomenclature. Same as in Method 7C, section 12.1.
12.2 NO3^- concentration. Calculate the
NO3^- concentration in the KNO3 standard
solution (see section 7.2.4) using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.220

12.3 Sample Volume, Dry Basis, Corrected to Standard Conditions.
Same as in Method 7C, section 12.4.
12.4 Total g NO2 Per Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.221

Where:

250 = Volume of prepared sample, ml.
1000 = Total volume of KMnO4 solution, ml.
50 = Aliquot of KMnO4/NaOH solution, ml.
46.01 = Molecular weight of NO3^-.
62.01 = Molecular weight of NO3^-.

12.5 Sample Concentration. Same as in Method 7C, section 12.7.

13.0 Method Performance

13.1 Precision. The intra-laboratory relative standard deviation for
a single measurement is approximately 6 percent at 200 to 270 ppm
NOX.
13.2 Bias. The method does not exhibit any bias relative to Method
7.
13.3 Range. The lower detectable limit is similar to that of Method
7C. No upper limit has been established; however, when using the
recommended sampling conditions, the method has been found to collect
NOX emissions quantitatively up to 1782 mg NOX/
m\3\, as NO2 (932 ppm NOX).

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as Method 7C, section 16.0, References 1, 2, 4, and 5.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 288]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.222

Method 7E--Determination of Nitrogen Oxides Emissions From Stationary
Sources (Instrumental Analyzer Procedure)

1.0 Scope and Application

What is Method 7E?

Method 7E is a procedure for measuring nitrogen oxides
(NOX) in stationary source emissions using a continuous
instrumental analyzer. Quality assurance and quality control
requirements are included to assure that you, the tester, collect data
of known quality. You must document your adherence to these specific
requirements for equipment, supplies, sample collection and analysis,
calculations, and data analysis. This method does not completely
describe all equipment, supplies, and sampling and analytical procedures
you will need but refers to other methods for some of the details.
Therefore, to obtain reliable results, you should also have a thorough
knowledge of these additional test methods which are found in appendix A
to this part:
(a) Method 1--Sample and Velocity Traverses for Stationary Sources.
(b) Method 4--Determination of Moisture Content in Stack Gases.
1.1 Analytes. What does this method determine? This method measures
the concentration of nitrogen oxides as NO2.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Nitric oxide (NO).............. 10102-43-9 Typically <2% of
Nitrogen dioxide (NO2)......... 10102-44-0 Calibration Span.
------------------------------------------------------------------------

1.2 Applicability. When is this method required? The use of Method
7E may be required by specific New Source Performance Standards, Clean
Air Marketing rules, State Implementation Plans, and permits where
measurement of NOX concentrations in stationary source
emissions is required, either to determine compliance with an applicable

[[Page 289]]

emissions standard or to conduct performance testing of a continuous
monitoring system (CEMS). Other regulations may also require the use of
Method 7E.
1.3 Data Quality Objectives (DQO). How good must my collected data
be? Method 7E is designed to provide high-quality data for determining
compliance with Federal and State emission standards and for relative
accuracy testing of CEMS. In these and other applications, the principal
objective is to ensure the accuracy of the data at the actual emission
levels encountered. To meet this objective, the use of EPA traceability
protocol calibration gases and measurement system performance tests are
required.
1.4 Data Quality Assessment for Low Emitters. Is performance relief
granted when testing low-emission units? Yes. For low-emitting sources,
there are alternative performance specifications for analyzer
calibration error, system bias, drift, and response time. Also, the
alternative dynamic spiking procedure in section 16 may provide
performance relief for certain low-emitting units.

2.0 Summary of Method

In this method, a sample of the effluent gas is continuously sampled
and conveyed to the analyzer for measuring the concentration of
NOX. You may measure NO and NO2 separately or
simultaneously together but, for the purposes of this method,
NOX is the sum of NO and NO2. You must meet the
performance requirements of this method to validate your data.

3.0 Definitions

3.1 Analyzer Calibration Error, for non-dilution systems, means the
difference between the manufacturer certified concentration of a
calibration gas and the measured concentration of the same gas when it
is introduced into the analyzer in direct calibration mode.
3.2 Calibration Curve means the relationship between an analyzer's
response to the injection of a series of calibration gases and the
actual concentrations of those gases.
3.3 Calibration Gas means the gas mixture containing NOX
at a known concentration and produced and certified in accordance with
``EPA Traceability Protocol for Assay and Certification of Gaseous
Calibration Standards,'' September 1997, as amended August 25, 1999,
EPA-600/R-97/121 or more recent updates. The tests for analyzer
calibration error, drift, and system bias require the use of calibration
gas prepared according to this protocol. If a zero gas is used for the
low-level gas, it must meet the requirements under the definition for
``zero air material'' in 40 CFR 72.2 in place of being prepared by the
traceability protocol.
3.3.1 Low-Level Gas means a calibration gas with a concentration
that is less than 20 percent of the calibration span and may be a zero
gas.
3.3.2 Mid-Level Gas means a calibration gas with a concentration
that is 40 to 60 percent of the calibration span.
3.3.3 High-Level Gas means a calibration gas with a concentration
that is equal to the calibration span.
3.4 Calibration Span means the upper limit of the analyzer's
calibration that is set by the choice of high-level calibration gas. No
valid run average concentration may exceed the calibration span. To the
extent practicable, the measured emissions should be between 20 to 100
percent of the selected calibration span. This may not be practicable in
some cases of low-concentration measurements or testing for compliance
with an emission limit when emissions are substantially less than the
limit. In such cases, calibration spans that are practicable to
achieving the data quality objectives without being excessively high
should be chosen.
3.5 Centroidal Area means the central area of the stack or duct that
is no greater than 1 percent of the stack or duct cross section. This
area has the same geometric shape as the stack or duct.
3.6 Converter Efficiency Gas means a calibration gas with a known NO
or NO2 concentration and of Traceability Protocol quality.
3.7 Data Recorder means the equipment that permanently records the
concentrations reported by the analyzer.
3.8 Direct Calibration Mode means introducing the calibration gases
directly into the analyzer (or into the assembled measurement system at
a point downstream of all sample conditioning equipment) according to
manufacturer's recommended calibration procedure. This mode of
calibration applies to non-dilution-type measurement systems.
3.9 Drift means the difference between the pre- and post-run system
bias (or system calibration error) checks at a specific calibration gas
concentration level (i.e. low-, mid- or high-).
3.10 Gas Analyzer means the equipment that senses the gas being
measured and generates an output proportional to its concentration.
3.11 Interference Check means the test to detect analyzer responses
to compounds other than the compound of interest, usually a gas present
in the measured gas stream, that is not adequately accounted for in the
calibration procedure and may cause measurement bias.
3.12 Low-Concentration Analyzer means any analyzer that operates
with a calibration span of 20 ppm NOX or lower. Each analyzer
model used routinely to measure low NOX concentrations must
pass a manufacturer's stability test (MST). An MST subjects the analyzer
to a range of line voltages and temperatures that reflect potential
field conditions to demonstrate its stability following

[[Page 290]]

procedures similar to those provided in 40 CFR 53.23. Ambient-level
analyzers are exempt from the MST requirements of section 16.3. A copy
of this information must be included in each test report. Table 7E-5
lists the criteria to be met.
3.13 Measurement System means all of the equipment used to determine
the NOX concentration. The measurement system comprises six
major subsystems: Sample acquisition, sample transport, sample
conditioning, calibration gas manifold, gas analyzer, and data recorder.
3.14 Response Time means the time it takes the measurement system to
respond to a change in gas concentration occurring at the sampling point
when the system is operating normally at its target sample flow rate or
dilution ratio.
3.15 Run means a series of gas samples taken successively from the
stack or duct. A test normally consists of a specific number of runs.
3.16 System Bias means the difference between a calibration gas
measured in direct calibration mode and in system calibration mode.
System bias is determined before and after each run at the low- and mid-
or high-concentration levels. For dilution-type systems, pre- and post-
run system calibration error is measured rather than system bias.
3.17 System Calibration Error applies to dilution-type systems and
means the difference between the measured concentration of low-, mid-,
or high-level calibration gas and the certified concentration for each
gas when introduced in system calibration mode. For dilution-type
systems, a 3-point system calibration error test is conducted in lieu of
the analyzer calibration error test, and 2-point system calibration
error tests are conducted in lieu of system bias tests.
3.18 System Calibration Mode means introducing the calibration gases
into the measurement system at the probe, upstream of the filter and all
sample conditioning components.
3.19 Test refers to the series of runs required by the applicable
regulation.

4.0 Interferences

Note that interferences may vary among instruments and that
instrument-specific interferences must be evaluated through the
interference test.

5.0 Safety

What safety measures should I consider when using this method? This
method may require you to work with hazardous materials and in hazardous
conditions. We encourage you to establish safety procedures before using
the method. Among other precautions, you should become familiar with the
safety recommendations in the gas analyzer user's manual. Occupational
Safety and Health Administration (OSHA) regulations concerning cylinder
and noxious gases may apply. Nitric oxide and NO2 are toxic
and dangerous gases. Nitric oxide is immediately converted to
NO2 upon reaction with air. Nitrogen dioxide is a highly
poisonous and insidious gas. Inflammation of the lungs from exposure may
cause only slight pain or pass unnoticed, but the resulting edema
several days later may cause death. A concentration of 100 ppm is
dangerous for even a short exposure, and 200 ppm may be fatal.
Calibration gases must be handled with utmost care and with adequate
ventilation. Emission-level exposure to these gases should be avoided.

6.0 Equipment and Supplies

The performance criteria in this method will be met or exceeded if
you are properly using equipment designed for this application.
6.1 What do I need for the measurement system? You may use any
equipment and supplies meeting the following specifications:
(1) Sampling system components that are not evaluated in the system
bias or system calibration error test must be glass, Teflon, or
stainless steel. Other materials are potentially acceptable, subject to
approval by the Administrator.
(2) The interference, calibration error, and system bias criteria
must be met.
(3) Sample flow rate must be maintained within 10 percent of the
flow rate at which the system response time was measured.
(4) All system components (excluding sample conditioning components,
if used) must maintain the sample temperature above the moisture dew
point. Ensure minimal contact between any condensate and the sample gas.
Section 6.2 provides example equipment specifications for a
NOX measurement system. Figure 7E-1 is a diagram of an
example dry-basis measurement system that is likely to meet the method
requirements and is provided as guidance. For wet-basis systems, you may
use alternative equipment and supplies as needed (some of which are
described in Section 6.2), provided that the measurement system meets
the applicable performance specifications of this method.
6.2 Measurement System Components
6.2.1 Sample Probe. Glass, stainless steel, or other approved
material, of sufficient length to traverse the sample points.
6.2.2 Particulate Filter. An in-stack or out-of-stack filter. The
filter must be made of material that is non-reactive to the gas being
sampled. The filter media for out-of-stack filters must be included in
the system bias test. The particulate filter requirement may be waived
in applications where no significant particulate matter is expected
(e.g., for emission testing of a combustion turbine firing natural gas).

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6.2.3 Sample Line. The sample line from the probe to the
conditioning system/sample pump should be made of Teflon or other
material that does not absorb or otherwise alter the sample gas. For a
dry-basis measurement system (as shown in Figure 7E-1), the temperature
of the sample line must be maintained at a sufficiently high level to
prevent condensation before the sample conditioning components. For wet-
basis measurement systems, the temperature of the sample line must be
maintained at a sufficiently high level to prevent condensation before
the analyzer.
6.2.4 Conditioning Equipment. For dry basis measurements, a
condenser, dryer or other suitable device is required to remove moisture
continuously from the sample gas. Any equipment needed to heat the probe
or sample line to avoid condensation prior to the sample conditioning
component is also required.
For wet basis systems, you must keep the sample above its dew point
either by: (1) Heating the sample line and all sample transport
components up to the inlet of the analyzer (and, for hot-wet extractive
systems, also heating the analyzer) or (2) by diluting the sample prior
to analysis using a dilution probe system. The components required to do
either of the above are considered to be conditioning equipment.
6.2.5 Sampling Pump. For systems similar to the one shown in Figure
7E-1, a leak-free pump is needed to pull the sample gas through the
system at a flow rate sufficient to minimize the response time of the
measurement system. The pump may be constructed of any material that is
non-reactive to the gas being sampled. For dilution-type measurement
systems, an ejector pump (eductor) is used to create a vacuum that draws
the sample through a critical orifice at a constant rate.
6.2.6 Calibration Gas Manifold. Prepare a system to allow the
introduction of calibration gases either directly to the gas analyzer in
direct calibration mode or into the measurement system, at the probe, in
system calibration mode, or both, depending upon the type of system
used. In system calibration mode, the system should be able to flood the
sampling probe and vent excess gas. Alternatively, calibration gases may
be introduced at the calibration valve following the probe. Maintain a
constant pressure in the gas manifold. For in-stack dilution-type
systems, a gas dilution subsystem is required to transport large volumes
of purified air to the sample probe and a probe controller is needed to
maintain the proper dilution ratio.
6.2.7 Sample Gas Manifold. For the type of system shown in Figure
7E-1, the sample gas manifold diverts a portion of the sample to the
analyzer, delivering the remainder to the by-pass discharge vent. The
manifold should also be able to introduce calibration gases directly to
the analyzer (except for dilution-type systems). The manifold must be
made of material that is non-reactive to the gas sampled or the
calibration gas and be configured to safely discharge the bypass gas.
6.2.8 NOX Analyzer. An instrument that continuously measures
NOX in the gas stream and meets the applicable specifications
in section 13.0. An analyzer that operates on the principle of
chemiluminescence with an NO2 to NO converter is one example
of an analyzer that has been used successfully in the past. Analyzers
operating on other principles may also be used provided the performance
criteria in section 13.0 are met.
6.2.8.1 Dual Range Analyzers. For certain applications, a wide range
of gas concentrations may be encountered, necessitating the use of two
measurement ranges. Dual-range analyzers are readily available for these
applications. These analyzers are often equipped with automated range-
switching capability, so that when readings exceed the full-scale of the
low measurement range, they are recorded on the high range. As an
alternative to using a dual-range analyzer, you may use two segments of
a single, large measurement scale to serve as the low and high ranges.
In all cases, when two ranges are used, you must quality-assure both
ranges using the proper sets of calibration gases. You must also meet
the interference, calibration error, system bias, and drift checks.
However, we caution that when you use two segments of a large
measurement scale for dual range purposes, it may be difficult to meet
the performance specifications on the low range due to signal-to-noise
ratio considerations.
6.2.8.2 Low Concentration Analyzer. When an analyzer is routinely
calibrated with a calibration span of 20 ppmv or less, the
manufacturer's stability test (MST) is required. See Table 7E-5 for test
parameters.
6.2.9 Data Recording. A strip chart recorder, computerized data
acquisition system, digital recorder, or data logger for recording
measurement data may be used.

7.0 Reagents and Standards

7.1 Calibration Gas. What calibration gases do I need? Your
calibration gas must be NO in N2 and certified (or
recertified) within an uncertainty of 2.0 percent in accordance with
``EPA Traceability Protocol for Assay and Certification of Gaseous
Calibration Standards'' September 1997, as amended August 25, 1999, EPA-
600/R-97/121. Blended gases meeting the Traceability Protocol are
allowed if the additional gas components are shown not to interfere with
the analysis. If a zero gas is used for the low-level gas, it must meet
the requirements under the definition for ``zero air material'' in 40
CFR 72.2. The calibration gas must not be used after its expiration
date. Except for applications under part 75 of

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this chapter, it is acceptable to prepare calibration gas mixtures from
EPA Traceability Protocol gases in accordance with Method 205 in
appendix M to part 51 of this chapter. For part 75 applications, the use
of Method 205 is subject to the approval of the Administrator. The goal
and recommendation for selecting calibration gases is to bracket the
sample concentrations. The following calibration gas concentrations are
required:
7.1.1 High-Level Gas. This concentration is chosen to set the
calibration span as defined in Section 3.4.
7.1.2 Mid-Level Gas. 40 to 60 percent of the calibration span.
7.1.3 Low-Level Gas. Less than 20 percent of the calibration span.
7.1.4 Converter Efficiency Gas. What reagents do I need for the
converter efficiency test? The converter efficiency gas is a
manufacturer-certified gas with a concentration sufficient to show
NO2 conversion at the concentrations encountered in the
source. A test gas concentration in the 40 to 60 ppm range is suggested,
but other concentrations may be more appropriate to specific sources.
For the test described in section 8.2.4.1, NO2 is required.
For the alternative converter efficiency tests in section 16.2, NO is
required.
7.2 Interference Check. What reagents do I need for the interference
check? Use the appropriate test gases listed in Table 7E-3 or others not
listed that can potentially interfere (as indicated by the test facility
type, instrument manufacturer, etc.) to conduct the interference check.
These gases should be manufacturer certified but do not have to be
prepared by the EPA traceability protocol.

8.0 Sample Collection, Preservation, Storage, and Transport

Emission Test Procedure

Since you are allowed to choose different options to comply with
some of the performance criteria, it is your responsibility to identify
the specific options you have chosen, to document that the performance
criteria for that option have been met, and to identify any deviations
from the method.
8.1 What sampling site and sampling points do I select?
8.1.1 Unless otherwise specified in an applicable regulation or by
the Administrator, when this method is used to determine compliance with
an emission standard, conduct a stratification test as described in
section 8.1.2 to determine the sampling traverse points to be used. For
performance testing of continuous emission monitoring systems, follow
the sampling site selection and traverse point layout procedures
described in the appropriate performance specification or applicable
regulation (e.g., Performance Specification 2 in appendix B to this
part).
8.1.2 Determination of Stratification. Perform a stratification test
at each test site to determine the appropriate number of sample traverse
points. If testing for multiple pollutants or diluents at the same site,
a stratification test using only one pollutant or diluent satisfies this
requirement. A stratification test is not required for small stacks that
are less than 4 inches in diameter. To test for stratification, use a
probe of appropriate length to measure the NOX (or pollutant
of interest) concentration at twelve traverse points located according
to Table 1-1 or Table 1-2 of Method 1. Alternatively, you may measure at
three points on a line passing through the centroidal area. Space the
three points at 16.7, 50.0, and 83.3 percent of the measurement line.
Sample for a minimum of twice the system response time (see section
8.2.6) at each traverse point. Calculate the individual point and mean
NOX concentrations. If the concentration at each traverse
point differs from the mean concentration for all traverse points by no
more than: (a) 5.0 percent of the mean concentration; or (b) 0.5 ppm
(whichever is less restrictive), the gas stream is considered
unstratified and you may collect samples from a single point that most
closely matches the mean. If the 5.0 percent or 0.5 ppm criterion is not
met, but the concentration at each traverse point differs from the mean
concentration for all traverse points by no more than: (a) 10.0 percent
of the mean; or (b) 1.0 ppm (whichever is less restrictive), the gas
stream is considered to be minimally stratified, and you may take
samples from three points. Space the three points at 16.7, 50.0, and
83.3 percent of the measurement line. Alternatively, if a twelve-point
stratification test was performed and the emissions were shown to be
minimally stratified (all points within 10.0 percent of their mean or
within 1.0 ppm), and if the stack diameter (or equivalent diameter, for
a rectangular stack or duct) is greater than 2.4 meters (7.8 ft), then
you may use 3-point sampling and locate the three points along the
measurement line exhibiting the highest average concentration during the
stratification test, at 0.4, 1.0 and 2.0 meters from the stack or duct
wall. If the gas stream is found to be stratified because the 10.0
percent or 1.0 ppm criterion for a 3-point test is not met, locate
twelve traverse points for the test in accordance with Table 1-1 or
Table 1-2 of Method 1.
8.2 Initial Measurement System Performance Tests. What initial
performance criteria must my system meet before I begin collecting
samples? Before measuring emissions, perform the following procedures:
(a) Calibration gas verification,
(b) Measurement system preparation,
(c) Calibration error test,
(d) NO2 to NO conversion efficiency test, if applicable,
(e) System bias check,
(f) System response time test, and

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(g) Interference check
8.2.1 Calibration Gas Verification. How must I verify the
concentrations of my calibration gases? Obtain a certificate from the
gas manufacturer documenting the quality of the gas. Confirm that the
manufacturer certification is complete and current. Ensure that your
calibration gas certifications have not expired. This documentation
should be available on-site for inspection. To the extent practicable,
select a high-level gas concentration that will result in the measured
emissions being between 20 and 100 percent of the calibration span.
8.2.2 Measurement System Preparation. How do I prepare my
measurement system? Assemble, prepare, and precondition the measurement
system according to your standard operating procedure. Adjust the system
to achieve the correct sampling rate or dilution ratio (as applicable).
8.2.3 Calibration Error Test. How do I confirm my analyzer
calibration is correct? After you have assembled, prepared and
calibrated your sampling system and analyzer, you must conduct a 3-point
analyzer calibration error test (or a 3-point system calibration error
test for dilution systems) before the first run and again after any
failed system bias test (or 2-point system calibration error test for
dilution systems) or failed drift test. Introduce the low-, mid-, and
high-level calibration gases sequentially. For non-dilution-type
measurement systems, introduce the gases in direct calibration mode. For
dilution-type measurement systems, introduce the gases in system
calibration mode.
(1) For non-dilution systems, you may adjust the system to maintain
the correct flow rate at the analyzer during the test, but you may not
make adjustments for any other purpose. For dilution systems, you must
operate the measurement system at the appropriate dilution ratio during
all system calibration error checks, and may make only the adjustments
necessary to maintain the proper ratio.
(2) Record the analyzer's response to each calibration gas on a form
similar to Table 7E-1. For each calibration gas, calculate the analyzer
calibration error using Equation 7E-1 in section 12.2 or the system
calibration error using Equation 7E-3 in section 12.4 (as applicable).
The calibration error specification in section 13.1 must be met for the
low-, mid-, and high-level gases. If the calibration error specification
is not met, take corrective action and repeat the test until an
acceptable 3-point calibration is achieved.
8.2.4 NO2 to NO Conversion Efficiency Test. Before or
after each field test, you must conduct an NO2 to NO
conversion efficiency test if your system converts NO2 to NO
before analyzing for NOX. You may risk testing multiple
facilities before performing this test provided you pass this test at
the conclusion of the final facility test. A failed final conversion
efficiency test in this case will invalidate all tests performed
subsequent to the test in which the converter efficiency test was
passed. Follow the procedures in section 8.2.4.1, or 8.2.4.2. If
desired, the converter efficiency factor derived from this test may be
used to correct the test results for converter efficiency if the
NO2 fraction in the measured test gas is known. Use Equation
7E-8 in section 12.8 for this correction.
8.2.4.1 Introduce NO2 converter efficiency gas to the
analyzer in direct calibration mode and record the NOX
concentration displayed by the analyzer. Calculate the converter
efficiency using Equation 7E-7 in section 12.7. The specification for
converter efficiency in section 13.5 must be met. The user is cautioned
that state-of-the-art NO2 calibration gases may have limited
shelf lives, and this could affect the ability to pass the 90-percent
conversion efficiency requirement.
8.2.4.2 Alternatively, either of the procedures for determining
conversion efficiency using NO in section 16.2 may be used.
8.2.5 Initial System Bias and System Calibration Error Checks.
Before sampling begins, determine whether the high-level or mid-level
calibration gas best approximates the emissions and use it as the
upscale gas. Introduce the upscale gas at the probe upstream of all
sample conditioning components in system calibration mode. Record the
time it takes for the measured concentration to increase to a value that
is at least 95 percent or within 0.5 ppm (whichever is less restrictive)
of a stable response for both the low-level and upscale gases. Continue
to observe the gas concentration reading until it has reached a final,
stable value. Record this value on a form similar to Table 7E-2.
(1) Next, introduce the low-level gas in system calibration mode and
record the time required for the concentration response to decrease to a
value that is within 5.0 percent or 0.5 ppm (whichever is less
restrictive) of the certified low-range gas concentration. If the low-
level gas is a zero gas, use the procedures described above and observe
the change in concentration until the response is 0.5 ppm or 5.0 percent
of the upscale gas concentration (whichever is less restrictive).
(2) Continue to observe the low-level gas reading until it has
reached a final, stable value and record the result on a form similar to
Table 7E-2. Operate the measurement system at the normal sampling rate
during all system bias checks. Make only the adjustments necessary to
achieve proper calibration gas flow rates at the analyzer.
(3) From these data, calculate the measurement system response time
(see section 8.2.6) and then calculate the initial system bias using
Equation 7E-2 in section 12.3. For

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dilution systems, calculate the system calibration error in lieu of
system bias using equation 7E-3 in section 12.4. See section 13.2 for
acceptable performance criteria for system bias and system calibration
error. If the initial system bias (or system calibration error)
specification is not met, take corrective action. Then, you must repeat
the applicable calibration error test from section 8.2.3 and the initial
system bias (or 2-point system calibration error) check until acceptable
results are achieved, after which you may begin sampling.

(Note: For dilution-type systems, data from the 3-point system
calibration error test described in section 8.2.3 may be used to meet
the initial 2-point system calibration error test requirement of this
section, if the calibration gases were injected as described in this
section, and if response time data were recorded).

8.2.6 Measurement System Response Time. As described in section
8.2.5, you must determine the measurement system response time during
the initial system bias (or 2-point system calibration error) check.
Observe the times required to achieve 95 percent of a stable response
for both the low-level and upscale gases. The longer interval is the
response time.
8.2.7 Interference Check. Conduct an interference response test of
the gas analyzer prior to its initial use in the field. If you have
multiple analyzers of the same make and model, you need only perform
this alternative interference check on one analyzer. You may also meet
the interference check requirement if the instrument manufacturer
performs this or a similar check on an analyzer of the same make and
model of analyzer that you use and provides you with documented results.
Analytical quenching must be evaluated and remedied unless a dilution
system and ambient-level analyzer are used. The analyzer must be checked
for quenching at concentrations of approximately 4 and 12 percent
CO2 at a mid-range concentration for each analyzer range
which is commonly used. The analyzer must be rechecked after it has been
repaired or modified or on another periodic basis.
(1) You may introduce the appropriate interference test gases (that
are potentially encountered during a test, see examples in Table 7E-3)
into the analyzer separately or as mixtures. Test the analyzer with the
interference gas alone at the highest concentration expected at a test
source and again with the interference gas and NOX at a
representative NOX test concentration. For analyzers
measuring NOX greater than 20 ppm, use a calibration gas with
an NOX concentration of 80 to 100 ppm and set this
concentration equal to the calibration span. For analyzers measuring
less than 20 ppm NOX, select an NO concentration for the
calibration span that reflects the emission levels at the sources to be
tested, and perform the interference check at that level. Measure the
total interference response of the analyzer to these gases in ppmv.
Record the responses and determine the interference using Table 7E-4.
The specification in section 13.4 must be met.
(2) A copy of this data, including the date completed and signed
certification, must be available for inspection at the test site and
included with each test report. This interference test is valid for the
life of the instrument unless major analytical components (e.g., the
detector) are replaced with different model parts. If major components
are replaced with different model parts, the interference gas check must
be repeated before returning the analyzer to service. If major
components are replaced, the interference gas check must be repeated
before returning the analyzer to service. The tester must ensure that
any specific technology, equipment, or procedures that are intended to
remove interference effects are operating properly during testing.
8.3 Dilution-Type Systems--Special Considerations. When a dilution-
type measurement system is used, there are three important
considerations that must be taken into account to ensure the quality of
the emissions data. First, the critical orifice size and dilution ratio
must be selected properly so that the sample dew point will be below the
sample line and analyzer temperatures. Second, a high-quality, accurate
probe controller must be used to maintain the dilution ratio during the
test. The probe controller should be capable of monitoring the dilution
air pressure, eductor vacuum, and sample flow rates. Third, differences
between the molecular weight of calibration gas mixtures and the stack
gas molecular weight must be addressed because these can affect the
dilution ratio and introduce measurement bias.
8.4 Sample Collection.
(1) Position the probe at the first sampling point. Purge the system
for at least two times the response time before recording any data.
Then, traverse all required sampling points, sampling at each point for
an equal length of time and maintaining the appropriate sample flow rate
or dilution ratio (as applicable). You must record at least one valid
data point per minute during the test run.
(2) Each time the probe is removed from the stack and replaced, you
must recondition the sampling system for at least two times the system
response time prior to your next recording. If the average of any run
exceeds the calibration span value, that run is invalid.
(3) You may satisfy the multipoint traverse requirement by sampling
sequentially using a single-hole probe or a multi-hole probe designed to
sample at the prescribed

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points with a flow within 10 percent of mean flow rate. Notwithstanding,
for applications under part 75 of this chapter, the use of multi-hole
probes is subject to the approval of the Administrator.
8.5 Post-Run System Bias Check and Drift Assessment.
How do I confirm that each sample I collect is valid? After each
run, repeat the system bias check or 2-point system calibration error
check (for dilution systems) to validate the run. Do not make
adjustments to the measurement system (other than to maintain the target
sampling rate or dilution ratio) between the end of the run and the
completion of the post-run system bias or system calibration error
check. Note that for all post-run system bias or 2-point system
calibration error checks, you may inject the low-level gas first and the
upscale gas last, or vice-versa. You may risk sampling for multiple runs
before performing the post-run bias or system calibration error check
provided you pass this test at the conclusion of the group of runs. A
failed final test in this case will invalidate all runs subsequent to
the last passed test.
(1) If you do not pass the post-run system bias (or system
calibration error) check, then the run is invalid. You must diagnose and
fix the problem and pass another calibration error test (Section 8.2.3)
and system bias (or 2-point system calibration error) check (Section
8.2.5) before repeating the run. Record the system bias (or system
calibration error) results on a form similar to Table 7E-2.
(2) After each run, calculate the low-level and upscale drift, using
Equation 7E-4 in section 12.5. If the post-run low- and upscale bias (or
2-point system calibration error) checks are passed, but the low-or
upscale drift exceeds the specification in section 13.3, the run data
are valid, but a 3-point calibration error test and a system bias (or 2-
point system calibration error) check must be performed and passed
before any more test runs are done.
(3) For dilution systems, data from a 3-point system calibration
error test may be used to met the pre-run 2-point system calibration
error requirement for the first run in a test sequence. Also, the post-
run bias (or 2-point calibration error) check data may be used as the
pre-run data for the next run in the test sequence at the discretion of
the tester.
8.6 Alternative Interference and System Bias Checks (Dynamic Spike
Procedure). If I want to use the dynamic spike procedure to validate my
data, what procedure should I follow? Except for applications under part
75 of this chapter, you may use the dynamic spiking procedure and
requirements provided in section 16.1 during each test as an alternative
to the interference check and the pre- and post-run system bias checks.
The calibration error test is still required under this option. Use of
the dynamic spiking procedure for Part 75 applications is subject to the
approval of the Administrator.
8.7 Moisture correction. You must determine the moisture content of
the flue gas and correct the measured gas concentrations to a dry basis
using Method 4 or other appropriate methods, subject to the approval of
the Administrator, when the moisture basis (wet or dry) of the
measurements made with this method is different from the moisture basis
of either: (1) The applicable emissions limit; or (2) the CEMS being
evaluated for relative accuracy. Moisture correction is also required if
the applicable limit is in lb/mmBtu and the moisture basis of the Method
7E NOX analyzer is different from the moisture basis of the
Method 3A diluent gas (CO2 or O2) analyzer.

9.0 Quality Control

What quality control measures must I take?

The following table is a summary of the mandatory, suggested, and
alternative quality assurance and quality control measures and the
associated frequency and acceptance criteria. All of the QC data, along
with the sample run data, must be documented and included in the test
report.

Summary Table of AQ/QC
----------------------------------------------------------------------------------------------------------------
Status Process or element QA/QC specification Acceptance criteria Checking frequency
----------------------------------------------------------------------------------------------------------------
S............. Identify Data User... Regulatory Agency or other Before designing
primary end user of data. test.
S............. Analyzer Design...... Analyzer resolution <2.0% of full-scale range... Manufacturer design.
or sensitivity.
M............. Interference gas Sum of responses 2.5% of calibration span
Alternatively, sum of
responses:
0.5 ppmv for
calibration spans of 5 to
10 ppmv.
0.2 ppmv for
calibration spans <5 ppmv.
See Table 7E-3..............
M............. Calibration Gases.... Traceability protocol Valid certificate required
(G1, G2). Uncertainty 2.0%
of tag value.
M............. High-level gas....... Equal to the calibration Each test.
span.
M............. Mid-level gas........ 40 to 60% of calibration Each test.
span.

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M............. Low-level gas........ <20% of calibration span.... Each test.
S............. Data Recorder Design. Data resolution...... 0.5% of full- Manufacturer design.
scale range.
S............. Sample Extraction.... Probe material....... SS or quartz if stack >500 East test.
[deg]F.
M............. Sample Extraction.... Probe, filter and For dry-basis analyzers, Each run.
sample line keep sample above the dew
temperature. point by heating, prior to
sample conditioning.
For wet-basis analyzers,
keep sample above dew point
at all times, by heating or
dilution.
S............. Sample Extraction.... Calibration valve SS.......................... Each test.
material.
S............. Sample Extraction.... Sample pump material. Inert to sample constituents Each test.
S............. Sample Extraction.... Manifolding material. Inert to sample constituents Each test.
S............. Moisture Removal..... Equipment efficiency. <5% target compound removal. Verified through
system bias check.
S............. Particulate Removal.. Filter inertness..... Pass system bias check...... Each bias check.
M............. Analyzer & Analyzer calibration Within 2.0 percent of the Before initial run
Calibration Gas error (of 3-point calibration span of the and after a failed
Performance. system calibration analyzer for the low-, mid- system bias test or
error for dilution , and high-level drift test.
systems). calibration gases.
Alternative specification:
0.5 ppmv
absolute difference.
M............. System Performance... System bias (or pre- Within 5.0% of the analyzer Before and after
and post-run 2-point calibration span for low- each run.
system calibration sacle and upscale
error for dilution calibration gases.
(Systems).
Alternative specification:
0.5 ppmv
absolute difference.
M............. System Performance... System response time. Determines minimum sampling During initial
time per point. sampling system
bias test.
M............. System Performance... Drift................ 3.0% of After each test run.
calibration span for low-
level and mid- or high-
level gases.
Alternative specification:
0.5 ppmv
absolute difference.
M............. System Performance... NO2-NO conversion 90% of certified Before or after each
efficiency. test gas concentration. test.
M............. System Performance... Purge time........... 2 times system Before starting the
response time. first run and when
probe is removed
from and re-
inserted into the
stack.
M............. System Performance... Minimum sample time Two times the system Each sample point.
at each point. response time.
M............. System Performance... Stable sample flow Within 10% of flow rate Each run.
rate (surrogate for established during system
maintaining system response time check.
response time).
M............. Sample Point Stratification test.. All points within: Prior to first run.
Selection.
5% of mean for 1-point
sampling.
10% of mean for 3-point....
Alternatively, all points
within:
0.5 ppm of mean for 1-point
sampling.
1.0 ppm of mean for 3-point
sampling.
A............. Multiple sample No. of openings in Multi-hole probe with Each run.
points probe. verifiable constant flow
simultaneously. through all holes within
10% of mean flow rate
(requires Administrative
approval for Part 75).
M............. Data Recording....... Frequency............ 1 minute average. During run.
S............. Data Parameters...... Sample concentration All 1-minute averages within Each run.
range. calibration span.
M............. Date Parameters...... Average concentration Run average calibration span.
----------------------------------------------------------------------------------------------------------------
S = Suggest.
M = Mandatory.

[[Page 297]]

A = Alternative.
Agency.

10.0 Calibration and Standardization

What measurement system calibrations are required?

(1) The initial 3-point calibration error test as described in
section 8.2.3 and the system bias (or system calibration error) checks
described in section 8.2.5 are required and must meet the specifications
in section 13 before you start the test. Make all necessary adjustments
to calibrate the gas analyzer and data recorder. Then, after the test
commences, the system bias or system calibration error checks described
in section 8.5 are required before and after each run. Your analyzer
must be calibrated for all species of NOX that it detects.
Analyzers that measure NO and NO2 separately without using a
converter must be calibrated with both NO and NO2.
(2) You must include a copy of the manufacturer's certification of
the calibration gases used in the testing as part of the test report.
This certification must include the 13 documentation requirements in the
EPA Traceability Protocol For Assay and Certification of Gaseous
Calibration Standards, September 1997, as amended August 25, 1999. When
Method 205 is used to produce diluted calibration gases, you must
document that the specifications for the gas dilution system are met for
the test. You must also include the date of the most recent dilution
system calibration against flow standards and the name of the person or
manufacturer who carried out the calibration in the test report.

11.0 Analytical Procedures

Because sample collection and analysis are performed together (see
section 8), additional discussion of the analytical procedure is not
necessary.

12.0 Calculations and Data Analysis

You must follow the procedures for calculations and data analysis
listed in this section.
12.1 Nomenclature. The terms used in the equations are defined as
follows:

ACE = Analyzer calibration error, percent of calibration span.
BWS = Moisture content of sample gas as measured by Method 4
or other approved method, percent/100.
CAvg = Average unadjusted gas concentration indicated by data
recorder for the test run, ppmv.
CD = Pollutant concentration adjusted to dry conditions,
ppmv.
CDir = Measured concentration of a calibration gas (low, mid,
or high) when introduced in direct calibration mode, ppmv.
CGas = Average effluent gas concentration adjusted for bias,
ppmv.
CM = Average of initial and final system calibration bias (or
2-point system calibration error) check responses for the
upscale calibration gas, ppmv.
CMA = Actual concentration of the upscale calibration gas,
ppmv.
CNative = NOX concentration in the stack gas as
calculated in section 12.6, ppmv.
CO = Average of the initial and final system calibration bias
(or 2-point system calibration error) check responses from the
low-level (or zero) calibration gas, ppmv.
COA = Actual concentration of the low-level calibration gas,
ppmv.
CS = Measured concentration of a calibration gas (low, mid,
or high) when introduced in system calibration mode, ppmv.
CSS = Concentration of NOX measured in the spiked
sample, ppmv.
CSpike = Concentration of NOX in the undiluted
spike gas, ppmv.
CCalc = Calculated concentration of NOX in the
spike gas diluted in the sample, ppmv.
CV = Manufacturer certified concentration of a calibration
gas (low, mid, or high), ppmv.
CW = Pollutant concentration measured under moist sample
conditions, wet basis, ppmv.
CS = Calibration span, ppmv.
D = Drift assessment, percent of calibration span.
DF = Dilution system dilution factor or spike gas dilution factor,
dimensionless.
EffNO2 = NO2 to NO converter efficiency, percent.
NOXCorr = The NOX concentration corrected for the
converter efficiency, ppmv.
NOXFinal = The final NOX concentration observed
during the converter efficiency test in section 16.2.2, ppmv.
NOXPeak = The highest NOX concentration observed
during the converter efficiency test in section 16.2.2, ppmv.
QSpike = Flow rate of spike gas introduced in system
calibration mode, L/min.
QTotal = Total sample flow rate during the spike test, L/min.
R = Spike recovery, percent.
SB = System bias, percent of calibration span.
SBi = Pre-run system bias, percent of calibration span.
SBfinal = Post-run system bias, percent of calibration span.
SCE = System calibration error, percent of calibration span.
SCEi = Pre-run system calibration error, percent of
calibration span.

[[Page 298]]

SCEFinal = Post-run system calibration error, percent of
calibration span.
12.2 Analyzer Calibration Error. For non-dilution systems, use
Equation 7E-1 to calculate the analyzer calibration error for the low-,
mid-, and high-level calibration gases.
[GRAPHIC] [TIFF OMITTED] TR15MY06.001

12.3 System Bias. For non-dilution systems, use Equation 7E-2 to
calculate the system bias separately for the low-level and upscale
calibration gases.
[GRAPHIC] [TIFF OMITTED] TR15MY06.002

12.4 System Calibration Error. Use Equation 7E-3 to calculate the
system calibration error for dilution systems. Equation 7E-3 applies to
both the initial 3-point system calibration error test and the
subsequent 2-point calibration error checks between test runs. In this
equation, the term ``Cs'' refers to the diluted calibration
gas concentration measured by the analyzer.
[GRAPHIC] [TIFF OMITTED] TR22MY08.000

12.5 Drift Assessment. Use Equation 7E-4 to separately calculate the
low-level and upscale drift over each test run. For dilution systems,
replace ``SBfinal'' and ``SBi'' with
``SCEfinal'' and ``SCEi'', respectively, to
calculate and evaluate drift.
[GRAPHIC] [TIFF OMITTED] TR15MY06.004

12.6 Effluent Gas Concentration. For each test run, calculate
Cavg, the arithmetic average of all valid NOX
concentration values (e.g., 1-minute averages). Then adjust the value of
Cavg for bias using Equation 7E-5a if you use a non-zero gas
as your low-level calibration gas, or Equation 7E-5b if you use a zero
gas as your low-level calibration gas.
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12.7 NO2--NO Conversion Efficiency. If the NOX
converter efficiency test described in section 8.2.4.1 is performed,
calculate the efficiency using Equation 7E-7.
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12.8 NO2--NO Conversion Efficiency Correction. If
desired, calculate the total NOX concentration with a
correction for converter efficiency using Equations 7E-8.
[GRAPHIC] [TIFF OMITTED] TR15MY06.007

12.9 Alternative NO2 Converter Efficiency. If the alternative
procedure of section 16.2.2 is used, determine the NOX
concentration decrease from NOXPeak after the minimum 30-
minute test interval using Equation 7E-9. This decrease from
NOXPeak must meet the requirement in section 13.5 for the
converter to be acceptable.
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[[Page 299]]

12.10 Moisture Correction. Use Equation 7E-10 if your measurements
need to be corrected to a dry basis.
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12.11 Calculated Spike Gas Concentration and Spike Recovery for the
Example Alternative Dy-namic Spiking Procedure in section 16.1.3. Use
Equation 7E-11 to determine the calculated spike gas concentration. Use
Equation 7E-12 to calculate the spike recovery.
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13.0 Method Performance

13.1 Calibration Error. This specification is applicable to both the
analyzer calibration error and the 3-point system calibration error
tests described in section 8.2.3. At each calibration gas level (low,
mid, and high) the calibration error must either be within 2.0 percent
of the calibration span. Alternatively, the results are acceptable if
|Cdir - Cv| or |Cs-Cv| (as
applicable) is 0.5 ppmv.
13.2 System Bias. This specification is applicable to both the
system bias and 2-point system calibration error tests described in
section 8.2.5 and 8.5. The pre- and post-run system bias (or system
calibration error) must be within 5.0 percent of the calibration span
for the low-level and upscale calibration gases. Alternatively, the
results are acceptable if | Cs -Cdir | is
0.5 ppmv or if | Cs- Cv | is
0.5 ppmv (as applicable).
13.3 Drift. For each run, the low-level and upscale drift must be
less than or equal to 3.0 percent of the calibration span. The drift is
also acceptable if the pre- and post-run bias (or the pre- and post-run
system calibration error) responses do not differ by more than 0.5 ppmv
at each gas concentration (i.e. | Cs post-run-
Cs pre-run | 0.5 ppmv).
13.4 Interference Check. The total interference response (i.e., the
sum of the interference responses of all tested gaseous components) must
not be greater than 2.50 percent of the calibration span for the
analyzer tested. In summing the interferences, use the larger of the
absolute values obtained for the interferent tested with and without the
pollutant present. The results are also acceptable if the sum of the
responses does not exceed 0.5 ppmv for a calibration span of 5 to 10
ppmv, or 0.2 ppmv for a calibration span <5 ppmv.
13.5 NO2 to NO Conversion Efficiency Test (as applicable). The
NO2 to NO conversion efficiency, calculated according to
Equation 7E-7, must be greater than or equal to 90 percent. The
alternative conversion efficiency check, described in section 16.2.2 and
cal-culated according to Equation 7E-9, must not result in a decrease
from NOXPeak by more than 2.0 percent.
13.6 Alternative Dynamic Spike Procedure. Recoveries of both pre-
test spikes and post-test spikes must be within 100 10 percent. If the
absolute difference between the calculated spike value and measured
spike value is equal to or less than 0.20 ppmv, then the requirements of
the ADSC are met.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 Dynamic Spike Procedure. Except for applications under part 75
of this chapter, you may use a dynamic spiking procedure to validate
your test data for a specific test matrix in place of the interference
check and pre- and post-run system bias checks. For part 75
applications, use of this procedure is subject to the approval of the
Administrator. Best results are obtained for this procedure when source
emissions are steady and not varying. Fluctuating emissions may render
this alternative procedure difficult to pass. To use this alternative,
you must meet the following requirements.
16.1.1 Procedure Documentation. You must detail the procedure you
followed in the test report, including how the spike was measured,
added, verified during the run, and calculated after the test.
16.1.2 Spiking Procedure Requirements. The spikes must be prepared
from EPA Traceability Protocol gases. Your procedure must be designed to
spike field samples at two target levels both before and after the test.
Your target spike levels should bracket the average sample
NOX concentrations. The higher target concentration must be
less than the calibration span. You must collect at least 5 data points
for each target concentration. The spiking procedure must be performed
before the first run and repeated after the last run of the test
program.

[[Page 300]]

16.1.3 Example Spiking Procedure. Determine the NO concentration
needed to generate concentrations that are 50 and 150 percent of the
anticipated NOX concentration in the stack at the total
sampling flow rate while keeping the spike flow rate at or below 10
percent of this total. Use a mass flow meter (accurate within 2.0
percent) to generate these NO spike gas concentrations at a constant
flow rate. Use Equation 7E-11 in section 12.11 to determine the
calculated spike concentration in the collected sample.
(1) Prepare the measurement system and conduct the analyzer
calibration error test as described in sections 8.2.2 and 8.2.3.
Following the sampling procedures in section 8.1, determine the stack
NOX concentration and use this concentration as the average
stack concentration (Cavg) for the first spike level, or if
desired, for both pre-test spike levels. Introduce the first level spike
gas into the system in system calibration mode and begin sample
collection. Wait for at least two times the system response time before
measuring the spiked sample concentration. Then record at least five
successive 1-minute averages of the spiked sample gas. Monitor the spike
gas flow rate and maintain at the determined addition rate. Average the
five 1-minute averages and determine the spike recovery using Equation
7E-12. Repeat this procedure for the other pre-test spike level. The
recovery at each level must be within the limits in section 13.6 before
proceeding with the test.
(2) Conduct the number of runs required for the test. Then repeat
the above procedure for the post-test spike evaluation. The last run of
the test may serve as the average stack concentration for the post-test
spike test calculations. The results of the post-test spikes must meet
the limits in section 13.6.
16.2 Alternative NO2 to NO Conversion Efficiency
Procedures. You may use either of the following procedures to determine
converter efficiency in place of the procedure in section 8.2.4.1.
16.2.1 The procedure for determining conversion efficiency using NO
in 40 CFR 86.123-78.
16.2.2 Bag Procedure. Perform the analyzer calibration error test to
document the calibration (both NO and NOX modes, as
applicable). Fill a Tedlar or equivalent bag approximately half full
with either ambient air, pure oxygen, or an oxygen standard gas with at
least 19.5 percent by volume oxygen content. Fill the remainder of the
bag with mid- to high-level NO in N2 (or other appropriate
concentration) calibration gas. (Note that the concentration of the NO
standard should be sufficiently high enough for the diluted
concentration to be easily and accurately measured on the scale used.
The size of the bag should be large enough to accommodate the procedure
and time required. Verify through the manufacturer that the Tedlar
alternative is suitable for NO and make this verifed information
available for inspection.)
(1) Immediately attach the bag to the inlet of the NOX
analyzer (or external converter if used). In the case of a dilution-
system, introduce the gas at a point upstream of the dilution assembly.
Measure the NOX concentration for a period of 30 minutes. If
the NOX concentration drops more than 2 percent absolute from
the peak value observed, then the NO2 converter has failed to
meet the criteria of this test. Take corrective action. The highest
NOX value observed is considered to be NOXPeak.
The final NOX value observed is considered to be
NOXfinal.
(2) [Reserved]
16.3 Manufacturer's Stability Test. A manufacturer's stability test
is required for all analyzers that routinely measure emissions below 20
ppmv and is optional but recommended for other analyzers. This test
evaluates each analyzer model by subjecting it to the tests listed in
Table 7E-5 following procedures similar to those in 40 CFR 53.23 for
thermal stability and insensitivity to supply voltage variations. If the
analyzer will be used under temperature conditions that are outside the
test conditions in Table B-4 of Part 53.23, alternative test
temperatures that better reflect the analyzer field environment should
be used. Alternative procedures or documentation that establish the
analyzer's stability over the appropriate line voltages and temperatures
are acceptable.

17.0 References

1. ``ERA Traceability Protocol for Assay and Certification of
Gaseous Calibration Standards'' September 1997 as amended, ERA-600/R-97/
121.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 301]]

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Table 7E-3--Example Interference Check Gas Concentrations
------------------------------------------------------------------------
Concentrations \2\ sample conditioning
type
Potential interferent gas \1\ ---------------------------------------
Hot wet Dried
------------------------------------------------------------------------
CO2............................. 5 and 15%......... 5 and 15%
H2O............................. 25%............... 1%
NO.............................. 15 ppmv........... 15 ppmv
NO2............................. 15 ppmv........... 15 ppmv
N2O............................. 10 ppmv........... 10 ppmv
CO.............................. 50 ppmv........... 50 ppmv
NH3............................. 10 ppmv........... 10 ppmv
CH4............................. 50 ppmv........... 50 ppmv
SO2............................. 20 ppmv........... 20 ppmv
H2.............................. 50 ppmv........... 50 ppmv
HCl............................. 10 ppmv........... 10 ppmv
------------------------------------------------------------------------
\1\ Any applicable gas may be eliminated or tested at a reduced level if
the manufacturer has provided reliable means for limiting or scrubbing
that gas to a specified level.
\2\ As practicable, gas concentrations should be the highest expected at
test sites.

Table 7E-4--Interference Response

Date of Test:__________________________________________________________
Analyzer Type:_________________________________________________________
Model No.:_____________________________________________________________
Serial No:_____________________________________________________________
Calibration Span:______________________________________________________

------------------------------------------------------------------------
Test gas type Concentration (ppm) Analyzer response
------------------------------------------------------------------------

------------------------------------------------------------------------

------------------------------------------------------------------------
Sum of Responses .....................
------------------------------------------------------------------------
% of Calibration Span .....................
------------------------------------------------------------------------

Table 7E-5--Manufacturer Stability Test
------------------------------------------------------------------------
Test description Acceptance criteria (note 1)
------------------------------------------------------------------------
Thermal Stability............ Temperature range when drift does not
exceed 3.0% of analyzer range over a 12-
hour run when measured with NOX present
@ 80% of calibration span.
Fault Conditions............. Identify conditions which, when they
occur, result in performance which is
not in compliance with the
Manufacturer's Stability Test criteria.
These are to be indicated visually or
electrically to alert the operator of
the problem.
Insensitivity to Supply 10.0% (or manufacturers alternative)
Voltage Variations. variation from nominal voltage must
produce a drift of 2.0% of
calibration span for either zero or
concentration 80% NOX
present.
Analyzer Calibration Error... For a low-, medium-, and high-calibration
gas, the difference between the
manufacturer certified value and the
analyzer response in direct calibration
mode, no more than 2.0% of calibration
span.
------------------------------------------------------------------------
Note 1: If the instrument is to be used as a Low Range analyzer, all
tests must be performed at a calibration span of 20 ppm or less.

Method 8--Determination of Sulfuric Acid and Sulfur Dioxide Emissions
From Stationary Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 5, and Method 6.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Sulfuric acid, including: 7664-93-9, 7449- 0.05 mg/m\3\ (0.03 x
Sulfuric acid (H2SO4) mist, 11-9. 10 7 lb/ft\3\).
Sulfur trioxide (SO3).
Sulfur dioxide (SO2).......... 7449-09-5........ 1.2 mg/m\3\ (3 x 10
9 lb/ft\3\).
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of H2SO4 (including H2SO4
mist and SO3) and gaseous SO2 emissions from
stationary sources.

Note: Filterable particulate matter may be determined along with
H2SO4 and SO2 (subject to the approval
of the Administrator) by inserting a heated glass fiber filter between
the probe and isopropanol impinger (see section 6.1.1 of Method 6). If
this option is chosen, particulate analysis is gravimetric only;
sulfuric acid is not determined separately.

[[Page 305]]

1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

A gas sample is extracted isokinetically from the stack. The
H2SO4 and the SO2 are separated, and
both fractions are measured separately by the barium-thorin titration
method.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Possible interfering agents of this method are fluorides, free
ammonia, and dimethyl aniline. If any of these interfering agents is
present (this can be determined by knowledge of the process),
alternative methods, subject to the approval of the Administrator, are
required.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. Same as Method 5, section 6.1, with the
following additions and exceptions:
6.1.1 Sampling Train. A schematic of the sampling train used in this
method is shown in Figure 8-1; it is similar to the Method 5 sampling
train, except that the filter position is different, and the filter
holder does not have to be heated. See Method 5, section 6.1.1, for
details and guidelines on operation and maintenance.
6.1.1.1 Probe Liner. Borosilicate or quartz glass, with a heating
system to prevent visible condensation during sampling. Do not use metal
probe liners.
6.1.1.2 Filter Holder. Borosilicate glass, with a glass frit filter
support and a silicone rubber gasket. Other gasket materials (e.g.,
Teflon or Viton) may be used, subject to the approval of the
Administrator. The holder design shall provide a positive seal against
leakage from the outside or around the filter. The filter holder shall
be placed between the first and second impingers. Do not heat the filter
holder.
6.1.1.3 Impingers. Four, of the Greenburg-Smith design, as shown in
Figure 8-1. The first and third impingers must have standard tips. The
second and fourth impingers must be modified by replacing the insert
with an approximately 13-mm (\1/2\-in.) ID glass tube, having an
unconstricted tip located 13 mm (\1/2\ in.) from the bottom of the
impinger. Similar collection systems, subject to the approval of the
Administrator, may be used.
6.1.1.4 Temperature Sensor. Thermometer, or equivalent, to measure
the temperature of the gas leaving the impinger train to within 1 [deg]C
(2 [deg]F).
6.2 Sample Recovery. The following items are required for sample
recovery:
6.2.1 Wash Bottles. Two polyethylene or glass bottles, 500-ml.
6.2.2 Graduated Cylinders. Two graduated cylinders (volumetric
flasks may be used), 250-ml, 1-liter.
6.2.3 Storage Bottles. Leak-free polyethylene bottles, 1-liter size
(two for each sampling run).
6.2.4 Trip Balance. 500-g capacity, to measure to 0.5 g (necessary
only if a moisture content analysis is to be done).
6.3 Analysis. The following items are required for sample analysis:
6.3.1 Pipettes. Volumetric 10-ml, 100-ml.
6.3.2 Burette. 50-ml.
6.3.3 Erlenmeyer Flask. 250-ml (one for each sample, blank, and
standard).
6.3.4 Graduated Cylinder. 100-ml.
6.3.5 Dropping Bottle. To add indicator solution, 125-ml size.

7.0 Reagents and Standards

7.1 Sample Collection. The following reagents are required for
sample collection:
7.1.1 Filters and Silica Gel. Same as in Method 5, sections 7.1.1
and 7.1.2, respectively.
7.1.2 Water. Same as in Method 6, section 7.1.1.
7.1.3 Isopropanol, 80 Percent by Volume. Mix 800 ml of isopropanol
with 200 ml of water.

Note: Check for peroxide impurities using the procedure outlined in
Method 6, section 7.1.2.1.

7.1.4 Hydrogen Peroxide (H\2\O\2\), 3 Percent by Volume. Dilute 100
ml of 30 percent H2O2) to 1 liter with water.
Prepare fresh daily.
7.1.5 Crushed Ice.
7.2 Sample Recovery. The reagents and standards required for sample
recovery are:
7.2.1 Water. Same as in section 7.1.2.
7.2.2 Isopropanol, 80 Percent. Same as in section 7.1.3.
7.3 Sample Analysis. Same as Method 6, section 7.3.

[[Page 306]]

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Pretest Preparation. Same as Method 5, section 8.1, except that
filters should be inspected but need not be desiccated, weighed, or
identified. If the effluent gas can be considered dry (i.e., moisture-
free), the silica gel need not be weighed.
8.2 Preliminary Determinations. Same as Method 5, section 8.2.
8.3 Preparation of Sampling Train. Same as Method 5, section 8.3,
with the following exceptions:
8.3.1 Use Figure 8-1 instead of Figure 5-1.
8.3.2 Replace the second sentence of Method 5, section 8.3.1 with:
Place 100 ml of 80 percent isopropanol in the first impinger, 100 ml of
3 percent H2O2 in both the second and third
impingers; retain a portion of each reagent for use as a blank solution.
Place about 200 g of silica gel in the fourth impinger.
8.3.3 Ignore any other statements in section 8.3 of Method 5 that
are obviously not applicable to the performance of Method 8.

Note: If moisture content is to be determined by impinger analysis,
weigh each of the first three impingers (plus absorbing solution) to the
nearest 0.5 g, and record these weights. Weigh also the silica gel (or
silica gel plus container) to the nearest 0.5 g, and record.)

8.4 Metering System Leak-Check Procedure. Same as Method 5, section
8.4.1.
8.5 Pretest Leak-Check Procedure. Follow the basic procedure in
Method 5, section 8.4.2, noting that the probe heater shall be adjusted
to the minimum temperature required to prevent condensation, and also
that verbage such as ``* * * plugging the inlet to the filter holder * *
* '' found in section 8.4.2.2 of Method 5 shall be replaced by `` * * *
plugging the inlet to the first impinger * * * ''. The pretest leak-
check is recommended, but is not required.
8.6 Sampling Train Operation. Follow the basic procedures in Method
5, section 8.5, in conjunction with the following special instructions:
8.6.1 Record the data on a sheet similar to that shown in Figure 8-2
(alternatively, Figure 5-2 in Method 5 may be used). The sampling rate
shall not exceed 0.030 m\3\/min (1.0 cfm) during the run. Periodically
during the test, observe the connecting line between the probe and first
impinger for signs of condensation. If condensation does occur, adjust
the probe heater setting upward to the minimum temperature required to
prevent condensation. If component changes become necessary during a
run, a leak-check shall be performed immediately before each change,
according to the procedure outlined in section 8.4.3 of Method 5 (with
appropriate modifications, as mentioned in section 8.5 of this method);
record all leak rates. If the leakage rate(s) exceeds the specified
rate, the tester shall either void the run or plan to correct the sample
volume as outlined in section 12.3 of Method 5. Leak-checks immediately
after component changes are recommended, but not required. If these
leak-checks are performed, the procedure in section 8.4.2 of Method 5
(with appropriate modifications) shall be used.
8.6.2 After turning off the pump and recording the final readings at
the conclusion of each run, remove the probe from the stack. Conduct a
post-test (mandatory) leak-check as outlined in section 8.4.4 of Method
5 (with appropriate modifications), and record the leak rate. If the
post-test leakage rate exceeds the specified acceptable rate, either
correct the sample volume, as outlined in section 12.3 of Method 5, or
void the run.
8.6.3 Drain the ice bath and, with the probe disconnected, purge the
remaining part of the train by drawing clean ambient air through the
system for 15 minutes at the average flow rate used for sampling.

Note: Clean ambient air can be provided by passing air through a
charcoal filter. Alternatively, ambient air (without cleaning) may be
used.

8.7 Calculation of Percent Isokinetic. Same as Method 5, section
8.6.
8.8 Sample Recovery. Proper cleanup procedure begins as soon as the
probe is removed from the stack at the end of the sampling period. Allow
the probe to cool. Treat the samples as follows:
8.8.1 Container No. 1.
8.8.1.1 If a moisture content analysis is to be performed, clean and
weigh the first impinger (plus contents) to the nearest 0.5 g, and
record this weight.
8.8.1.2 Transfer the contents of the first impinger to a 250-ml
graduated cylinder. Rinse the probe, first impinger, all connecting
glassware before the filter, and the front half of the filter holder
with 80 percent isopropanol. Add the isopropanol rinse solution to the
cylinder. Dilute the contents of the cylinder to 225 ml with 80 percent
isopropanol, and transfer the cylinder contents to the storage
container. Rinse the cylinder with 25 ml of 80 percent isopropanol, and
transfer the rinse to the storage container. Add the filter to the
solution in the storage container and mix. Seal the container to protect
the solution against evaporation. Mark the level of liquid on the
container, and identify the sample container.
8.8.2 Container No. 2.
8.8.2.1 If a moisture content analysis is to be performed, clean and
weigh the second and third impingers (plus contents) to the nearest 0.5
g, and record the weights. Also, weigh the spent silica gel (or silica
gel plus impinger) to the nearest 0.5 g, and record the weight.

[[Page 307]]

8.8.2.2 Transfer the solutions from the second and third impingers
to a 1-liter graduated cylinder. Rinse all connecting glassware
(including back half of filter holder) between the filter and silica gel
impinger with water, and add this rinse water to the cylinder. Dilute
the contents of the cylinder to 950 ml with water. Transfer the solution
to a storage container. Rinse the cylinder with 50 ml of water, and
transfer the rinse to the storage container. Mark the level of liquid on
the container. Seal and identify the sample container.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
7.1.3......................... Isopropanol check Ensure acceptable
level of peroxide
impurities in
isopropanol.
8.4, 8.5, 10.1................ Sampling Ensure accurate
equipment leak- measurement of stack
check and gas flow rate,
calibration. sample volume.
10.2.......................... Barium standard Ensure normality
solution determination.
standardization.
11.2.......................... Replicate Ensure precision of
titrations. titration
determinations.
------------------------------------------------------------------------

9.2 Volume Metering System Checks. Same as Method 5, section 9.2.

10.0 Calibration and Standardization

10.1 Sampling Equipment. Same as Method 5, section 10.0.
10.2 Barium Standard Solution. Same as Method 6, section 10.5.

11.0 Analytical Procedure

11.1. Sample Loss. Same as Method 6, section 11.1.
11.2. Sample Analysis.
11.2.1 Container No. 1. Shake the container holding the isopropanol
solution and the filter. If the filter breaks up, allow the fragments to
settle for a few minutes before removing a sample aliquot. Pipette a
100-ml aliquot of this solution into a 250-ml Erlenmeyer flask, add 2 to
4 drops of thorin indicator, and titrate to a pink endpoint using 0.0100
N barium standard solution. Repeat the titration with a second aliquot
of sample, and average the titration values. Replicate titrations must
agree within 1 percent or 0.2 ml, whichever is greater.
11.2.2 Container No. 2. Thoroughly mix the solution in the container
holding the contents of the second and third impingers. Pipette a 10-ml
aliquot of sample into a 250-ml Erlenmeyer flask. Add 40 ml of
isopropanol, 2 to 4 drops of thorin indicator, and titrate to a pink
endpoint using 0.0100 N barium standard solution. Repeat the titration
with a second aliquot of sample, and average the titration values.
Replicate titrations must agree within 1 percent or 0.2 ml, whichever is
greater.
11.2.3 Blanks. Prepare blanks by adding 2 to 4 drops of thorin
indicator to 100 ml of 80 percent isopropanol. Titrate the blanks in the
same manner as the samples.

12.0 Data Analysis and Calculations

Carry out calculations retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after final
calculation.
12.1 Nomenclature. Same as Method 5, section 12.1, with the
following additions and exceptions:

CH2SO4 = Sulfuric acid (including SO3)
concentration, g/dscm (lb/dscf).
CSO2 = Sulfur dioxide concentration, g/dscm (lb/dscf).
N = Normality of barium perchlorate titrant, meq/ml.
Va = Volume of sample aliquot titrated, 100 ml for
H2SO4 and 10 ml for SO2.
Vsoln = Total volume of solution in which the sample is
contained, 1000 ml for the SO2 sample and 250 ml
for the H2SO4 sample.
Vt = Volume of barium standard solution titrant used for the
sample, ml.
Vtb = Volume of barium standard solution titrant used for the
blank, ml.

12.2 Average Dry Gas Meter Temperature and Average Orifice Pressure
Drop. See data sheet (Figure 8-2).
12.3 Dry Gas Volume. Same as Method 5, section 12.3.
12.4 Volume of Water Vapor Condensed and Moisture Content. Calculate
the volume of water vapor using Equation 5-2 of Method 5; the weight of
water collected in the impingers and silica gel can be converted
directly to milliliters (the specific gravity of water is 1 g/ml).
Calculate the moisture content of the stack gas (Bws) using
Equation 5-3 of Method 5. The note in section 12.5 of Method 5 also
applies to this method. Note that if the effluent gas stream can be
considered dry, the volume of water vapor and moisture content need not
be calculated.
12.5 Sulfuric Acid Mist (Including SO3) Concentration.

[[Page 308]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.223

Where:

K3 = 0.04904 g/meq for metric units,
K3 = 1.081 x 10^-4 lb/meq for English units.

12.6 Sulfur Dioxide Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.224

Where:

K4 = 0.03203 g/meq for metric units,
K4 = 7.061 x 10^-5 lb/meq for English units.

12.7 Isokinetic Variation. Same as Method 5, section 12.11.
12.8 Stack Gas Velocity and Volumetric Flow Rate. Calculate the
average stack gas velocity and volumetric flow rate, if needed, using
data obtained in this method and the equations in sections 12.6 and 12.7
of Method 2.

13.0 Method Performance

13.1 Analytical Range. Collaborative tests have shown that the
minimum detectable limits of the method are 0.06 mg/m\3\ (4 x
10^-9 lb/ft\3\) for H2SO4 and 1.2 mg/
m\3\ (74 x 10^-9 lb/ft\3\) for SO2. No upper
limits have been established. Based on theoretical calculations for 200
ml of 3 percent H2O2 solution, the upper
concentration limit for SO2 in a 1.0 m\3\ (35.3 ft\3\) gas
sample is about 12,000 mg/m\3\ (7.7 x 10^-4 lb/ft\3\). The
upper limit can be extended by increasing the quantity of peroxide
solution in the impingers.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as section 17.0 of Methods 5 and 6.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 309]]

[GRAPHIC] [TIFF OMITTED] TR27FE14.015

[[Page 310]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.226

Method 9--Visual Determination of the Opacity of Emissions From
Stationary Sources

Many stationary sources discharge visible emissions into the
atmosphere; these emissions are usually in the shape of a plume. This
method involves the determination of plume opacity by qualified
observers. The method includes procedures for the training and
certification of observers, and procedures to be used in the field for
determination of plume opacity. The appearance of a plume as viewed by
an observer depends upon a number of variables, some of which may be
controllable and some of which may not be controllable in the field.
Variables which can be controlled to an extent to which they no longer
exert a significant influence upon

[[Page 311]]

plume appearance include: Angle of the observer with respect to the
plume; angle of the observer with respect to the sun; point of
observation of attached and detached steam plume; and angle of the
observer with respect to a plume emitted from a rectangular stack with a
large length to width ratio. The method includes specific criteria
applicable to these variables.
Other variables which may not be controllable in the field are
luminescence and color contrast between the plume and the background
against which the plume is viewed. These variables exert an influence
upon the appearance of a plume as viewed by an observer, and can affect
the ability of the observer to accurately assign opacity values to the
observed plume. Studies of the theory of plume opacity and field studies
have demonstrated that a plume is most visible and presents the greatest
apparent opacity when viewed against a contrasting background. It
follows from this, and is confirmed by field trials, that the opacity of
a plume, viewed under conditions where a contrasting background is
present can be assigned with the greatest degree of accuracy. However,
the potential for a positive error is also the greatest when a plume is
viewed under such contrasting conditions. Under conditions presenting a
less contrasting background, the apparent opacity of a plume is less and
approaches zero as the color and luminescence contrast decrease toward
zero. As a result, significant negative bias and negative errors can be
made when a plume is viewed under less contrasting conditions. A
negative bias decreases rather than increases the possibility that a
plant operator will be cited for a violation of opacity standards due to
observer error.
Studies have been undertaken to determine the magnitude of positive
errors which can be made by qualified observers while reading plumes
under contrasting conditions and using the procedures set forth in this
method. The results of these studies (field trials) which involve a
total of 769 sets of 25 readings each are as follows:
(1) For black plumes (133 sets at a smoke generator), 100 percent of
the sets were read with a positive error \1\ of less than 7.5 percent
opacity; 99 percent were read with a positive error of less than 5
percent opacity.
---------------------------------------------------------------------------

\1\ For a set, positive error = average opacity determined by
observers' 25 observations--average opacity determined from
transmissometer's 25 recordings.
---------------------------------------------------------------------------

(2) For white plumes (170 sets at a smoke generator, 168 sets at a
coal-fired power plant, 298 sets at a sulfuric acid plant), 99 percent
of the sets were read with a positive error of less than 7.5 percent
opacity; 95 percent were read with a positive error of less than 5
percent opacity.
The positive observational error associated with an average of
twenty-five readings is therefore established. The accuracy of the
method must be taken into account when determining possible violations
of applicable opacity standards.

1. Principle and Applicability

1.1 Principle. The opacity of emissions from stationary sources is
determined visually by a qualified observer.
1.2 Applicability. This method is applicable for the determination
of the opacity of emissions from stationary sources pursuant to Sec.
60.11(b) and for qualifying observers for visually determining opacity
of emissions.

2. Procedures

The observer qualified in accordance with section 3 of this method
shall use the following procedures for visually determining the opacity
of emissions:
2.1 Position. The qualified observer shall stand at a distance
sufficient to provide a clear view of the emissions with the sun
oriented in the 140[deg] sector to his back. Consistent with maintaining
the above requirement, the observer shall, as much as possible, make his
observations from a position such that his line of vision is
approximately perpendicular to the plume direction, and when observing
opacity of emissions from rectangular outlets (e.g., roof monitors, open
baghouses, noncircular stacks), approximately perpendicular to the
longer axis of the outlet. The observer's line of sight should not
include more than one plume at a time when multiple stacks are involved,
and in any case the observer should make his observations with his line
of sight perpendicular to the longer axis of such a set of multiple
stacks (e.g., stub stacks on baghouses).
2.2 Field Records. The observer shall record the name of the plant,
emission location, type facility, observer's name and affiliation, a
sketch of the observer's position relative to the source, and the date
on a field data sheet (Figure 9-1). The time, estimated distance to the
emission location, approximate wind direction, estimated wind speed,
description of the sky condition (presence and color of clouds), and
plume background are recorded on a field data sheet at the time opacity
readings are initiated and completed.
2.3 Observations. Opacity observations shall be made at the point of
greatest opacity in that portion of the plume where condensed water
vapor is not present. The observer shall not look continuously at the
plume, but instead shall observe the plume momentarily at 15-second
intervals.
2.3.1 Attached Steam Plumes. When condensed water vapor is present
within the

[[Page 312]]

plume as it emerges from the emission outlet, opacity observations shall
be made beyond the point in the plume at which condensed water vapor is
no longer visible. The observer shall record the approximate distance
from the emission outlet to the point in the plume at which the
observations are made.
2.3.2 Detached Steam Plume. When water vapor in the plume condenses
and becomes visible at a distinct distance from the emission outlet, the
opacity of emissions should be evaluated at the emission outlet prior to
the condensation of water vapor and the formation of the steam plume.
2.4 Recording Observations. Opacity observations shall be recorded
to the nearest 5 percent at 15-second intervals on an observational
record sheet. (See Figure 9-2 for an example.) A minimum of 24
observations shall be recorded. Each momentary observation recorded
shall be deemed to represent the average opacity of emissions for a 15-
second period.
2.5 Data Reduction. Opacity shall be determined as an average of 24
consecutive observations recorded at 15-second intervals. Divide the
observations recorded on the record sheet into sets of 24 consecutive
observations. A set is composed of any 24 consecutive observations. Sets
need not be consecutive in time and in no case shall two sets overlap.
For each set of 24 observations, calculate the average by summing the
opacity of the 24 observations and dividing this sum by 24. If an
applicable standard specifies an averaging time requiring more than 24
observations, calculate the average for all observations made during the
specified time period. Record the average opacity on a record sheet.
(See Figure 9-1 for an example.)

3. Qualifications and Testing

3.1 Certification Requirements. To receive certification as a
qualified observer, a candidate must be tested and demonstrate the
ability to assign opacity readings in 5 percent increments to 25
different black plumes and 25 different white plumes, with an error not
to exceed 15 percent opacity on any one reading and an average error not
to exceed 7.5 percent opacity in each category. Candidates shall be
tested according to the procedures described in section 3.2. Smoke
generators used pursuant to section 3.2 shall be equipped with a smoke
meter which meets the requirements of section 3.3.
The certification shall be valid for a period of 6 months, at which
time the qualification procedure must be repeated by any observer in
order to retain certification.
3.2 Certification Procedure. The certification test consists of
showing the candidate a complete run of 50 plumes--25 black plumes and
25 white plumes--generated by a smoke generator. Plumes within each set
of 25 black and 25 white runs shall be presented in random order. The
candidate assigns an opacity value to each plume and records his
observation on a suitable form. At the completion of each run of 50
readings, the score of the candidate is determined. If a candidate fails
to qualify, the complete run of 50 readings must be repeated in any
retest. The smoke test may be administered as part of a smoke school or
training program, and may be preceded by training or familiarization
runs of the smoke generator during which candidates are shown black and
white plumes of known opacity.
3.3 Smoke Generator Specifications. Any smoke generator used for the
purposes of section 3.2 shall be equipped with a smoke meter installed
to measure opacity across the diameter of the smoke generator stack. The
smoke meter output shall display instack opacity based upon a pathlength
equal to the stack exit diameter, on a full 0 to 100 percent chart
recorder scale. The smoke meter optical design and performance shall
meet the specifications shown in Table 9-1. The smoke meter shall be
calibrated as prescribed in section 3.3.1 prior to the conduct of each
smoke reading test. At the completion of each test, the zero and span
drift shall be checked and if the drift exceeds 1 percent opacity, the
condition shall be corrected prior to conducting any subsequent test
runs. The smoke meter shall be demonstrated, at the time of
installation, to meet the specifications listed in Table 9-1. This
demonstration shall be repeated following any subsequent repair or
replacement of the photocell or associated electronic circuitry
including the chart recorder or output meter, or every 6 months,
whichever occurs first.

Table 9-1--Smoke Meter Design and Performance Specifications
------------------------------------------------------------------------
Parameter Specification
------------------------------------------------------------------------
a. Light source.......................... Incandescent lamp operated at
nominal rated voltage.
b. Spectral response of photocell........ Photopic (daylight spectral
response of the human eye--
Citation 3).
c. Angle of view......................... 15[deg] maximum total angle.
d. Angle of projection................... 15[deg] maximum total angle.
e. Calibration error..................... 3% opacity, maximum.
f. Zero and span drift................... 1% opacity, 30 minutes.
g. Response time......................... 5 seconds.
------------------------------------------------------------------------

3.3.1 Calibration. The smoke meter is calibrated after allowing a
minimum of 30 minutes warmup by alternately producing simulated opacity
of 0 percent and 100 percent. When stable response at 0 percent or 100
percent is noted, the smoke meter is adjusted to produce an output of 0
percent or 100 percent, as appropriate. This calibration shall be
repeated until stable 0 percent and 100

[[Page 313]]

percent readings are produced without adjustment. Simulated 0 percent
and 100 percent opacity values may be produced by alternately switching
the power to the light source on and off while the smoke generator is
not producing smoke.
3.3.2 Smoke Meter Evaluation. The smoke meter design and performance
are to be evaluated as follows:
3.3.2.1 Light Source. Verify from manufacturer's data and from
voltage measurements made at the lamp, as installed, that the lamp is
operated within 5 percent of the nominal rated voltage.
3.3.2.2 Spectral Response of Photocell. Verify from manufacturer's
data that the photocell has a photopic response; i.e., the spectral
sensitivity of the cell shall closely approximate the standard spectral-
luminosity curve for photopic vision which is referenced in (b) of Table
9-1.

[[Page 314]]

[GRAPHIC] [TIFF OMITTED] TC01JN92.154

Figure 9-2--Observation Record
Page ---- of ----
Company........................... Observer................. ........
Location.......................... Type facility............ ........
Test Number....................... Point of emissions....... ........
Date..............................

[[Page 315]]

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Seconds Steam plume (check if applicable)
Hr. Min. ----------------------------------------------------------------------------- Comments
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Figure 9-2--Observation Record (Continued)
Page ---- of ----
Company........................... Observer................. ........
Location.......................... Type facility............ ........
Test Number....................... Point of emissions....... ........
Date..............................

[[Page 316]]

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3.3.2.3 Angle of View. Check construction geometry to ensure that
the total angle of view of the smoke plume, as seen by the photocell,
does not exceed 15[deg]. The total angle of view may be calculated from:
k = 2 tan^-1d/2L, where k = total angle of view; d = the sum
of the photocell diameter + the diameter of the limiting aperture; and L
= the distance from the photocell to the limiting aperture. The limiting
aperture is the point in the path between the photocell and the smoke
plume where the angle of view is most restricted. In smoke generator
smoke meters this is normally an orifice plate.
3.3.2.4 Angle of Projection. Check construction geometry to ensure
that the total angle of projection of the lamp on the smoke plume does
not exceed 15[deg]. The total angle of projection may be calculated
from: k = 2 tan^-1d/2L, where k = total angle of projection; d
= the sum of the length of the lamp

[[Page 317]]

filament + the diameter of the limiting aperture; and L = the distance
from the lamp to the limiting aperture.
3.3.2.5 Calibration Error. Using neutral-density filters of known
opacity, check the error between the actual response and the theoretical
linear response of the smoke meter. This check is accomplished by first
calibrating the smoke meter according to 3.3.1 and then inserting a
series of three neutral-density filters of nominal opacity of 20, 50,
and 75 percent in the smoke meter pathlength. Filters calibrated within
2 percent shall be used. Care should be taken when inserting the
filters to prevent stray light from affecting the meter. Make a total of
five nonconsecutive readings for each filter. The maximum error on any
one reading shall be 3 percent opacity.
3.3.2.6 Zero and Span Drift. Determine the zero and span drift by
calibrating and operating the smoke generator in a normal manner over a
1-hour period. The drift is measured by checking the zero and span at
the end of this period.
3.3.2.7 Response Time. Determine the response time by producing the
series of five simulated 0 percent and 100 percent opacity values and
observing the time required to reach stable response. Opacity values of
0 percent and 100 percent may be simulated by alternately switching the
power to the light source off and on while the smoke generator is not
operating.

4. Bibliography

1. Air Pollution Control District Rules and Regulations, Los Angeles
County Air Pollution Control District, Regulation IV, Prohibitions, Rule
50.
2. Weisburd, Melvin I., Field Operations and Enforcement Manual for
Air, U.S. Environmental Protection Agency, Research Triangle Park, NC.
APTD-1100, August 1972, pp. 4.1-4.36.
3. Condon, E.U., and Odishaw, H., Handbook of Physics, McGraw-Hill
Co., New York, NY, 1958, Table 3.1, p. 6-52.

Alternate Method 1--Determination of the Opacity of Emissions From
Stationary Sources Remotely by Lidar

This alternate method provides the quantitative determination of the
opacity of an emissions plume remotely by a mobile lidar system (laser
radar; Light Detection and Ranging). The method includes procedures for
the calibration of the lidar and procedures to be used in the field for
the lidar determination of plume opacity. The lidar is used to measure
plume opacity during either day or nighttime hours because it contains
its own pulsed light source or transmitter. The operation of the lidar
is not dependent upon ambient lighting conditions (light, dark, sunny or
cloudy).
The lidar mechanism or technique is applicable to measuring plume
opacity at numerous wavelengths of laser radiation. However, the
performance evaluation and calibration test results given in support of
this method apply only to a lidar that employs a ruby (red light) laser
[Reference 5.1].

1. Principle and Applicability

1.1 Principle. The opacity of visible emissions from stationary
sources (stacks, roof vents, etc.) is measured remotely by a mobile
lidar (laser radar).
1.2 Applicability. This method is applicable for the remote
measurement of the opacity of visible emissions from stationary sources
during both nighttime and daylight conditions, pursuant to 40 CFR Sec.
60.11(b). It is also applicable for the calibration and performance
verification of the mobile lidar for the measurement of the opacity of
emissions. A performance/design specification for a basic lidar system
is also incorporated into this method.
1.3 Definitions.
Azimuth angle: The angle in the horizontal plane that designates
where the laser beam is pointed. It is measured from an arbitrary fixed
reference line in that plane.
Backscatter: The scattering of laser light in a direction opposite
to that of the incident laser beam due to reflection from particulates
along the beam's atmospheric path which may include a smoke plume.
Backscatter signal: The general term for the lidar return signal
which results from laser light being backscattered by atmospheric and
smoke plume particulates.
Convergence distance: The distance from the lidar to the point of
overlap of the lidar receiver's field-of-view and the laser beam.
Elevation angle: The angle of inclination of the laser beam
referenced to the horizontal plane.
Far region: The region of the atmosphere's path along the lidar
line-of-sight beyond or behind the plume being measured.
Lidar: Acronym for Light Detection and Ranging.
Lidar range: The range or distance from the lidar to a point of
interest along the lidar line-of-sight.
Near region: The region of the atmospheric path along the lidar
line-of-sight between the lidar's convergence distance and the plume
being measured.
Opacity: One minus the optical transmittance of a smoke plume,
screen target, etc.
Pick interval: The time or range intervals in the lidar backscatter
signal whose minimum average amplitude is used to calculate opacity. Two
pick intervals are required, one in the near region and one in the far
region.
Plume: The plume being measured by lidar.
Plume signal: The backscatter signal resulting from the laser light
pulse passing through a plume.

[[Page 318]]

1/R\2\Correction: The correction made for the systematic decrease in
lidar backscatter signal amplitude with range.
Reference signal: The backscatter signal resulting from the laser
light pulse passing through ambient air.
Sample interval: The time period between successive samples for a
digital signal or between successive measurements for an analog signal.
Signal spike: An abrupt, momentary increase and decrease in signal
amplitude.
Source: The source being tested by lidar.
Time reference: The time (to) when the laser pulse
emerges from the laser, used as the reference in all lidar time or range
measurements.

2. Procedures

The mobile lidar calibrated in accordance with Paragraph 3 of this
method shall use the following procedures for remotely measuring the
opacity of stationary source emissions:
2.1 Lidar Position. The lidar shall be positioned at a distance from
the plume sufficient to provide an unobstructed view of the source
emissions. The plume must be at a range of at least 50 meters or three
consecutive pick intervals (whichever is greater) from the lidar's
transmitter/receiver convergence distance along the line-of-sight. The
maximum effective opacity measurement distance of the lidar is a
function of local atmospheric conditions, laser beam diameter, and plume
diameter. The test position of the lidar shall be selected so that the
diameter of the laser beam at the measurement point within the plume
shall be no larger than three-fourths the plume diameter. The beam
diameter is calculated by Equation (AM1-1):

D(lidar) = A + Rq0.75 D(Plume) (AM1-1)

Where:

D(Plume) = diameter of the plume (cm),
q = laser beam divergence measured in radians
R = range from the lidar to the source (cm)
D(Lidar) = diameter of the laser beam at range R (cm),
A = diameter of the laser beam or pulse where it leaves the laser.

The lidar range, R, is obtained by aiming and firing the laser at the
emissions source structure immediately below the outlet. The range value
is then determined from the backscatter signal which consists of a
signal spike (return from source structure) and the atmospheric
backscatter signal [Reference 5.1]. This backscatter signal should be
recorded.
When there is more than one source of emissions in the immediate
vicinity of the plume, the lidar shall be positioned so that the laser
beam passes through only a single plume, free from any interference of
the other plumes for a minimum of 50 meters or three consecutive pick
intervals (whichever is greater) in each region before and beyond the
plume along the line-of-sight (determined from the backscatter signals).
The lidar shall initially be positioned so that its line-of-sight is
approximately perpendicular to the plume.
When measuring the opacity of emissions from rectangular outlets
(e.g., roof monitors, open baghouses, noncircular stacks, etc.), the
lidar shall be placed in a position so that its line-of-sight is
approximately perpendicular to the longer (major) axis of the outlet.
2.2 Lidar Operational Restrictions. The lidar receiver shall not be
aimed within an angle of 15[deg] (cone angle) of the sun.
This method shall not be used to make opacity measurements if
thunderstorms, snowstorms, hail storms, high wind, high-ambient dust
levels, fog or other atmospheric conditions cause the reference signals
to consistently exceed the limits specified in section 2.3.
2.3 Reference Signal Requirements. Once placed in its proper
position for opacity measurement, the laser is aimed and fired with the
line-of-sight near the outlet height and rotated horizontally to a
position clear of the source structure and the associated plume. The
backscatter signal obtained from this position is called the ambient-air
or reference signal. The lidar operator shall inspect this signal
[Section V of Reference 5.1] to: (1) determine if the lidar line-of-
sight is free from interference from other plumes and from physical
obstructions such as cables, power lines, etc., for a minimum of 50
meters or three consecutive pick intervals (whichever is greater) in
each region before and beyond the plume, and (2) obtain a qualitative
measure of the homogeneity of the ambient air by noting any signal
spikes.
Should there be any signal spikes on the reference signal within a
minimum of 50 meters or three consecutive pick intervals (whichever is
greater) in each region before and beyond the plume, the laser shall be
fired three more times and the operator shall inspect the reference
signals on the display. If the spike(s) remains, the azimuth angle shall
be changed and the above procedures conducted again. If the spike(s)
disappears in all three reference signals, the lidar line-of-sight is
acceptable if there is shot-to-shot consistency and there is no
interference from other plumes.
Shot-to-shot consistency of a series of reference signals over a
period of twenty seconds is verified in either of two ways. (1) The
lidar operator shall observe the reference signal amplitudes. For shot-
to-shot consistency the ratio of Rf to Rn
[amplitudes of the near and far region pick intervals (Section 2.6.1)]
shall vary by not more than 6% between shots; or (2) the lidar operator
shall accept any one of the reference signals and

[[Page 319]]

treat the other two as plume signals; then the opacity for each of the
subsequent reference signals is calculated (Equation AM1-2). For shot-
to-shot consistency, the opacity values shall be within 3% of 0%
opacity and the associated So values less than or equal to 8%
(full scale) [Section 2.6].
If a set of reference signals fails to meet the requirements of this
section, then all plume signals [Section 2.4] from the last set of
acceptable reference signals to the failed set shall be discarded.
2.3.1 Initial and Final Reference Signals. Three reference signals
shall be obtained within a 90-second time period prior to any data run.
A final set of three reference signals shall be obtained within three
(3) minutes after the completion of the same data run.
2.3.2 Temporal Criterion for Additional Reference Signals. An
additional set of reference signals shall be obtained during a data run
if there is a change in wind direction or plume drift of 30[deg] or more
from the direction that was prevalent when the last set of reference
signals was obtained. An additional set of reference signals shall also
be obtained if there is an increase in value of SIn (near
region standard deviation, Equation AM1-5) or SIf (far region
standard deviation, Equation AM1-6) that is greater than 6% (full scale)
over the respective values calculated from the immediately previous
plume signal, and this increase in value remains for 30 seconds or
longer. An additional set of reference signals shall also be obtained if
there is a change in amplitude in either the near or the far region of
the plume signal, that is greater than 6% of the near signal amplitude
and this change in amplitude remains for 30 seconds or more.
2.4 Plume Signal Requirements. Once properly aimed, the lidar is
placed in operation with the nominal pulse or firing rate of six pulses/
minute (1 pulse/10 seconds). The lidar operator shall observe the plume
backscatter signals to determine the need for additional reference
signals as required by section 2.3.2. The plume signals are recorded
from lidar start to stop and are called a data run. The length of a data
run is determined by operator discretion. Short-term stops of the lidar
to record additional reference signals do not constitute the end of a
data run if plume signals are resumed within 90 seconds after the
reference signals have been recorded, and the total stop or interrupt
time does not exceed 3 minutes.
2.4.1 Non-hydrated Plumes. The laser shall be aimed at the region of
the plume which displays the greatest opacity. The lidar operator must
visually verify that the laser is aimed clearly above the source exit
structure.
2.4.2 Hydrated Plumes. The lidar will be used to measure the opacity
of hydrated or so-called steam plumes. As listed in the reference
method, there are two types, i.e., attached and detached steam plumes.
2.4.2.1 Attached Steam Plumes. When condensed water vapor is present
within a plume, lidar opacity measurements shall be made at a point
within the residual plume where the condensed water vapor is no longer
visible. The laser shall be aimed into the most dense region (region of
highest opacity) of the residual plume.
During daylight hours the lidar operator locates the most dense
portion of the residual plume visually. During nighttime hours a high-
intensity spotlight, night vision scope, or low light level TV, etc.,
can be used as an aid to locate the residual plume. If visual
determination is ineffective, the lidar may be used to locate the most
dense region of the residual plume by repeatedly measuring opacity,
along the longitudinal axis or center of the plume from the emissions
outlet to a point just beyond the steam plume. The lidar operator should
also observe color differences and plume reflectivity to ensure that the
lidar is aimed completely within the residual plume. If the operator
does not obtain a clear indication of the location of the residual
plume, this method shall not be used.
Once the region of highest opacity of the residual plume has been
located, aiming adjustments shall be made to the laser line-of-sight to
correct for the following: movement to the region of highest opacity out
of the lidar line-of-sight (away from the laser beam) for more than 15
seconds, expansion of the steam plume (air temperature lowers and/or
relative humidity increases) so that it just begins to encroach on the
field-of-view of the lidar's optical telescope receiver, or a decrease
in the size of the steam plume (air temperature higher and/or relative
humidity decreases) so that regions within the residual plume whose
opacity is higher than the one being monitored, are present.
2.4.2.2 Detached Steam Plumes. When the water vapor in a hydrated
plume condenses and becomes visible at a finite distance from the stack
or source emissions outlet, the opacity of the emissions shall be
measured in the region of the plume clearly above the emissions outlet
and below condensation of the water vapor.
During daylight hours the lidar operators can visually determine if
the steam plume is detached from the stack outlet. During nighttime
hours a high-intensity spotlight, night vision scope, low light level
TV, etc., can be used as an aid in determining if the steam plume is
detached. If visual determination is ineffective, the lidar may be used
to determine if the steam plume is detached by repeatedly measuring
plume opacity from the outlet to the steam plume along the plume's
longitudinal axis or center line. The lidar operator should also observe
color differences and plume reflectivity to detect a

[[Page 320]]

detached plume. If the operator does not obtain a clear indication of
the location of the detached plume, this method shall not be used to
make opacity measurements between the outlet and the detached plume.
Once the determination of a detached steam plume has been confirmed,
the laser shall be aimed into the region of highest opacity in the plume
between the outlet and the formation of the steam plume. Aiming
adjustments shall be made to the lidar's line-of-sight within the plume
to correct for changes in the location of the most dense region of the
plume due to changes in wind direction and speed or if the detached
steam plume moves closer to the source outlet encroaching on the most
dense region of the plume. If the detached steam plume should move too
close to the source outlet for the lidar to make interference-free
opacity measurements, this method shall not be used.
2.5 Field Records. In addition to the recording recommendations
listed in other sections of this method the following records should be
maintained. Each plume measured should be uniquely identified. The name
of the facility, type of facility, emission source type, geographic
location of the lidar with respect to the plume, and plume
characteristics should be recorded. The date of the test, the time
period that a source was monitored, the time (to the nearest second) of
each opacity measurement, and the sample interval should also be
recorded. The wind speed, wind direction, air temperature, relative
humidity, visibility (measured at the lidar's position), and cloud cover
should be recorded at the beginning and end of each time period for a
given source. A small sketch depicting the location of the laser beam
within the plume should be recorded.
If a detached or attached steam plume is present at the emissions
source, this fact should be recorded. Figures AM1-I and AM1-II are
examples of logbook forms that may be used to record this type of data.
Magnetic tape or paper tape may also be used to record data.

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[[Page 322]]

[GRAPHIC] [TIFF OMITTED] TC01JN92.156

[[Page 323]]

[GRAPHIC] [TIFF OMITTED] TC01JN92.157

2.6 Opacity Calculation and Data Analysis. Referring to the
reference signal and plume signal in Figure AM1-III, the measured
opacity (Op) in percent for each lidar measurement is
calculated using Equation AM1-2. (Op = 1-Tp;
Tp is the plume transmittance.)

[[Page 324]]

[GRAPHIC] [TIFF OMITTED] TC01JN92.158

Where:

In = near-region pick interval signal amplitude, plume
signal, 1/R\2\ corrected,
If = far-region pick interval signal amplitude, plume signal,
1/R\2\ corrected,
Rn = near-region pick interval signal amplitude, reference
signal, 1/R\2\ corrected, and
Rf = far-region pick interval signal amplitude, reference
signal, 1/R\2\ corrected.

The 1/R\2\ correction to the plume and reference signal amplitudes
is made by multiplying the amplitude for each successive sample interval
from the time reference, by the square of the lidar time (or range)
associated with that sample interval [Reference 5.1].
The first step in selecting the pick intervals for Equation AM1-2 is
to divide the plume signal amplitude by the reference signal amplitude
at the same respective ranges to obtain a ``normalized'' signal. The
pick intervals selected using this normalized signal, are a minimum of
15 m (100 nanoseconds) in length and consist of at least 5 contiguous
sample intervals. In addition, the following criteria, listed in order
of importance, govern pick interval selection. (1) The intervals shall
be in a region of the normalized signal where the reference signal meets
the requirements of section 2.3 and is everywhere greater than zero. (2)
The intervals (near and far) with the minimum average amplitude are
chosen. (3) If more than one interval with the same minimum average
amplitude is found, the interval closest to the plume is chosen. (4) The
standard deviation, So, for the calculated opacity shall be
8% or less. (So is calculated by Equation AM1-7).
If So is greater than 8%, then the far pick interval
shall be changed to the next interval of minimal average amplitude. If
So is still greater than 8%, then this procedure is repeated
for the far pick interval. This procedure may be repeated once again for
the near pick interval, but if So remains greater than 8%,
the plume signal shall be discarded.
The reference signal pick intervals, Rn and
Rf, must be chosen over the same time interval as the plume
signal pick intervals, In and If, respectively
[Figure AM1-III]. Other methods of selecting pick intervals may be used
if they give equivalent results. Field-oriented examples of pick
interval selection are available in Reference 5.1.
The average amplitudes for each of the pick intervals,
In, If, Rn, Rf, shall be
calculated by averaging the respective individual amplitudes of the
sample intervals from the plume signal and the associated reference
signal each corrected for 1/R\2\. The amplitude of In shall
be calculated according to Equation (AM-3).
[GRAPHIC] [TIFF OMITTED] TC01JN92.159

Where:

Ini = the amplitude of the ith sample interval (near-region),
M = sum of the individual amplitudes for the sample
intervals,
m = number of sample intervals in the pick interval, and
In = average amplitude of the near-region pick interval.

Similarly, the amplitudes for If, Rn, and
Rf are calculated with the three expressions in Equation
(AM1-4).
[GRAPHIC] [TIFF OMITTED] TC01JN92.160

The standard deviation, SIn, of the set of amplitudes for
the near-region pick interval, In, shall be calculated using
Equation (AM1-5).
Similarly, the standard deviations SIf, SRn,
and SRf are calculated with the three expressions in Equation
(AM1-6).

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[GRAPHIC] [TIFF OMITTED] TC01JN92.161

[GRAPHIC] [TIFF OMITTED] TC01JN92.162

The standard deviation, So, for each associated opacity
value, Op, shall be calculated using Equation (AM1-7).
[GRAPHIC] [TIFF OMITTED] TC01JN92.163

The calculated values of In, If,
Rn, Rf, SIn, SIf,
SRn, SRf, Op, and So should
be recorded. Any plume signal with an So greater than 8%
shall be discarded.
2.6.1 Azimuth Angle Correction. If the azimuth angle correction to
opacity specified in this section is performed, then the elevation angle
correction specified in section 2.6.2 shall not be performed. When
opacity is measured in the residual region of an attached steam plume,
and the lidar line-of-sight is not perpendicular to the plume, it may be
necessary to correct the opacity measured by the lidar to obtain the
opacity that would be measured on a path perpendicular to the plume. The
following method, or any other method which produces equivalent results,
shall be used to determine the need for a correction, to calculate the
correction, and to document the point within the plume at which the
opacity was measured.
Figure AM1-IV(b) shows the geometry of the opacity correction. L' is
the path through the plume along which the opacity measurement is made.
P' is the path perpendicular to the plume at the same point. The angle
is the angle between L' and the plume center line. The angle
(/2-), is the angle between the L' and P'. The
measured opacity, Op, measured along the path L' shall be
corrected to obtain the corrected opacity, Opc, for the path
P', using Equation (AM1-8).
[GRAPHIC] [TIFF OMITTED] TC01JN92.164

[[Page 326]]

The correction in Equation (AM1-8) shall be performed if the inequality
in Equation (AM1-9) is true.
[GRAPHIC] [TIFF OMITTED] TC01JN92.165

Figure AM1-IV(a) shows the geometry used to calculate and
the position in the plume at which the lidar measurement is made. This
analysis assumes that for a given lidar measurement, the range from the
lidar to the plume, the elevation angle of the lidar from the horizontal
plane, and the azimuth angle of the lidar from an arbitrary fixed
reference in the horizontal plane can all be obtained directly.

[[Page 327]]

[GRAPHIC] [TIFF OMITTED] TC01JN92.166

Rs = range from lidar to source*
s = elevation angle of Rs*
Rp = range from lidar to plume at the opacity measurement
point*
p = elevation angle of Rp*
Ra = range from lidar to plume at some arbitrary point,
Pa, so the drift angle of the plume can be
determined*

[[Page 328]]

a = elevation angle of Ra*
a = angle between Rp and Ra
R's = projection of Rs in the horizontal plane
R'p = projection of Rp in the horizontal plane
R'a = projection of Ra in the horizontal plane
c' = angle between R's and R'p*
a' = angle between R'p and R'a*
R = distance from the source to the opacity measurement point
projected in the horizontal plane
Rk = distance from opacity measurement point Pp to
the point in the plume Pa.
[GRAPHIC] [TIFF OMITTED] TC01JN92.167

The correction angle shall be determined using Equation
AM1-10.
---------------------------------------------------------------------------

*Obtained directly from lidar. These values should be recorded.

Where:

a = Cos^-1 (Cosp
Cosa Cosa' +
Sinp Sina),
and
Rk = (Rp2 + Ra2 - 2 Rp
Ra Cosa)\1/2\

R, the distance from the source to the opacity
measurement point projected in the horizontal plane, shall be determined
using Equation AM1-11.
[GRAPHIC] [TIFF OMITTED] TC01JN92.168

Where:

R's = Rs Cos s, and
R'p = Rp Cos p.

In the special case where the plume centerline at the opacity
measurement point is horizontal, parallel to the ground, Equation AM1-12
may be used to determine instead of Equation AM1-10.
[GRAPHIC] [TIFF OMITTED] TC01JN92.169

Where:

Rs = (R'\2\s +
Rp\2\Sin\2\p)^1/2.

If the angle is such that 30[deg] or
150[deg], the azimuth angle correction shall not be
performed and the associated opacity value shall be discarded.
2.6.2 Elevation Angle Correction. An individual lidar-measured
opacity, Op, shall be corrected for elevation angle if the
laser elevation or inclination angle, p [Figure
AM1-V], is greater than or equal to the value calculated in Equation
AM1-13.
[GRAPHIC] [TIFF OMITTED] TC01JN92.170

The measured opacity, Op, along the lidar path L, is adjusted
to obtain the corrected opacity, Opc, for the
actual plume (horizontal) path, P, by using Equation (AM1-14).

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[GRAPHIC] [TIFF OMITTED] TC01JN92.171

Where:

p = lidar elevation or inclination angle,
Op = measured opacity along path L, and
Opc = corrected opacity for the actual plume thickness P.
The values for p, Op and
Opc should be recorded.

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[GRAPHIC] [TIFF OMITTED] TC01JN92.172

2.6.3 Determination of Actual Plume Opacity. Actual opacity of the
plume shall be determined by Equation AM1-15.
[GRAPHIC] [TIFF OMITTED] TC01JN92.173

2.6.4 Calculation of Average Actual Plume Opacity. The average of
the actual plume opacity, Opa, shall be calculated as the
average of the consecutive individual actual opacity values,
Opa, by Equation AM1-16.

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[GRAPHIC] [TIFF OMITTED] TC01JN92.174

Where:

(Opa)k = the kth actual opacity value in an
averaging interval containing n opacity values; k is a summing
index.
M = the sum of the individual actual opacity values.
n = the number of individual actual opacity values contained in the
averaging interval.
Opa = average actual opacity calculated over the averaging
interval.

3. Lidar Performance Verification

The lidar shall be subjected to two types of performance
verifications that shall be performed in the field. The annual
calibration, conducted at least once a year, shall be used to directly
verify operation and performance of the entire lidar system. The routine
verification, conducted for each emission source measured, shall be used
to insure proper performance of the optical receiver and associated
electronics.
3.1 Annual Calibration Procedures. Either a plume from a smoke
generator or screen targets shall be used to conduct this calibration.
If the screen target method is selected, five screens shall be
fabricated by placing an opaque mesh material over a narrow frame (wood,
metal extrusion, etc.). The screen shall have a surface area of at least
one square meter. The screen material should be chosen for precise
optical opacities of about 10, 20, 40, 60, and 80%. Opacity of each
target shall be optically determined and should be recorded. If a smoke
generator plume is selected, it shall meet the requirements of section
3.3 of Reference Method 9. This calibration shall be performed in the
field during calm (as practical) atmospheric conditions. The lidar shall
be positioned in accordance with section 2.1.
The screen targets must be placed perpendicular to and coincident
with the lidar line-of-sight at sufficient height above the ground
(suggest about 30 ft) to avoid ground-level dust contamination.
Reference signals shall be obtained just prior to conducting the
calibration test.
The lidar shall be aimed through the center of the plume within 1
stack diameter of the exit, or through the geometric center of the
screen target selected. The lidar shall be set in operation for a 6-
minute data run at a nominal pulse rate of 1 pulse every 10 seconds.
Each backscatter return signal and each respective opacity value
obtained from the smoke generator transmissometer, shall be obtained in
temporal coincidence. The data shall be analyzed and reduced in
accordance with section 2.6 of this method. This calibration shall be
performed for 0% (clean air), and at least five other opacities
(nominally 10, 20, 40, 60, and 80%).
The average of the lidar opacity values obtained during a 6-minute
calibration run shall be calculated and should be recorded. Also the
average of the opacity values obtained from the smoke generator
transmissometer for the same 6-minute run shall be calculated and should
be recorded.
Alternate calibration procedures that do not meet the above
requirements but produce equivalent results may be used.
3.2 Routine Verification Procedures. Either one of two techniques
shall be used to conduct this verification. It shall be performed at
least once every 4 hours for each emission source measured. The
following parameters shall be directly verified.
1) The opacity value of 0% plus a minimum of 5 (nominally 10, 20,
40, 60, and 80%) opacity values shall be verified through the PMT
detector and data processing electronics.
2) The zero-signal level (receiver signal with no optical signal
from the source present) shall be inspected to insure that no spurious
noise is present in the signal. With the entire lidar receiver and
analog/digital electronics turned on and adjusted for normal operating
performance, the following procedures shall be used for Techniques 1 and
2, respectively.
3.2.1 Procedure for Technique 1. This test shall be performed with
no ambient or stray light reaching the PMT detector. The narrow band
filter (694.3 nanometers peak) shall be removed from its position in
front of the PMT detector. Neutral density filters of nominal opacities
of 10, 20, 40, 60, and 80% shall be used. The recommended test
configuration is depicted in Figure AM1-VI.

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[GRAPHIC] [TIFF OMITTED] TC01JN92.175

The zero-signal level shall be measured and should be recorded, as
indicated in Figure AM1-VI(a). This simulated clear-air or 0% opacity
value shall be tested in using the selected light source depicted in
Figure AM1-VI(b).
The light source either shall be a continuous wave (CW) laser with
the beam mechanically chopped or a light emitting diode controlled with
a pulse generator (rectangular pulse). (A laser beam may have to be
attenuated so as not to saturate the PMT detector). This signal level
shall be measured

[[Page 333]]

and should be recorded. The opacity value is calculated by taking two
pick intervals [Section 2.6] about 1 microsecond apart in time and using
Equation (AM1-2) setting the ratio Rn/Rf = 1. This
calculated value should be recorded.
The simulated clear-air signal level is also employed in the optical
test using the neutral density filters. Using the test configuration in
Figure AM1-VI(c), each neutral density filter shall be separately placed
into the light path from the light source to the PMT detector. The
signal level shall be measured and should be recorded. The opacity value
for each filter is calculated by taking the signal level for that
respective filter (If), dividing it by the 0% opacity signal
level (In) and performing the remainder of the calculation by
Equation (AM1-2) with Rn/Rf = 1. The calculated
opacity value for each filter should be recorded.
The neutral density filters used for Technique 1 shall be calibrated
for actual opacity with accuracy of 2% or better. This calibration
shall be done monthly while the filters are in use and the calibrated
values should be recorded.
3.2.2 Procedure for Technique 2. An optical generator (built-in
calibration mechanism) that contains a light-emitting diode (red light
for a lidar containing a ruby laser) is used. By injecting an optical
signal into the lidar receiver immediately ahead of the PMT detector, a
backscatter signal is simulated. With the entire lidar receiver
electronics turned on and adjusted for normal operating performance, the
optical generator is turned on and the simulation signal (corrected for
1/R\2\) is selected with no plume spike signal and with the opacity
value equal to 0%. This simulated clear-air atmospheric return signal is
displayed on the system's video display. The lidar operator then makes
any fine adjustments that may be necessary to maintain the system's
normal operating range.
The opacity values of 0% and the other five values are selected one
at a time in any order. The simulated return signal data should be
recorded. The opacity value shall be calculated. This measurement/
calculation shall be performed at least three times for each selected
opacity value. While the order is not important, each of the opacity
values from the optical generator shall be verified. The calibrated
optical generator opacity value for each selection should be recorded.
The optical generator used for Technique 2 shall be calibrated for
actual opacity with an accuracy of 1% or better. This calibration shall
be done monthly while the generator is in use and calibrated value
should be recorded.
Alternate verification procedures that do not meet the above
requirements but produce equivalent results may be used.
3.3 Deviation. The permissible error for the annual calibration and
routine verification are:
3.3.1 Annual Calibration Deviation.
3.3.1.1 Smoke Generator. If the lidar-measured average opacity for
each data run is not within 5% (full scale) of the respective smoke
generator's average opacity over the range of 0% through 80%, then the
lidar shall be considered out of calibration.
3.3.1.2 Screens. If the lidar-measured average opacity for each data
run is not within 3% (full scale) of the laboratory-determined opacity
for each respective simulation screen target over the range of 0%
through 80%, then the lidar shall be considered out of calibration.
3.3.2 Routine Verification Error. If the lidar-measured average
opacity for each neutral density filter (Technique 1) or optical
generator selection (Technique 2) is not within 3% (full scale) of the
respective laboratory calibration value then the lidar shall be
considered non-operational.

4. Performance/Design Specification for Basic Lidar System

4.1 Lidar Design Specification. The essential components of the
basic lidar system are a pulsed laser (transmitter), optical receiver,
detector, signal processor, recorder, and an aiming device that is used
in aiming the lidar transmitter and receiver. Figure AM1-VII shows a
functional block diagram of a basic lidar system.

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[GRAPHIC] [TIFF OMITTED] TC01JN92.176

4.2 Performance Evaluation Tests. The owner of a lidar system shall
subject such a lidar system to the performance verification tests
described in section 3, prior to first use of this method. The annual
calibration shall be performed for three separate, complete

[[Page 335]]

runs and the results of each should be recorded. The requirements of
section 3.3.1 must be fulfilled for each of the three runs.
Once the conditions of the annual calibration are fulfilled the
lidar shall be subjected to the routine verification for three separate
complete runs. The requirements of section 3.3.2 must be fulfilled for
each of the three runs and the results should be recorded. The
Administrator may request that the results of the performance evaluation
be submitted for review.

5. References

5.1 The Use of Lidar for Emissions Source Opacity Determination,
U.S. Environmental Protection Agency, National Enforcement
Investigations Center, Denver, CO. EPA-330/1-79-003-R, Arthur W.
Dybdahl, current edition [NTIS No. PB81-246662].
5.2 Field Evaluation of Mobile Lidar for the Measurement of Smoke
Plume Opacity, U.S. Environmental Protection Agency, National
Enforcement Investigations Center, Denver, CO. EPA/NEIC-TS-128, February
1976.
5.3 Remote Measurement of Smoke Plume Transmittance Using Lidar, C.
S. Cook, G. W. Bethke, W. D. Conner (EPA/RTP). Applied Optics 11, pg
1742. August 1972.
5.4 Lidar Studies of Stack Plumes in Rural and Urban Environments,
EPA-650/4-73-002, October 1973.
5.5 American National Standard for the Safe Use of Lasers ANSI Z
136.1-176, March 8, 1976.
5.6 U.S. Army Technical Manual TB MED 279, Control of Hazards to
Health from Laser Radiation, February 1969.
5.7 Laser Institute of America Laser Safety Manual, 4th Edition.
5.8 U.S. Department of Health, Education and Welfare, Regulations
for the Administration and Enforcement of the Radiation Control for
Health and Safety Act of 1968, January 1976.
5.9 Laser Safety Handbook, Alex Mallow, Leon Chabot, Van Nostrand
Reinhold Co., 1978.

Method 10--Determination of Carbon Monoxide Emissions From Stationary
Sources (Instrumental Analyzer Procedure)

1.0 Scope and Application

What is Method 10?

Method 10 is a procedure for measuring carbon monoxide (CO) in
stationary source emissions using a continuous instrumental analyzer.
Quality assurance and quality control requirements are included to
assure that you, the tester, collect data of known quality. You must
document your adherence to these specific requirements for equipment,
supplies, sample collection and analysis, calculations, and data
analysis. This method does not completely describe all equipment,
supplies, and sampling and analytical procedures you will need but
refers to other methods for some of the details. Therefore, to obtain
reliable results, you should also have a thorough knowledge of these
additional test methods which are found in appendix A to this part:
(a) Method 1--Sample and Velocity Traverses for Stationary Sources.
(b) Method 4--Determination of Moisture Content in Stack Gases.
(c) Method 7E--Determination of Nitrogen Oxides Emissions from
Stationary Sources (Instrumental Analyzer Procedure).
1.1 Analytes. What does this method determine? This method measures
the concentration of carbon monoxide.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
CO............................. 630-08-0 Typically <2% of
Calibration Span.
------------------------------------------------------------------------

1.2 Applicability. When is this method required? The use of Method
10 may be required by specific New Source Performance Standards, State
Implementation Plans, and permits where CO concentrations in stationary
source emissions must be measured, either to determine compliance with
an applicable emission standard or to conduct performance testing of a
continuous emission monitoring system (CEMS). Other regulations may also
require the use of Method 10.
1.3 Data Quality Objectives. Refer to section 1.3 of Method 7E.

2.0 Summary of Method

In this method, you continuously or intermittently sample the
effluent gas and convey the sample to an analyzer that measures the
concentration of CO. You must meet the performance requirements of this
method to validate your data.

3.0 Definitions

Refer to section 3.0 of Method 7E for the applicable definitions.

4.0 Interferences

Substances having a strong absorption of infrared energy may
interfere to some extent in some analyzers. Instrumental correction may
be used to compensate for the interference. You may also use silica gel
and ascarite traps to eliminate the interferences. If this option is
used, correct the measured

[[Page 336]]

gas volume for the carbon dioxide (CO2) removed in the trap.

5.0 Safety

Refer to section 5.0 of Method 7E.

6.0 Equipment and Supplies

What do I need for the measurement system?

6.1 Continuous Sampling. Figure 7E-1 of Method 7E is a schematic
diagram of an acceptable measurement system. The components are the same
as those in sections 6.1 and 6.2 of Method 7E, except that the CO
analyzer described in section 6.2 of this method must be used instead of
the analyzer described in section 6.2 of Method 7E. You must follow the
noted specifications in section 6.1 of Method 7E except that the
requirements to use stainless steel, Teflon, or non-reactive glass
filters do not apply. Also, a heated sample line is not required to
transport dry gases or for systems that measure the CO concentration on
a dry basis.
6.2 Integrated Sampling.
6.2.1 Air-Cooled Condenser or Equivalent. To remove any excess
moisture.
6.2.2 Valve. Needle valve, or equivalent, to adjust flow rate.
6.2.3 Pump. Leak-free diaphragm type, or equivalent, to transport
gas.
6.2.4 Rate Meter. Rotameter, or equivalent, to measure a flow range
from 0 to 1.0 liter per minute (0.035 cfm).
6.2.5 Flexible Bag. Tedlar, or equivalent, with a capacity of 60 to
90 liters (2 to 3 ft\3\). (Verify through the manufacturer that the
Tedlar alternative is suitable for CO and make this verified information
available for inspection.) Leak-test the bag in the laboratory before
using by evacuating with a pump followed by a dry gas meter. When the
evacuation is complete, there should be no flow through the meter. Gas
tanks may be used in place of bags if the samples are analyzed within
one week.
6.3 What analyzer must I use? You must use an instrument that
continuously measures CO in the gas stream and meets the specifications
in section 13.0. The dual-range analyzer provisions in section 6.2.8.1
of Method 7E apply.

7.0 Reagents and Standards

7.1 Calibration Gas. What calibration gases do I need? Refer to
section 7.1 of Method 7E for the calibration gas requirements.
7.2 Interference Check. What additional reagents do I need for the
interference check? Use the appropriate test gases listed in Table 7E-3
of Method 7E (i.e., potential interferents, as identified by the
instrument manufacturer) to conduct the interference check.

8.0 Sample Collection, Preservation, Storage, and Transport

Emission Test Procedure

8.1 Sampling Site and Sampling Points. You must follow section 8.1
of Method 7E.
8.2 Initial Measurement System Performance Tests. You must follow
the procedures in section 8.2 of Method 7E. If a dilution-type
measurement system is used, the special considerations in section 8.3 of
Method 7E also apply.
8.3 Interference Check. You must follow the procedures of section
8.2.7 of Method 7E.
8.4 Sample Collection.
8.4.1 Continuous Sampling. You must follow the procedures of section
8.4 of Method 7E.
8.4.2 Integrated Sampling. Evacuate the flexible bag. Set up the
equipment as shown in Figure 10-1 with the bag disconnected. Place the
probe in the stack and purge the sampling line. Connect the bag, making
sure that all connections are leak-free. Sample at a rate proportional
to the stack velocity. If needed, the CO2 content of the gas
may be determined by using the Method 3 integrated sample procedures, or
by weighing an ascarite CO2 removal tube used and computing
CO2 concentration from the gas volume sampled and the weight
gain of the tube. Data may be recorded on a form similar to Table 10-1.
If a tank is used for sample collection, follow procedures similar to
those in Sections 8.1.2, 8.2.3, 8.3, and 12.4 of Method 25 as
appropriate to prepare the tank, conduct the sampling, and correct the
measured sample concentration.
8.5 Post-Run System Bias Check, Drift Assessment, and Alternative
Dynamic Spike Procedure. You must follow the procedures in sections 8.5
and 8.6 of Method 7E.

9.0 Quality Control

Follow the quality control procedures in section 9.0 of Method 7E.

10.0 Calibration and Standardization

Follow the procedures for calibration and standardization in section
10.0 of Method 7E.

11.0 Analytical Procedures

Because sample collection and analysis are performed together (see
section 8), additional discussion of the analytical procedure is not
necessary.

12.0 Calculations and Data Analysis

You must follow the procedures for calculations and data analysis in
section 12.0 of Method 7E, as applicable, substituting CO for
NOX as applicable.
12.1 Concentration Correction for CO2 Removal. Correct
the CO concentration for CO2 removal (if applicable) using
Eq. 10-1.

[[Page 337]]

[GRAPHIC] [TIFF OMITTED] TR15MY06.011

Where:

CAvg = Average gas concentration for the test run, ppm.
CCO stack = Average unadjusted stack gas CO concentration
indicated by the data recorder for the test run, ppmv.
FCO2 = Volume fraction of CO2 in the sample, i.e.,
percent CO2 from Orsat analysis divided by 100.

13.0 Method Performance

The specifications for analyzer calibration error, system bias,
drift, interference check, and alternative dynamic spike procedure are
the same as in section 13.0 of Method 7E.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

The dynamic spike procedure and the manufacturer stability test are
the same as in sections 16.1 and 16.3 of Method 7E

17.0 References

1. ``EPA Traceability Protocol for Assay and Certification of
Gaseous Calibration Standards-- September 1997 as amended, EPA-600/R-97/
121

18.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR15MY06.016

[[Page 338]]

Table 10-1--Field Data
[Integrated sampling]
------------------------------------------------------------------------

------------------------------------------------------------------------
Location: Date:
------------------------------------------------------------------------
Test: Operator:
------------------------------------------------------------------------
Clock Time Rotameter Reading Comments
liters/min (cfm)
------------------------------------------------------------------------

------------------------------------------------------------------------

Method 10A--Determination of Carbon Monoxide Emissions in Certifying
Continuous Emission Monitoring Systems at Petroleum Refineries

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 4, and Method 5.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Carbon monoxide (CO).............. 630-08-0 3 ppmv
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of CO emissions at petroleum refineries. This method serves as the
reference method in the relative accuracy test for nondispersive
infrared (NDIR) CO continuous emission monitoring systems (CEMS) that
are required to be installed in petroleum refineries on fluid catalytic
cracking unit catalyst regenerators (Sec. 60.105(a)(2) of this part).
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

An integrated gas sample is extracted from the stack, passed through
an alkaline permanganate solution to remove sulfur oxides and nitrogen
oxides, and collected in a Tedlar or equivalent bag. (Verify through the
manufacturer that the Tedlar alternative is suitable for NO and make
this verified information available for inspection.) The CO
concentration in the sample is measured spectrophotometrically using the
reaction of CO with p-sulfaminobenzoic acid.

3.0 Definitions [Reserved]

4.0 Interferences

Sulfur oxides, nitric oxide, and other acid gases interfere with the
colorimetric reaction. They are removed by passing the sampled gas
through an alkaline potassium permanganate scrubbing solution. Carbon
dioxide (CO2) does not interfere, but, because it is removed
by the scrubbing solution, its concentration must be measured
independently and an appropriate volume correction made to the sampled
gas.

5.0 Safety

[[Page 339]]

Reacts exothermically with limited amounts of water.

6.0 Equipment and Supplies

6.1 Sample Collection. The sampling train shown in Figure 10A-1 is
required for sample collection. Component parts are described below:
6.1.1 Probe. Stainless steel, sheathed Pyrex glass, or equivalent,
equipped with a glass wool plug to remove particulate matter.
6.1.2 Sample Conditioning System. Three Greenburg-Smith impingers
connected in series with leak-free connections.
6.1.3 Pump. Leak-free pump with stainless steel and Teflon parts to
transport sample at a flow rate of 300 ml/min (0.01 ft\3\/min) to the
flexible bag.
6.1.4 Surge Tank. Installed between the pump and the rate meter to
eliminate the pulsation effect of the pump on the rate meter.
6.1.5 Rate Meter. Rotameter, or equivalent, to measure flow rate at
300 ml/min (0.01 ft\3\/min). Calibrate according to section 10.2.
6.1.6 Flexible Bag. Tedlar, or equivalent, with a capacity of 10
liters (0.35 ft\3\) and equipped with a sealing quick-connect plug. The
bag must be leak-free according to section 8.1. For protection, it is
recommended that the bag be enclosed within a rigid container.
6.1.7 Valves. Stainless-steel needle valve to adjust flow rate, and
stainless-steel three-way valve, or equivalent.
6.1.8 CO2 Analyzer. Fyrite, or equivalent, to measure
CO2 concentration to within O.5 percent.
6.1.9 Volume Meter. Dry gas meter, capable of measuring the sample
volume under calibration conditions of 300 ml/min (0.01 ft\3\/min) for
10 minutes.
6.1.10 Pressure Gauge. A water filled U-tube manometer, or
equivalent, of about 30 cm (12 in.) to leak-check the flexible bag.
6.2 Sample Analysis.
6.2.1 Spectrophotometer. Single- or double-beam to measure
absorbance at 425 and 600 nm. Slit width should not exceed 20 nm.
6.2.2 Spectrophotometer Cells. 1-cm pathlength.
6.2.3 Vacuum Gauge. U-tube mercury manometer, 1 meter (39 in.), with
1-mm divisions, or other gauge capable of measuring pressure to within 1
mm Hg.
6.2.4 Pump. Capable of evacuating the gas reaction bulb to a
pressure equal to or less than 40 mm Hg absolute, equipped with coarse
and fine flow control valves.
6.2.5 Barometer. Mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 1 mm Hg.
6.2.6 Reaction Bulbs. Pyrex glass, 100-ml with Teflon stopcock
(Figure 10A-2), leak-free at 40 mm Hg, designed so that 10 ml of the
colorimetric reagent can be added and removed easily and accurately.
Commercially available gas sample bulbs such as Supelco Catalog No. 2-
2161 may also be used.
6.2.7 Manifold. Stainless steel, with connections for three reaction
bulbs and the appropriate connections for the manometer and sampling bag
as shown in Figure 10A-3.
6.2.8 Pipets. Class A, 10-ml size.
6.2.9 Shaker Table. Reciprocating-stroke type such as Eberbach
Corporation, Model 6015. A rocking arm or rotary-motion type shaker may
also be used. The shaker must be large enough to accommodate at least
six gas sample bulbs simultaneously. It may be necessary to construct a
table top extension for most commercial shakers to provide sufficient
space for the needed bulbs (Figure 10A-4).
6.2.10 Valve. Stainless steel shut-off valve.
6.2.11 Analytical Balance. Capable of weighing to 0.1 mg.

7.0 Reagents and Standards

Unless otherwise indicated, all reagents shall conform to the
specifications established by the Committee on Analytical Reagents of
the American Chemical Society, where such specifications are available;
otherwise, the best available grade shall be used.
7.1 Sample Collection.
7.1.1 Water. Deionized distilled, to conform to ASTM D 1193-77 or
91, Type 3 (incorporated by reference--see Sec. 60.17). If high
concentrations of organic matter are not expected to be present, the
potassium permanganate test for oxidizable organic matter may be
omitted.
7.1.2 Alkaline Permanganate Solution, 0.25 M KMnO4/1.5 M
Sodium Hydroxide (NaOH). Dissolve 40 g KMnO4 and 60 g NaOH in
approximately 900 ml water, cool, and dilute to 1 liter.
7.2 Sample Analysis.
7.2.1 Water. Same as in section 7.1.1.
7.2.2 1 M Sodium Hydroxide Solution. Dissolve 40 g NaOH in
approximately 900 ml of water, cool, and dilute to 1 liter.
7.2.3 0.1 M NaOH Solution. Dilute 50 ml of the 1 M NaOH solution
prepared in section 7.2.2 to 500 ml.
7.2.4 0.1 M Silver Nitrate (AgNO3) Solution. Dissolve 8.5
g AgNO3 in water, and dilute to 500 ml.
7.2.5 0.1 M Para-Sulfaminobenzoic Acid (p-SABA) Solution. Dissolve
10.0 g p-SABA in 0.1 M NaOH, and dilute to 500 ml with 0.1 M NaOH.
7.2.6 Colorimetric Solution. To a flask, add 100 ml of 0.1 M p-SABA
solution and 100 ml of 0.1 M AgNO3 solution. Mix, and add 50
ml of 1 M NaOH with shaking. The resultant solution should be clear and
colorless. This solution is acceptable for use for a period of 2 days.

[[Page 340]]

7.2.7 Standard Gas Mixtures. Traceable to National Institute of
Standards and Technology (NIST) standards and containing between 50 and
1000 ppm CO in nitrogen. At least two concentrations are needed to span
each calibration range used (Section 10.3). The calibration gases must
be certified by the manufacturer to be within 2 percent of the specified
concentrations.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sample Bag Leak-Checks. While a bag leak-check is required after
bag use, it should also be done before the bag is used for sample
collection. The bag should be leak-checked in the inflated and deflated
condition according to the following procedure:
8.1.1 Connect the bag to a water manometer, and pressurize the bag
to 5 to 10 cm H2O (2 to 4 in H2O). Allow the bag
to stand for 60 minutes. Any displacement in the water manometer
indicates a leak.
8.1.2 Evacuate the bag with a leakless pump that is connected to the
downstream side of a flow indicating device such as a 0- to 100-ml/min
rotameter or an impinger containing water. When the bag is completely
evacuated, no flow should be evident if the bag is leak-free.
8.2 Sample Collection.
8.2.1 Evacuate the bag completely using a vacuum pump. Assemble the
apparatus as shown in Figure 10A-1. Loosely pack glass wool in the tip
of the probe. Place 400 ml of alkaline permanganate solution in the
first two impingers and 250 ml in the third. Connect the pump to the
third impinger, and follow this with the surge tank, rate meter, and 3-
way valve. Do not connect the bag to the system at this time.
8.2.2 Leak-check the sampling system by plugging the probe inlet,
opening the 3-way valve, and pulling a vacuum of approximately 250 mm Hg
on the system while observing the rate meter for flow. If flow is
indicated on the rate meter, do not proceed further until the leak is
found and corrected.
8.2.3 Purge the system with sample gas by inserting the probe into
the stack and drawing the sample gas through the system at 300 ml/min
10 percent for 5 minutes. Connect the evacuated bag to the system,
record the starting time, and sample at a rate of 300 ml/min for 30
minutes, or until the bag is nearly full. Record the sampling time, the
barometric pressure, and the ambient temperature. Purge the system as
described above immediately before each sample.
8.2.4 The scrubbing solution is adequate for removing sulfur oxides
and nitrogen oxides from 50 liters (1.8 ft\3\) of stack gas when the
concentration of each is less than 1,000 ppm and the CO2
concentration is less than 15 percent. Replace the scrubber solution
after every fifth sample.
8.3 Carbon Dioxide Measurement. Measure the CO2 content
in the stack to the nearest 0.5 percent each time a CO sample is
collected. A simultaneous grab sample analyzed by the Fyrite analyzer is
acceptable.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

9.2 Volume Metering System Checks. Same as Method 5, section 9.2.

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.

10.1 Gas Bulb Calibration. Weigh the empty bulb to the nearest 0.1
g. Fill the bulb to the stopcock with water, and again weigh to the
nearest 0.1 g. Subtract the tare weight, and calculate the volume in
liters to three significant figures using the density of water at the
measurement temperature. Record the volume on the bulb. Alternatively,
mark an identification number on the bulb, and record the volume in a
notebook.
10.2 Rate Meter Calibration. Assemble the system as shown in Figure
10A-1 (the impingers may be removed), and attach a volume meter to the
probe inlet. Set the rotameter at 300 ml/min, record the volume meter
reading, start the pump, and pull ambient air through the system for 10
minutes. Record the final volume meter reading. Repeat the procedure and
average the results to determine the volume of gas that passed through
the system.
10.3 Spectrophotometer Calibration Curve.
10.3.1 Collect the standards as described in section 8.2. Prepare at
least two sets of three bulbs as standards to span the 0 to 400 or 400
to 1000 ppm range. If any samples span both concentration ranges,
prepare a calibration curve for each range using separate reagent
blanks. Prepare a set of three bulbs containing colorimetric reagent but
no CO to serve as a reagent blank. Analyze each standard and blank
according to the sample analysis procedure of section 11.0 Reject the

[[Page 341]]

standard set where any of the individual bulb absorbances differs from
the set mean by more than 10 percent.
10.3.2 Calculate the average absorbance for each set (3 bulbs) of
standards using Equation 10A-1 and Table 10A-1. Construct a graph of
average absorbance for each standard against its corresponding
concentration. Draw a smooth curve through the points. The curve should
be linear over the two concentration ranges discussed in section 13.3.

11.0 Analytical Procedure

11.1 Assemble the system shown in Figure 10A-3, and record the
information required in Table 10A-1 as it is obtained. Pipet 10.0 ml of
the colorimetric reagent into each gas reaction bulb, and attach the
bulbs to the system. Open the stopcocks to the reaction bulbs, but leave
the valve to the bag closed. Turn on the pump, fully open the coarse-
adjust flow valve, and slowly open the fine-adjust valve until the
pressure is reduced to at least 40 mm Hg. Now close the coarse adjust
valve, and observe the manometer to be certain that the system is leak-
free. Wait a minimum of 2 minutes. If the pressure has increased less
than 1 mm Hg, proceed as described below. If a leak is present, find and
correct it before proceeding further.
11.2 Record the vacuum pressure (Pv) to the nearest 1 mm
Hg, and close the reaction bulb stopcocks. Open the bag valve, and allow
the system to come to atmospheric pressure. Close the bag valve, open
the pump coarse adjust valve, and evacuate the system again. Repeat this
fill/evacuation procedure at least twice to flush the manifold
completely. Close the pump coarse adjust valve, open the bag valve, and
let the system fill to atmospheric pressure. Open the stopcocks to the
reaction bulbs, and let the entire system come to atmospheric pressure.
Close the bulb stopcocks, remove the bulbs, record the room temperature
and barometric pressure (Pbar, to nearest mm Hg), and place
the bulbs on the shaker table with their main axis either parallel to or
perpendicular to the plane of the table top. Purge the bulb-filling
system with ambient air for several minutes between samples. Shake the
samples for exactly 2 hours.
11.3 Immediately after shaking, measure the absorbance (A) of each
bulb sample at 425 nm if the concentration is less than or equal to 400
ppm CO or at 600 nm if the concentration is above 400 ppm.

Note: This may be accomplished with multiple bulb sets by
sequentially collecting sets and adding to the shaker at staggered
intervals, followed by sequentially removing sets from the shaker for
absorbance measurement after the two-hour designated intervals have
elapsed.

11.4 Use a small portion of the sample to rinse a spectrophotometer
cell several times before taking an aliquot for analysis. If one cell is
used to analyze multiple samples, rinse the cell with deionized
distilled water several times between samples. Prepare and analyze
standards and a reagent blank as described in section 10.3. Use water as
the reference. Reject the analysis if the blank absorbance is greater
than 0.1. All conditions should be the same for analysis of samples and
standards. Measure the absorbances as soon as possible after shaking is
completed.
11.5 Determine the CO concentration of each bag sample using the
calibration curve for the appropriate concentration range as discussed
in section 10.3.

12.0 Calculations and Data Analysis

Carry out calculations retaining at least one extra decimal figure
beyond that of the acquired data. Round off figures after final
calculation.
12.1 Nomenclature.

A = Sample absorbance, uncorrected for the reagent blank.
Ar = Absorbance of the reagent blank.
As = Average sample absorbance per liter, units/liter.
Bw = Moisture content in the bag sample.
C = CO concentration in the stack gas, dry basis, ppm.
Cb = CO concentration of the bag sample, dry basis, ppm.
Cg = CO concentration from the calibration curve, ppm.
F = Volume fraction of CO2 in the stack.
n = Number of reaction bulbs used per bag sample.
Pb = Barometric pressure, mm Hg.
Pv = Residual pressure in the sample bulb after evacuation,
mm Hg.
Pw = Vapor pressure of H2O in the bag (from Table
10A-2), mm Hg.
Vb = Volume of the sample bulb, liters.
Vr = Volume of reagent added to the sample bulb, 0.0100
liter.

12.2 Average Sample Absorbance per Liter. Calculate As
for each gas bulb using Equation 10A-1, and record the value in Table
10A-1. Calculate the average As for each bag sample, and
compare the three values to the average. If any single value differs by
more than 10 percent from the average, reject this value, and calculate
a new average using the two remaining values.
[GRAPHIC] [TIFF OMITTED] TR17OC00.227

Note: A and Ar must be at the same wavelength.

12.3 CO Concentration in the Bag. Calculate Cb using
Equations 10A-2 and 10A-3. If condensate is visible in the bag,
calculate Bw using Table 10A-2 and the temperature and
barometric pressure in the analysis room. If

[[Page 342]]

condensate is not visible, calculate Bw using the temperature
and barometric pressure at the sampling site.
[GRAPHIC] [TIFF OMITTED] TR17OC00.228

[GRAPHIC] [TIFF OMITTED] TR17OC00.229

12.4 CO Concentration in the Stack.
[GRAPHIC] [TIFF OMITTED] TR17OC00.230

13.0 Method Performance

13.1 Precision. The estimated intralaboratory standard deviation of
the method is 3 percent of the mean for gas samples analyzed in
duplicate in the concentration range of 39 to 412 ppm. The
interlaboratory precision has not been established.
13.2 Accuracy. The method contains no significant biases when
compared to an NDIR analyzer calibrated with NIST standards.
13.3 Range. Approximately 3 to 1800 ppm CO. Samples having
concentrations below 400 ppm are analyzed at 425 nm, and samples having
concentrations above 400 ppm are analyzed at 600 nm.
13.4 Sensitivity. The detection limit is 3 ppmv based on a change in
concentration equal to three times the standard deviation of the reagent
blank solution.
13.5 Stability. The individual components of the colorimetric
reagent are stable for at least one month. The colorimetric reagent must
be used within two days after preparation to avoid excessive blank
correction. The samples in the bag should be stable for at least one
week if the bags are leak-free.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Butler, F.E., J.E. Knoll, and M.R. Midgett. Development and
Evaluation of Methods for Determining Carbon Monoxide Emissions. U.S.
Environmental Protection Agency, Research Triangle Park, N.C. June 1985.
33 pp.
2. Ferguson, B.B., R.E. Lester, and W.J. Mitchell. Field Evaluation
of Carbon Monoxide and Hydrogen Sulfide Continuous Emission Monitors at
an Oil Refinery. U.S. Environmental Protection Agency, Research Triangle
Park, N.C. Publication No. EPA-600/4-82-054. August 1982. 100 pp.
3. Lambert, J.L., and R.E. Weins. Induced Colorimetric Method for
Carbon Monoxide. Analytical Chemistry. 46(7):929-930. June 1974.
4. Levaggi, D.A., and M. Feldstein. The Colorimetric Determination
of Low Concentrations of Carbon Monoxide. Industrial Hygiene Journal.
25:64-66. January-February 1964.
5. Repp, M. Evaluation of Continuous Monitors For Carbon Monoxide in
Stationary Sources. U.S. Environmental Protection Agency. Research
Triangle Park, N.C. Publication No. EPA-600/2-77-063. March 1977. 155
pp.
6. Smith, F., D.E. Wagoner, and R.P. Donovan. Guidelines for
Development of a Quality Assurance Program: Volume VIII--Determination
of CO Emissions from Stationary Sources by NDIR Spectrometry. U.S.
Environmental Protection Agency. Research Triangle Park, N.C.
Publication No. EPA-650/4-74-005-h. February 1975. 96 pp.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 343]]

Table 10A-1--Data Recording Sheet for Samples Analyzed in Triplicate
--------------------------------------------------------------------------------------------------------------------------------------------------------
Partial
Room Bulb Reagent pressure Abs
Sample No./type temp Stack Bulb No. vol. vol. in of gas in Pb, mm Shaking versus A-Ar As Avg As
[deg]C %CO2 liters bulb, bulb, mm Hg time, min water
liter Hg
--------------------------------------------------------------------------------------------------------------------------------------------------------
blank
--------------------------------------------------------------------------------------------------------------------------------------------------------

------------------------------------------------------------------------------------------------------------------
Std. 1
------------------------------------------------------------------------------------------------------------------

--------------------------------------------------------------------------------------------------------------------------------------------------------

------------------------------------------------------------------------------------------------------------------
Std. 2
------------------------------------------------------------------------------------------------------------------

--------------------------------------------------------------------------------------------------------------------------------------------------------

------------------------------------------------------------------------------------------------------------------
Sample 1
------------------------------------------------------------------------------------------------------------------

--------------------------------------------------------------------------------------------------------------------------------------------------------
Sample 2
------------------------------------------------------------------------------------------------------------------

--------------------------------------------------------------------------------------------------------------------------------------------------------

------------------------------------------------------------------------------------------------------------------

------------------------------------------------------------------------------------------------------------------
Sample 3
--------------------------------------------------------------------------------------------------------------------------------------------------------

[[Page 344]]

Table 10A-2--Moisture Correction
----------------------------------------------------------------------------------------------------------------
Vapor pressure Temperature Vapor pressure
Temperature [deg]C of H2O, mm Hg [deg]C of H2, mm Hg
----------------------------------------------------------------------------------------------------------------
4............................................................... 6.1 18 15.5
6............................................................... 7.0 20 17.5
8............................................................... 8.0 22 19.8
10.............................................................. 9.2 24 22.4
12.............................................................. 10.5 26 25.2
14.............................................................. 12.0 28 28.3
16.............................................................. 13.6 30 31.8
----------------------------------------------------------------------------------------------------------------

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[[Page 346]]

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Method 10B--Determination of Carbon Monoxide Emissions From Stationary
Sources

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Carbon monoxide (CO)............. 630-08-0 Not determined.
------------------------------------------------------------------------

1.2 Applicability. This method applies to the measurement of CO
emissions at petroleum refineries and from other sources when specified
in an applicable subpart of the regulations.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 An integrated gas sample is extracted from the sampling point,
passed through a conditioning system to remove interferences, and
collected in a Tedlar or equivalent bag. (Verify through the
manufacturer that the Tedlar alternative is suitable for NO and make
this verifying information available for inspection.) The CO is
separated from the sample by gas chromatography (GC) and catalytically
reduced to methane (CH4) which is determined by flame
ionization detection (FID). The analytical portion of this method is
identical to applicable sections in Method 25 detailing CO measurement.

[[Page 348]]

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Carbon dioxide (CO2) and organics potentially can
interfere with the analysis. Most of the CO2 is removed from
the sample by the alkaline permanganate conditioning system; any
residual CO2 and organics are separated from the CO by GC.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. Same as in Method 10A, section 6.1.
6.2 Sample Analysis. A GC/FID analyzer, capable of quantifying CO in
the sample and consisting of at least the following major components, is
required for sample analysis. [Alternatively, complete Method 25
analytical systems (Method 25, section 6.3) are acceptable alternatives
when calibrated for CO and operated in accordance with the Method 25
analytical procedures (Method 25, section 11.0).]
6.2.1 Separation Column. A column capable of separating CO from
CO2 and organic compounds that may be present. A 3.2-mm (\1/
8\-in.) OD stainless steel column packed with 1.7 m (5.5 ft.) of 60/80
mesh Carbosieve S-II (available from Supelco) has been used successfully
for this purpose.
6.2.2 Reduction Catalyst. Same as in Method 25, section 6.3.1.2.
6.2.3 Sample Injection System. Same as in Method 25, Section
6.3.1.4, equipped to accept a sample line from the bag.
6.2.4 Flame Ionization Detector. Meeting the linearity
specifications of section 10.3 and having a minimal instrument range of
10 to 1,000 ppm CO.
6.2.5 Data Recording System. Analog strip chart recorder or digital
integration system, compatible with the FID, for permanently recording
the analytical results.

7.0 Reagents and Standards

7.1 Sample Collection. Same as in Method 10A, section 7.1.
7.2 Sample Analysis.
7.2.1 Carrier, Fuel, and Combustion Gases. Same as in Method 25,
sections 7.2.1, 7.2.2, and 7.2.3, respectively.
7.2.2 Calibration Gases. Three standard gases with nominal CO
concentrations of 20, 200, and 1,000 ppm CO in nitrogen. The calibration
gases shall be certified by the manufacturer to be 2 percent of the
specified concentrations.
7.2.3 Reduction Catalyst Efficiency Check Calibration Gas. Standard
CH4 gas with a nominal concentration of 1,000 ppm in air.

8.0 Sample Collection, Preservation, Storage, and Transport

Same as in Method 10A, section 8.0.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.0........................... Sample bag/ Ensures that negative
sampling system bias introduced
leak-checks. through leakage is
minimized.
10.1.......................... Carrier gas blank Ensures that positive
check. bias introduced by
contamination of
carrier gas is less
than 5 ppmv.
10.2.......................... Reduction Ensures that negative
catalyst bias introduced by
efficiency check. inefficient
reduction catalyst
is less than 5
percent.
10.3.......................... Analyzer Ensures linearity of
calibration. analyzer response to
standards.
11.2.......................... Triplicate sample Ensures precision of
analyses. analytical results.
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 Carrier Gas Blank Check. Analyze each new tank of carrier gas
with the GC analyzer according to section 11.2 to check for
contamination. The corresponding concentration must be less than 5 ppm
for the tank to be acceptable for use.
10.2 Reduction Catalyst Efficiency Check. Prior to initial use, the
reduction catalyst shall be tested for reduction efficiency. With the
heated reduction catalyst bypassed, make triplicate injections of the
1,000 ppm CH4 gas (Section 7.2.3) to calibrate the analyzer.
Repeat the procedure using 1,000 ppm CO gas (Section 7.2.2) with the
catalyst in operation. The reduction catalyst operation is acceptable if
the CO response is within 5 percent of the certified gas value.
10.3 Analyzer Calibration. Perform this test before the system is
first placed into operation. With the reduction catalyst in operation,
conduct a linearity check of the analyzer using the standards specified
in section 7.2.2. Make triplicate injections of each calibration gas,
and then calculate the average response factor (area/ppm) for each gas,
as

[[Page 349]]

well as the overall mean of the response factor values. The instrument
linearity is acceptable if the average response factor of each
calibration gas is within 2.5 percent of the overall mean value and if
the relative standard deviation (calculated in section 12.8 of Method
25) for each set of triplicate injections is less than 2 percent. Record
the overall mean of the response factor values as the calibration
response factor (R).

11.0 Analytical Procedure

11.1 Preparation for Analysis. Before putting the GC analyzer into
routine operation, conduct the calibration procedures listed in section
10.0. Establish an appropriate carrier flow rate and detector
temperature for the specific instrument used.
11.2 Sample Analysis. Purge the sample loop with sample, and then
inject the sample. Analyze each sample in triplicate, and calculate the
average sample area (A). Determine the bag CO concentration according to
section 12.2.

12.0 Calculations and Data Analysis

Carry out calculations retaining at least one extra significant
figure beyond that of the acquired data. Round off results only after
the final calculation.
12.1 Nomenclature.
A = Average sample area.
Bw = Moisture content in the bag sample, fraction.
C = CO concentration in the stack gas, dry basis, ppm.
Cb = CO concentration in the bag sample, dry basis, ppm.
F = Volume fraction of CO2 in the stack, fraction.
Pbar = Barometric pressure, mm Hg.
Pw = Vapor pressure of the H2O in the bag (from
Table 10A-2, Method 10A), mm Hg.
R = Mean calibration response factor, area/ppm.

12.2 CO Concentration in the Bag. Calculate Cb using
Equations 10B-1 and 10B-2. If condensate is visible in the bag,
calculate Bw using Table 10A-2 of Method 10A and the
temperature and barometric pressure in the analysis room. If condensate
is not visible, calculate Bw using the temperature and
barometric pressure at the sampling site.
[GRAPHIC] [TIFF OMITTED] TR17OC00.235

[GRAPHIC] [TIFF OMITTED] TR17OC00.236

12.3 CO Concentration in the Stack
[GRAPHIC] [TIFF OMITTED] TR17OC00.237

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as in Method 25, section 16.0, with the addition of the
following:

1. Butler, F.E, J.E. Knoll, and M.R. Midgett. Development and
Evaluation of Methods for Determining Carbon Monoxide Emissions. Quality
Assurance Division, Environmental Monitoring Systems Laboratory, U.S.
Environmental Protection Agency, Research Triangle Park, NC. June 1985.
33 pp.

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

[36 FR 24877, Dec. 23, 1971]

Editorial Note: For Federal Register citations affecting appendix A-
4 to part 60, see the List of CFR sections Affected, which appears in
the Finding Aids section of the printed volume and at www.fdsys.gov.

Sec. Appendix A-5 to Part 60--Test Methods 11 through 15A

Method 11--Determination of hydrogen sulfide content of fuel gas streams
in petroleum refineries
Method 12--Determination of inorganic lead emissions from stationary
sources
Method 13A--Determination of total fluoride emissions from stationary
sources--SPADNS zirconium lake method
Method 13B--Determination of total fluoride emissions from stationary
sources--Specific ion electrode method
Method 14--Determination of fluoride emissions from potroom roof
monitors for primary aluminum plants
Method 14A--Determination of Total Fluoride Emissions from Selected
Sources at Primary Aluminum Production Facilities
Method 15--Determination of hydrogen sulfide, carbonyl sulfide, and
carbon disulfide emissions from stationary sources
Method 15A--Determination of total reduced sulfur emissions from sulfur
recovery plants in petroleum refineries
The test methods in this appendix are referred to in Sec. 60.8
(Performance Tests) and Sec. 60.11 (Compliance With Standards and
Maintenance Requirements) of 40 CFR part 60, subpart A (General
Provisions). Specific uses of these test methods are described in the
standards of performance contained in the subparts, beginning with
Subpart D.
Within each standard of performance, a section title ``Test Methods
and Procedures'' is provided to: (1) Identify the test methods

[[Page 350]]

to be used as reference methods to the facility subject to the
respective standard and (2) identify any special instructions or
conditions to be followed when applying a method to the respective
facility. Such instructions (for example, establish sampling rates,
volumes, or temperatures) are to be used either in addition to, or as a
substitute for procedures in a test method. Similarly, for sources
subject to emission monitoring requirements, specific instructions
pertaining to any use of a test method as a reference method are
provided in the subpart or in Appendix B.
Inclusion of methods in this appendix is not intended as an
endorsement or denial of their applicability to sources that are not
subject to standards of performance. The methods are potentially
applicable to other sources; however, applicability should be confirmed
by careful and appropriate evaluation of the conditions prevalent at
such sources.
The approach followed in the formulation of the test methods
involves specifications for equipment, procedures, and performance. In
concept, a performance specification approach would be preferable in all
methods because this allows the greatest flexibility to the user. In
practice, however, this approach is impractical in most cases because
performance specifications cannot be established. Most of the methods
described herein, therefore, involve specific equipment specifications
and procedures, and only a few methods in this appendix rely on
performance criteria.
Minor changes in the test methods should not necessarily affect the
validity of the results and it is recognized that alternative and
equivalent methods exist. section 60.8 provides authority for the
Administrator to specify or approve (1) equivalent methods, (2)
alternative methods, and (3) minor changes in the methodology of the
test methods. It should be clearly understood that unless otherwise
identified all such methods and changes must have prior approval of the
Administrator. An owner employing such methods or deviations from the
test methods without obtaining prior approval does so at the risk of
subsequent disapproval and retesting with approved methods.
Within the test methods, certain specific equipment or procedures
are recognized as being acceptable or potentially acceptable and are
specifically identified in the methods. The items identified as
acceptable options may be used without approval but must be identified
in the test report. The potentially approvable options are cited as
``subject to the approval of the Administrator'' or as ``or
equivalent.'' Such potentially approvable techniques or alternatives may
be used at the discretion of the owner without prior approval. However,
detailed descriptions for applying these potentially approvable
techniques or alternatives are not provided in the test methods. Also,
the potentially approvable options are not necessarily acceptable in all
applications. Therefore, an owner electing to use such potentially
approvable techniques or alternatives is responsible for: (1) assuring
that the techniques or alternatives are in fact applicable and are
properly executed; (2) including a written description of the
alternative method in the test report (the written method must be clear
and must be capable of being performed without additional instruction,
and the degree of detail should be similar to the detail contained in
the test methods); and (3) providing any rationale or supporting data
necessary to show the validity of the alternative in the particular
application. Failure to meet these requirements can result in the
Administrator's disapproval of the alternative.

Method 11--Determination of Hydrogen Sulfide Content of Fuel Gas Streams
in Petroleum Refineries

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Hydrogen sulfide (H2S)........... 7783-06-4 8 mg/m\3\--740 mg/
m\3\, (6 ppm--520
ppm).
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of the H2S content of fuel gas streams at petroleum
refineries.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A sample is extracted from a source and passed through a series
of midget impingers containing a cadmium sulfate (CdSO4)
solution; H2S is absorbed, forming cadmium sulfide (CdS). The
latter compound is then measured iodometrically.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Any compound that reduces iodine (I2) or oxidizes the
iodide ion will interfere in this procedure, provided it is collected in
the CdSO4 impingers. Sulfur dioxide in concentrations of up
to 2,600 mg/m\3\ is removed

[[Page 351]]

with an impinger containing a hydrogen peroxide
(H2O2) solution. Thiols precipitate with
H2S. In the absence of H2S, only traces of thiols
are collected. When methane-and ethane-thiols at a total level of 300
mg/m\3\ are present in addition to H2S, the results vary from
2 percent low at an H2S concentration of 400 mg/m\3\ to 14
percent high at an H2S concentration of 100 mg/m\3\. Carbonyl
sulfide at a concentration of 20 percent does not interfere. Certain
carbonyl-containing compounds react with iodine and produce recurring
end points. However, acetaldehyde and acetone at concentrations of 1 and
3 percent, respectively, do not interfere.
4.2 Entrained H2O2 produces a negative
interference equivalent to 100 percent of that of an equimolar quantity
of H2S. Avoid the ejection of H2O2 into
the CdSO4 impingers.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The following items are needed for sample
collection:
6.1.1 Sampling Line. Teflon tubing, 6- to 7- mm (\1/4\-in.) ID, to
connect the sampling train to the sampling valve.
6.1.2 Impingers. Five midget impingers, each with 30-ml capacity.
The internal diameter of the impinger tip must be 1 mm 0.05 mm. The
impinger tip must be positioned 4 to 6 mm from the bottom of the
impinger.
6.1.3 Tubing. Glass or Teflon connecting tubing for the impingers.
6.1.4 Ice Water Bath. To maintain absorbing solution at a low
temperature.
6.1.5 Drying Tube. Tube packed with 6- to 16- mesh indicating-type
silica gel, or equivalent, to dry the gas sample and protect the meter
and pump. If the silica gel has been used previously, dry at 175 [deg]C
(350 [deg]F) for 2 hours. New silica gel may be used as received.
Alternatively, other types of desiccants (equivalent or better) may be
used, subject to approval of the Administrator.

Note: Do not use more than 30 g of silica gel. Silica gel adsorbs
gases such as propane from the fuel gas stream, and use of excessive
amounts of silica gel could result in errors in the determination of
sample volume.

6.1.6 Sampling Valve. Needle valve, or equivalent, to adjust gas
flow rate. Stainless steel or other corrosion-resistant material.
6.1.7 Volume Meter. Dry gas meter (DGM), sufficiently accurate to
measure the sample volume within 2 percent, calibrated at the selected
flow rate (about 1.0 liter/min) and conditions actually encountered
during sampling. The meter shall be equipped with a temperature sensor
(dial thermometer or equivalent) capable of measuring temperature to
within 3 [deg]C (5.4 [deg]F). The gas meter should have a petcock, or
equivalent, on the outlet connector which can be closed during the leak-
check. Gas volume for one revolution of the meter must not be more than
10 liters.
6.1.8 Rate Meter. Rotameter, or equivalent, to measure flow rates in
the range from 0.5 to 2 liters/min (1 to 4 ft\3\/hr).
6.1.9 Graduated Cylinder. 25-ml size.
6.1.10 Barometer. Mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 2.5 mm Hg (0.1 in. Hg). In many
cases, the barometric reading may be obtained from a nearby National
Weather Service station, in which case, the station value (which is the
absolute barometric pressure) shall be requested and an adjustment for
elevation differences between the weather station and the sampling point
shall be applied at a rate of minus 2.5 mm Hg (0.1 in Hg) per 30 m (100
ft) elevation increase or vice-versa for elevation decrease.
6.1.11 U-tube Manometer. 0-; to 30-cm water column, for leak-check
procedure.
6.1.12 Rubber Squeeze Bulb. To pressurize train for leak-check.
6.1.13 Tee, Pinchclamp, and Connecting Tubing. For leak-check.
6.1.14 Pump. Diaphragm pump, or equivalent. Insert a small surge
tank between the pump and rate meter to minimize the pulsation effect of
the diaphragm pump on the rate meter. The pump is used for the air purge
at the end of the sample run; the pump is not ordinarily used during
sampling, because fuel gas streams are usually sufficiently pressurized
to force sample gas

[[Page 352]]

through the train at the required flow rate. The pump need not be leak-
free unless it is used for sampling.
6.1.15 Needle Valve or Critical Orifice. To set air purge flow to 1
liter/min.
6.1.16 Tube Packed with Active Carbon. To filter air during purge.
6.1.17 Volumetric Flask. One 1000-ml.
6.1.18 Volumetric Pipette. One 15-ml.
6.1.19 Pressure-Reduction Regulator. Depending on the sampling
stream pressure, a pressure-reduction regulator may be needed to reduce
the pressure of the gas stream entering the Teflon sample line to a safe
level.
6.1.20 Cold Trap. If condensed water or amine is present in the
sample stream, a corrosion-resistant cold trap shall be used immediately
after the sample tap. The trap shall not be operated below 0 [deg]C (32
[deg]F) to avoid condensation of C3 or C4
hydrocarbons.
6.2 Sample Recovery. The following items are needed for sample
recovery:
6.2.1 Sample Container. Iodine flask, glass-stoppered, 500-ml size.
6.2.2 Volumetric Pipette. One 50-ml.
6.2.3 Graduated Cylinders. One each 25- and 250-ml.
6.2.4 Erlenmeyer Flasks. 125-ml.
6.2.5 Wash Bottle.
6.2.6 Volumetric Flasks. Three 1000-ml.
6.3 Sample Analysis. The following items are needed for sample
analysis:
6.3.1 Flask. Glass-stoppered iodine flask, 500-ml.
6.3.2 Burette. 50-ml.
6.3.3 Erlenmeyer Flask. 125-ml.
6.3.4 Volumetric Pipettes. One 25-ml; two each 50- and 100-ml.
6.3.5 Volumetric Flasks. One 1000-ml; two 500-ml.
6.3.6 Graduated Cylinders. One each 10- and 100-ml.

7.0 Reagents and Standards

7.1 Sample Collection. The following reagents are required for
sample collection:
7.1.1 CdSO4 Absorbing Solution. Dissolve 41 g of
3CdSO48H2O and 15 ml of 0.1 M sulfuric acid in a
1-liter volumetric flask that contains approximately \3/4\ liter of
water. Dilute to volume with deionized, distilled water. Mix thoroughly.
The pH should be 3 0.1. Add 10 drops of Dow-Corning Antifoam B. Shake
well before use. This solution is stable for at least one month. If
Antifoam B is not used, a more labor-intensive sample recovery procedure
is required (see section 11.2).
7.1.2 Hydrogen Peroxide, 3 Percent. Dilute 30 percent
H2O2 to 3 percent as needed. Prepare fresh daily.
7.1.3 Water. Deionized distilled to conform to ASTM D 1193-77 or 91,
Type 3 (incorporated by reference--see Sec. 60.17). The
KMnO4 test for oxidizable organic matter may be omitted when
high concentrations of organic matter are not expected to be present.
7.2 Sample Recovery. The following reagents are needed for sample
recovery:
7.2.1 Water. Same as section 7.1.3.
7.2.2 Hydrochloric Acid (HCl) Solution, 3 M. Add 240 ml of
concentrated HCl (specific gravity 1.19) to 500 ml of water in a 1-liter
volumetric flask. Dilute to 1 liter with water. Mix thoroughly.
7.2.3 Iodine (I2) Solution, 0.1 N. Dissolve 24 g of
potassium iodide (KI) in 30 ml of water. Add 12.7 g of resublimed iodine
(I2) to the KI solution. Shake the mixture until the
I2 is completely dissolved. If possible, let the solution
stand overnight in the dark. Slowly dilute the solution to 1 liter with
water, with swirling. Filter the solution if it is cloudy. Store
solution in a brown-glass reagent bottle.
7.2.4 Standard I2 Solution, 0.01 N. Pipette 100.0 ml of
the 0.1 N iodine solution into a 1-liter volumetric flask, and dilute to
volume with water. Standardize daily as in section 10.2.1. This solution
must be protected from light. Reagent bottles and flasks must be kept
tightly stoppered.
7.3 Sample Analysis. The following reagents and standards are needed
for sample analysis:
7.3.1 Water. Same as in section 7.1.3.
7.3.2 Standard Sodium Thiosulfate Solution, 0.1 N. Dissolve 24.8 g
of sodium thiosulfate pentahydrate
(Na2S2O35H2O) or 15.8 g of
anhydrous sodium thiosulfate (Na2S2O3)
in 1 liter of water, and add 0.01 g of anhydrous sodium carbonate
(Na2CO3) and 0.4 ml of chloroform
(CHCl3) to stabilize. Mix thoroughly by shaking or by
aerating with nitrogen for approximately 15 minutes, and store in a
glass-stoppered, reagent bottle. Standardize as in section 10.2.2.
7.3.3 Standard Sodium Thiosulfate Solution, 0.01 N. Pipette 50.0 ml
of the standard 0.1 N Na2S2O3 solution
into a volumetric flask, and dilute to 500 ml with water.

Note: A 0.01 N phenylarsine oxide (C6H5AsO)
solution may be prepared instead of 0.01 N
Na2S2O3 (see section 7.3.4).

7.3.4 Standard Phenylarsine Oxide Solution, 0.01 N. Dissolve 1.80 g
of (C6H5AsO) in 150 ml of 0.3 N sodium hydroxide.
After settling, decant 140 ml of this solution into 800 ml of water.
Bring the solution to pH 6-7 with 6 N HCl, and dilute to 1 liter with
water. Standardize as in section 10.2.3.
7.3.5 Starch Indicator Solution. Suspend 10 g of soluble starch in
100 ml of water, and add 15 g of potassium hydroxide (KOH) pellets. Stir
until dissolved, dilute with 900 ml of water, and let stand for 1 hour.
Neutralize the alkali with concentrated HCl, using an

[[Page 353]]

indicator paper similar to Alkacid test ribbon, then add 2 ml of glacial
acetic acid as a preservative.

Note: Test starch indicator solution for decomposition by titrating
with 0.01 N I2 solution, 4 ml of starch solution in 200 ml of
water that contains 1 g of KI. If more than 4 drops of the 0.01 N
I2 solution are required to obtain the blue color, a fresh
solution must be prepared.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sampling Train Preparation. Assemble the sampling train as shown
in Figure 11-1, connecting the five midget impingers in series. Place 15
ml of 3 percent H2O2 solution in the first
impinger. Leave the second impinger empty. Place 15 ml of the
CdSO4 solution in the third, fourth, and fifth impingers.
Place the impinger assembly in an ice water bath container, and place
water and crushed ice around the impingers. Add more ice during the run,
if needed.
8.2 Leak-Check Procedure.
8.2.1 Connect the rubber bulb and manometer to the first impinger,
as shown in Figure 11-1. Close the petcock on the DGM outlet. Pressurize
the train to 25 cm water with the bulb, and close off the tubing
connected to the rubber bulb. The train must hold 25 cm water pressure
with not more than a 1 cm drop in pressure in a 1-minute interval.
Stopcock grease is acceptable for sealing ground glass joints.
8.2.2 If the pump is used for sampling, it is recommended, but not
required, that the pump be leak-checked separately, either prior to or
after the sampling run. To leak-check the pump, proceed as follows:
Disconnect the drying tube from the impinger assembly. Place a vacuum
gauge at the inlet to either the drying tube or the pump, pull a vacuum
of 250 mm Hg (10 in. Hg), plug or pinch off the outlet of the flow
meter, and then turn off the pump. The vacuum should remain stable for
at least 30 seconds. If performed prior to the sampling run, the pump
leak-check should precede the leak-check of the sampling train described
immediately above; if performed after the sampling run, the pump leak-
check should follow the sampling train leak-check.
8.3 Purge the connecting line between the sampling valve and the
first impinger by disconnecting the line from the first impinger,
opening the sampling valve, and allowing process gas to flow through the
line for one to two minutes. Then, close the sampling valve, and
reconnect the line to the impinger train. Open the petcock on the dry
gas meter outlet. Record the initial DGM reading.
8.4 Open the sampling valve, and then adjust the valve to obtain a
rate of approximately 1 liter/min (0.035 cfm). Maintain a constant (10
percent) flow rate during the test. Record the DGM temperature.
8.5 Sample for at least 10 minutes. At the end of the sampling time,
close the sampling valve, and record the final volume and temperature
readings. Conduct a leak-check as described in Section 8.2. A yellow
color in the final cadmium sulfate impinger indicates depletion of the
absorbing solution. An additional cadmium sulfate impinger should be
added for subsequent samples and the sample with yellow color in the
final impinger should be voided.
8.6 Disconnect the impinger train from the sampling line. Connect
the charcoal tube and the pump as shown in Figure 11-1. Purge the train
[at a rate of 1 liter/min (0.035 ft\3\/min)] with clean ambient air for
15 minutes to ensure that all H2S is removed from the
H2O2. For sample recovery, cap the open ends, and
remove the impinger train to a clean area that is away from sources of
heat. The area should be well lighted, but not exposed to direct
sunlight.
8.7 Sample Recovery.
8.7.1 Discard the contents of the H2O2
impinger. Carefully rinse with water the contents of the third, fourth,
and fifth impingers into a 500-ml iodine flask.

Note: The impingers normally have only a thin film of CdS remaining
after a water rinse. If Antifoam B was not used or if significant
quantities of yellow CdS remain in the impingers, the alternative
recovery procedure in section 11.2 must be used.

8.7.2 Proceed to section 11 for the analysis.

9.0 Quality Control

10.0 Calibration and Standardization

Note: Maintain a log of all calibrations.

10.1 Calibration. Calibrate the sample collection equipment as
follows.
10.1.1 Dry Gas Meter.
10.1.1.1 Initial Calibration. The DGM shall be calibrated before its
initial use in the field. Proceed as follows: First, assemble the
following components in series: Drying tube, needle valve, pump,
rotameter, and DGM.

[[Page 354]]

Then, leak-check the metering system as follows: Place a vacuum gauge
(at least 760 mm Hg) at the inlet to the drying tube, and pull a vacuum
of 250 mm Hg (10 in. Hg); plug or pinch off the outlet of the flow
meter, and then turn off the pump. The vacuum shall remain stable for at
least 30 seconds. Carefully release the vacuum gauge before releasing
the flow meter end. Next, calibrate the DGM (at the sampling flow rate
specified by the method) as follows: Connect an appropriately sized wet-
test meter (e.g., 1 liter per revolution) to the inlet of the drying
tube. Make three independent calibration runs, using at least five
revolutions of the DGM per run. Calculate the calibration factor, Y
(wet-test meter calibration volume divided by the DGM volume, both
volumes adjusted to the same reference temperature and pressure), for
each run, and average the results. If any Y value deviates by more than
2 percent from the average, the DGM is unacceptable for use. Otherwise,
use the average as the calibration factor for subsequent test runs.
10.1.1.2 Post-Test Calibration Check. After each field test series,
conduct a calibration check as in section 10.1.1.1, above, except for
the following two variations: (a) three or more revolutions of the DGM
may be used and (b) only two independent runs need be made. If the
calibration factor does not deviate by more than 5 percent from the
initial calibration factor (determined in section 10.1.1.1), then the
DGM volumes obtained during the test series are acceptable. If the
calibration factor deviates by more than 5 percent, recalibrate the DGM
as in section 10.1.1.1, and for the calculations, use the calibration
factor (initial or recalibration) that yields the lower gas volume for
each test run.
10.1.2 Temperature Sensors. Calibrate against mercury-in-glass
thermometers. An alternative mercury-free thermometer may be used if the
thermometer is at a minimum equivalent in terms of performance or
suitably effective for the specific temperature measurement application.
10.1.3 Rate Meter. The rate meter need not be calibrated, but should
be cleaned and maintained according to the manufacturer's instructions.
10.1.4 Barometer. Calibrate against a mercury barometer.
10.2 Standardization.
10.2.1 Iodine Solution Standardization. Standardize the 0.01 N
I2 solution daily as follows: Pipette 25 ml of the
I2 solution into a 125-ml Erlenmeyer flask. Add 2 ml of 3 M
HCl. Titrate rapidly with standard 0.01 N
Na2S2O3 solution or with 0.01 N
C6H5AsO until the solution is light yellow, using
gentle mixing. Add four drops of starch indicator solution, and continue
titrating slowly until the blue color just disappears. Record the volume
of Na2S2O3 solution used,
VSI, or the volume of C6H5AsO solution
used, VAI, in ml. Repeat until replicate values agree within
0.05 ml. Average the replicate titration values which agree within 0.05
ml, and calculate the exact normality of the I2 solution
using Equation 11-3. Repeat the standardization daily.
10.2.2 Sodium Thiosulfate Solution Standardization. Standardize the
0.1 N Na2S2O3 solution as follows:
Oven-dry potassium dichromate (K2Cr2O7)
at 180 to 200 [deg]C (360 to 390 [deg]F). To the nearest milligram,
weigh 2 g of the dichromate (W). Transfer the dichromate to a 500-ml
volumetric flask, dissolve in water, and dilute to exactly 500 ml. In a
500-ml iodine flask, dissolve approximately 3 g of KI in 45 ml of water,
then add 10 ml of 3 M HCl solution. Pipette 50 ml of the dichromate
solution into this mixture. Gently swirl the contents of the flask once,
and allow it to stand in the dark for 5 minutes. Dilute the solution
with 100 to 200 ml of water, washing down the sides of the flask with
part of the water. Titrate with 0.1 N
Na2S2O3 until the solution is light
yellow. Add 4 ml of starch indicator and continue titrating slowly to a
green end point. Record the volume of
Na2S2O3 solution used, VS,
in ml. Repeat until replicate values agree within 0.05 ml. Calculate the
normality using Equation 11-1. Repeat the standardization each week or
after each test series, whichever time is shorter.
10.2.3 Phenylarsine Oxide Solution Standardization. Standardize the
0.01 N C6H5AsO (if applicable) as follows: Oven-
dry K2Cr2O7 at 180 to 200 [deg]C (360
to 390 [deg]F). To the nearest milligram, weigh 2 g of the dichromate
(W). Transfer the dichromate to a 500-ml volumetric flask, dissolve in
water, and dilute to exactly 500 ml. In a 500-ml iodine flask, dissolve
approximately 0.3 g of KI in 45 ml of water, then add 10 ml of 3 M HCl.
Pipette 5 ml of the dichromate solution into the iodine flask. Gently
swirl the contents of the flask once, and allow it to stand in the dark
for 5 minutes. Dilute the solution with 100 to 200 ml of water, washing
down the sides of the flask with part of the water. Titrate with 0.01 N
C6H5AsO until the solution is light yellow. Add 4
ml of starch indicator, and continue titrating slowly to a green end
point. Record the volume of C6H5AsO used,
VA, in ml. Repeat until replicate analyses agree within 0.05
ml. Calculate the normality using Equation 11-2. Repeat the
standardization each week or after each test series, whichever time is
shorter.

11.0 Analytical Procedure

Conduct the titration analyses in a clean area away from direct
sunlight.
11.1 Pipette exactly 50 ml of 0.01 N I2 solution into a
125-ml Erlenmeyer flask. Add 10 ml of 3 M HCl to the solution.
Quantitatively rinse the acidified I2 into the iodine flask.
Stopper the flask immediately, and shake briefly.

[[Page 355]]

11.2 Use these alternative procedures if Antifoam B was not used or
if significant quantities of yellow CdS remain in the impingers. Extract
the remaining CdS from the third, fourth, and fifth impingers using the
acidified I2 solution. Immediately after pouring the
acidified I2 into an impinger, stopper it and shake for a few
moments, then transfer the liquid to the iodine flask. Do not transfer
any rinse portion from one impinger to another; transfer it directly to
the iodine flask. Once the acidified I2 solution has been
poured into any glassware containing CdS, the container must be tightly
stoppered at all times except when adding more solution, and this must
be done as quickly and carefully as possible. After adding any acidified
I2 solution to the iodine flask, allow a few minutes for
absorption of the H2S before adding any further rinses.
Repeat the I2 extraction until all CdS is removed from the
impingers. Extract that part of the connecting glassware that contains
visible CdS. Quantitatively rinse all the I2 from the
impingers, connectors, and the beaker into the iodine flask using water.
Stopper the flask and shake briefly.
11.3 Allow the iodine flask to stand about 30 minutes in the dark
for absorption of the H2S into the I2, then
complete the titration analysis as outlined in sections 11.5 and 11.6.

Note: Iodine evaporates from acidified I2 solutions.
Samples to which acidified I2 has been added may not be
stored, but must be analyzed in the time schedule stated above.

11.4 Prepare a blank by adding 45 ml of CdSO4 absorbing
solution to an iodine flask. Pipette exactly 50 ml of 0.01 N
I2 solution into a 125-ml Erlenmeyer flask. Add 10 ml of 3 M
HCl. Stopper the flask, shake briefly, let stand 30 minutes in the dark,
and titrate with the samples.

Note: The blank must be handled by exactly the same procedure as
that used for the samples.

11.5 Using 0.01 N Na2S2O3 solution
(or 0.01 N C6H5AsO, if applicable), rapidly
titrate each sample in an iodine flask using gentle mixing, until
solution is light yellow. Add 4 ml of starch indicator solution, and
continue titrating slowly until the blue color just disappears. Record
the volume of Na2S2O3 solution used,
VTT, or the volume of C6H5AsO solution
used, VAT, in ml.
11.6 Titrate the blanks in the same manner as the samples. Run
blanks each day until replicate values agree within 0.05 ml. Average the
replicate titration values which agree within 0.05 ml.

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures only after
the final calculation.
12.1 Nomenclature.

CH2S = Concentration of H2S at standard
conditions, mg/dscm.
NA = Normality of standard C6H5AsO
solution, g-eq/liter.
NI = Normality of standard I2 solution, g-eq/
liter.
NS = Normality of standard (0.1 N)
Na2S2O3 solution, g-eq/liter.
NT = Normality of standard (0.01 N)
Na2S2O3 solution, assumed to
be 0.1 NS, g-eq/liter.
Pbar = Barometric pressure at the sampling site, mm Hg.
Pstd = Standard absolute pressure, 760 mm Hg.
Tm = Average DGM temperature, [deg]K.
Tstd = Standard absolute temperature, 293 [deg]K.
VA = Volume of C6H5AsO solution used
for standardization, ml.
VAI = Volume of standard C6H5AsO
solution used for titration analysis, ml.
VI = Volume of standard I2 solution used for
standardization, ml.
VIT = Volume of standard I2 solution used for
titration analysis, normally 50 ml.
Vm = Volume of gas sample at meter conditions, liters.
Vm(std) = Volume of gas sample at standard conditions,
liters.
VSI = Volume of ``0.1 N
Na2S2O3 solution used for
standardization, ml.
VT = Volume of standard (0.01 N)
Na2S2O3 solution used in
standardizing iodine solution (see section 10.2.1), ml.
VTT = Volume of standard (0.01 N)
Na2S2O3 solution used for
titration analysis, ml.
W = Weight of K2Cr2O7 used to
standardize Na2s2O3 or
C6H5AsO solutions, as applicable (see
sections 10.2.2 and 10.2.3), g.
Y = DGM calibration factor.
12.2 Normality of the Standard (0.1 N) Sodium Thiosulfate Solution.
[GRAPHIC] [TIFF OMITTED] TR17OC00.238

Where:

2.039 = Conversion factor
= (6 g-eq I2/mole
K2Cr2O7) (1,000 ml/liter)/(294.2 g
K2Cr2O7/mole) (10 aliquot factor)

12.3 Normality of Standard Phenylarsine Oxide Solution (if
applicable).
[GRAPHIC] [TIFF OMITTED] TR17OC00.239

Where:

0.2039 = Conversion factor.
= (6 g-eq I2/mole
K2Cr2O7) (1,000 ml/liter)/(294.2 g
K2Cr2O7/mole) (100 aliquot factor)

12.4 Normality of Standard Iodine Solution.
[GRAPHIC] [TIFF OMITTED] TR17OC00.240

[[Page 356]]

Note: If C6H5AsO is used instead of
Na2S2O3, replace NT and
VT in Equation 11-3 with NA and VAS,
respectively (see sections 10.2.1 and 10.2.3).

12.5 Dry Gas Volume. Correct the sample volume measured by the DGM
to standard conditions (20 [deg]C and 760 mm Hg).
[GRAPHIC] [TIFF OMITTED] TR17OC00.241

12.6 Concentration of H2S. Calculate the concentration of
H2S in the gas stream at standard conditions using Equation
11-5:
[GRAPHIC] [TIFF OMITTED] TR17OC00.242

Where:

17.04 x 10\3\ = Conversion factor
= (34.07 g/mole H2S) (1,000 liters/m\3\) (1,000mg/g)/
(1,000 ml/liter) (2H2S eq/mole)

Note: If C6H5AsO is used instead of
NaS22O3, replace NA and VAT
in Equation 11-5 with NA and VAT, respectively
(see sections 11.5 and 10.2.3).

13.0 Method Performance

13.1 Precision. Collaborative testing has shown the intra-laboratory
precision to be 2.2 percent and the inter-laboratory precision to be 5
percent.
13.2 Bias. The method bias was shown to be -4.8 percent when only
H2S was present. In the presence of the interferences cited
in section 4.0, the bias was positive at low H2S
concentration and negative at higher concentrations. At 230 mg
H2S/m\3\, the level of the compliance standard, the bias was
+ 2.7 percent. Thiols had no effect on the precision.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Determination of Hydrogen Sulfide, Ammoniacal Cadmium Chloride
Method. API Method 772-54. In: Manual on Disposal of Refinery Wastes,
Vol. V: Sampling and Analysis of Waste Gases and Particulate Matter.
American Petroleum Institute, Washington, D.C. 1954.
2. Tentative Method of Determination of Hydrogen Sulfide and
Mercaptan Sulfur in Natural Gas. Natural Gas Processors Association,
Tulsa, OK. NGPA Publication No. 2265-65. 1965.
3. Knoll, J.D., and M.R. Midgett. Determination of Hydrogen Sulfide
in Refinery Fuel Gases. Environmental Monitoring Series, Office of
Research and Development, USEPA. Research Triangle Park, NC 27711. EPA
600/4-77-007.
4. Scheil, G.W., and M.C. Sharp. Standardization of Method 11 at a
Petroleum Refinery. Midwest Research Institute Draft Report for USEPA.
Office of Research and Development. Research Triangle Park, NC 27711.
EPA Contract No. 68-02-1098. August 1976. EPA 600/4-77-088a (Volume 1)
and EPA 600/4-77-088b (Volume 2).

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 357]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.243

Method 12--Determination of Inorganic Lead Emissions From Stationary
Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3, and
Method 5.

1.0 Scope and Application

1.1 Analytes.

[[Page 358]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Inorganic Lead Compounds as lead 7439-92-1 see section 13.3.
(Pb).
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of inorganic lead emissions from stationary sources, only as specified
in an applicable subpart of the regulations.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Particulate and gaseous Pb emissions are withdrawn
isokinetically from the source and are collected on a filter and in
dilute nitric acid. The collected samples are digested in acid solution
and are analyzed by atomic absorption spectrophotometry using an air/
acetylene flame.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Copper. High concentrations of copper may interfere with the
analysis of Pb at 217.0 nm. This interference can be avoided by
analyzing the samples at 283.3 nm.
4.2 Matrix Effects. Analysis for Pb by flame atomic absorption
spectrophotometry is sensitive to the chemical composition and to the
physical properties (e.g., viscosity, pH) of the sample. The analytical
procedure requires the use of the Method of Standard Additions to check
for these matrix effects, and requires sample analysis using the Method
of Standard Additions if significant matrix effects are found to be
present.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. A schematic of the sampling train used in
performing this method is shown in Figure 12-1 in section 18.0; it is
similar to the Method 5 train. The following items are needed for sample
collection:
6.1.1 Probe Nozzle, Probe Liner, Pitot Tube, Differential Pressure
Gauge, Filter Holder, Filter Heating System, Temperature Sensor,
Metering System, Barometer, and Gas Density Determination Equipment.
Same as Method 5, sections 6.1.1.1 through 6.1.1.7, 6.1.1.9, 6.1.2, and
6.1.3, respectively.
6.1.2 Impingers. Four impingers connected in series with leak-free
ground glass fittings or any similar leak-free noncontaminating fittings
are needed. For the first, third, and fourth impingers, use the
Greenburg-Smith design, modified by replacing the tip with a 1.3 cm (\1/
2\ in.) ID glass tube extending to about 1.3 cm (\1/2\ in.) from the
bottom of the flask. For the second impinger, use the Greenburg-Smith
design with the standard tip.
6.1.3 Temperature Sensor. Place a temperature sensor, capable of
measuring temperature to within 1 [deg]C (2 [deg]F) at the outlet of the
fourth impinger for monitoring purposes.
6.2 Sample Recovery. The following items are needed for sample
recovery:
6.2.1 Probe-Liner and Probe-Nozzle Brushes, Petri Dishes, Graduated
Cylinder and/or Balance, Plastic Storage Containers, and Funnel and
Rubber Policeman. Same as Method 5, sections 6.2.1 and 6.2.4 through
6.2.7, respectively.
6.2.2 Wash Bottles. Glass (2).
6.2.3 Sample Storage Containers. Chemically resistant, borosilicate
glass bottles, for 0.1 N nitric acid (HNO3) impinger and
probe solutions and washes, 1000-ml. Use screw-cap liners that are
either rubber-backed Teflon or leak-free and resistant to chemical
attack by 0.1 N HNO3. (Narrow mouth glass bottles have been
found to be less prone to leakage.)
6.2.4 Funnel. Glass, to aid in sample recovery.
6.3 Sample Analysis. The following items are needed for sample
analysis:
6.3.1 Atomic Absorption Spectrophotometer. With lead hollow cathode
lamp and burner for air/acetylene flame.
6.3.2 Hot Plate.

[[Page 359]]

6.3.3 Erlenmeyer Flasks. 125-ml, 24/40 standard taper.
6.3.4 Membrane Filters. Millipore SCWPO 4700, or equivalent.
6.3.5 Filtration Apparatus. Millipore vacuum filtration unit, or
equivalent, for use with the above membrane filter.
6.3.6 Volumetric Flasks. 100-ml, 250-ml, and 1000-ml.

7.0 Reagents and Standards

7.1 Sample Collection. The following reagents are needed for sample
collection:
7.1.1 Filter. Gelman Spectro Grade, Reeve Angel 934 AH, MSA 1106 BH,
all with lot assay for Pb, or other high-purity glass fiber filters,
without organic binder, exhibiting at least 99.95 percent efficiency
(<0.05 percent penetration) on 0.3 micron dioctyl phthalate smoke
particles. Conduct the filter efficiency test using ASTM D 2986-71, 78,
or 95a (incorporated by reference--see Sec. 60.17) or use test data
from the supplier's quality control program.
7.1.2 Silica Gel, Crushed Ice, and Stopcock Grease. Same as Method
5, sections 7.1.2, 7.1.4, and 7.1.5, respectively.
7.1.3 Water. Deionized distilled, to conform to ASTM D 1193-77 or
91, Type 3 (incorporated by reference--see Sec. 60.17). If high
concentrations of organic matter are not expected to be present, the
potassium permanganate test for oxidizable organic matter may be
omitted.
7.1.4 Nitric Acid, 0.1 N. Dilute 6.5 ml of concentrated
HNO3 to 1 liter with water. (It may be desirable to run
blanks before field use to eliminate a high blank on test samples.)
7.2 Sample Recovery. 0.1 N HNO3 (Same as in section 7.1.4
above).
7.3 Sample Analysis. The following reagents and standards are needed
for sample analysis:
7.3.1 Water. Same as in section 7.1.3.
7.3.2 Nitric Acid, Concentrated.
7.3.3 Nitric Acid, 50 Percent (v/v). Dilute 500 ml of concentrated
HNO3 to 1 liter with water.
7.3.4 Stock Lead Standard Solution, 1000 g Pb/ml. Dissolve
0.1598 g of lead nitrate [Pb(NO3)2] in about 60 ml
water, add 2 ml concentrated HNO3, and dilute to 100 ml with
water.
7.3.5 Working Lead Standards. Pipet 0.0, 1.0, 2.0, 3.0, 4.0, and 5.0
ml of the stock lead standard solution (Section 7.3.4) into 250-ml
volumetric flasks. Add 5 ml of concentrated HNO3 to each
flask, and dilute to volume with water. These working standards contain
0.0, 4.0, 8.0, 12.0, 16.0, and 20.0 g Pb/ml, respectively.
Prepare, as needed, additional standards at other concentrations in a
similar manner.
7.3.6 Air. Suitable quality for atomic absorption spectrophotometry.
7.3.7 Acetylene. Suitable quality for atomic absorption
spectrophotometry.
7.3.8 Hydrogen Peroxide, 3 Percent (v/v). Dilute 10 ml of 30 percent
H2O2 to 100 ml with water.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Pretest Preparation. Follow the same general procedure given in
Method 5, section 8.1, except that the filter need not be weighed.
8.2 Preliminary Determinations. Follow the same general procedure
given in Method 5, section 8.2.
8.3 Preparation of Sampling Train. Follow the same general procedure
given in Method 5, section 8.3, except place 100 ml of 0.1 N
HNO3 (instead of water) in each of the first two impingers.
As in Method 5, leave the third impinger empty and transfer
approximately 200 to 300 g of preweighed silica gel from its container
to the fourth impinger. Set up the train as shown in Figure 12-1.
8.4 Leak-Check Procedures. Same as Method 5, section 8.4.
8.5 Sampling Train Operation. Same as Method 5, section 8.5.
8.6 Calculation of Percent Isokinetic. Same as Method 5, section
8.6.
8.7 Sample Recovery. Same as Method 5, sections 8.7.1 through
8.7.6.1, with the addition of the following:
8.7.1 Container No. 2 (Probe).
8.7.1.1 Taking care that dust on the outside of the probe or other
exterior surfaces does not get into the sample, quantitatively recover
sample matter and any condensate from the probe nozzle, probe fitting,
probe liner, and front half of the filter holder by washing these
components with 0.1 N HNO3 and placing the wash into a glass
sample storage container. Measure and record (to the nearest 2 ml) the
total amount of 0.1 N HNO3 used for these rinses. Perform the
0.1 N HNO3 rinses as follows:
8.7.1.2 Carefully remove the probe nozzle, and rinse the inside
surfaces with 0.1 N HNO3 from a wash bottle while brushing
with a stainless steel, Nylon-bristle brush. Brush until the 0.1 N
HNO3 rinse shows no visible particles, then make a final
rinse of the inside surface with 0.1 N HNO3.
8.7.1.3 Brush and rinse with 0.1 N HNO3 the inside parts
of the Swagelok fitting in a similar way until no visible particles
remain.
8.7.1.4 Rinse the probe liner with 0.1 N HNO3. While
rotating the probe so that all inside surfaces will be rinsed with 0.1 N
HNO3, tilt the probe, and squirt 0.1 N HNO3

[[Page 360]]

into its upper end. Let the 0.1 N HNO3 drain from the lower
end into the sample container. A glass funnel may be used to aid in
transferring liquid washes to the container. Follow the rinse with a
probe brush. Hold the probe in an inclined position, squirt 0.1 N
HNO3 into the upper end of the probe as the probe brush is
being pushed with a twisting action through the probe; hold the sample
container underneath the lower end of the probe, and catch any 0.1 N
HNO3 and sample matter that is brushed from the probe. Run
the brush through the probe three times or more until no visible sample
matter is carried out with the 0.1 N HNO3 and none remains on
the probe liner on visual inspection. With stainless steel or other
metal probes, run the brush through in the above prescribed manner at
least six times, since metal probes have small crevices in which sample
matter can be entrapped. Rinse the brush with 0.1 N HNO3, and
quantitatively collect these washings in the sample container. After the
brushing, make a final rinse of the probe as described above.
8.7.1.5 It is recommended that two people clean the probe to
minimize loss of sample. Between sampling runs, keep brushes clean and
protected from contamination.
8.7.1.6 After ensuring that all joints are wiped clean of silicone
grease, brush and rinse with 0.1 N HNO3 the inside of the
from half of the filter holder. Brush and rinse each surface three times
or more, if needed, to remove visible sample matter. Make a final rinse
of the brush and filter holder. After all 0.1 N HNO3 washings
and sample matter are collected in the sample container, tighten the lid
on the sample container so that the fluid will not leak out when it is
shipped to the laboratory. Mark the height of the fluid level to
determine whether leakage occurs during transport. Label the container
to identify its contents clearly.
8.7.2 Container No. 3 (Silica Gel). Note the color of the indicating
silica gel to determine if it has been completely spent, and make a
notation of its condition. Transfer the silica gel from the fourth
impinger to the original container, and seal. A funnel may be used to
pour the silica gel from the impinger and a rubber policeman may be used
to remove the silica gel from the impinger. It is not necessary to
remove the small amount of particles that may adhere to the walls and
are difficult to remove. Since the gain in weight is to be used for
moisture calculations, do not use any water or other liquids to transfer
the silica gel. If a balance is available in the field, follow the
procedure for Container No. 3 in section 11.4.2.
8.7.3 Container No. 4 (Impingers). Due to the large quantity of
liquid involved, the impinger solutions may be placed in several
containers. Clean each of the first three impingers and connecting
glassware in the following manner:
8.7.3.1. Wipe the impinger ball joints free of silicone grease, and
cap the joints.
8.7.3.2. Rotate and agitate each impinger, so that the impinger
contents might serve as a rinse solution.
8.7.3.3. Transfer the contents of the impingers to a 500-ml
graduated cylinder. Remove the outlet ball joint cap, and drain the
contents through this opening. Do not separate the impinger parts (inner
and outer tubes) while transferring their contents to the cylinder.
Measure the liquid volume to within 2 ml. Alternatively, determine the
weight of the liquid to within 0.5 g. Record in the log the volume or
weight of the liquid present, along with a notation of any color or film
observed in the impinger catch. The liquid volume or weight is needed,
along with the silica gel data, to calculate the stack gas moisture
content (see Method 5, Figure 5-6).
8.7.3.4. Transfer the contents to Container No. 4.

Note: In sections 8.7.3.5 and 8.7.3.6, measure and record the total
amount of 0.1 N HNO3 used for rinsing.

8.7.3.5. Pour approximately 30 ml of 0.1 N HNO3 into each
of the first three impingers and agitate the impingers. Drain the 0.1 N
HNO3 through the outlet arm of each impinger into Container
No. 4. Repeat this operation a second time; inspect the impingers for
any abnormal conditions.
8.7.3.6. Wipe the ball joints of the glassware connecting the
impingers free of silicone grease and rinse each piece of glassware
twice with 0.1 N HNO3; transfer this rinse into Container No.
4. Do not rinse or brush the glass-fritted filter support. Mark the
height of the fluid level to determine whether leakage occurs during
transport. Label the container to identify its contents clearly.
8.8 Blanks.
8.8.1 Nitric Acid. Save 200 ml of the 0.1 N HNO3 used for
sampling and cleanup as a blank. Take the solution directly from the
bottle being used and place into a glass sample container labeled ``0.1
N HNO3 blank.''
8.8.2 Filter. Save two filters from each lot of filters used in
sampling. Place these filters in a container labeled ``filter blank.''

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

[[Page 361]]

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.4, 10.1..................... Sampling Ensure accuracy and
equipment leak- precision of
checks and sampling
calibration. measurements.
10.2.......................... Spectrophotometer Ensure linearity of
calibration. spectrophotometer
response to
standards.
11.5.......................... Check for matrix Eliminate matrix
effects. effects.
------------------------------------------------------------------------

9.2 Volume Metering System Checks. Same as Method 5, section 9.2.

10.0 Calibration and Standardizations

Note: Maintain a laboratory log of all calibrations.

10.1 Sampling Equipment. Same as Method 5, section 10.0.
10.2 Spectrophotometer.
10.2.1 Measure the absorbance of the standard solutions using the
instrument settings recommended by the spectrophotometer manufacturer.
Repeat until good agreement (3 percent) is obtained between two
consecutive readings. Plot the absorbance (y-axis) versus concentration
in g Pb/ml (x-axis). Draw or compute a straight line through
the linear portion of the curve. Do not force the calibration curve
through zero, but if the curve does not pass through the origin or at
least lie closer to the origin than 0.003 absorbance units, check for
incorrectly prepared standards and for curvature in the calibration
curve.
10.2.2 To determine stability of the calibration curve, run a blank
and a standard after every five samples, and recalibrate as necessary.

11.0 Analytical Procedures

11.1 Sample Loss Check. Prior to analysis, check the liquid level in
Containers Number 2 and Number 4. Note on the analytical data sheet
whether leakage occurred during transport. If a noticeable amount of
leakage occurred, either void the sample or take steps, subject to the
approval of the Administrator, to adjust the final results.
11.2 Sample Preparation.
11.2.1 Container No. 1 (Filter). Cut the filter into strips and
transfer the strips and all loose particulate matter into a 125-ml
Erlenmeyer flask. Rinse the petri dish with 10 ml of 50 percent
HNO3 to ensure a quantitative transfer, and add to the flask.

Note: If the total volume required in section 11.2.3 is expected to
exceed 80 ml, use a 250-ml flask in place of the 125-ml flask.

11.2.2 Containers No. 2 and No. 4 (Probe and Impingers). Combine the
contents of Containers No. 2 and No. 4, and evaporate to dryness on a
hot plate.
11.2.3 Sample Extraction for Lead.
11.2.3.1 Based on the approximate stack gas particulate
concentration and the total volume of stack gas sampled, estimate the
total weight of particulate sample collected. Next, transfer the residue
from Containers No. 2 and No. 4 to the 125-ml Erlenmeyer flask that
contains the sampling filter using a rubber policeman and 10 ml of 50
percent HNO3 for every 100 mg of sample collected in the
train or a minimum of 30 ml of 50 percent HNO3, whichever is
larger.
11.2.3.2 Place the Erlenmeyer flask on a hot plate, and heat with
periodic stirring for 30 minutes at a temperature just below boiling. If
the sample volume falls below 15 ml, add more 50 percent
HNO3. Add 10 ml of 3 percent H2O2, and
continue heating for 10 minutes. Add 50 ml of hot (80 [deg]C, 176
[deg]F) water, and heat for 20 minutes. Remove the flask from the hot
plate, and allow to cool. Filter the sample through a Millipore membrane
filter, or equivalent, and transfer the filtrate to a 250-ml volumetric
flask. Dilute to volume with water.
11.2.4 Filter Blank. Cut each filter into strips, and place each
filter in a separate 125-ml Erlenmeyer flask. Add 15 ml of 50 percent
HNO3, and treat as described in section 11.2.3 using 10 ml of
3 percent H2O2 and 50 ml of hot water. Filter and
dilute to a total volume of 100 ml using water.
11.2.5 Nitric Acid Blank, 0.1 N. Take the entire 200 ml of 0.1 N
HNO3 to dryness on a steam bath, add 15 ml of 50 percent
HNO3, and treat as described in section 11.2.3 using 10 ml of
3 percent H202 and 50 ml of hot water. Dilute to a
total volume of 100 ml using water.
11.3 Spectrophotometer Preparation. Turn on the power; set the
wavelength, slit width, and lamp current; and adjust the background
corrector as instructed by the manufacturer's manual for the particular
atomic absorption spectrophotometer. Adjust the burner and flame
characteristics as necessary.
11.4 Analysis.
11.4.1 Lead Determination. Calibrate the spectrophotometer as
outlined in section 10.2, and determine the absorbance for each source
sample, the filter blank, and 0.1 N HNO3 blank. Analyze each
sample three times in this manner. Make appropriate dilutions, as
needed, to bring all sample Pb concentrations into the linear absorbance
range of the spectrophotometer. Because instruments vary between
manufacturers, no detailed operating instructions will be given here.
Instead, the instructions provided with the particular instrument should
be followed. If the Pb concentration of a sample is at the low end of
the calibration curve and

[[Page 362]]

high accuracy is required, the sample can be taken to dryness on a hot
plate and the residue dissolved in the appropriate volume of water to
bring it into the optimum range of the calibration curve.
11.4.2 Container No. 3 (Silica Gel). This step may be conducted in
the field. Weigh the spent silica gel (or silica gel plus impinger) to
the nearest 0.5 g; record this weight.
11.5 Check for Matrix Effects. Use the Method of Standard Additions
as follows to check at least one sample from each source for matrix
effects on the Pb results:
11.5.1 Add or spike an equal volume of standard solution to an
aliquot of the sample solution.
11.5.2 Measure the absorbance of the resulting solution and the
absorbance of an aliquot of unspiked sample.
11.5.3 Calculate the Pb concentration Cm in g/ml
of the sample solution using Equation 12-1 in section 12.5.
Volume corrections will not be required if the solutions as analyzed
have been made to the same final volume. Therefore, Cm and
Ca represent Pb concentration before dilutions.
Method of Standard Additions procedures described on pages 9-4 and
9-5 of the section entitled ``General Information'' of the Perkin Elmer
Corporation Atomic Absorption Spectrophotometry Manual, Number 303-0152
(Reference 1 in section 17.0) may also be used. In any event, if the
results of the Method of Standard Additions procedure used on the single
source sample do not agree to within 5 percent of the value obtained by
the routine atomic absorption analysis, then reanalyze all samples from
the source using the Method of Standard Additions procedure.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

Am = Absorbance of the sample solution.
An = Cross-sectional area of nozzle, m\2\ (ft\2\).
At = Absorbance of the spiked sample solution.
Bws = Water in the gas stream, proportion by volume.
Ca = Lead concentration in standard solution, g/ml.
Cm = Lead concentration in sample solution analyzed during
check for matrix effects, g/ml.
Cs = Lead concentration in stack gas, dry basis, converted to
standard conditions, mg/dscm (gr/dscf).
I = Percent of isokinetic sampling.
L1 = Individual leakage rate observed during the leak-check
conducted prior to the first component change, m\3\/min
(ft\3\/min)
La = Maximum acceptable leakage rate for either a pretest
leak-check or for a leak-check following a component change;
equal to 0.00057 m\3\/min (0.020 cfm) or 4 percent of the
average sampling rate, whichever is less.
Li = Individual leakage rate observed during the leak-check
conducted prior to the ``ith'' component change (i = 1, 2, 3 *
* * n), m\3\/min (cfm).
Lp = Leakage rate observed during the post-test leak-check,
m\3\/min (cfm).
mt = Total weight of lead collected in the sample,
g.
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 lb/lb-
mole).
Pbar = Barometric pressure at the sampling site, mm Hg (in.
Hg).
Ps = Absolute stack gas pressure, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
R = Ideal gas constant, 0.06236 [(mm Hg) (m\3\)]/[([deg]K) (g-mole)]
{21.85 [(in. Hg) (ft\3\)]/[([deg]R) (lb-mole)]}.
Tm = Absolute average dry gas meter temperature (see Figure
5-3 of Method 5), [deg]K ([deg]R).
Tstd = Standard absolute temperature, 293 [deg]K (528
[deg]R).
vs = Stack gas velocity, m/sec (ft/sec).
Vm = Volume of gas sample as measured by the dry gas meter,
dry basis, m\3\ (ft\3\).
Vm(std) = Volume of gas sample as measured by the dry gas
meter, corrected to standard conditions, m\3\ (ft\3\).
Vw(std) = Volume of water vapor collected in the sampling
train, corrected to standard conditions, m\3\ (ft\3\).
Y = Dry gas meter calibration factor.
FH = Average pressure differential across the orifice meter (see Figure
5-3 of Method 5), mm H2O (in. H2O).
k = Total sampling time, min.
kl = Sampling time interval, from the beginning of a run
until the first component change, min.
ki = Sampling time interval, between two successive component
changes, beginning with the interval between the first and
second changes, min.
kp = Sampling time interval, from the final (n\th\) component
change until the end of the sampling run, min.
nw = Density of water, 0.9982 g/ml (0.002201 lb/ml).

12.2 Average Dry Gas Meter Temperatures (Tm) and Average
Orifice Pressure Drop (FH). See data sheet (Figure 5-3 of Method 5).
12.3 Dry Gas Volume, Volume of Water Vapor, and Moisture Content.
Using data obtained in this test, calculate Vm(std),
Vw(std), and Bws according to the procedures
outlined in Method 5, sections 12.3 through 12.5.
12.4 Total Lead in Source Sample. For each source sample, correct
the average absorbance for the contribution of the filter blank and the
0.1 N HNO3 blank. Use the calibration curve and this
corrected absorbance to determine the Pb concentration in the sample
aspirated into the spectrophotometer.

[[Page 363]]

Calculate the total Pb content mt (in g) in the
original source sample; correct for all the dilutions that were made to
bring the Pb concentration of the sample into the linear range of the
spectrophotometer.
12.5 Sample Lead Concentration. Calculate the Pb concentration of
the sample using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.244

12.6 Lead Concentration. Calculate the stack gas Pb concentration
Cs using Equation 12-2:
[GRAPHIC] [TIFF OMITTED] TR17OC00.245

Where:

K3 = 0.001 mg/g for metric units.
= 1.54 x 10^-5 gr/g for English units

12.7 Stack Gas Velocity and Volumetric Flow Rate. Calculate the
average stack gas velocity and volumetric flow rate using data obtained
in this method and the equations in sections 12.2 and 12.3 of Method 2.
12.8 Isokinetic Variation. Same as Method 5, section 12.11.

13.0 Method Performance

13.1 Precision. The within-laboratory precision, as measured by the
coefficient of variation, ranges from 0.2 to 9.5 percent relative to a
run-mean concentration. These values were based on tests conducted at a
gray iron foundry, a lead storage battery manufacturing plant, a
secondary lead smelter, and a lead recovery furnace of an alkyl lead
manufacturing plant. The concentrations encountered during these tests
ranged from 0.61 to 123.3 mg Pb/m\3\.
13.2 Analytical Range. For a minimum analytical accuracy of 10
percent, the lower limit of the range is 100 g. The upper limit
can be extended considerably by dilution.
13.3 Analytical Sensitivity. Typical sensitivities for a 1-percent
change in absorption (0.0044 absorbance units) are 0.2 and 0.5
g Pb/ml for the 217.0 and 283.3 nm lines, respectively.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 Simultaneous Determination of Particulate Matter and Lead
Emissions. Method 12 may be used to simultaneously determine Pb
provided:
(1) Acetone is used to remove particulate from the probe and inside
of the filter holder as specified by Method 5,
(2) 0.1 N HNO3 is used in the impingers,
(3) A glass fiber filter with a low Pb background is used, and
(4) The entire train contents, including the impingers, are treated
and analyzed for Pb as described in Sections 8.0 and 11.0 of this
method.
16.2 Filter Location. A filter may be used between the third and
fourth impingers provided the filter is included in the analysis for Pb.
16.3 In-Stack Filter. An in-stack filter may be used provided: (1) A
glass-lined probe and at least two impingers, each containing 100 ml of
0.1 N HNO3 after the in-stack filter, are used and (2) the
probe and impinger contents are recovered and analyzed for Pb. Recover
sample from the nozzle with acetone if a particulate analysis is to be
made.
16.4 Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-
AES) Analysis. ICP-AES may be used as an alternative to atomic
absorption analysis provided the following conditions are met:
16.4.1 Sample collection, sample preparation, and analytical
preparation procedures are as defined in the method except as necessary
for the ICP-AES application.
16.4.2 The limit of quantitation for the ICP-AES must be
demonstrated, and the sample concentrations reported should be no less
than two times the limit of quantitation. The limit of quantitation is
defined as ten times the standard deviation of the blank value. The
standard deviation of the blank value is determined from the analysis of
seven blanks. It has been reported that for mercury and those elements
that form hydrides, a continuous-flow generator coupled to an ICP-AES
offers detection limits comparable to cold vapor atomic absorption.
16.5 Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) Analysis.
ICP-MS may be used as an alternative to atomic absorption analysis.
16.6 Cold Vapor Atomic Fluorescence Spectrometry (CVAFS) Analysis.
CVAFS may be used as an alternative to atomic absorption analysis.

17.0 References

Same as Method 5, section 17.0, References 2, 3, 4, 5, and 7, with
the addition of the following:

1. Perkin Elmer Corporation. Analytical Methods for Atomic
Absorption Spectrophotometry. Norwalk, Connecticut. September 1976.
2. American Society for Testing and Materials. Annual Book of ASTM
Standards, Part 31: Water, Atmospheric Analysis. Philadelphia, PA 1974.
p. 40-42.
3. Kelin, R., and C. Hach. Standard Additions--Uses and Limitations
in Spectrophotometric Analysis. Amer. Lab. 9:21-27. 1977.

[[Page 364]]

4. Mitchell, W.J., and M.R. Midgett. Determining Inorganic and Alkyl
Lead Emissions from Stationary Sources. U.S. Environmental Protection
Agency. Emission Monitoring and Support Laboratory. Research Triangle
Park, NC. (Presented at National APCA Meeting, Houston. June 26, 1978).

18.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.246

[[Page 365]]

Method 13A--Determination of Total Fluoride Emissions From Stationary
Sources (Spadns Zirconium Lake Method)

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3, and
Method 5.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total fluorides as Fluorine.... 7782-41-4 Not determined.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of fluoride (F^-) emissions from sources as specified in the
regulations. It does not measure fluorocarbons, such as Freons.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary

Gaseous and particulate F^- are withdrawn isokinetically
from the source and collected in water and on a filter. The total
F^- is then determined by the SPADNS Zirconium Lake
Colorimetric method.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Chloride. Large quantities of chloride will interfere with the
analysis, but this interference can be prevented by adding silver
sulfate into the distillation flask (see section 11.3). If chloride ion
is present, it may be easier to use the specific ion electrode method of
analysis (Method 13B).
4.2 Grease. Grease on sample-exposed surfaces may cause low
F^- results due to adsorption.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. A schematic of the sampling train used in
performing this method is shown in Figure 13A-1; it is similar to the
Method 5 sampling train except that the filter position is
interchangeable. The sampling train consists of the following
components:
6.1.1 Probe Nozzle, Pitot Tube, Differential Pressure Gauge, Filter
Heating System, Temperature Sensor, Metering System, Barometer, and Gas
Density Determination Equipment. Same as Method 5, sections 6.1.1.1,
6.1.1.3 through 6.1.1.7, 6.1.1.9, 6.1.2, and 6.1.3, respectively. The
filter heating system and temperature sensor are needed only when
moisture condensation is a problem.
6.1.2 Probe Liner. Borosilicate glass or 316 stainless steel. When
the filter is located immediately after the probe, a probe heating
system may be used to prevent filter plugging resulting from moisture
condensation, but the temperature in the probe shall not be allowed to
exceed 120 14 [deg]C (248 25 [deg]F).
6.1.3 Filter Holder. With positive seal against leakage from the
outside or around the filter. If the filter is located between the probe
and first impinger, use borosilicate

[[Page 366]]

glass or stainless steel with a 20-mesh stainless steel screen filter
support and a silicone rubber gasket; do not use a glass frit or a
sintered metal filter support. If the filter is located between the
third and fourth impingers, borosilicate glass with a glass frit filter
support and a silicone rubber gasket may be used. Other materials of
construction may be used, subject to the approval of the Administrator.
6.1.4 Impingers. Four impingers connected as shown in Figure 13A-1
with ground-glass (or equivalent), vacuum-tight fittings. For the first,
third, and fourth impingers, use the Greenburg-Smith design, modified by
replacing the tip with a 1.3-cm (\1/2\ in.) ID glass tube extending to
1.3 cm (\1/2\ in.) from the bottom of the flask. For the second
impinger, use a Greenburg-Smith impinger with the standard tip.
Modifications (e.g., flexible connections between the impingers or
materials other than glass) may be used, subject to the approval of the
Administrator. Place a temperature sensor, capable of measuring
temperature to within 1 [deg]C (2 [deg]F), at the outlet of the fourth
impinger for monitoring purposes.
6.2 Sample Recovery. The following items are needed for sample
recovery:
6.2.1 Probe-liner and Probe-Nozzle Brushes, Wash Bottles, Graduated
Cylinder and/or Balance, Plastic Storage Containers, Funnel and Rubber
Policeman, and Funnel. Same as Method 5, sections 6.2.1, 6.2.2 and 6.2.5
to 6.2.8, respectively.
6.2.2 Sample Storage Container. Wide-mouth, high-density
polyethylene bottles for impinger water samples, 1 liter.
6.3 Sample Preparation and Analysis. The following items are needed
for sample preparation and analysis:
6.3.1 Distillation Apparatus. Glass distillation apparatus assembled
as shown in Figure 13A-2.
6.3.2 Bunsen Burner.
6.3.3 Electric Muffle Furnace. Capable of heating to 600 [deg]C
(1100 [deg]F).
6.3.4 Crucibles. Nickel, 75- to 100-ml.
6.3.5 Beakers. 500-ml and 1500-ml.
6.3.6 Volumetric Flasks. 50-ml.
6.3.7 Erlenmeyer Flasks or Plastic Bottles. 500-ml.
6.3.8 Constant Temperature Bath. Capable of maintaining a constant
temperature of 1.0 [deg]C at room temperature conditions.
6.3.9 Balance. 300-g capacity, to measure to 0.5 g.
6.3.10 Spectrophotometer. Instrument that measures absorbance at 570
nm and provides at least a 1-cm light path.
6.3.11 Spectrophotometer Cells. 1-cm path length.

7.0 Reagents and Standards

Unless otherwise indicated, all reagents are to conform to the
specifications established by the Committee on Analytical Reagents of
the American Chemical Society, where such specifications are available.
Otherwise, use the best available grade.
7.1 Sample Collection. The following reagents are needed for sample
collection:
7.1.1 Filters.
7.1.1.1 If the filter is located between the third and fourth
impingers, use a Whatman No. 1 filter, or equivalent, sized to fit the
filter holder.
7.1.1.2 If the filter is located between the probe and first
impinger, use any suitable medium (e.g., paper, organic membrane) that
can withstand prolonged exposure to temperatures up to 135 [deg]C (275
[deg]F), and has at least 95 percent collection efficiency (<5 percent
penetration) for 0.3 m dioctyl phthalate smoke particles.
Conduct the filter efficiency test before the test series, using ASTM D
2986-71, 78, or 95a (incorporated by reference--see Sec. 60.17), or use
test data from the supplier's quality control program. The filter must
also have a low F^- blank value (<0.015 mg F^-/cm\2\
of filter area). Before the test series, determine the average
F^- blank value of at least three filters (from the lot to be
used for sampling) using the applicable procedures described in sections
8.3 and 8.4 of this method. In general, glass fiber filters have high
and/or variable F^- blank values, and will not be acceptable
for use.
7.1.2 Water. Deionized distilled, to conform to ASTM D 1193-77 or
91, Type 3 (incorporated by reference--see Sec. 60.17). If high
concentrations of organic matter are not expected to be present, the
potassium permanganate test for oxidizable organic matter may be
deleted.
7.1.3 Silica Gel, Crushed Ice, and Stopcock Grease. Same as Method
5, sections 7.1.2, 7.1.4, and 7.1.5, respectively.
7.2 Sample Recovery. Water, as described in section 7.1.2, is needed
for sample recovery.
7.3 Sample Preparation and Analysis. The following reagents and
standards are needed for sample preparation and analysis:
7.3.1 Calcium Oxide (CaO). Certified grade containing 0.005 percent
F^- or less.
7.3.2 Phenolphthalein Indicator. Dissolve 0.1 g of phenolphthalein
in a mixture of 50 ml of 90 percent ethanol and 50 ml of water.
7.3.3 Silver Sulfate (Ag2SO4).
7.3.4 Sodium Hydroxide (NaOH), Pellets.
7.3.5 Sulfuric Acid (H2SO4), Concentrated.
7.3.6 Sulfuric Acid, 25 Percent (v/v). Mix 1 part of concentrated
H2SO4 with 3 parts of water.
7.3.7 Filters. Whatman No. 541, or equivalent.
7.3.8 Hydrochloric Acid (HCl), Concentrated.
7.3.9 Water. Same as in section 7.1.2.
7.3.10 Fluoride Standard Solution, 0.01 mg F^-/ml. Dry
approximately 0.5 g of sodium fluoride (NaF) in an oven at 110 [deg]C
(230 [deg]F) for at least 2 hours. Dissolve 0.2210 g of NaF in

[[Page 367]]

1 liter of water. Dilute 100 ml of this solution to 1 liter with water.
7.3.11 SPADNS Solution [4,5 Dihydroxyl-3-(p-Sulfophenylazo)-2,7-
Naphthalene-Disulfonic Acid Trisodium Salt]. Dissolve 0.960 0.010 g of
SPADNS reagent in 500 ml water. If stored in a well-sealed bottle
protected from the sunlight, this solution is stable for at least 1
month.
7.3.12 Spectrophotometer Zero Reference Solution. Add 10 ml of
SPADNS solution to 100 ml water, and acidify with a solution prepared by
diluting 7 ml of concentrated HCl to 10 ml with deionized, distilled
water. Prepare daily.
7.3.13 SPADNS Mixed Reagent. Dissolve 0.135 0.005 g of zirconyl
chloride octahydrate (ZrOCl2 8H2O) in 25 ml of
water. Add 350 ml of concentrated HCl, and dilute to 500 ml with
deionized, distilled water. Mix equal volumes of this solution and
SPADNS solution to form a single reagent. This reagent is stable for at
least 2 months.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Pretest Preparation. Follow the general procedure given in
Method 5, section 8.1, except that the filter need not be weighed.
8.2 Preliminary Determinations. Follow the general procedure given
in Method 5, section 8.2, except that the nozzle size must be selected
such that isokinetic sampling rates below 28 liters/min (1.0 cfm) can be
maintained.
8.3 Preparation of Sampling Train. Follow the general procedure
given in Method 5, section 8.3, except for the following variation:
Assemble the train as shown in Figure 13A-1 with the filter between the
third and fourth impingers. Alternatively, if a 20-mesh stainless steel
screen is used for the filter support, the filter may be placed between
the probe and first impinger. A filter heating system to prevent
moisture condensation may be used, but shall not allow the temperature
to exceed 120 14 [deg]C (248 25 [deg]F). Record the filter location on
the data sheet (see section 8.5).
8.4 Leak-Check Procedures. Follow the leak-check procedures given in
Method 5, section 8.4.
8.5 Sampling Train Operation. Follow the general procedure given in
Method 5, section 8.5, keeping the filter and probe temperatures (if
applicable) at 120 14 [deg]C (248 25 [deg]F) and isokinetic sampling
rates below 28 liters/min (1.0 cfm). For each run, record the data
required on a data sheet such as the one shown in Method 5, Figure 5-3.
8.6 Sample Recovery. Proper cleanup procedure begins as soon as the
probe is removed from the stack at the end of the sampling period. Allow
the probe to cool.
8.6.1 When the probe can be safely handled, wipe off all external
particulate matter near the tip of the probe nozzle, and place a cap
over it to keep from losing part of the sample. Do not cap off the probe
tip tightly while the sampling train is cooling down as this would
create a vacuum in the filter holder, thus drawing water from the
impingers into the filter holder.
8.6.2 Before moving the sample train to the cleanup site, remove the
probe from the sample train, wipe off any silicone grease, and cap the
open outlet of the probe. Be careful not to lose any condensate that
might be present. Remove the filter assembly, wipe off any silicone
grease from the filter holder inlet, and cap this inlet. Remove the
umbilical cord from the last impinger, and cap the impinger. After
wiping off any silicone grease, cap off the filter holder outlet and any
open impinger inlets and outlets. Ground-glass stoppers, plastic caps,
or serum caps may be used to close these openings.
8.6.3 Transfer the probe and filter-impinger assembly to the cleanup
area. This area should be clean and protected from the wind so that the
chances of contaminating or losing the sample will be minimized.
8.6.4 Inspect the train prior to and during disassembly, and note
any abnormal conditions. Treat the samples as follows:
8.6.4.1 Container No. 1 (Probe, Filter, and Impinger Catches).
8.6.4.1.1 Using a graduated cylinder, measure to the nearest ml, and
record the volume of the water in the first three impingers; include any
condensate in the probe in this determination. Transfer the impinger
water from the graduated cylinder into a polyethylene container. Add the
filter to this container. (The filter may be handled separately using
procedures subject to the Administrator's approval.) Taking care that
dust on the outside of the probe or other exterior surfaces does not get
into the sample, clean all sample-exposed surfaces (including the probe
nozzle, probe fitting, probe liner, first three impingers, impinger
connectors, and filter holder) with water. Use less than 500 ml for the
entire wash. Add the washings to the sample container. Perform the water
rinses as follows:
8.6.4.1.2 Carefully remove the probe nozzle and rinse the inside
surface with water from a wash bottle. Brush with a Nylon bristle brush,
and rinse until the rinse shows no visible particles, after which make a
final rinse of the inside surface. Brush and rinse the inside parts of
the Swagelok fitting with water in a similar way.
8.6.4.1.3 Rinse the probe liner with water. While squirting the
water into the upper end of the probe, tilt and rotate the probe so that
all inside surfaces will be wetted with water. Let the water drain from
the lower end into the sample container. A funnel (glass or
polyethylene) may be used to aid in transferring the liquid washes to
the container. Follow the rinse with a probe brush. Hold the probe in an
inclined position, and squirt water into

[[Page 368]]

the upper end as the probe brush is being pushed with a twisting action
through the probe. Hold the sample container underneath the lower end of
the probe, and catch any water and particulate matter that is brushed
from the probe. Run the brush through the probe three times or more.
With stainless steel or other metal probes, run the brush through in the
above prescribed manner at least six times since metal probes have small
crevices in which particulate matter can be entrapped. Rinse the brush
with water, and quantitatively collect these washings in the sample
container. After the brushing, make a final rinse of the probe as
described above.
8.6.4.1.4 It is recommended that two people clean the probe to
minimize sample losses. Between sampling runs, keep brushes clean and
protected from contamination.
8.6.4.1.5 Rinse the inside surface of each of the first three
impingers (and connecting glassware) three separate times. Use a small
portion of water for each rinse, and brush each sample-exposed surface
with a Nylon bristle brush, to ensure recovery of fine particulate
matter. Make a final rinse of each surface and of the brush.
8.6.4.1.6 After ensuring that all joints have been wiped clean of
the silicone grease, brush and rinse with water the inside of the filter
holder (front-half only, if filter is positioned between the third and
fourth impingers). Brush and rinse each surface three times or more if
needed. Make a final rinse of the brush and filter holder.
8.6.4.1.7 After all water washings and particulate matter have been
collected in the sample container, tighten the lid so that water will
not leak out when it is shipped to the laboratory. Mark the height of
the fluid level to transport. Label the container clearly to identify
its contents.
8.6.4.2 Container No. 2 (Sample Blank). Prepare a blank by placing
an unused filter in a polyethylene container and adding a volume of
water equal to the total volume in Container No. 1. Process the blank in
the same manner as for Container No. 1.
8.6.4.3 Container No. 3 (Silica Gel). Note the color of the
indicating silica gel to determine whether it has been completely spent,
and make a notation of its condition. Transfer the silica gel from the
fourth impinger to its original container, and seal. A funnel may be
used to pour the silica gel and a rubber policeman to remove the silica
gel from the impinger. It is not necessary to remove the small amount of
dust particles that may adhere to the impinger wall and are difficult to
remove. Since the gain in weight is to be used for moisture
calculations, do not use any water or other liquids to transfer the
silica gel. If a balance is available in the field, follow the
analytical procedure for Container No. 3 in section 11.4.2.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

9.2 Volume Metering System Checks. Same as Method 5, section 9.2.

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.

10.1 Sampling Equipment. Calibrate the probe nozzle, pitot tube,
metering system, probe heater, temperature sensors, and barometer
according to the procedures outlined in Method 5, sections 10.1 through
10.6. Conduct the leak-check of the metering system according to the
procedures outlined in Method 5, section 8.4.1.
10.2 Spectrophotometer.
10.2.1 Prepare the blank standard by adding 10 ml of SPADNS mixed
reagent to 50 ml of water.
10.2.2 Accurately prepare a series of standards from the 0.01 mg
F^-/ml standard fluoride solution (Section 7.3.10) by diluting
0, 2, 4, 6, 8, 10, 12, and 14 ml to 100 ml with deionized, distilled
water. Pipet 50 ml from each solution, and transfer each to a separate
100-ml beaker. Then add 10 ml of SPADNS mixed reagent (Section 7.3.13)
to each. These standards will contain 0, 10, 20, 30, 40, 50, 60, and 70
g F^-(0 to 1.4 g/ml), respectively.
10.2.3 After mixing, place the blank and calibration standards in a
constant temperature bath for 30 minutes before reading the absorbance
with the spectrophotometer. Adjust all samples to this same temperature
before analyzing.
10.2.4 With the spectrophotometer at 570 nm, use the blank standard
to set the absorbance to zero. Determine the absorbance of the
standards.
10.2.5 Prepare a calibration curve by plotting g
F^-/50 ml versus absorbance on linear graph paper. Prepare the
standard curve initially and thereafter whenever the SPADNS mixed
reagent is newly made. Also, run a

[[Page 369]]

calibration standard with each set of samples and, if it differs from
the calibration curve by more than 2 percent, prepare a new standard
curve.

11.0 Analytical Procedures

11.1 Sample Loss Check. Note the liquid levels in Containers No. 1
and No. 2, determine whether leakage occurred during transport, and note
this finding on the analytical data sheet. If noticeable leakage has
occurred, either void the sample or use methods, subject to the approval
of the Administrator, to correct the final results.
11.2 Sample Preparation. Treat the contents of each sample container
as described below:
11.2.1 Container No. 1 (Probe, Filter, and Impinger Catches). Filter
this container's contents, including the sampling filter, through
Whatman No. 541 filter paper, or equivalent, into a 1500-ml beaker.
11.2.1.1 If the filtrate volume exceeds 900 ml, make the filtrate
basic (red to phenolphthalein) with NaOH, and evaporate to less than 900
ml.
11.2.1.2 Place the filtered material (including sampling filter) in
a nickel crucible, add a few ml of water, and macerate the filters with
a glass rod.
11.2.1.2.1 Add 100 mg CaO to the crucible, and mix the contents
thoroughly to form a slurry. Add two drops of phenolphthalein indicator.
Place the crucible in a hood under infrared lamps or on a hot plate at
low heat. Evaporate the water completely. During the evaporation of the
water, keep the slurry basic (red to phenolphthalein) to avoid loss of
F^-. If the indicator turns colorless (acidic) during the
evaporation, add CaO until the color turns red again.
11.2.1.2.2 After evaporation of the water, place the crucible on a
hot plate under a hood, and slowly increase the temperature until the
Whatman No. 541 and sampling filters char. It may take several hours to
char the filters completely.
11.2.1.2.3 Place the crucible in a cold muffle furnace. Gradually
(to prevent smoking) increase the temperature to 600 [deg]C (1100
[deg]F), and maintain this temperature until the contents are reduced to
an ash. Remove the crucible from the furnace, and allow to cool.
11.2.1.2.4 Add approximately 4 g of crushed NaOH to the crucible,
and mix. Return the crucible to the muffle furnace, and fuse the sample
for 10 minutes at 600 [deg]C.
11.2.1.2.5 Remove the sample from the furnace, and cool to ambient
temperature. Using several rinsings of warm water, transfer the contents
of the crucible to the beaker containing the filtrate. To ensure
complete sample removal, rinse finally with two 20-ml portions of 25
percent H2SO4, and carefully add to the beaker.
Mix well, and transfer to a 1-liter volumetric flask. Dilute to volume
with water, and mix thoroughly. Allow any undissolved solids to settle.
11.2.2 Container No. 2 (Sample Blank). Treat in the same manner as
described in section 11.2.1 above.
11.2.3 Adjustment of Acid/Water Ratio in Distillation Flask. Place
400 ml of water in the distillation flask, and add 200 ml of
concentrated H2SO4. Add some soft glass beads and
several small pieces of broken glass tubing, and assemble the apparatus
as shown in Figure 13A-2. Heat the flask until it reaches a temperature
of 175 [deg]C (347 [deg]F) to adjust the acid/water ratio for subsequent
distillations. Discard the distillate.

Caution: Use a protective shield when carrying out this procedure.
Observe standard precautions when mixing H2SO4
with water. Slowly add the acid to the flask with constant swirling.

11.3 Distillation.
11.3.1 Cool the contents of the distillation flask to below 80
[deg]C (180 [deg]F). Pipet an aliquot of sample containing less than
10.0 mg F^- directly into the distillation flask, and add
water to make a total volume of 220 ml added to the distillation flask.
(To estimate the appropriate aliquot size, select an aliquot of the
solution, and treat as described in section 11.4.1. This will be an
approximation of the F^- content because of possible
interfering ions.)

Note: If the sample contains chloride, add 5 mg of
Ag2SO4 to the flask for every mg of chloride.

11.3.2 Place a 250-ml volumetric flask at the condenser exit. Heat
the flask as rapidly as possible with a Bunsen burner, and collect all
the distillate up to 175 [deg]C (347 [deg]F). During heatup, play the
burner flame up and down the side of the flask to prevent bumping.
Conduct the distillation as rapidly as possible (15 minutes or less).
Slow distillations have been found to produce low F^-
recoveries. Be careful not to exceed 175 [deg]C (347 [deg]F) to avoid
causing H2SO4 to distill over. If F^-
distillation in the mg range is to be followed by a distillation in the
fractional mg range, add 220 ml of water and distill it over as in the
acid adjustment step to remove residual F^- from the
distillation system.
11.3.3 The acid in the distillation flask may be used until there is
carry-over of interferences or poor F^- recovery. Check for
interference and for recovery efficiency every tenth distillation using
a water blank and a standard solution. Change the acid whenever the
F^- recovery is less than 90 percent or the blank value
exceeds 0.1 g/ml.
11.4 Sample Analysis.
11.4.1 Containers No. 1 and No. 2.
11.4.1.1 After distilling suitable aliquots from Containers No. 1
and No. 2 according to section 11.3, dilute the distillate in the
volumetric flasks to exactly 250 ml with water, and mix thoroughly.
Pipet a suitable aliquot

[[Page 370]]

of each sample distillate (containing 10 to 40 g F^-/
ml) into a beaker, and dilute to 50 ml with water. Use the same aliquot
size for the blank. Add 10 ml of SPADNS mixed reagent (Section 7.3.13),
and mix thoroughly.
11.4.1.2 After mixing, place the sample in a constant-temperature
bath containing the standard solutions for 30 minutes before reading the
absorbance on the spectrophotometer.

Note: After the sample and colorimetric reagent are mixed, the color
formed is stable for approximately 2 hours. Also, a 3 [deg]C (5.4
[deg]F) temperature difference between the sample and standard solutions
produces an error of approximately 0.005 mg F^-/liter. To
avoid this error, the absorbencies of the sample and standard solutions
must be measured at the same temperature.

11.4.1.3 Set the spectrophotometer to zero absorbance at 570 nm with
the zero reference solution (Section 7.3.12), and check the
spectrophotometer calibration with the standard solution (Section
7.3.10). Determine the absorbance of the samples, and determine the
concentration from the calibration curve. If the concentration does not
fall within the range of the calibration curve, repeat the procedure
using a different size aliquot.
11.4.2 Container No. 3 (Silica Gel). Weigh the spent silica gel (or
silica gel plus impinger) to the nearest 0.5 g using a balance. This
step may be conducted in the field.

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after final
calculation. Other forms of the equations may be used, provided that
they yield equivalent results.
12.1 Nomenclature.

Ad = Aliquot of distillate taken for color development, ml.
At = Aliquot of total sample added to still, ml.
Bws = Water vapor in the gas stream, portion by volume.
Cs = Concentration of F^- in stack gas, mg/dscm
(gr/dscf).
Fc = F^- concentration from the calibration curve,
g.
Ft = Total F^- in sample, mg.
Tm = Absolute average dry gas meter (DGM) temperature (see
Figure 5-3 of Method 5), [deg]K ([deg]R).
Ts = Absolute average stack gas temperature (see Figure 5-3
of Method 5), [deg]K ([deg]R).
Vd = Volume of distillate as diluted, ml.
Vm(std) = Volume of gas sample as measured by DGM at standard
conditions, dscm (dscf).
Vt = Total volume of F^- sample, after final
dilution, ml.
Vw(std) = Volume of water vapor in the gas sample at standard
conditions, scm (scf)

12.2 Average DGM Temperature and Average Orifice Pressure Drop (see
Figure 5-3 of Method 5).
12.3 Dry Gas Volume. Calculate Vm(std), and adjust for
leakage, if necessary, using Equation 5-1 of Method 5.
12.4 Volume of Water Vapor and Moisture Content. Calculate
Vw(std) and Bws from the data obtained in this
method. Use Equations 5-2 and 5-3 of Method 5.
12.5 Total Fluoride in Sample. Calculate the amount of F^-
in the sample using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.247

Where:

K = 10^-3 mg/g (metric units)
= 1.54 x 10^-5 gr/g (English units)

12.6 Fluoride Concentration in Stack Gas. Determine the
F^- concentration in the stack gas using the following
equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.248

12.7 Isokinetic Variation. Same as Method 5, section 12.11.

13.0 Method Performance

The following estimates are based on a collaborative test done at a
primary aluminum smelter. In the test, six laboratories each sampled the
stack simultaneously using two sampling trains for a total of 12 samples
per sampling run. Fluoride concentrations encountered during the test
ranged from 0.1 to 1.4 mg F^-/m\3\.
13.1 Precision. The intra- and inter-laboratory standard deviations,
which include sampling and analysis errors, were 0.044 mg F^-/
m\3\ with 60 degrees of freedom and 0.064 mg F^-/m\3\ with
five degrees of freedom, respectively.
13.2 Bias. The collaborative test did not find any bias in the
analytical method.
13.3 Range. The range of this method is 0 to 1.4 g
F-/ml.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 Compliance with ASTM D 3270-73T, 80, 91, or 95 (incorporated by
reference--see Sec. 60.17) ``Analysis of Fluoride Content of the
Atmosphere and Plant Tissues (Semiautomated Method) is an acceptable
alternative for the requirements specified in sections 11.2, 11.3, and
11.4.1 when applied to suitable aliquots of Containers 1 and 2 samples.

[[Page 371]]

17.0 References

1. Bellack, Ervin. Simplified Fluoride Distillation Method. J. of
the American Water Works Association. 50:5306. 1958.
2. Mitchell, W.J., J.C. Suggs, and F.J. Bergman. Collaborative Study
of EPA Method 13A and Method 13B. Publication No. EPA-300/4-77-050. U.S.
Environmental Protection Agency, Research Triangle Park, NC. December
1977.
3. Mitchell, W.J., and M.R. Midgett. Adequacy of Sampling Trains and
Analytical Procedures Used for Fluoride. Atm. Environ. 10:865-872. 1976.

18.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.249

[[Page 372]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.250

Method 13B--Determination of Total Fluoride Emissions From Stationary
Sources (Specific Ion Electrode Method)

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 5, and Method 13A.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total fluorides as Fluorine.... 7782-41-4 Not determined.
------------------------------------------------------------------------

2.0 Summary

Gaseous and particulate F^- are withdrawn isokinetically
from the source and collected in water and on a filter. The total
F^- is then determined by the specific ion electrode method.

3.0 Definitions [Reserved]

4.0 Interferences

Grease on sample-exposed surfaces may cause low F^-
results because of adsorption.

5.0 Safety

[[Page 373]]

user of this test method to establish appropriate safety and health
practices and to determine the applicability of regulatory limitations
prior to performing this test method.
5.2 Corrosive Reagents. The following reagents are hazardous.
Personal protective equipment and safe procedures are useful in
preventing chemical splashes. If contact occurs, immediately flush with
copious amounts of water at least 15 minutes. Remove clothing under
shower and decontaminate. Treat residual chemical burn as thermal burn.
5.2.1 Sodium Hydroxide (NaOH). Causes severe damage to eye tissues
and to skin. Inhalation causes irritation to nose, throat, and lungs.
Reacts exothermically with limited amounts of water.
5.2.2 Sulfuric Acid (H2SO4). Rapidly
destructive to body tissue. Will cause third degree burns. Eye damage
may result in blindness. Inhalation may be fatal from spasm of the
larynx, usually within 30 minutes. May cause lung tissue damage with
edema. 1 mg/m\3\ for 8 hours will cause lung damage or, in higher
concentrations, death. Provide ventilation to limit inhalation. Reacts
violently with metals and organics.

6.0 Equipment and Supplies

6.1 Sample Collection and Sample Recovery. Same as Method 13A,
sections 6.1 and 6.2, respectively.
6.2 Sample Preparation and Analysis. The following items are
required for sample preparation and analysis:
6.2.1 Distillation Apparatus, Bunsen Burner, Electric Muffle
Furnace, Crucibles, Beakers, Volumetric Flasks, Erlenmeyer Flasks or
Plastic Bottles, Constant Temperature Bath, and Balance. Same as Method
13A, sections 6.3.1 to 6.3.9, respectively.
6.2.2 Fluoride Ion Activity Sensing Electrode.
6.2.3 Reference Electrode. Single junction, sleeve type.
6.2.4 Electrometer. A pH meter with millivolt-scale capable of 0.1-
mv resolution, or a specific ion meter made specifically for specific
ion electrode use.
6.2.5 Magnetic Stirrer and Tetrafluoroethylene (TFE) Fluorocarbon-
Coated Stirring Bars.
6.2.6 Beakers. Polyethylene, 100-ml.

7.0 Reagents and Standards

8.0 Sample Collection, Preservation, Storage, and Transport

Same as Method 13A, section 8.0.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

[[Page 374]]

9.2 Volume Metering System Checks. Same as Method 5, section 9.2.

10.0 Calibration and Standardizations

Note: Maintain a laboratory log of all calibrations.

10.1 Sampling Equipment. Same as Method 13A, section 10.1.
10.2 Fluoride Electrode. Prepare fluoride standardizing solutions by
serial dilution of the 0.1 M fluoride standard solution. Pipet 10 ml of
0.1 M fluoride standard solution into a 100-ml volumetric flask, and
make up to the mark with water for a 10^-2 M standard
solution. Use 10 ml of 10^-2 M solution to make a
10^-3 M solution in the same manner. Repeat the dilution
procedure, and make 10^-4 and 10^-5 M solutions.
10.2.1 Pipet 50 ml of each standard into a separate beaker. Add 50
ml of TISAB to each beaker. Place the electrode in the most dilute
standard solution. When a steady millivolt reading is obtained, plot the
value on the linear axis of semilog graph paper versus concentration on
the log axis. Plot the nominal value for concentration of the standard
on the log axis, (e.g., when 50 ml of 10^-2 M standard is
diluted with 50 ml of TISAB, the concentration is still designated
``10^-2 M'').
10.2.2 Between measurements, soak the fluoride sensing electrode in
water for 30 seconds, and then remove and blot dry. Analyze the
standards going from dilute to concentrated standards. A straight-line
calibration curve will be obtained, with nominal concentrations of
10^-4, 10^-3, 10^-2, 10^-1
fluoride molarity on the log axis plotted versus electrode potential (in
mv) on the linear scale. Some electrodes may be slightly nonlinear
between 10^-5 and 10^-4 M. If this occurs, use
additional standards between these two concentrations.
10.2.3 Calibrate the fluoride electrode daily, and check it hourly.
Prepare fresh fluoride standardizing solutions daily (10^-2 M
or less). Store fluoride standardizing solutions in polyethylene or
polypropylene containers.

Note: Certain specific ion meters have been designed specifically
for fluoride electrode use and give a direct readout of fluoride ion
concentration. These meters may be used in lieu of calibration curves
for fluoride measurements over a narrow concentration ranges. Calibrate
the meter according to the manufacturer's instructions.

11.0 Analytical Procedures

11.1 Sample Loss Check, Sample Preparation, and Distillation. Same
as Method 13A, sections 11.1 through 11.3, except that the note
following section 11.3.1 is not applicable.
11.2 Analysis.
11.2.1 Containers No. 1 and No. 2. Distill suitable aliquots from
Containers No. 1 and No. 2. Dilute the distillate in the volumetric
flasks to exactly 250 ml with water, and mix thoroughly. Pipet a 25-ml
aliquot from each of the distillate into separate beakers. Add an equal
volume of TISAB, and mix. The sample should be at the same temperature
as the calibration standards when measurements are made. If ambient
laboratory temperature fluctuates more than 2 [deg]C from the
temperature at which the calibration standards were measured, condition
samples and standards in a constant-temperature bath before measurement.
Stir the sample with a magnetic stirrer during measurement to minimize
electrode response time. If the stirrer generates enough heat to change
solution temperature, place a piece of temperature insulating material,
such as cork, between the stirrer and the beaker. Hold dilute samples
(below 10^-4 M fluoride ion content) in polyethylene beakers
during measurement.
11.2.2 Insert the fluoride and reference electrodes into the
solution. When a steady millivolt reading is obtained, record it. This
may take several minutes. Determine concentration from the calibration
curve. Between electrode measurements, rinse the electrode with water.
11.2.3 Container No. 3 (Silica Gel). Same as in Method 13A, section
11.4.2.

12.0 Data Analysis and Calculations

M = F^- concentration from calibration curve, molarity.

12.2 Average DGM Temperature and Average Orifice Pressure Drop, Dry
Gas Volume, Volume of Water Vapor and Moisture Content, Fluoride
Concentration in Stack Gas, and Isokinetic Variation. Same as Method
13A, sections 12.2 to 12.4, 12.6, and 12.7, respectively.
12.3 Total Fluoride in Sample. Calculate the amount of F^-
in the sample using Equation 13B-1:
[GRAPHIC] [TIFF OMITTED] TR17OC00.251

Where:

K = 19 [(mgl)/(moleml)] (metric units)
= 0.292 [(grl)/(moleml)] (English units)

13.0 Method Performance

[[Page 375]]

sampling run. Fluoride concentrations encountered during the test ranged
from 0.1 to 1.4 mg F^-/m\3\.
13.1 Precision. The intra-laboratory and inter-laboratory standard
deviations, which include sampling and analysis errors, are 0.037 mg
F^-/m\3\ with 60 degrees of freedom and 0.056 mg
F^-/m\3\ with five degrees of freedom, respectively.
13.2 Bias. The collaborative test did not find any bias in the
analytical method.
13.3 Range. The range of this method is 0.02 to 2,000 g
F^-/ml; however, measurements of less than 0.1 g
F^-/ml require extra care.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 Compliance with ASTM D 3270-73T, 91, 95 ``Analysis for Fluoride
Content of the Atmosphere and Plant Tissues (Semiautomated Method)'' is
an acceptable alternative for the distillation and analysis requirements
specified in sections 11.1 and 11.2 when applied to suitable aliquots of
Containers 1 and 2 samples.

17.0 References

Same as Method 13A, section 16.0, References 1 and 2, with the
following addition:

1. MacLeod, Kathryn E., and Howard L. Crist. Comparison of the
SPADNS-Zirconium Lake and Specific Ion Electrode Methods of Fluoride
Determination in Stack Emission Samples. Analytical Chemistry. 45:1272-
1273. 1973.

18.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 14--Determination of Fluoride Emissions From Potroom Roof
Monitors for Primary Aluminum Plants

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 5, Method 13A, and Method 13B.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total fluorides as Fluorine....... 7782-41-4 Not determined.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of fluoride emissions from roof monitors at primary aluminum reduction
plant potroom groups.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Gaseous and particulate fluoride roof monitor emissions are
drawn into a permanent sampling manifold through several large nozzles.
The sample is transported from the sampling manifold to ground level
through a duct. The fluoride content of the gas in the duct is
determined using either Method 13A or Method 13B. Effluent velocity and
volumetric flow rate are determined using anemometers located in the
roof monitor.

3.0 Definitions

Potroom means a building unit which houses a group of electrolytic
cells in which aluminum is produced.
Potroom group means an uncontrolled potroom, a potroom which is
controlled individually, or a group of potrooms or potroom segments
ducted to a common control system.
Roof monitor means that portion of the roof of a potroom where gases
not captured at the cell exit from the potroom.

4.0 Interferences

Same as section 4.0 of either Method 13A or Method 13B, with the
addition of the following:
4.1 Magnetic Field Effects. Anemometer readings can be affected by
potroom magnetic field effects. section 6.1 provides for minimization of
this interference through proper shielding or encasement of anemometer
components.

5.0 Safety

[[Page 376]]

6.0 Equipment and Supplies

Same as section 6.0 of either Method 13A or Method 13B, as
applicable, with the addition of the following:
6.1 Velocity Measurement Apparatus.
6.1.1 Anemometer Specifications. Propeller anemometers, or
equivalent. Each anemometer shall meet the following specifications:
6.1.1.1 Its propeller shall be made of polystyrene, or similar
material of uniform density. To ensure uniformity of performance among
propellers, it is desirable that all propellers be made from the same
mold.
6.1.1.2 The propeller shall be properly balanced, to optimize
performance.
6.1.1.3 When the anemometer is mounted horizontally, its threshold
velocity shall not exceed 15 m/min (50 ft/min).
6.1.1.4 The measurement range of the anemometer shall extend to at
least 600 m/min (2,000 ft/min).
6.1.1.5 The anemometer shall be able to withstand prolonged exposure
to dusty and corrosive environments; one way of achieving this is to
purge the bearings of the anemometer continuously with filtered air
during operation.
6.1.1.6 All anemometer components shall be properly shielded or
encased, such that the performance of the anemometer is uninfluenced by
potroom magnetic field effects.
6.1.1.7 A known relationship shall exist between the electrical
output signal from the anemometer generator and the propeller shaft rpm
(see section 10.2.1). Anemometers having other types of output signals
(e.g., optical) may be used, subject to the approval of the
Administrator. If other types of anemometers are used, there must be a
known relationship between output signal and shaft rpm (see section
10.2.2).
6.1.1.8 Each anemometer shall be equipped with a suitable readout
system (see section 6.1.3).
6.1.2 Anemometer Installation Requirements.
6.1.2.1 Single, Isolated Potroom. If the affected facility consists
of a single, isolated potroom (or potroom segment), install at least one
anemometer for every 85 m (280 ft) of roof monitor length. If the length
of the roof monitor divided by 85 m (280 ft) is not a whole number,
round the fraction to the nearest whole number to determine the number
of anemometers needed. For monitors that are less than 130 m (430 ft) in
length, use at least two anemometers. Divide the monitor cross-section
into as many equal areas as anemometers, and locate an anemometer at the
centroid of each equal area. See exception in section 6.1.2.3.
6.1.2.2 Two or More Potrooms. If the affected facility consists of
two or more potrooms (or potroom segments) ducted to a common control
device, install anemometers in each potroom (or segment) that contains a
sampling manifold. Install at least one anemometer for every 85 m (280
ft) of roof monitor length of the potroom (or segment). If the potroom
(or segment) length divided by 85 m (280 ft) is not a whole number,
round the fraction to the nearest whole number to determine the number
of anemometers needed. If the potroom (or segment) length is less than
130 m (430 ft), use at least two anemometers. Divide the potroom (or
segment) monitor cross-section into as many equal areas as anemometers,
and locate an anemometer at the centroid of each equal area. See
exception in section 6.1.2.3.
6.1.2.3 Placement of Anemometer at the Center of Manifold. At least
one anemometer shall be installed in the immediate vicinity (i.e.,
within 10 m (33 ft)) of the center of the manifold (see section 6.2.1).
For its placement in relation to the width of the monitor, there are two
alternatives. The first is to make a velocity traverse of the width of
the roof monitor where an anemometer is to be placed and install the
anemometer at a point of average velocity along this traverse. The
traverse may be made with any suitable low velocity measuring device,
and shall be made during normal process operating conditions. The second
alternative is to install the anemometer half-way across the width of
the roof monitor. In this latter case, the velocity traverse need not be
conducted.
6.1.3 Recorders. Recorders that are equipped with suitable auxiliary
equipment (e.g., transducers) for converting the output signal from each
anemometer to a continuous recording of air flow velocity or to an
integrated measure of volumetric flowrate shall be used. A suitable
recorder is one that allows the output signal from the propeller
anemometer to be read to within 1 percent when the velocity is between
100 and 120 m/min (330 and 390 ft/min). For the purpose of recording
velocity, ``continuous'' shall mean one readout per 15-minute or shorter
time interval. A constant amount of time shall elapse between readings.
Volumetric flow rate may be determined by an electrical count of
anemometer revolutions. The recorders or counters shall permit
identification of the velocities or flowrates measured by each
individual anemometer.
6.1.4 Pitot Tube. Standard-type pitot tube, as described in section
6.7 of Method 2, and having a coefficient of 0.99 0.01.
6.1.5 Pitot Tube (Optional). Isolated, Type S pitot, as described in
section 6.1 of Method 2, and having a known coefficient, determined as
outlined in section 4.1 of Method 2.
6.1.6 Differential Pressure Gauge. Inclined manometer, or
equivalent, as described in section 6.1.2 of Method 2.
6.2 Roof Monitor Air Sampling System.
6.2.1 Manifold System and Ductwork. A minimum of one manifold system
shall be installed for each potroom group. The manifold

[[Page 377]]

system and ductwork shall meet the following specifications:
6.2.1.1 The manifold system and connecting duct shall be permanently
installed to draw an air sample from the roof monitor to ground level. A
typical installation of a duct for drawing a sample from a roof monitor
to ground level is shown in Figure 14-1 in section 17.0. A plan of a
manifold system that is located in a roof monitor is shown in Figure 14-
2. These drawings represent a typical installation for a generalized
roof monitor. The dimensions on these figures may be altered slightly to
make the manifold system fit into a particular roof monitor, but the
general configuration shall be followed.
6.2.1.2 There shall be eight nozzles, each having a diameter of 0.40
to 0.50 m.
6.2.1.3 The length of the manifold system from the first nozzle to
the eighth shall be 35 m (115 ft) or eight percent of the length of the
potroom (or potroom segment) roof monitor, whichever is greater.
Deviation from this requirement is subject to the approval of the
Administrator.
6.2.1.4 The duct leading from the roof monitor manifold system shall
be round with a diameter of 0.30 to 0.40 m (1.0 to 1.3 ft). All
connections in the ductwork shall be leak-free.
6.2.1.5 As shown in Figure 14-2, each of the sample legs of the
manifold shall have a device, such as a blast gate or valve, to enable
adjustment of the flow into each sample nozzle.
6.2.1.6 The manifold system shall be located in the immediate
vicinity of one of the propeller anemometers (see section 8.1.1.4) and
as close as possible to the midsection of the potroom (or potroom
segment). Avoid locating the manifold system near the end of a potroom
or in a section where the aluminum reduction pot arrangement is not
typical of the rest of the potroom (or potroom segment). The sample
nozzles shall be centered in the throat of the roof monitor (see Figure
14-1).
6.2.1.7 All sample-exposed surfaces within the nozzles, manifold,
and sample duct shall be constructed with 316 stainless steel.
Alternatively, aluminum may be used if a new ductwork is conditioned
with fluoride-laden roof monitor air for a period of six weeks before
initial testing. Other materials of construction may be used if it is
demonstrated through comparative testing, to the satisfaction of the
Administrator, that there is no loss of fluorides in the system.
6.2.1.8 Two sample ports shall be located in a vertical section of
the duct between the roof monitor and the exhaust fan (see section
6.2.2). The sample ports shall be at least 10 duct diameters downstream
and three diameters upstream from any flow disturbance such as a bend or
contraction. The two sample ports shall be situated 90[deg] apart. One
of the sample ports shall be situated so that the duct can be traversed
in the plane of the nearest upstream duct bend.
6.2.2 Exhaust Fan. An industrial fan or blower shall be attached to
the sample duct at ground level (see Figure 14-1). This exhaust fan
shall have a capacity such that a large enough volume of air can be
pulled through the ductwork to maintain an isokinetic sampling rate in
all the sample nozzles for all flow rates normally encountered in the
roof monitor. The exhaust fan volumetric flow rate shall be adjustable
so that the roof monitor gases can be drawn isokinetically into the
sample nozzles. This control of flow may be achieved by a damper on the
inlet to the exhauster or by any other workable method.
6.3 Temperature Measurement Apparatus. To monitor and record the
temperature of the roof monitor effluent gas, and consisting of the
following:
6.3.1 Temperature Sensor. A temperature sensor shall be installed in
the roof monitor near the sample duct. The temperature sensor shall
conform to the specifications outlined in Method 2, section 6.3.
6.3.2 Signal Transducer. Transducer, to change the temperature
sensor voltage output to a temperature readout.
6.3.3 Thermocouple Wire. To reach from roof monitor to signal
transducer and recorder.
6.3.4 Recorder. Suitable recorder to monitor the output from the
thermocouple signal transducer.

7.0 Reagents and Standards

Same as section 7.0 of either Method 13A or Method 13B, as
applicable.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Roof Monitor Velocity Determination.
8.1.1 Velocity Estimate(s) for Setting Isokinetic Flow. To assist in
setting isokinetic flow in the manifold sample nozzles, the anticipated
average velocity in the section of the roof monitor containing the
sampling manifold shall be estimated before each test run. Any
convenient means to make this estimate may be used (e.g., the velocity
indicated by the anemometer in the section of the roof monitor
containing the sampling manifold may be continuously monitored during
the 24-hour period before the test run). If there is question as to
whether a single estimate of average velocity is adequate for an entire
test run (e.g., if velocities are anticipated to be significantly
different during different potroom operations), the test run may be
divided into two or more ``sub-runs,'' and a different estimated average
velocity may be used for each sub-run (see section 8.4.2).
8.1.2 Velocity Determination During a Test Run. During the actual
test run, record the

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velocity or volumetric flowrate readings of each propeller anemometer in
the roof monitor. Readings shall be taken from each anemometer at equal
time intervals of 15 minutes or less (or continuously).
8.2 Temperature Recording. Record the temperature of the roof
monitor effluent gases at least once every 2 hours during the test run.
8.3 Pretest Ductwork Conditioning. During the 24-hour period
immediately preceding the test run, turn on the exhaust fan, and draw
roof monitor air through the manifold system and ductwork. Adjust the
fan to draw a volumetric flow through the duct such that the velocity of
gas entering the manifold nozzles approximates the average velocity of
the air exiting the roof monitor in the vicinity of the sampling
manifold.
8.4 Manifold Isokinetic Sample Rate Adjustment(s).
8.4.1 Initial Adjustment. Before the test run (or first sub-run, if
applicable; see sections 8.1.1 and 8.4.2), adjust the fan such that air
enters the manifold sample nozzles at a velocity equal to the
appropriate estimated average velocity determined under section 8.1.1.
Use Equation 14-1 (Section 12.2.2) to determine the correct stream
velocity needed in the duct at the sampling location, in order for
sample gas to be drawn isokinetically into the manifold nozzles. Next,
verify that the correct stream velocity has been achieved, by performing
a pitot tube traverse of the sample duct (using either a standard or
Type S pitot tube); use the procedure outlined in Method 2.
8.4.2 Adjustments During Run. If the test run is divided into two or
more ``sub-runs'' (see section 8.1.1), additional isokinetic rate
adjustment(s) may become necessary during the run. Any such adjustment
shall be made just before the start of a sub-run, using the procedure
outlined in section 8.4.1 above.

Note: Isokinetic rate adjustments are not permissible during a sub-
run.

8.5 Pretest Preparation, Preliminary Determinations, Preparation of
Sampling Train, Leak-Check Procedures, Sampling Train Operation, and
Sample Recovery. Same as Method 13A, sections 8.1 through 8.6, with the
exception of the following:
8.5.1 A single train shall be used for the entire sampling run.
Alternatively, if two or more sub-runs are performed, a separate train
may be used for each sub-run; note, however, that if this option is
chosen, the area of the sampling nozzle shall be the same (2 percent)
for each train. If the test run is divided into sub-runs, a complete
traverse of the duct shall be performed during each sub-run.
8.5.2 Time Per Run. Each test run shall last 8 hours or more; if
more than one run is to be performed, all runs shall be of approximately
the same (10 percent) length. If questions exist as to the
representativeness of an 8-hour test, a longer period should be
selected. Conduct each run during a period when all normal operations
are performed underneath the sampling manifold. For most recently-
constructed plants, 24 hours are required for all potroom operations and
events to occur in the area beneath the sampling manifold. During the
test period, all pots in the potroom group shall be operated such that
emissions are representative of normal operating conditions in the
potroom group.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality Control
Section Measure Effect
------------------------------------------------------------------------
8.0, 10.0..................... Sampling Ensure accurate
equipment leak- measurement of gas
check and flow rate in duct
calibration. and of sample
volume.
10.3, 10.4.................... Initial and Ensure accurate and
periodic precise measurement
performance of roof monitor
checks of roof effluent gas
monitor effluent temperature and flow
gas rate.
characterization
apparatus.
11.0.......................... Interference/ Minimize negative
recovery effects of used
efficiency check acid.
during
distillation.
------------------------------------------------------------------------

9.2 Volume Metering System Checks. Same as Method 5, section 9.2.

10.0 Calibration and Standardization

Same as section 10.0 of either Method 13A or Method 13B, as
applicable, with the addition of the following:
10.1 Manifold Intake Nozzles. The manifold intake nozzles shall be
calibrated when the manifold system is installed or, alternatively, the
manifold may be preassembled and the nozzles calibrated on the ground
prior to installation. The following procedures shall be observed:
10.1.1 Adjust the exhaust fan to draw a volumetric flow rate (refer
to Equation 14-1) such that the entrance velocity into each manifold
nozzle approximates the average effluent velocity in the roof monitor.
10.1.2 Measure the velocity of the air entering each nozzle by
inserting a standard pitot tube into a 2.5 cm or less diameter hole (see
Figure 14-2) located in the manifold between each blast gate (or valve)
and nozzle. Note that a standard pitot tube is used, rather

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than a type S, to eliminate possible velocity measurement errors due to
cross-section blockage in the small (0.13 m diameter) manifold leg
ducts. The pitot tube tip shall be positioned at the center of each
manifold leg duct. Take care to ensure that there is no leakage around
the pitot tube, which could affect the indicated velocity in the
manifold leg.
10.1.3 If the velocity of air being drawn into each nozzle is not
the same, open or close each blast gate (or valve) until the velocity in
each nozzle is the same. Fasten each blast gate (or valve) so that it
will remain in position, and close the pitot port holes.
10.2 Initial Calibration of Propeller Anemometers.
10.2.1 Anemometers that meet the specifications outlined in section
6.1.1 need not be calibrated, provided that a reference performance
curve relating anemometer signal output to air velocity (covering the
velocity range of interest) is available from the manufacturer. If a
reference performance curve is not available from the manufacturer, such
a curve shall be generated.
For the purpose of this method, a ``reference'' performance curve is
defined as one that has been derived from primary standard calibration
data, with the anemometer mounted vertically. ``Primary standard'' data
are obtainable by: (a) direct calibration of one or more of the
anemometers by the National Institute of Standards and Technology
(NIST); (b) NIST-traceable calibration; or (c) Calibration by direct
measurement of fundamental parameters such as length and time (e.g., by
moving the anemometers through still air at measured rates of speed, and
recording the output signals).
10.2.2 Anemometers having output signals other than electrical
(e.g., optical) may be used, subject to the approval of the
Administrator. If other types of anemometers are used, a reference
performance curve shall be generated, using procedures subject to the
approval of the Administrator.
10.2.3 The reference performance curve shall be derived from at
least the following three points: 60 15, 900 100, and 1800 100 rpm.
10.3 Initial Performance Checks. Conduct these checks within 60 days
before the first performance test.
10.3.1 Anemometers. A performance-check shall be conducted as
outlined in sections 10.3.1.1 through 10.3.1.3. Alternatively, any other
suitable method that takes into account the signal output, propeller
condition, and threshold velocity of the anemometer may be used, subject
to the approval of the Administrator.
10.3.1.1 Check the signal output of the anemometer by using an
accurate rpm generator (see Figure 14-3) or synchronous motors to spin
the propeller shaft at each of the three rpm settings described in
section 10.2.3, and measuring the output signal at each setting. If, at
each setting, the output signal is within 5 percent of the
manufacturer's value, the anemometer can be used. If the anemometer
performance is unsatisfactory, the anemometer shall either be replaced
or repaired.
10.3.1.2 Check the propeller condition, by visually inspecting the
propeller, making note of any significant damage or warpage; damaged or
deformed propellers shall be replaced.
10.3.1.3 Check the anemometer threshold velocity as follows: With
the anemometer mounted as shown in Figure 14-4(A), fasten a known weight
(a straight-pin will suffice) to the anemometer propeller at a fixed
distance from the center of the propeller shaft. This will generate a
known torque; for example, a 0.1-g weight, placed 10 cm from the center
of the shaft, will generate a torque of 1.0 g-cm. If the known torque
causes the propeller to rotate downward, approximately 90[deg] [see
Figure 14-4(B)], then the known torque is greater than or equal to the
starting torque; if the propeller fails to rotate approximately 90[deg],
the known torque is less than the starting torque. By trying different
combinations of weight and distance, the starting torque of a particular
anemometer can be satisfactorily estimated. Once an estimate of the
starting torque has been obtained, the threshold velocity of the
anemometer (for horizontal mounting) can be estimated from a graph such
as Figure 14-5 (obtained from the manufacturer). If the horizontal
threshold velocity is acceptable [<15 m/min (50 ft/min), when this
technique is used], the anemometer can be used. If the threshold
velocity of an anemometer is found to be unacceptably high, the
anemometer shall either be replaced or repaired.
10.3.2 Recorders and Counters. Check the calibration of each
recorder and counter (see section 6.1.2) at a minimum of three points,
approximately spanning the expected range of velocities. Use the
calibration procedures recommended by the manufacturer, or other
suitable procedures (subject to the approval of the Administrator). If a
recorder or counter is found to be out of calibration by an average
amount greater than 5 percent for the three calibration points, replace
or repair the system; otherwise, the system can be used.
10.3.3 Temperature Measurement Apparatus. Check the calibration of
the Temperature Measurement Apparatus, using the procedures outlined in
section 10.3 of Method 2, at temperatures of 0, 100, and 150 [deg]C (32,
212, and 302 [deg]F). If the calibration is off by more than 5 [deg]C (9
[deg]F) at any of the temperatures, repair or replace the apparatus;
otherwise, the apparatus can be used.
10.4 Periodic Performance Checks. Repeat the procedures outlined in
section 10.3 no

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more than 12 months after the initial performance checks. If the above
systems pass the performance checks (i.e., if no repair or replacement
of any component is necessary), continue with the performance checks on
a 12-month interval basis. However, if any of the above systems fail the
performance checks, repair or replace the system(s) that failed, and
conduct the periodic performance checks on a 3-month interval basis,
until sufficient information (to the satisfaction of the Administrator)
is obtained to establish a modified performance check schedule and
calculation procedure.

Note: If any of the above systems fails the 12-month periodic
performance checks, the data for the past year need not be recalculated.

11.0 Analytical Procedures

Same as section 11.0 of either Method 13A or Method 13B.

12.0 Data Analysis and Calculations

Same as section 12.0 of either Method 13A or Method 13B, as
applicable, with the following additions and exceptions:
12.1 Nomenclature.

A = Roof monitor open area, m\2\ (ft\2\).
Bws = Water vapor in the gas stream, portion by volume.
Cs = Average fluoride concentration in roof monitor air, mg
F/dscm (gr/dscf).
Dd = Diameter of duct at sampling location, m (ft).
Dn = Diameter of a roof monitor manifold nozzle, m (ft).
F = Emission Rate multiplication factor, dimensionless.
Ft = Total fluoride mass collected during a particular sub-
run (from Equation 13A-1 of Method 13A or Equation 13B-1 of
Method 13B), mg F^- (gr F^-).
Md = Mole fraction of dry gas, dimensionless.
Prm = Pressure in the roof monitor; equal to barometric
pressure for this application.
Qsd = Average volumetric flow from roof monitor at standard
conditions on a dry basis, m\3\/min.
Trm = Average roof monitor temperature (from section 8.2),
[deg]C ( [deg]F).
Vd = Desired velocity in duct at sampling location, m/sec.
Vm = Anticipated average velocity (from section 8.1.1) in
sampling duct, m/sec.
Vmt = Arithmetic mean roof monitor effluent gas velocity, m/
sec.
Vs = Actual average velocity in the sampling duct (from
Equation 2-9 of Method 2 and data obtained from Method 13A or
13B), m/sec.

12.2 Isokinetic Sampling Check.
12.2.1 Calculate the arithmetic mean of the roof monitor effluent
gas velocity readings (vm) as measured by the anemometer in
the section of the roof monitor containing the sampling manifold. If two
or more sub-runs have been performed, the average velocity for each sub-
run may be calculated separately.
12.2.2 Calculate the expected average velocity (vd) in
the duct, corresponding to each value of vm obtained under
section 12.2.1, using Equation 14-1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.252

Where:

8 = number of required manifold nozzles.
60 = sec/min.

12.2.3 Calculate the actual average velocity (vs) in the
sampling duct for each run or sub-run according to Equation 2-9 of
Method 2, using data obtained during sampling (Section 8.0 of Method
13A).
12.2.4 Express each vs value from section 12.2.3 as a percentage of
the corresponding vd value from section 12.2.2.
12.2.4.1 If vs is less than or equal to 120 percent of
vd, the results are acceptable (note that in cases where the
above calculations have been performed for each sub-run, the results are
acceptable if the average percentage for all sub-runs is less than or
equal to 120 percent).
12.2.4.2 If vs is more than 120 percent of vd,
multiply the reported emission rate by the following factor:
[GRAPHIC] [TIFF OMITTED] TR17OC00.253

12.3 Average Velocity of Roof Monitor Effluent Gas. Calculate the
arithmetic mean roof monitor effluent gas velocity (vmt)
using all the velocity or volumetric flow readings from section 8.1.2.
12.4 Average Temperature of Roof Monitor Effluent Gas. Calculate the
arithmetic mean roof monitor effluent gas temperature (Tm)
using all the temperature readings recorded in section 8.2.
12.5 Concentration of Fluorides in Roof Monitor Effluent Gas.
12.5.1 If a single sampling train was used throughout the run,
calculate the average fluoride concentration for the roof monitor using
Equation 13A-2 of Method 13A.
12.5.2 If two or more sampling trains were used (i.e., one per sub-
run), calculate the average fluoride concentration for the run using
Equation 14-3:
[GRAPHIC] [TIFF OMITTED] TR17OC00.254

[[Page 381]]

Where:

n = Total number of sub-runs.
12.6 Mole Fraction of Dry Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.255

12.7 Average Volumetric Flow Rate of Roof Monitor Effluent Gas.
Calculate the arithmetic mean volumetric flow rate of the roof monitor
effluent gases using Equation 14-5.
[GRAPHIC] [TIFF OMITTED] TR17OC00.256

Where:

K1 = 0.3858 K/mm Hg for metric units,
= 17.64 [deg]R/in. Hg for English units.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as section 16.0 of either Method 13A or Method 13B, as
applicable, with the addition of the following:

1. Shigehara, R.T. A Guideline for Evaluating Compliance Test
Results (Isokinetic Sampling Rate Criterion). U.S. Environmental
Protection Agency, Emission Measurement Branch, Research Triangle Park,
NC. August 1977.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

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[GRAPHIC] [TIFF OMITTED] TR17OC00.257

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[GRAPHIC] [TIFF OMITTED] TR17OC00.258

[[Page 384]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.259

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[GRAPHIC] [TIFF OMITTED] TR17OC00.260

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[GRAPHIC] [TIFF OMITTED] TR17OC00.261

Method 14A--Determination of Total Fluoride Emissions from Selected
Sources at Primary Aluminum Production Facilities

1.0 Scope and Application
1.1 Analytes.

[[Page 387]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total fluorides................. None assigned..... Not determined.
Includes hydrogen fluoride...... 007664-39-3....... Not determined.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of total fluorides (TF) emissions from sources specified in the
applicable regulation. This method was developed by consensus with the
Aluminum Association and the U.S. Environmental Protection Agency (EPA).
2.0 Summary of Method
2.1 Total fluorides, in the form of solid and gaseous fluorides, are
withdrawn from the ascending air stream inside of an aluminum reduction
potroom and, prior to exiting the potroom roof monitor, into a specific
cassette arrangement. The cassettes are connected by tubing to
flowmeters and a manifold system that allows for the equal distribution
of volume pulled through each cassette, and finally to a dry gas meter.
The cassettes have a specific internal arrangement of one unaltered
cellulose filter and support pad in the first section of the cassette
for solid fluoride retention and two cellulose filters with support pads
that are impregnated with sodium formate for the chemical absorption of
gaseous fluorides in the following two sections of the cassette. A
minimum of eight cassettes shall be used for a potline and shall be
strategically located at equal intervals across the potroom roof so as
to encompass a minimum of 8 percent of the total length of the potroom.
A greater number of cassettes may be used should the regulated facility
choose to do so. The mass flow rate of pollutants is determined with
anemometers and temperature sensing devices located immediately below
the opening of the roof monitor and spaced evenly within the cassette
group.
3.0 Definitions
3.1 Cassette. A segmented, styrene acrylonitrile cassette
configuration with three separate segments and a base, for the purpose
of this method, to capture and retain fluoride from potroom gases.
3.2 Cassette arrangement. The cassettes, tubing, manifold system,
flowmeters, dry gas meter, and any other related equipment associated
with the actual extraction of the sample gas stream.
3.3 Cassette group. That section of the potroom roof monitor where a
distinct group of cassettes is located.
3.4 Potline. A single, discrete group of electrolytic reduction
cells electrically connected in series, in which alumina is reduced to
form aluminum.
3.5 Potroom. A building unit that houses a group of electrolytic
reduction cells in which aluminum is produced.
3.6 Potroom group. An uncontrolled potroom, a potroom that is
controlled individually, or a group of potrooms or potroom segments
ducted to a common primary control system.
3.7 Primary control system. The equipment used to capture the gases
and particulate matter generated during the reduction process and the
emission control device(s) used to remove pollutants prior to discharge
of the cleaned gas to the atmosphere.
3.8 Roof monitor. That portion of the roof of a potroom building
where gases, not captured at the cell, exit from the potroom.
3.9 Total fluorides (TF). Elemental fluorine and all fluoride
compounds as measured by Methods 13A or 13B of this appendix or by an
approved alternative method.
4.0 Interferences and Known Limitations
4.1 There are two principal categories of limitations that must be
addressed when using this method. The first category is sampling bias
and the second is analytical bias. Biases in sampling can occur when
there is an insufficient number of cassettes located along the roof
monitor of a potroom or if the distribution of those cassettes is
spatially unequal. Known sampling biases also can occur when there are
leaks within the cassette arrangement and if anemometers and temperature
devices are not providing accurate data. Applicable instruments must be
properly calibrated to avoid sampling bias. Analytical biases can occur
when instrumentation is not calibrated or fails calibration and the
instrument is used out of proper calibration. Additionally, biases can
occur in the laboratory if fusion crucibles retain residual fluorides
over lengthy periods of use. This condition could result in falsely
elevated fluoride values. Maintaining a clean work environment in the
laboratory is crucial to producing accurate values.
4.2 Biases during sampling can be avoided by properly spacing the
appropriate number of cassettes along the roof monitor, conducting leak
checks of the cassette arrangement, calibrating the dry gas meter every
30 days, verifying the accuracy of individual flowmeters (so that there
is no more than 5 percent difference in the volume pulled between any
two flowmeters), and calibrating or replacing anemometers and
temperature sensing devices as necessary to maintain true data
generation.
4.3 Analytical biases can be avoided by calibrating instruments
according to the manufacturer's specifications prior to conducting any
analyses, by performing internal and external audits of up to 10 percent
of all samples analyzed, and by rotating individual crucibles as the
``blank'' crucible to detect any potential residual fluoride carry-over
to samples. Should any contamination be discovered in the blank
crucible, the crucible shall be thoroughly cleaned to remove any
detected residual fluorides and a ``blank'' analysis conducted again to
evaluate the effectiveness of the cleaning. The crucible

[[Page 388]]

shall remain in service as long as no detectable residual fluorides are
present.
5.0 Safety
5.1 This method may involve the handling of hazardous materials in
the analytical phase. This method does not purport to address all of the
potential safety hazards associated with its use. It is the
responsibility of the user to establish appropriate safety and health
practices and determine the applicability of regulatory limitations
prior to performing this test method.
5.2 Corrosive reagents. The following reagents are hazardous.
Personal protective equipment and safe procedures are useful in
preventing chemical splashes. If contact occurs, immediately flush with
copious amounts of water for at least 15 minutes. Remove clothing under
shower and decontaminate. Treat residual chemical burn as thermal burn.
5.3 Sodium Hydroxide (NaOH). Causes severe damage to eyes and skin.
Inhalation causes irritation to nose, throat, and lungs. Reacts
exothermically with limited amounts of water.
5.4 Perchloric Acid (HClO4). Corrosive to eyes, skin,
nose, and throat. Provide ventilation to limit exposure. Very strong
oxidizer. Keep separate from water and oxidizable materials to prevent
vigorous evolution of heat, spontaneous combustion, or explosion. Heat
solutions containing HClO4 only in hoods specifically designed for
HClO4.
6.0 Equipment and Supplies
6.1 Sampling.
6.1.1 Cassette arrangement. The cassette itself is a three-piece,
styrene acrylonitrile cassette unit (a Gelman Sciences product), 37
millimeter (mm), with plastic connectors. In the first section (the
intake section), an untreated Gelman Sciences 37 mm, 0.8 micrometer
(m) DM-800 metricel membrane filter and cellulose support pad,
or equivalent, is situated. In the second and third segments of the
cassette there is placed one each of Gelman Sciences 37 mm, 5 m
GLA-5000 low-ash PVC filter with a cellulose support pad or equivalent
product. Each of these two filters and support pads shall have been
immersed in a solution of 10 percent sodium formate (volume/volume in an
ethyl alcohol solution). The impregnated pads shall be placed in the
cassette segments while still wet and heated at 50 [deg]C (122 [deg]F)
until the pad is completely dry. It is important to check for a proper
fit of the filter and support pad to the cassette segment to ensure that
there are no areas where gases could bypass the filter. Once all of the
cassette segments have been prepared, the cassette shall be assembled
and a plastic plug shall be inserted into the exhaust hole of the
cassette. Prior to placing the cassette into service, the space between
each segment shall be taped with an appropriately durable tape to
prevent the infiltration of gases through the points of connection, and
an aluminum nozzle shall be inserted into the intake hole of the
cassette. The aluminum nozzle shall have a short section of tubing
placed over the opening of the nozzle, with the tubing plugged to
prevent dust from entering the nozzle and to prepare the nozzle for the
cassette arrangement leak check. An alternate nozzle type can be used if
historical results or scientific demonstration of applicability can be
shown.
6.1.2 Anemometers and temperature sensing devices. To calculate the
mass flow rate of TF from the roof monitor under standard conditions,
anemometers that meet the specifications in section 2.1.1 in Method 14
of this appendix or an equivalent device yielding equivalent information
shall be used. A recording mechanism capable of accurately recording the
exit gas temperature at least every 2 hours shall be used.
6.1.3 Barometer. To correct the volumetric flow from the potline
roof monitor to standard conditions, a mercury (Hg), aneroid, or other
barometer capable of measuring atmospheric pressure to within 2.5 mm
[0.1 inch (in)] Hg shall be used.

Note: The barometric reading may be obtained from a nearby National
Weather Service Station. In this case, the station value (which is
absolute barometric pressure) shall be requested and an adjustment for
elevation differences between the weather station and the sampling point
shall be made at a rate of minus 2.5 mm (0.1 in) Hg per 30 meters (m)
[100 feet (ft)] elevation increase or plus 2.5 mm (0.1 in) Hg per 30 m
(100 ft) elevation decrease.

6.2 Sample recovery.
6.2.1 Hot plate.
6.2.2 Muffle furnace.
6.2.3 Nickel crucible.
6.2.4 Stirring rod. Teflon.
6.2.5 Volumetric flask. 50-milliliter (ml).
6.2.6 Plastic vial. 50-ml.
6.3 Analysis.
6.3.1 Primary analytical method. An automated analyzer having the
following components or equivalent: a multichannel proportioning pump,
multiposition sampler, voltage stabilizer, colorimeter, instrument
recording device, microdistillation apparatus, flexible Teflon heating
bath, vacuum pump, pulse suppressers and an air flow system.
6.3.2 Secondary analytical method. Specific Ion Electrode (SIE).
7.0 Reagents and Standards
7.1 Water. Deionized distilled to conform to ASTM Specification D
1193-77, Type 3 (incorporated by reference in Sec. 60.17(a)(22) of this
part). The KMnO4 test for oxidizable organic matter may be
omitted when high concentrations of organic matter are not expected to
be present.
7.2 Calcium oxide.
7.3 Sodium hydroxide (NaOH). Pellets.

[[Page 389]]

7.4 Perchloric acid (HClO4). Mix 1:1 with water. Sulfuric
acid (H2SO4) may be used in place of
HClO4.
7.5 Audit samples. The audit samples discussed in section 9.1 shall
be prepared from reagent grade, water soluble stock reagents, or
purchased as an aqueous solution from a commercial supplier. If the
audit stock solution is purchased from a commercial supplier, the
standard solution must be accompanied by a certificate of analysis or an
equivalent proof of fluoride concentration.
8.0 Sample Collection and Analysis
8.1 Preparing cassette arrangement for sampling. The cassettes are
initially connected to flexible tubing. The tubing is connected to
flowmeters and a manifold system. The manifold system is connected to a
dry gas meter (Research Appliance Company model 201009 or equivalent).
The length of tubing is managed by pneumatically or electrically
operated hoists located in the roof monitor, and the travel of the
tubing is controlled by encasing the tubing in aluminum conduit. The
tubing is lowered for cassette insertion by operating a control box at
floor level. Once the cassette has been securely inserted into the
tubing and the leak check performed, the tubing and cassette are raised
to the roof monitor level using the floor level control box.
Arrangements similar to the one described are acceptable if the
scientific sample collection principles are followed.
8.2 Test run sampling period. A test run shall comprise a minimum of
a 24-hour sampling event encompassing at least eight cassettes per
potline (or four cassettes per potroom group). Monthly compliance shall
be based on three test runs during the month. Test runs of greater than
24 hours are allowed; however, three such runs shall be conducted during
the month.
8.3 Leak-check procedures.
8.3.1 Pretest leak check. A pretest leak-check is recommended;
however, it is not required. To perform a pretest leak-check after the
cassettes have been inserted into the tubing, isolate the cassette to be
leak-checked by turning the valves on the manifold to stop all flows to
the other sampling points connected to the manifold and meter. The
cassette, with the plugged tubing section securing the intake of the
nozzle, is subjected to the highest vacuum expected during the run. If
no leaks are detected, the tubing plug can be briefly removed as the dry
gas meter is rapidly turned off.
8.3.2 Post-test leak check. A leak check is required at the
conclusion of each test run for each cassette. The leak check shall be
performed in accordance with the procedure outlined in section 8.3.1 of
this method except that it shall be performed at a vacuum greater than
the maximum vacuum reached during the test run. If the leakage rate is
found to be no greater than 4 percent of the average sampling rate, the
results are acceptable. If the leakage rate is greater than 4 percent of
the average sampling rate, either record the leakage rate and correct
the sampling volume as discussed in section 12.4 of this method or void
the test run if the minimum number of cassettes were used. If the number
of cassettes used was greater than the minimum required, discard the
leaking cassette and use the remaining cassettes for the emission
determination.
8.3.3 Anemometers and temperature sensing device placement. Install
the recording mechanism to record the exit gas temperature. Anemometers
shall be installed as required in section 6.1.2 of Method 14 of this
appendix, except replace the word ``manifold'' with ``cassette group''
in section 6.1.2.3. These two different instruments shall be located
near each other along the roof monitor. See conceptual configurations in
Figures 14A-1, 14A-2, and 14A-3 of this method. Fewer temperature
devices than anemometers may be used if at least one temperature device
is located within the span of the cassette group. Other anemometer
location siting scenarios may be acceptable as long as the exit velocity
of the roof monitor gases is representative of the entire section of the
potline being sampled.
8.4 Sampling. The actual sample run shall begin with the removal of
the tubing and plug from the cassette nozzle. Each cassette is then
raised to the roof monitor area, the dry gas meter is turned on, and the
flowmeters are set to the calibration point, which allows an equal
volume of sampled gas to enter each cassette. The dry gas meter shall be
set to a range suitable for the specific potroom type being sampled that
will yield valid data known from previous experience or a range
determined by the use of the calculation in section 12 of this method.
Parameters related to the test run that shall be recorded, either during
the test run or after the test run if recording devices are used,
include: anemometer data, roof monitor exit gas temperature, dry gas
meter temperature, dry gas meter volume, and barometric pressure. At the
conclusion of the test run, the cassettes shall be lowered, the dry gas
meter turned off, and the volume registered on the dry gas meter
recorded. The post-test leak check procedures described in section 8.3.2
of this method shall be performed. All data relevant to the test shall
be recorded on a field data sheet and maintained on file.
8.5 Sample recovery.
8.5.1 The cassettes shall be brought to the laboratory with the
intake nozzle contents protected with the section of plugged tubing
previously described. The exterior of cassettes shall carefully be wiped
free of any dust or debris, making sure that any falling dust or debris
does not present a potential laboratory contamination problem.

[[Page 390]]

8.5.2 Carefully remove all tape from the cassettes and remove the
initial filter, support pad, and all loose solids from the first
(intake) section of the cassette. Fold the filter and support pad
several times and, along with all loose solids removed from the interior
of the first section of the cassette, place them into a nickel crucible.
Using water, wash the interior of the nozzle into the same nickel
crucible. Add 0.1 gram (g) [0.1 milligram (mg)] of calcium oxide and a
sufficient amount of water to make a loose slurry. Mix the contents of
the crucible thoroughly with a Teflon'' stirring rod. After rinsing any
adhering residue from the stirring rod back into the crucible, place the
crucible on a hot plate or in a muffle furnace until all liquid is
evaporated and allow the mixture to gradually char for 1 hour.
8.5.3 Transfer the crucible to a cold muffle furnace and ash at 600
[deg]C (1,112 [deg]F). Remove the crucible after the ashing phase and,
after the crucible cools, add 3.0 g (0.1 g) of NaOH pellets. Place this
mixture in a muffle furnace at 600 [deg]C (1,112 [deg]F) for 3 minutes.
Remove the crucible and roll the melt so as to reach all of the ash with
the molten NaOH. Let the melt cool to room temperature. Add 10 to 15 ml
of water to the crucible and place it on a hot plate at a low
temperature setting until the melt is soft or suspended. Transfer the
contents of the crucible to a 50-ml volumetric flask. Rinse the crucible
with 20 ml of 1:1 perchloric acid or 20 ml of 1:1 sulfuric acid in two
(2) 10 ml portions. Pour the acid rinse slowly into the volumetric flask
and swirl the flask after each addition. Cool to room temperature. The
product of this procedure is particulate fluorides.
8.5.4 Gaseous fluorides can be isolated for analysis by folding the
gaseous fluoride filters and support pads to approximately \1/4\ of
their original size and placing them in a 50-ml plastic vial. To the
vial add exactly 10 ml of water and leach the sample for a minimum of 1
hour. The leachate from this process yields the gaseous fluorides for
analysis.
9.0 Quality Control
9.1 Laboratory auditing. Laboratory audits of specific and known
concentrations of fluoride shall be submitted to the laboratory with
each group of samples submitted for analysis. An auditor shall prepare
and present the audit samples as a ``blind'' evaluation of laboratory
performance with each group of samples submitted to the laboratory. The
audits shall be prepared to represent concentrations of fluoride that
could be expected to be in the low, medium and high range of actual
results. Average recoveries of all three audits must equal 90 to 110
percent for acceptable results; otherwise, the laboratory must
investigate procedures and instruments for potential problems.

Note: The analytical procedure allows for the analysis of individual
or combined filters and pads from the cassettes provided that equal
volumes (10 percent) are sampled through each cassette.

10.0 Calibrations

10.1 Equipment evaluations. To ensure the integrity of this method,
periodic calibrations and equipment replacements are necessary.
10.1.1 Metering system. At 30-day intervals the metering system
shall be calibrated. Connect the metering system inlet to the outlet of
a wet test meter that is accurate to 1 percent. Refer to Figure 5-4 of
Method 5 of this appendix. The wet-test meter shall have a capacity of
30 liters/revolution [1 cubic foot (ft\3\)/revolution]. A spirometer of
400 liters (14 ft\3\) or more capacity, or equivalent, may be used for
calibration; however, a wet-test meter is usually more practical. The
wet-test meter shall be periodically tested with a spirometer or a
liquid displacement meter to ensure the accuracy. Spirometers or wet-
test meters of other sizes may be used, provided that the specified
accuracies of the procedure are maintained. Run the metering system pump
for about 15 min. with the orifice manometer indicating a median reading
as expected in field use to allow the pump to warm up and to thoroughly
wet the interior of the wet-test meter. Then, at each of a minimum of
three orifice manometer settings, pass an exact quantity of gas through
the wet-test meter and record the volume indicated by the dry gas meter.
Also record the barometric pressure, the temperatures of the wet test
meter, the inlet temperatures of the dry gas meter, and the temperatures
of the outlet of the dry gas meter. Record all calibration data on a
form similar to the one shown in Figure 5-5 of Method 5 of this appendix
and calculate Y, the dry gas meter calibration factor, and FH@, the
orifice calibration factor at each orifice setting. Allowable tolerances
for Y and FH@ are given in Figure 5-6 of Method 5 of this appendix.
Allowable tolerances for Y and FH@ are given in Figure 5-5 of Method 5
of this appendix.
10.1.2 Estimating volumes for initial test runs. For a facility's
initial test runs, the regulated facility must have a target or desired
volume of gases to be sampled and a target range of volumes to use
during the calibration of the dry gas meter. Use Equations 14A-1 and
14A-2 in section 12 of this method to derive the target dry gas meter
volume (Fv) for these purposes.
10.1.3 Calibration of anemometers and temperature sensing devices.
If the standard anemometers in Method 14 of this appendix are used, the
calibration and integrity evaluations in sections 10.3.1.1 through
10.3.1.3 of Method 14 of this appendix shall be used as well as the
recording device described in section 2.1.3 of Method 14. The
calibrations or complete change-outs of anemometers shall take place at
a minimum of once per year.

[[Page 391]]

The temperature sensing and recording devices shall be calibrated
according to the manufacturer's specifications.
10.1.4 Calibration of flowmeters. The calibration of flowmeters is
necessary to ensure that an equal volume of sampled gas is entering each
of the individual cassettes and that no large differences, which could
possibly bias the sample, exist between the cassettes.
10.1.4.1 Variable area, 65 mm flowmeters or equivalent shall be
used. These flowmeters can be mounted on a common base for convenience.
These flowmeters shall be calibrated by attaching a prepared cassette,
complete with filters and pads, to the flowmeter and then to the system
manifold. This manifold is an aluminum cylinder with valved inlets for
connections to the flowmeters/cassettes and one outlet to a dry gas
meter. The connection is then made to the wet-test meter and finally to
a dry gas meter. All connections are made with tubing.
10.1.4.2 Turn the dry gas meter on for 15 min. in preparation for
the calibration. Turn the dry gas meter off and plug the intake hole of
the cassette. Turn the dry gas meter back on to evaluate the entire
system for leaks. If the dry gas meter shows a leakage rate of less than
0.02 ft\3\/min at 10 in. of Hg vacuum as noted on the dry gas meter, the
system is acceptable to further calibration.
10.1.4.3 With the dry gas meter turned on and the flow indicator
ball at a selected flow rate, record the exact amount of gas pulled
through the flowmeter by taking measurements from the wet test meter
after exactly 10 min. Record the room temperature and barometric
pressure. Conduct this test for all flowmeters in the system with all
flowmeters set at the same indicator ball reading. When all flowmeters
have gone through the procedure above, correct the volume pulled through
each flowmeter to standard conditions. The acceptable difference between
the highest and lowest flowmeter rate is 5 percent. Should one or more
flowmeters be outside of the acceptable limit of 5 percent, repeat the
calibration procedure at a lower or higher indicator ball reading until
all flowmeters show no more than 5 percent difference among them.
10.1.4.4 This flowmeter calibration shall be conducted at least once
per year.
10.1.5 Miscellaneous equipment calibrations. Miscellaneous equipment
used such as an automatic recorder/ printer used to measure dry gas
meter temperatures shall be calibrated according to the manufacturer's
specifications in order to maintain the accuracy of the equipment.
11.0 Analytical Procedure
11.1 The preferred primary analytical determination of the
individual isolated samples or the combined particulate and gaseous
samples shall be performed by an automated methodology. The analytical
method for this technology shall be based on the manufacturer's
instructions for equipment operation and shall also include the analysis
of five standards with concentrations in the expected range of the
actual samples. The results of the analysis of the five standards shall
have a coefficient of correlation of at least 0.99. A check standard
shall be analyzed as the last sample of the group to determine if
instrument drift has occurred. The acceptable result for the check
standard is 95 to 105 percent of the standard's true value.
11.2 The secondary analytical method shall be by specific ion
electrode if the samples are distilled or if a TISAB IV buffer is used
to eliminate aluminum interferences. Five standards with concentrations
in the expected range of the actual samples shall be analyzed, and a
coefficient of correlation of at least 0.99 is the minimum acceptable
limit for linearity. An exception for this limit for linearity is a
condition when low-level standards in the range of 0.01 to 0.48
g fluoride/ml are analyzed. In this situation, a minimum
coefficient of correlation of 0.97 is required. TISAB II shall be used
for low-level analyses.
12.0 Data Analysis and Calculations
12.1 Carry out calculations, retaining at least one extra decimal
point beyond that of the acquired data. Round off values after the final
calculation. Other forms of calculations may be used as long as they
give equivalent results.
12.2 Estimating volumes for initial test runs.
[GRAPHIC] [TIFF OMITTED] TR07OC97.000

Where

Fv = Desired volume of dry gas to be sampled, ft\3\.
Fd = Desired or analytically optimum mass of TF per cassette,
micrograms of TF per cassette (g/cassette).
X = Number of cassettes used.

[[Page 392]]

Fe = Typical concentration of TF in emissions to be sampled,
g/ft \3\, calculated from Equation 14A-2.
[GRAPHIC] [TIFF OMITTED] TR07OC97.001

Where

Re = Typical emission rate from the facility, pounds of TF
per ton (lb/ton) of aluminum.
Rp = Typical production rate of the facility, tons of
aluminum per minute (ton/min).
Vr = Typical exit velocity of the roof monitor gases, feet
per minute (ft/min).
Ar = Open area of the roof monitor, square feet (ft\2\).

12.2.1 Example calculation. Assume that the typical emission rate
(Re) is 1.0 lb TF/ton of aluminum, the typical roof vent gas
exit velocity (Vr) is 250 ft/min, the typical production rate
(Rp) is 0.10 ton/min, the known open area for the roof
monitor (Ar) is 8,700 ft\2\, and the desired (analytically
optimum) mass of TF per cassette is 1,500 g. First calculate
the concentration of TF per cassette (Fe) in g/ft\3\
using Equation 14A-2. Then calculate the desired volume of gas to be
sampled (Fv) using Equation 14A-1.
[GRAPHIC] [TIFF OMITTED] TR07OC97.002

[GRAPHIC] [TIFF OMITTED] TR07OC97.003

This is a total of 575.40 ft\3\ for eight cassettes or 71.925 ft\3\/
cassette.
12.3 Calculations of TF emissions from field and laboratory data
that would yield a production related emission rate can be calculated as
follows:
12.3.1 Obtain a standard cubic feet (scf) value for the volume
pulled through the dry gas meter for all cassettes by using the field
and calibration data and Equation 5-1 of Method 5 of this appendix.
12.3.2 Derive the average quantity of TF per cassette (in g
TF/cassette) by adding all laboratory data for all cassettes and
dividing this value by the total number of cassettes used. Divide this
average TF value by the corrected dry gas meter volume for each
cassette; this value then becomes TFstd (g/ft\3\).
12.3.3 Calculate the production-based emission rate (Re)
in lb/ton using Equation 14A-5.
[GRAPHIC] [TIFF OMITTED] TR07OC97.004

12.3.4 As an example calculation, assume eight cassettes located in
a potline were used to sample for 72 hours during the run. The analysis
of all eight cassettes yielded a total of 3,000 g of TF. The
dry gas meter volume was corrected to yield a total of 75 scf per
cassette, which yields a value for TFstd of 3,000/75 = 5
g/ft\3\. The open area of the roof monitor for the potline
(Ar) is 17,400 ft\2\. The exit velocity of the roof monitor
gases (Vr) is 250 ft/min. The production rate of aluminum
over the previous 720 hours was 5,000 tons,

[[Page 393]]

which is 6.94 tons/hr or 0.116 ton/min (Rp). Substituting
these values into Equation 14A-5 yields:
[GRAPHIC] [TIFF OMITTED] TR07OC97.005

12.4 Corrections to volumes due to leakage. Should the post-test
leak check leakage rate exceed 4 percent as described in section 8.3.2
of this method, correct the volume as detailed in Case I in section 6.3
of Method 5 of this appendix.

[[Page 394]]

[GRAPHIC] [TIFF OMITTED] TR07OC97.020

[[Page 395]]

[GRAPHIC] [TIFF OMITTED] TR07OC97.021

[[Page 396]]

[GRAPHIC] [TIFF OMITTED] TR07OC97.022

[[Page 397]]

Method 15--Determination of Hydrogen Sulfide, Carbonyl Sulfide, and
Carbon Disulfide Emissions From Stationary Sources

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Sensitivity (See Sec
Analyte CAS No. 13.2)
------------------------------------------------------------------------
Carbon disulfide [CS2]......... 75-15-0 0.5 ppmv
Carbonyl sulfide [COS]......... 463-58-1 0.5 ppmv
Hydrogen sulfide [H2S]......... 7783-06-4 0.5 ppmv
------------------------------------------------------------------------

1.2 Applicability.
1.2.1 This method applies to the determination of emissions of
reduced sulfur compounds from tail gas control units of sulfur recovery
plants, H2S in fuel gas for fuel gas combustion devices, and
where specified in other applicable subparts of the regulations.
1.2.2 The method described below uses the principle of gas
chromatographic (GC) separation and flame photometric detection (FPD).
Since there are many systems or sets of operating conditions that
represent useable methods for determining sulfur emissions, all systems
which employ this principle, but differ only in details of equipment and
operation, may be used as alternative methods, provided that the
calibration precision and sample-line loss criteria are met.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted from the emission source and diluted
with clean dry air (if necessary). An aliquot of the diluted sample is
then analyzed for CS2, COS, and H2S by GC/FPD.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Moisture Condensation. Moisture condensation in the sample
delivery system, the analytical column, or the FPD burner block can
cause losses or interferences. This potential is eliminated by heating
the probe, filter box, and connections, and by maintaining the
SO2 scrubber in an ice water bath. Moisture is removed in the
SO2 scrubber and heating the sample beyond this point is not
necessary provided the ambient temperature is above 0 [deg]C (32
[deg]F). Alternatively, moisture may be eliminated by heating the sample
line, and by conditioning the sample with dry dilution air to lower its
dew point below the operating temperature of the GC/FPD analytical
system prior to analysis.
4.2 Carbon Monoxide (CO) and Carbon Dioxide (CO2). CO and
CO2 have substantial desensitizing effects on the FPD even
after 9:1 dilution. (Acceptable systems must demonstrate that they have
eliminated this interference by some procedure such as eluting CO and
CO2 before any of the sulfur compounds to be measured.)
Compliance with this requirement can be demonstrated by submitting
chromatograms of calibration gases with and without CO2 in
the diluent gas. The CO2 level should be approximately 10
percent for the case with CO2 present. The two chromatograms
should show agreement within the precision limits of section 13.3.
4.3 Elemental Sulfur. The condensation of sulfur vapor in the
sampling system can lead to blockage of the particulate filter. This
problem can be minimized by observing the filter for buildup and
changing as needed.
4.4 Sulfur Dioxide (SO2). SO2 is not a
specific interferent but may be present in such large amounts that it
cannot be effectively separated from the other compounds of interest.
The SO2 scrubber described in section 6.1.3 will effectively
remove SO2 from the sample.
4.5 Alkali Mist. Alkali mist in the emissions of some control
devices may cause a rapid increase in the SO2 scrubber pH,
resulting in low sample recoveries. Replacing the SO2
scrubber contents after each run will minimize the chances of
interference in these cases.

5.0 Safety

[[Page 398]]

6.0 Equipment and Supplies

6.1 Sample Collection. See Figure 15-1. The sampling train component
parts are discussed in the following sections:
6.1.1 Probe. The probe shall be made of Teflon or Teflon-lined
stainless steel and heated to prevent moisture condensation. It shall be
designed to allow calibration gas to enter the probe at or near the
sample point entry. Any portion of the probe that contacts the stack gas
must be heated to prevent moisture condensation. The probe described in
section 6.1.1 of Method 16A having a nozzle directed away from the gas
stream is recommended for sources having particulate or mist emissions.
Where very high stack temperatures prohibit the use of Teflon probe
components, glass or quartz-lined probes may serve as substitutes.
6.1.2 Particulate Filter. 50-mm Teflon filter holder and a 1- to 2-
micron porosity Teflon filter (available through Savillex Corporation,
5325 Highway 101, Minnetonka, Minnesota 55343). The filter holder must
be maintained in a hot box at a temperature of at least 120 [deg]C (248
[deg]F).
6.1.3 SO2 Scrubber. Three 300-ml Teflon segment impingers
connected in series with flexible, thick-walled, Teflon tubing.
(Impinger parts and tubing available through Savillex.) The first two
impingers contain 100 ml of citrate buffer, and the third impinger is
initially dry. The tip of the tube inserted into the solution should be
constricted to less than 3-mm (\1/8\-in.) ID and should be immersed to a
depth of at least 50 cm (2 in.). Immerse the impingers in an ice water
bath and maintain near 0 [deg]C. The scrubber solution will normally
last for a 3-hour run before needing replacement. This will depend upon
the effects of moisture and particulate matter on the solution strength
and pH. Connections between the probe, particulate filter, and
SO2 scrubber shall be made of Teflon and as short in length
as possible. All portions of the probe, particulate filter, and
connections prior to the SO2 scrubber (or alternative point
of moisture removal) shall be maintained at a temperature of at least
120 [deg]C (248 [deg]F).
6.1.4 Sample Line. Teflon, no greater than 13-mm (\1/2\-in.) ID.
Alternative materials, such as virgin Nylon, may be used provided the
line-loss test is acceptable.
6.1.5 Sample Pump. The sample pump shall be a leakless Teflon-coated
diaphragm type or equivalent.
6.2 Analysis. The following items are needed for sample analysis:
6.2.1 Dilution System. The dilution system must be constructed such
that all sample contacts are made of Teflon, glass, or stainless steel.
It must be capable of approximately a 9:1 dilution of the sample.
6.2.2 Gas Chromatograph (see Figure 15-2). The gas chromatograph
must have at least the following components:
6.2.2.1 Oven. Capable of maintaining the separation column at the
proper operating temperature 1 [deg]C.
6.2.2.2 Temperature Gauge. To monitor column oven, detector, and
exhaust temperature 1 [deg]C.
6.2.2.3 Flow System. Gas metering system to measure sample, fuel,
combustion gas, and carrier gas flows.
6.2.2.4 Flame Photometric Detector.
6.2.2.4.1 Electrometer. Capable of full scale amplification of
linear ranges of 10^-9 to 10^-4 amperes full scale.
6.2.2.4.2 Power Supply. Capable of delivering up to 750 volts.
6.2.2.5 Recorder. Compatible with the output voltage range of the
electrometer.
6.2.2.6 Rotary Gas Valves. Multiport Teflon-lined valves equipped
with sample loop. Sample loop volumes shall be chosen to provide the
needed analytical range. Teflon tubing and fittings shall be used
throughout to present an inert surface for sample gas. The GC shall be
calibrated with the sample loop used for sample analysis.
6.2.2.7 GC Columns. The column system must be demonstrated to be
capable of resolving three major reduced sulfur compounds:
H2S, COS, and CS2. To demonstrate that adequate
resolution has been achieved, a chromatogram of a calibration gas
containing all three reduced sulfur compounds in the concentration range
of the applicable standard must be submitted. Adequate resolution will
be defined as base line separation of adjacent peaks when the amplifier
attenuation is set so that the smaller peak is at least 50 percent of
full scale. Base line separation is defined as a return to zero (5
percent) in the interval between peaks. Systems not meeting this
criteria may be considered alternate methods subject to the approval of
the Administrator.
6.3 Calibration System (See Figure 15-3). The calibration system
must contain the following components:
6.3.1 Flow System. To measure air flow over permeation tubes within
2 percent. Each flowmeter shall be calibrated after each complete test
series with a wet-test meter. If the flow measuring device differs from
the wet-test meter by more than 5 percent, the completed test shall be
discarded. Alternatively, use the flow data that will yield the lowest
flow measurement. Calibration with a wet-test meter before a test is
optional. Flow over the permeation device may also be determined using a
soap bubble flowmeter.
6.3.2 Constant Temperature Bath. Device capable of maintaining the
permeation tubes at the calibration temperature within 0.1 [deg]C.

[[Page 399]]

6.3.3 Temperature Sensor. Thermometer or equivalent to monitor bath
temperature within 0.1 [deg]C.

7.0 Reagents and Standards

7.1 Fuel. Hydrogen gas (H2). Prepurified grade or better.
7.2 Combustion Gas. Oxygen (O2) or air, research purity
or better.
7.3 Carrier Gas. Prepurified grade or better.
7.4 Diluent. Air containing less than 0.5 ppmv total sulfur
compounds and less than 10 ppmv each of moisture and total hydrocarbons.
7.5 Calibration Gases.
7.5.1 Permeation Devices. One each of H2S, COS, and
CS2, gravimetrically calibrated and certified at some
convenient operating temperature. These tubes consist of hermetically
sealed FEP Teflon tubing in which a liquified gaseous substance is
enclosed. The enclosed gas permeates through the tubing wall at a
constant rate. When the temperature is constant, calibration gases
covering a wide range of known concentrations can be generated by
varying and accurately measuring the flow rate of diluent gas passing
over the tubes. These calibration gases are used to calibrate the GC/FPD
system and the dilution system.
7.5.2 Cylinder Gases. Cylinder gases may be used as alternatives to
permeation devices. The gases must be traceable to a primary standard
(such as permeation tubes) and not used beyond the certification
expiration date.
7.6 Citrate Buffer. Dissolve 300 g of potassium citrate and 41 g of
anhydrous citric acid in 1 liter of water. Alternatively, 284 g of
sodium citrate may be substituted for the potassium citrate. Adjust the
pH to between 5.4 and 5.6 with potassium citrate or citric acid, as
required.
8.0 Sample Collection, Preservation, Transport, and Storage
8.1 Pretest Procedures. After the complete measurement system has
been set up at the site and deemed to be operational, the following
procedures should be completed before sampling is initiated. These
procedures are not required, but would be helpful in preventing any
problem which might occur later to invalidate the entire test.
8.1.1 Leak-Check. Appropriate leak-check procedures should be
employed to verify the integrity of all components, sample lines, and
connections. The following procedure is suggested: For components
upstream of the sample pump, attach the probe end of the sample line to
a manometer or vacuum gauge, start the pump and pull a vacuum greater
than 50 mm (2 in.) Hg, close off the pump outlet, and then stop the pump
and ascertain that there is no leak for 1 minute. For components after
the pump, apply a slight positive pressure and check for leaks by
applying a liquid (detergent in water, for example) at each joint.
Bubbling indicates the presence of a leak. As an alternative to the
initial leak-test, the sample line loss test described in section 8.3.1
may be performed to verify the integrity of components.
8.1.2 System Performance. Since the complete system is calibrated at
the beginning and end of each day of testing, the precise calibration of
each component is not critical. However, these components should be
verified to operate properly. This verification can be performed by
observing the response of flowmeters or of the GC output to changes in
flow rates or calibration gas concentrations, respectively, and
ascertaining the response to be within predicted limits. If any
component or the complete system fails to respond in a normal and
predictable manner, the source of the discrepancy should be identified
and corrected before proceeding.
8.2 Sample Collection and Analysis
8.2.1 After performing the calibration procedures outlined in
section 10.0, insert the sampling probe into the test port ensuring that
no dilution air enters the stack through the port. Begin sampling and
dilute the sample approximately 9:1 using the dilution system. Note that
the precise dilution factor is the one determined in section 10.4.
Condition the entire system with sample for a minimum of 15 minutes
before beginning the analysis. Inject aliquots of the sample into the
GC/FPD analyzer for analysis. Determine the concentration of each
reduced sulfur compound directly from the calibration curves or from the
equation for the least-squares line.
8.2.2 If reductions in sample concentrations are observed during a
sample run that cannot be explained by process conditions, the sampling
must be interrupted to determine if the probe or filter is clogged with
particulate matter. If either is found to be clogged, the test must be
stopped and the results up to that point discarded. Testing may resume
after cleaning or replacing the probe and filter. After each run, the
probe and filter shall be inspected and, if necessary, replaced.
8.2.3 A sample run is composed of 16 individual analyses (injects)
performed over a period of not less than 3 hours or more than 6 hours.
8.3 Post-Test Procedures.
8.3.1 Sample Line Loss. A known concentration of H2S at
the level of the applicable standard, 20 percent, must be introduced
into the sampling system at the opening of the probe in sufficient
quantities to ensure that there is an excess of sample which must be
vented to the atmosphere. The sample must be transported through the
entire sampling system to the measurement system in the same manner as
the emission samples. The resulting measured concentration is compared
to the known value to determine

[[Page 400]]

the sampling system loss. For sampling losses greater than 20 percent,
the previous sample run is not valid. Sampling losses of 0-20 percent
must be corrected by dividing the resulting sample concentration by the
fraction of recovery. The known gas sample may be calibration gas as
described in section 7.5. Alternatively, cylinder gas containing
H2S mixed in nitrogen and verified according to section 7.1.4
of Method 16A may be used. The optional pretest procedures provide a
good guideline for determining if there are leaks in the sampling
system.
8.3.2 Determination of Calibration Drift. After each run, or after a
series of runs made within a 24-hour period, perform a partial
recalibration using the procedures in section 10.0. Only H2S
(or other permeant) need be used to recalibrate the GC/FPD analysis
system and the dilution system. Compare the calibration curves obtained
after the runs to the calibration curves obtained under section 10.3.
The calibration drift should not exceed the limits set forth in section
13.4. If the drift exceeds this limit, the intervening run or runs
should be considered invalid. As an option, the calibration data set
which gives the highest sample values may be chosen by the tester.

9.0 Quality Control

10.0 Calibration and Standardization

Prior to any sampling run, calibrate the system using the following
procedures. (If more than one run is performed during any 24-hour
period, a calibration need not be performed prior to the second and any
subsequent runs. However, the calibration drift must be determined as
prescribed in section 8.3.2 after the last run is made within the 24-
hour period.)

Note: This section outlines steps to be followed for use of the GC/
FPD and the dilution system. The calibration procedure does not include
detailed instructions because the operation of these systems is complex,
and it requires an understanding of the individual system being used.
Each system should include a written operating manual describing in
detail the operating procedures associated with each component in the
measurement system. In addition, the operator should be familiar with
the operating principles of the components, particularly the GC/FPD. The
references in section 16.0 are recommended for review for this purpose.

10.1 Calibration Gas Permeation Tube Preparation.
10.1.1 Insert the permeation tubes into the tube chamber. Check the
bath temperature to assure agreement with the calibration temperature of
the tubes within 0.1 [deg]C. Allow 24 hours for the tubes to
equilibrate. Alternatively, equilibration may be verified by injecting
samples of calibration gas at 1-hour intervals. The permeation tubes can
be assumed to have reached equilibrium when consecutive hourly samples
agree within 5 percent of their mean.
10.1.2 Vary the amount of air flowing over the tubes to produce the
desired concentrations for calibrating the analytical and dilution
systems. The air flow across the tubes must at all times exceed the flow
requirement of the analytical systems. The concentration in ppmv
generated by a tube containing a specific permeant can be calculated
using Equation 15-1 in section 12.2.
10.2 Calibration of Analytical System. Generate a series of three or
more known concentrations spanning the linear range of the FPD
(approximately 0.5 to 10 ppmv for a 1-ml sample) for each of the three
major sulfur compounds. Bypassing the dilution system, inject these
standards into the GC/FPD and monitor the responses until three
consecutive injections for each concentration agree within 5 percent of
their mean. Failure to attain this precision indicates a problem in the
calibration or analytical system. Any such problem must be identified
and corrected before proceeding.
10.3 Calibration Curves. Plot the GC/FPD response in current
(amperes) versus their causative concentrations in ppmv on log-log
coordinate graph paper for each sulfur compound. Alternatively, a least-
squares equation may be generated from the calibration data using
concentrations versus the appropriate instrument response units.
10.4 Calibration of Dilution System. Generate a known concentration
of H2S using the permeation tube system. Adjust the flow rate
of diluent air for the first dilution stage so that the desired level of
dilution is approximated. Inject the diluted calibration gas into the
GC/FPD system until the results

[[Page 401]]

of three consecutive injections for each dilution agree within 5 percent
of their mean. Failure to attain this precision in this step is an
indication of a problem in the dilution system. Any such problem must be
identified and corrected before proceeding. Using the calibration data
for H2S (developed under section 10.3), determine the diluted
calibration gas concentration in ppmv. Then calculate the dilution
factor as the ratio of the calibration gas concentration before dilution
to the diluted calibration gas concentration determined under this
section. Repeat this procedure for each stage of dilution required.
Alternatively, the GC/FPD system may be calibrated by generating a
series of three or more concentrations of each sulfur compound and
diluting these samples before injecting them into the GC/FPD system.
These data will then serve as the calibration data for the unknown
samples and a separate determination of the dilution factor will not be
necessary. However, the precision requirements are still applicable.

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this method (see
section 8.0).

12.0 Data Analysis and Calculations

12.1 Nomenclature.

C = Concentration of permeant produced, ppmv.
COS = Carbonyl sulfide concentration, ppmv.
CS2 = Carbon disulfide concentration, ppmv.
d = Dilution factor, dimensionless.
H2S = Hydrogen sulfide concentration, ppmv.
K = 24.04 L/g mole. (Gas constant at 20 [deg]C and 760 mm Hg)
L = Flow rate, L/min, of air over permeant 20 [deg]C, 760 mm Hg.
M = Molecular weight of the permeant, g/g-mole.
N = Number of analyses performed.
Pr = Permeation rate of the tube, g/min.

12.2 Permeant Concentration. Calculate the concentration generated
by a tube containing a specific permeant (see section 10.1) using the
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.262

12.3 Calculation of SO2 Equivalent. SO2
equivalent will be determined for each analysis made by summing the
concentrations of each reduced sulfur compound resolved during the given
analysis. The SO2 equivalent is expressed as SO2
in ppmv.
[GRAPHIC] [TIFF OMITTED] TR17OC00.263

12.4 Average SO2 Equivalent. This is determined using the
following equation. Systems that do not remove moisture from the sample
but condition the gas to prevent condensation must correct the average
SO2 equivalent for the fraction of water vapor present. This
is not done under applications where the emission standard is not
specified on a dry basis.
[GRAPHIC] [TIFF OMITTED] TR17OC00.264

Where:

Avg SO2 equivalent = Average SO2 equivalent in
ppmv, dry basis.
Average SO2 equivalent i = SO2 in ppmv
as determined by Equation 15-2.

13.0 Method Performance

13.1 Range. Coupled with a GC system using a 1-ml sample size, the
maximum limit of the FPD for each sulfur compound is approximately 10
ppmv. It may be necessary to dilute samples from sulfur recovery plants
a

[[Page 402]]

hundredfold (99:1), resulting in an upper limit of about 1000 ppmv for
each compound.
13.2 Sensitivity. The minimum detectable concentration of the FPD is
also dependent on sample size and would be about 0.5 ppmv for a 1-ml
sample.
13.3 Calibration Precision. A series of three consecutive injections
of the same calibration gas, at any dilution, shall produce results
which do not vary by more than 5 percent from the mean of the three
injections.
13.4 Calibration Drift. The calibration drift determined from the
mean of three injections made at the beginning and end of any run or
series of runs within a 24-hour period shall not exceed 5 percent.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References.

1. O'Keeffe, A.E., and G.C. Ortman. ``Primary Standards for Trace
Gas Analysis.'' Anal. Chem. 38,760. 1966.
2. Stevens, R.K., A.E. O'Keeffe, and G.C. Ortman. ``Absolute
Calibration of a Flame Photometric Detector to Volatile Sulfur Compounds
at Sub-Part-Per-Million Levels.'' Environmental Science and Technology
3:7. July 1969.
3. Mulik, J.D., R.K. Stevens, and R. Baumgardner. ``An Analytical
System Designed to Measure Multiple Malodorous Compounds Related to
Kraft Mill Activities.'' Presented at the 12th Conference on Methods in
Air Pollution and Industrial Hygiene Studies, University of Southern
California, Los Angeles, CA, April 6-8, 1971.
4. Devonald, R.H., R.S. Serenius, and A.D. McIntyre. ``Evaluation of
the Flame Photometric Detector for Analysis of Sulfur Compounds.'' Pulp
and Paper Magazine of Canada, 73,3. March 1972.
5. Grimley, K.W., W.S. Smith, and R.M. Martin. ``The Use of a
Dynamic Dilution System in the Conditioning of Stack Gases for Automated
Analysis by a Mobile Sampling Van.'' Presented at the 63rd Annual APCA
Meeting in St. Louis, MO. June 14-19, 1970.
6. General Reference. Standard Methods of Chemical Analysis Volume
III-A and III-B: Instrumental Analysis. Sixth Edition. Van Nostrand
Reinhold Co.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 403]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.265

[[Page 404]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.266

[[Page 405]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.267

Method 15A--Determination of Total Reduced Sulfur Emissions From Sulfur
Recovery Plants in Petroleum Refineries

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 6, Method 15,
and Method 16A.

1.0 Scope and Application

1.1 Analytes.

[[Page 406]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Reduced sulfur compounds...... None assigned... Not determined.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of emissions of reduced sulfur compounds from sulfur recovery plants
where the emissions are in a reducing atmosphere, such as in Stretford
units.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 An integrated gas sample is extracted from the stack, and
combustion air is added to the oxygen (O2)-deficient gas at a
known rate. The reduced sulfur compounds [including carbon disulfide
(CS2), carbonyl sulfide (COS), and hydrogen sulfide
(H2S)] are thermally oxidized to sulfur dioxide
(SO2), which is then collected in hydrogen peroxide as
sulfate ion and analyzed according to the Method 6 barium-thorin
titration procedure.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Reduced sulfur compounds, other than CS2, COS, and
H2S, that are present in the emissions will also be oxidized
to SO2, causing a positive bias relative to emission
standards that limit only the three compounds listed above. For example,
thiophene has been identified in emissions from a Stretford unit and
produced a positive bias of 30 percent in the Method 15A result.
However, these biases may not affect the outcome of the test at units
where emissions are low relative to the standard.
4.2 Calcium and aluminum have been shown to interfere in the Method
6 titration procedure. Since these metals have been identified in
particulate matter emissions from Stretford units, a Teflon filter is
required to minimize this interference.
4.3 Dilution of the hydrogen peroxide (H2O2)
absorbing solution can potentially reduce collection efficiency, causing
a negative bias. When used to sample emissions containing 7 percent
moisture or less, the midget impingers have sufficient volume to contain
the condensate collected during sampling. Dilution of the
H2O2 does not affect the collection of
SO2. At higher moisture contents, the potassium citrate-
citric acid buffer system used with Method 16A should be used to collect
the condensate.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The sampling train used in performing this
method is shown in Figure 15A-1, and component parts are discussed
below. Modifications to this sampling train are acceptable provided that
the system performance check is met.
6.1.1 Probe. 6.4-mm (\1/4\-in.) OD Teflon tubing sequentially
wrapped with heat-resistant fiber strips, a rubberized heating tape
(with a plug at one end), and heat-resistant adhesive tape. A flexible
thermocouple or some other suitable temperature-measuring device shall
be placed between the Teflon tubing and the fiber strips so that the
temperature can be monitored. The probe should be sheathed in stainless
steel to provide in-stack rigidity. A series of bored-out stainless
steel fittings placed at the front of the sheath will prevent flue gas
from entering between the probe and sheath. The sampling probe is
depicted in Figure 15A-2.
6.1.2 Particulate Filter. A 50-mm Teflon filter holder and a 1- to
2-mm porosity Teflon filter (available through Savillex Corporation,
5325 Highway 101, Minnetonka, Minnesota 55345). The filter holder must
be

[[Page 407]]

maintained in a hot box at a temperature high enough to prevent
condensation.
6.1.3 Combustion Air Delivery System. As shown in the schematic
diagram in Figure 15A-3. The rate meter should be selected to measure an
air flow rate of 0.5 liter/min (0.02 ft\3\/min).
6.1.4 Combustion Tube. Quartz glass tubing with an expanded
combustion chamber 2.54 cm (1 in.) in diameter and at least 30.5 cm (12
in.) long. The tube ends should have an outside diameter of 0.6 cm (\1/
4\ in.) and be at least 15.3 cm (6 in.) long. This length is necessary
to maintain the quartz-glass connector near ambient temperature and
thereby avoid leaks. Alternatively, the outlet may be constructed with a
90 degree glass elbow and socket that would fit directly onto the inlet
of the first peroxide impinger.
6.1.5 Furnace. Of sufficient size to enclose the combustion tube.
The furnace must have a temperature regulator capable of maintaining the
temperature at 1100 50 [deg]C (2,012 90 [deg]F). The furnace operating
temperature must be checked with a thermocouple to ensure accuracy.
Lindberg furnaces have been found to be satisfactory.
6.1.6 Peroxide Impingers, Stopcock Grease, Temperature Sensor,
Drying Tube, Valve, Pump, and Barometer. Same as in Method 6, sections
6.1.1.2, 6.1.1.4, 6.1.1.5, 6.1.1.6, 6.1.1.7, 6.1.1.8, and 6.1.2,
respectively, except that the midget bubbler of Method 6, section
6.1.1.2 is not required.
6.1.7 Vacuum Gauge and Rate Meter. At least 760 mm Hg (30 in. Hg)
gauge and rotameter, or equivalent, capable of measuring flow rate to 5
percent of the selected flow rate and calibrated as in section 10.2.
6.1.8 Volume Meter. Dry gas meter capable of measuring the sample
volume under the particular sampling conditions with an accuracy of 2
percent.
6.1.9 U-tube manometer. To measure the pressure at the exit of the
combustion gas dry gas meter.
6.2 Sample Recovery and Analysis. Same as Method 6, sections 6.2 and
6.3, except a 10-ml buret with 0.05-ml graduations is required for
titrant volumes of less than 10.0 ml, and the spectrophotometer is not
needed.

7.0 Reagents and Standards

7.1 Sample Collection. The following reagents and standards are
required for sample analysis:
7.1.1 Water. Same as Method 6, section 7.1.1.
7.1.2 Hydrogen Peroxide (H2O2), 3 Percent by
Volume. Same as Method 6, section 7.1.3 (40 ml is needed per sample).
7.1.3 Recovery Check Gas. Carbonyl sulfide in nitrogen [100 parts
per million by volume (ppmv) or greater, if necessary] in an aluminum
cylinder. Concentration certified by the manufacturer with an accuracy
of 2 percent or better, or verified by gas chromatography where the
instrument is calibrated with a COS permeation tube.
7.1.4 Combustion Gas. Air, contained in a gas cylinder equipped with
a two-stage regulator. The gas shall contain less than 50 ppb of reduced
sulfur compounds and less than 10 ppm total hydrocarbons.
7.2 Sample Recovery and Analysis. Same as Method 6, sections 7.2 and
7.3.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Preparation of Sampling Train. For the Method 6 part of the
train, measure 20 ml of 3 percent H2O2 into the
first and second midget impingers. Leave the third midget impinger empty
and add silica gel to the fourth impinger. Alternatively, a silica gel
drying tube may be used in place of the fourth impinger. Place crushed
ice and water around all impingers. Maintain the oxidation furnace at
1100 50 [deg]C (2,012 90 [deg]F) to ensure 100 percent oxidation of
COS. Maintain the probe and filter temperatures at a high enough level
(no visible condensation) to prevent moisture condensation and monitor
the temperatures with a thermocouple.
8.2 Leak-Check Procedure. Assemble the sampling train and leak-check
as described in Method 6, section 8.2. Include the combustion air
delivery system from the needle valve forward in the leak-check.
8.3 Sample Collection. Adjust the pressure on the second stage of
the regulator on the combustion air cylinder to 10 psig. Adjust the
combustion air flow rate to 0.5 0.05 L/min (1.1 0.1 ft\3\/hr) before
injecting combustion air into the sampling train. Then inject combustion
air into the sampling train, start the sample pump, and open the stack
sample gas valve. Carry out these three operations within 15 to 30
seconds to avoid pressurizing the sampling train. Adjust the total
sample flow rate to 2.0 0.2 L/min (4.2 0.4 ft\3\/hr). These flow rates
produce an O2 concentration of 5.0 percent in the stack gas,
which must be maintained constantly to allow oxidation of reduced sulfur
compounds to SO2. Adjust these flow rates during sampling as
necessary. Monitor and record the combustion air manometer reading at
regular intervals during the sampling period. Sample for 1 or 3 hours.
At the end of sampling, turn off the sample pump and combustion air
simultaneously (within 30 seconds of each other). All other procedures
are the same as in Method 6, section 8.3, except that the sampling train
should not be purged. After collecting the

[[Page 408]]

sample, remove the probe from the stack and conduct a leak-check
according to the procedures outlined in section 8.2 of Method 6
(mandatory). After each 3-hour test run (or after three 1-hour samples),
conduct one system performance check (see section 8.5). After this
system performance check and before the next test run, it is recommended
that the probe be rinsed and brushed and the filter replaced.

Note: In Method 15, a test run is composed of 16 individual analyses
(injects) performed over a period of not less than 3 hours or more than
6 hours. For Method 15A to be consistent with Method 15, the following
may be used to obtain a test run: (1) Collect three 60-minute samples or
(2) collect one 3-hour sample. (Three test runs constitute a test.)

8.4 Sample Recovery. Recover the hydrogen peroxide-containing
impingers as detailed in Method 6, section 8.4.
8.5 System Performance Check.
8.5.1 A system performance check is done (1) to validate the
sampling train components and procedure (before testing, optional) and
(2) to validate a test run (after a run, mandatory). Perform a check in
the field before testing consisting of at least two samples (optional),
and perform an additional check after each 3-hour run or after three 1-
hour samples (mandatory).
8.5.2 The checks involve sampling a known concentration of COS and
comparing the analyzed concentration with the known concentration. Mix
the recovery gas with N2 as shown in Figure 15A-4 if dilution
is required. Adjust the flow rates to generate a COS concentration in
the range of the stack gas or within 20 percent of the applicable
standard at a total flow rate of at least 2.5 L/min (5.3 ft\3\/hr). Use
Equation 15A-4 (see section 12.5) to calculate the concentration of
recovery gas generated. Calibrate the flow rate from both sources with a
soap bubble flow tube so that the diluted concentration of COS can be
accurately calculated. Collect 30-minute samples, and analyze in the
same manner as the emission samples. Collect the samples through the
probe of the sampling train using a manifold or some other suitable
device that will ensure extraction of a representative sample.
8.5.3 The recovery check must be performed in the field before
replacing the particulate filter and before cleaning the probe. A sample
recovery of 100 20 percent must be obtained for the data to be valid
and should be reported with the emission data, but should not be used to
correct the data. However, if the performance check results do not
affect the compliance or noncompliance status of the affected facility,
the Administrator may decide to accept the results of the compliance
test. Use Equation 15A-5 (see section 12.6) to calculate the recovery
efficiency.

9.0 Quality Control

10.0 Calibration and Standardization

10.1 Metering System, Temperature Sensors, Barometer, and Barium
Perchlorate Solution. Same as Method 6, sections 10.1, 10.2, 10.4, and
10.5, respectively.
10.2 Rate Meter. Calibrate with a bubble flow tube.

11.0 Analytical Procedure

11.1 Sample Loss Check and Sample Analysis. Same as Method 6,
sections 11.1 and 11.2.

12.0 Data Analysis and Calculations

In the calculations, retain at least one extra decimal figure beyond
that of the acquired data. Round off figures after final calculations.
12.1 Nomenclature.

CCOS = Concentration of COS recovery gas, ppm.
CRG(act) = Actual concentration of recovery check gas (after
dilution), ppm.
CRG(m) = Measured concentration of recovery check gas
generated, ppm.
CRS = Concentration of reduced sulfur compounds as
SO2, dry basis, corrected to standard conditions,
ppm.
N = Normality of barium perchlorate titrant, milliequivalents/ml.
Pbar = Barometric pressure at exit orifice of the dry gas
meter, mm Hg.
Pstd = Standard absolute pressure, 760 mm Hg.
QCOS = Flow rate of COS recovery gas, liters/min.
QN = Flow rate of diluent N2, liters/min.
R = Recovery efficiency for the system performance check, percent.
Tm = Average dry gas meter absolute temperature, [deg]K.

[[Page 409]]

Tstd = Standard absolute temperature, 293 [deg]K.
Va = Volume of sample aliquot titrated, ml.
Vms = Dry gas volume as measured by the sample train dry gas
meter, liters.
Vmc = Dry gas volume as measured by the combustion air dry
gas meter, liters.
Vms(std) = Dry gas volume measured by the sample train dry
gas meter, corrected to standard conditions, liters.
Vmc(std) = Dry gas volume measured by the combustion air dry
gas meter, corrected to standard conditions, liters.
Vsoln = Total volume of solution in which the sulfur dioxide
sample is contained, 100 ml.
Vt = Volume of barium perchlorate titrant used for the sample
(average of replicate titrations), ml.
Vtb = Volume of barium perchlorate titrant used for the
blank, ml.
Y = Calibration factor for sampling train dry gas meter.
Yc = Calibration factor for combustion air dry gas meter.
32.03 = Equivalent weight of sulfur dioxide, mg/meq.
[GRAPHIC] [TIFF OMITTED] TR17OC00.411

12.2 Dry Sample Gas Volume, Corrected to Standard Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.268

Where:

K1 = 0.3855 [deg]K/mm Hg for metric units,
= 17.65 [deg]R/in. Hg for English units.

12.3 Combustion Air Gas Volume, corrected to Standard Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.269

Note: Correct Pbar for the average pressure of the
manometer during the sampling period.

12.4 Concentration of reduced sulfur compounds as ppm
SO2.
[GRAPHIC] [TIFF OMITTED] TR17OC00.270

Where:

[[Page 410]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.271

12.5 Concentration of Generated Recovery Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.272

12.6 Recovery Efficiency for the System Performance Check.
[GRAPHIC] [TIFF OMITTED] TR17OC00.273

13.0 Method Performance

13.1 Analytical Range. The lower detectable limit is 0.1 ppmv when
sampling at 2 lpm for 3 hours or 0.3 ppmv when sampling at 2 lpm for 1
hour. The upper concentration limit of the method exceeds concentrations
of reduced sulfur compounds generally encountered in sulfur recovery
plants.
13.2 Precision. Relative standard deviations of 2.8 and 6.9 percent
have been obtained when sampling a stream with a reduced sulfur compound
concentration of 41 ppmv as SO2 for 1 and 3 hours,
respectively.
13.3 Bias. No analytical bias has been identified. However, results
obtained with this method are likely to contain a positive bias relative
to emission regulations due to the presence of nonregulated sulfur
compounds (that are present in petroleum) in the emissions. The
magnitude of this bias varies accordingly, and has not been quantified.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. American Society for Testing and Materials Annual Book of ASTM
Standards. Part 31: Water, Atmospheric Analysis. Philadelphia,
Pennsylvania. 1974. pp. 40-42.
2. Blosser, R.O., H.S. Oglesby, and A.K. Jain. A Study of Alternate
SO2 Scrubber Designs Used for TRS Monitoring. National
Council of the Paper Industry for Air and Stream Improvement, Inc., New
York, New York. Special Report 77-05. July 1977.
3. Curtis, F., and G.D. McAlister. Development and Evaluation of an
Oxidation/Method 6 TRS Emission Sampling Procedure. Emission Measurement
Branch, Emission Standards and Engineering Division, U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina. February
1980.
4. Gellman, I. A Laboratory and Field Study of Reduced Sulfur
Sampling and Monitoring Systems. National Council of the Paper Industry
for Air and Stream Improvement, Inc., New York, New York. Atmospheric
Quality Improvement Technical Bulletin No. 81. October 1975.
5. Margeson, J.H., et al. A Manual Method for TRS Determination.
Journal of Air Pollution Control Association. 35:1280-1286. December
1985.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 411]]

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[[Page 412]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.275

[[Page 413]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.276

[[Page 414]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.277

[36 FR 24877, Dec. 23, 1971]

Editorial Note: For Federal Register citations affecting appendix A-
5 to part 60, see the List of CFR sections Affected, which appears in
the Finding Aids section of the printed volume and at www.fdsys.gov.

[[Page 415]]

Sec. Appendix A-6 to Part 60--Test Methods 16 through 18

Method 16--Semicontinuous determination of sulfur emissions from
stationary sources
Method 16A--Determination of total reduced sulfur emissions from
stationary sources (impinger technique)
Method 16B--Determination of total reduced sulfur emissions from
stationary sources
Method 16C--Determination of Total Reduced Sulfur Emissions From
Stationary Sources
Method 17--Determination of particulate emissions from stationary
sources (in-stack filtration method)
Method 18--Measurement of gaseous organic compound emissions by gas
chromatography
The test methods in this appendix are referred to in Sec. 60.8
(Performance Tests) and Sec. 60.11 (Compliance With Standards and
Maintenance Requirements) of 40 CFR part 60, subpart A (General
Provisions). Specific uses of these test methods are described in the
standards of performance contained in the subparts, beginning with
Subpart D.
Within each standard of performance, a section title ``Test Methods
and Procedures'' is provided to: (1) Identify the test methods to be
used as reference methods to the facility subject to the respective
standard and (2) identify any special instructions or conditions to be
followed when applying a method to the respective facility. Such
instructions (for example, establish sampling rates, volumes, or
temperatures) are to be used either in addition to, or as a substitute
for procedures in a test method. Similarly, for sources subject to
emission monitoring requirements, specific instructions pertaining to
any use of a test method as a reference method are provided in the
subpart or in Appendix B.
Inclusion of methods in this appendix is not intended as an
endorsement or denial of their applicability to sources that are not
subject to standards of performance. The methods are potentially
applicable to other sources; however, applicability should be confirmed
by careful and appropriate evaluation of the conditions prevalent at
such sources.
The approach followed in the formulation of the test methods
involves specifications for equipment, procedures, and performance. In
concept, a performance specification approach would be preferable in all
methods because this allows the greatest flexibility to the user. In
practice, however, this approach is impractical in most cases because
performance specifications cannot be established. Most of the methods
described herein, therefore, involve specific equipment specifications
and procedures, and only a few methods in this appendix rely on
performance criteria.
Minor changes in the test methods should not necessarily affect the
validity of the results and it is recognized that alternative and
equivalent methods exist. section 60.8 provides authority for the
Administrator to specify or approve (1) equivalent methods, (2)
alternative methods, and (3) minor changes in the methodology of the
test methods. It should be clearly understood that unless otherwise
identified all such methods and changes must have prior approval of the
Administrator. An owner employing such methods or deviations from the
test methods without obtaining prior approval does so at the risk of
subsequent disapproval and retesting with approved methods.
Within the test methods, certain specific equipment or procedures
are recognized as being acceptable or potentially acceptable and are
specifically identified in the methods. The items identified as
acceptable options may be used without approval but must be identified
in the test report. The potentially approvable options are cited as
``subject to the approval of the Administrator'' or as ``or
equivalent.'' Such potentially approvable techniques or alternatives may
be used at the discretion of the owner without prior approval. However,
detailed descriptions for applying these potentially approvable
techniques or alternatives are not provided in the test methods. Also,
the potentially approvable options are not necessarily acceptable in all
applications. Therefore, an owner electing to use such potentially
approvable techniques or alternatives is responsible for: (1) assuring
that the techniques or alternatives are in fact applicable and are
properly executed; (2) including a written description of the
alternative method in the test report (the written method must be clear
and must be capable of being performed without additional instruction,
and the degree of detail should be similar to the detail contained in
the test methods); and (3) providing any rationale or supporting data
necessary to show the validity of the alternative in the particular
application. Failure to meet these requirements can result in the
Administrator's disapproval of the alternative.

Method 16--Semicontinuous Determination of Sulfur Emissions From
Stationary Sources

[[Page 416]]

at least the following additional test methods: Method 1, Method 4,
Method 15, and Method 16A.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Dimethyl disulfide [(CH3)2S2].. 62-49-20 50 ppb.
Dimethyl sulfide [(CH3)2S]..... 75-18-3 50 ppb.
Hydrogen sulfide [H2S]......... 7783-06-4 50 ppb.
Methyl mercaptan [CH4S]........ 74-93-1 50 ppb.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of total reduced sulfur (TRS) compounds from recovery furnaces, lime
kilns, and smelt dissolving tanks at kraft pulp mills and fuel gas
combustion devices at petroleum refineries.

Note: The method described below uses the principle of gas
chromatographic (GC) separation and flame photometric detection (FPD).
Since there are many systems or sets of operating conditions that
represent useable methods of determining sulfur emissions, all systems
which employ this principle, but differ only in details of equipment and
operation, may be used as alternative methods, provided that the
calibration precision and sample line loss criteria are met.

1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted from the emission source and an
aliquot is analyzed for hydrogen sulfide (H2S), methyl
mercaptan (MeSH), dimethyl sulfide (DMS), and dimethyl disulfide (DMDS)
by GC/FPD. These four compounds are known collectively as TRS.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Moisture. Moisture condensation in the sample delivery system,
the analytical column, or the FPD burner block can cause losses or
interferences. This is prevented by maintaining the probe, filter box,
and connections at a temperature of at least 120 [deg]C (248 [deg]F).
Moisture is removed in the SO2 scrubber and heating the
sample beyond this point is not necessary when the ambient temperature
is above 0 [deg]C (32 [deg]F). Alternatively, moisture may be eliminated
by heating the sample line, and by conditioning the sample with dry
dilution air to lower its dew point below the operating temperature of
the GC/FPD analytical system prior to analysis.
4.2 Carbon Monoxide (CO) and Carbon Dioxide (CO2). CO and
CO2 have a substantial desensitizing effect on the flame
photometric detector even after dilution. Acceptable systems must
demonstrate that they have eliminated this interference by some
procedure such as eluting these compounds before any of the compounds to
be measured. Compliance with this requirement can be demonstrated by
submitting chromatograms of calibration gases with and without
CO2 in the diluent gas. The CO2 level should be
approximately 10 percent for the case with CO2 present. The
two chromatograms should show agreement within the precision limits of
section 10.2.
4.3 Particulate Matter. Particulate matter in gas samples can cause
interference by eventual clogging of the analytical system. This
interference is eliminated by using the Teflon filter after the probe.
4.4 Sulfur Dioxide (SO2). Sulfur dioxide is not a
specific interferant but may be present in such large amounts that it
cannot effectively be separated from the other compounds of interest.
The SO2 scrubber described in section 6.1.3 will effectively
remove SO2 from the sample.

5.0 Safety

6.0 Equipment and Supplies

6.1. Sample Collection. The following items are needed for sample
collection.
6.1.1 Probe. Teflon or Teflon-lined stainless steel. The probe must
be heated to prevent moisture condensation. It must be designed to allow
calibration gas to enter the probe at or near the sample point entry.
Any portion of the probe that contacts the stack gas

[[Page 417]]

must be heated to prevent moisture condensation. Figure 16-1 illustrates
the probe used in lime kilns and other sources where significant amounts
of particulate matter are present. The probe is designed with the
deflector shield placed between the sample and the gas inlet holes to
reduce clogging of the filter and possible adsorption of sample gas. As
an alternative, the probe described in section 6.1.1 of Method 16A
having a nozzle directed away from the gas stream may be used at sources
having significant amounts of particulate matter.
6.1.2 Particulate Filter. 50-mm Teflon filter holder and a 1- to 2-
micron porosity Teflon filter (available through Savillex Corporation,
5325 Highway 101, Minnetonka, Minnesota 55343). The filter holder must
be maintained in a hot box at a temperature of at least 120 [deg]C (248
[deg]F).
6.1.3 SO2 Scrubber. Three 300-ml Teflon segmented
impingers connected in series with flexible, thick-walled, Teflon
tubing. (Impinger parts and tubing available through Savillex.) The
first two impingers contain 100 ml of citrate buffer and the third
impinger is initially dry. The tip of the tube inserted into the
solution should be constricted to less than 3 mm (\1/8\ in.) ID and
should be immersed to a depth of at least 5 cm (2 in.). Immerse the
impingers in an ice water bath and maintain near 0 [deg]C (32 [deg]F).
The scrubber solution will normally last for a 3-hour run before needing
replacement. This will depend upon the effects of moisture and
particulate matter on the solution strength and pH. Connections between
the probe, particulate filter, and SO2 scrubber must be made
of Teflon and as short in length as possible. All portions of the probe,
particulate filter, and connections prior to the SO2 scrubber
(or alternative point of moisture removal) must be maintained at a
temperature of at least 120 [deg]C (248 [deg]F).
6.1.4 Sample Line. Teflon, no greater than 1.3 cm (\1/2\ in.) ID.
Alternative materials, such as virgin Nylon, may be used provided the
line loss test is acceptable.
6.1.5 Sample Pump. The sample pump must be a leakless Teflon-coated
diaphragm type or equivalent.
6.2 Analysis. The following items are needed for sample analysis:
6.2.1 Dilution System. Needed only for high sample concentrations.
The dilution system must be constructed such that all sample contacts
are made of Teflon, glass, or stainless steel.
6.2.2 Gas Chromatograph. The gas chromatograph must have at least
the following components:
6.2.2.1 Oven. Capable of maintaining the separation column at the
proper operating temperature 1 [deg]C (2 [deg]F).
6.2.2.2 Temperature Gauge. To monitor column oven, detector, and
exhaust temperature 1 [deg]C (2 [deg]F).
6.2.2.3 Flow System. Gas metering system to measure sample, fuel,
combustion gas, and carrier gas flows.
6.2.2.4 Flame Photometric Detector.
6.2.2.4.1 Electrometer. Capable of full scale amplification of
linear ranges of 10^-9 to 10^-4 amperes full scale.
6.2.2.4.2 Power Supply. Capable of delivering up to 750 volts.
6.2.2.4.3 Recorder. Compatible with the output voltage range of the
electrometer.
6.2.2.4.4 Rotary Gas Valves. Multiport Teflon-lined valves equipped
with sample loop. Sample loop volumes must be chosen to provide the
needed analytical range. Teflon tubing and fittings must be used
throughout to present an inert surface for sample gas. The gas
chromatograph must be calibrated with the sample loop used for sample
analysis.
6.2.3 Gas Chromatogram Columns. The column system must be
demonstrated to be capable of resolving the four major reduced sulfur
compounds: H2S, MeSH, DMS, and DMDS. It must also demonstrate
freedom from known interferences. To demonstrate that adequate
resolution has been achieved, submit a chromatogram of a calibration gas
containing all four of the TRS compounds in the concentration range of
the applicable standard. Adequate resolution will be defined as base
line separation of adjacent peaks when the amplifier attenuation is set
so that the smaller peak is at least 50 percent of full scale. Baseline
separation is defined as a return to zero 5 percent in the interval
between peaks. Systems not meeting this criteria may be considered
alternate methods subject to the approval of the Administrator.
6.3 Calibration. A calibration system, containing the following
components, is required (see Figure 16-2).
6.3.1 Tube Chamber. Chamber of glass or Teflon of sufficient
dimensions to house permeation tubes.
6.3.2 Flow System. To measure air flow over permeation tubes at 2
percent. Flow over the permeation device may also be determined using a
soap bubble flowmeter.
6.3.3 Constant Temperature Bath. Device capable of maintaining the
permeation tubes at the calibration temperature within 0.1 [deg]C (0.2
[deg]F).
6.3.4 Temperature Gauge. Thermometer or equivalent to monitor bath
temperature within 1 [deg]C (2 [deg]F).

7.0 Reagents and Standards

7.1 Fuel. Hydrogen (H2), prepurified grade or better.
7.2 Combustion Gas. Oxygen (O2) or air, research purity
or better.
7.3 Carrier Gas. Prepurified grade or better.
7.4 Diluent (if required). Air containing less than 50 ppb total
sulfur compounds and less than 10 ppmv each of moisture and total
hydrocarbons.
7.5 Calibration Gases

[[Page 418]]

7.5.1 Permeation tubes, one each of H2S, MeSH, DMS, and
DMDS, gravimetrically calibrated and certified at some convenient
operating temperature. These tubes consist of hermetically sealed FEP
Teflon tubing in which a liquified gaseous substance is enclosed. The
enclosed gas permeates through the tubing wall at a constant rate. When
the temperature is constant, calibration gases covering a wide range of
known concentrations can be generated by varying and accurately
measuring the flow rate of diluent gas passing over the tubes. These
calibration gases are used to calibrate the GC/FPD system and the
dilution system.
7.5.2 Cylinder Gases. Cylinder gases may be used as alternatives to
permeation devices. The gases must be traceable to a primary standard
(such as permeation tubes) and not used beyond the certification
expiration date.
7.6 Citrate Buffer and Sample Line Loss Gas. Same as Method 15,
sections 7.6 and 7.7.

8.0 Sample Collection, Preservation, Storage, and Transport

Same as Method 15, section 8.0, except that the references to the
dilution system may not be applicable.

9.0 Quality Control

10.0 Calibration and Standardization

Same as Method 15, section 10.0, with the following addition and
exceptions:
10.1 Use the four compounds that comprise TRS instead of the three
reduced sulfur compounds measured by Method 15.
10.2 Flow Meter. Calibration before each test run is recommended,
but not required; calibration following each test series is mandatory.
Calibrate each flow meter after each complete test series with a wet-
test meter. If the flow measuring device differs from the wet-test meter
by 5 percent or more, the completed test runs must be voided.
Alternatively, the flow data that yield the lower flow measurement may
be used. Flow over the permeation device may also be determined using a
soap bubble flowmeter.

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this method (see
section 8.0).

12.0 Data Analysis and Calculations

12.1 Concentration of Reduced Sulfur Compounds. Calculate the
average concentration of each of the four analytes (i.e., DMDS, DMS,
H2S, and MeSH) over the sample run (specified in section 8.2
of Method 15 as 16 injections).
[GRAPHIC] [TIFF OMITTED] TR17OC00.278

Where:

Si = Concentration of any reduced sulfur compound from the
i\th\ sample injection, ppm.
C = Average concentration of any one of the reduced sulfur compounds for
the entire run, ppm.
N = Number of injections in any run period.

12.2 TRS Concentration. Using Equation 16-2, calculate the TRS
concentration for each sample run.
[GRAPHIC] [TIFF OMITTED] TR17OC00.279

Where:

CTRS = TRS concentration, ppmv.
CH2S = Hydrogen sulfide concentration, ppmv.
CMeSH = Methyl mercaptan concentration, ppmv.
CDMS = Dimethyl sulfide concentration, ppmv.
CDMDS = Dimethyl disulfide concentration, ppmv.
d = Dilution factor, dimensionless.

[[Page 419]]

12.3 Average TRS Concentration. Calculate the average TRS
concentration for all sample runs performed.
[GRAPHIC] [TIFF OMITTED] TR17OC00.280

Where:

Average TRS = Average total reduced sulfur in ppm.
TRSi = Total reduced sulfur in ppm as determined by Equation
16-2.
N = Number of samples.
Bwo = Fraction of volume of water vapor in the gas stream as
determined by Method 4--Determination of Moisture in Stack
Gases.

13.0 Method Performance

13.1 Analytical Range. The analytical range will vary with the
sample loop size. Typically, the analytical range may extend from 0.1 to
100 ppmv using 10- to 0.1-ml sample loop sizes. This eliminates the need
for sample dilution in most cases.
13.2 Sensitivity. Using the 10-ml sample size, the minimum
detectable concentration is approximately 50 ppb.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. O'Keeffe, A.E., and G.C. Ortman. ``Primary Standards for Trace
Gas Analysis.'' Analytical Chemical Journal, 38,76. 1966.
2. Stevens, R.K., A.E. O'Keeffe, and G.C. Ortman. ``Absolute
Calibration of a Flame Photometric Detector to Volatile Sulfur Compounds
at Sub-Part-Per-Million Levels.'' Environmental Science and Technology,
3:7. July 1969.
3. Mulik, J.D., R.K. Stevens, and R. Baumgardner. ``An Analytical
System Designed to Measure Multiple Malodorous Compounds Related to
Kraft Mill Activities.'' Presented at the 12th Conference on Methods in
Air Pollution and Industrial Hygiene Studies, University of Southern
California, Los Angeles, CA. April 6-8, 1971.
4. Devonald, R.H., R.S. Serenius, and A.D. McIntyre. ``Evaluation of
the Flame Photometric Detector for Analysis of Sulfur Compounds.'' Pulp
and Paper Magazine of Canada, 73,3. March 1972.
5. Grimley, K.W., W.S. Smith, and R.M. Martin. ``The Use of a
Dynamic Dilution System in the Conditioning of Stack Gases for Automated
Analysis by a Mobile Sampling Van.'' Presented at the 63rd Annual APCA
Meeting, St. Louis, MO. June 14-19, 1970.
6. General Reference. Standard Methods of Chemical Analysis, Volumes
III-A and III-B Instrumental Methods. Sixth Edition. Van Nostrand
Reinhold Co.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 420]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.281

[[Page 421]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.282

Method 16A--Determination of Total Reduced Sulfur Emissions From
Stationary Sources (Impinger Technique)

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 6, and Method
16.

1.0 Scope and Application

1.1 Analytes.

[[Page 422]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total reduced sulfur (TRS) N/A See section 13.1.
including:
Dimethyl disulfide [(CH3)2S2]. 62-49-20
Dimethyl sulfide [(CH3)2S].... 75-18-3
Hydrogen sulfide [H2S]........ 7783-06-4
Methyl mercaptan [CH4S]....... 74-93-1
Reduced sulfur (RS) including: N/A
H2S........................... 7783-06-4
Carbonyl sulfide [COS]........ 463-58-1
Carbon disulfide [CS2]........ 75-15-0
Reported as: Sulfur dioxide (SO2). 7449-09-5
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of TRS emissions from recovery boilers, lime kilns, and smelt dissolving
tanks at kraft pulp mills, reduced sulfur compounds (H2S,
carbonyl sulfide, and carbon disulfide) from sulfur recovery units at
onshore natural gas processing facilities, and from other sources when
specified in an applicable subpart of the regulations. The flue gas must
contain at least 1 percent oxygen for complete oxidation of all TRS to
SO2. Note: If sources other than kraft pulp mills experience
low oxygen levels in the emissions, the method results may be biased
low.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 An integrated gas sample is extracted from the stack.
SO2 is removed selectively from the sample using a citrate
buffer solution. TRS compounds are then thermally oxidized to
SO2, collected in hydrogen peroxide as sulfate, and analyzed
by the Method 6 barium-thorin titration procedure.

3.0 Definitions [Reserved]

4.0 Interferences

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The sampling train is shown in Figure 16A-1
and component parts are discussed below. Modifications to this sampling
train are acceptable provided the system performance check is met (see
section 8.5).
6.1.1 Probe. Teflon tubing, 6.4-mm (\1/4\-in.) diameter,
sequentially wrapped with heat-resistant fiber strips, a rubberized heat
tape

[[Page 423]]

(plug at one end), and heat-resistant adhesive tape. A flexible
thermocouple or other suitable temperature measuring device should be
placed between the Teflon tubing and the fiber strips so that the
temperature can be monitored to prevent softening of the probe. The
probe should be sheathed in stainless steel to provide in-stack
rigidity. A series of bored-out stainless steel fittings placed at the
front of the sheath will prevent moisture and particulate from entering
between the probe and sheath. A 6.4-mm (\1/4\-in.) Teflon elbow (bored
out) should be attached to the inlet of the probe, and a 2.54 cm (1 in.)
piece of Teflon tubing should be attached at the open end of the elbow
to permit the opening of the probe to be turned away from the
particulate stream; this will reduce the amount of particulate drawn
into the sampling train. The probe is depicted in Figure 16A-2.
6.1.2 Probe Brush. Nylon bristle brush with handle inserted into a
3.2-mm (\1/8\-in.) Teflon tubing. The Teflon tubing should be long
enough to pass the brush through the length of the probe.
6.1.3 Particulate Filter. 50-mm Teflon filter holder and a 1- to 2-
m porosity, Teflon filter (available through Savillex
Corporation, 5325 Highway 101, Minnetonka, Minnesota 55343). The filter
holder must be maintained in a hot box at a temperature sufficient to
prevent moisture condensation. A temperature of 121 [deg]C (250 [deg]F)
was found to be sufficient when testing a lime kiln under sub-freezing
ambient conditions.
6.1.4 SO2 Scrubber. Three 300-ml Teflon segmented
impingers connected in series with flexible, thick-walled, Teflon
tubing. (Impinger parts and tubing available through Savillex.) The
first two impingers contain 100 ml of citrate buffer and the third
impinger is initially dry. The tip of the tube inserted into the
solution should be constricted to less than 3 mm (\1/8\-in.) ID and
should be immersed to a depth of at least 5 cm (2 in.).
6.1.5 Combustion Tube. Quartz glass tubing with an expanded
combustion chamber 2.54 cm (1 in.) in diameter and at least 30.5 cm (12
in.) long. The tube ends should have an outside diameter of 0.6 cm (\1/
4\ in.) and be at least 15.3 cm (6 in.) long. This length is necessary
to maintain the quartz-glass connector near ambient temperature and
thereby avoid leaks. Alternatively, the outlet may be constructed with a
90-degree glass elbow and socket that would fit directly onto the inlet
of the first peroxide impinger.
6.1.6 Furnace. A furnace of sufficient size to enclose the
combustion chamber of the combustion tube with a temperature regulator
capable of maintaining the temperature at 800 100 [deg]C (1472 180
[deg]F). The furnace operating temperature should be checked with a
thermocouple to ensure accuracy.
6.1.7 Peroxide Impingers, Stopcock Grease, Temperature Sensor,
Drying Tube, Valve, Pump, and Barometer. Same as Method 6, sections
6.1.1.2, 6.1.1.4, 6.1.1.5, 6.1.1.6, 6.1.1.7, 6.1.1.8, and 6.1.2,
respectively, except that the midget bubbler of Method 6, section
6.1.1.2 is not required.
6.1.8 Vacuum Gauge. At least 760 mm Hg (30 in. Hg) gauge.
6.1.9 Rate Meter. Rotameter, or equivalent, accurate to within 5
percent at the selected flow rate of approximately 2 liters/min (4.2
ft\3\/hr).
6.1.10 Volume Meter. Dry gas meter capable of measuring the sample
volume under the sampling conditions of 2 liters/min (4.2 ft\3\/hr) with
an accuracy of 2 percent.
6.2 Sample Recovery. Polyethylene Bottles, 250-ml (one per sample).
6.3 Sample Preparation and Analysis. Same as Method 6, section 6.3,
except a 10-ml buret with 0.05-ml graduations is required, and the
spectrophotometer is not needed.

7.0 Reagents and Standards

7.1 Sample Collection. The following reagents are required for
sample analysis:
7.1.1 Water. Same as in Method 6, section 7.1.1.
7.1.2 Citrate Buffer. Dissolve 300 g of potassium citrate (or 284 g
of sodium citrate) and 41 g of anhydrous citric acid in 1 liter of water
(200 ml is needed per test). Adjust the pH to between 5.4 and 5.6 with
potassium citrate or citric acid, as required.
7.1.3 Hydrogen Peroxide, 3 percent. Same as in Method 6, section
7.1.3 (40 ml is needed per sample).
7.1.4 Recovery Check Gas. Hydrogen sulfide (100 ppmv or less) in
nitrogen, stored in aluminum cylinders. Verify the concentration by
Method 11 or by gas chromatography where the instrument is calibrated
with an H2S permeation tube as described below. For Method
11, the relative standard deviation should not exceed 5 percent on at
least three 20-minute runs.

Note: Alternatively, hydrogen sulfide recovery gas generated from a
permeation device gravimetrically calibrated and certified at some
convenient operating temperature may be used. The permeation rate of the
device must be such that at a dilution gas flow rate of 3 liters/min
(6.4 ft\3\/hr), an H2S concentration in the range of the
stack gas or within 20 percent of the standard can be generated.

7.1.5 Combustion Gas. Gas containing less than 50 ppb reduced sulfur
compounds and less than 10 ppmv total hydrocarbons. The

[[Page 424]]

gas may be generated from a clean-air system that purifies ambient air
and consists of the following components: Diaphragm pump, silica gel
drying tube, activated charcoal tube, and flow rate measuring device.
Flow from a compressed air cylinder is also acceptable.
7.2 Sample Recovery and Analysis. Same as Method 6, sections 7.2.1
and 7.3, respectively.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Preparation of Sampling Train.
8.1.1 For the SO2 scrubber, measure 100 ml of citrate
buffer into the first and second impingers; leave the third impinger
empty. Immerse the impingers in an ice bath, and locate them as close as
possible to the filter heat box. The connecting tubing should be free of
loops. Maintain the probe and filter temperatures sufficiently high to
prevent moisture condensation, and monitor with a suitable temperature
sensor.
8.1.2 For the Method 6 part of the train, measure 20 ml of 3 percent
hydrogen peroxide into the first and second midget impingers. Leave the
third midget impinger empty, and place silica gel in the fourth midget
impinger. Alternatively, a silica gel drying tube may be used in place
of the fourth impinger. Maintain the oxidation furnace at 800 100
[deg]C (1472 180 [deg]F). Place crushed ice and water around all
impingers.
8.2 Citrate Scrubber Conditioning Procedure. Condition the citrate
buffer scrubbing solution by pulling stack gas through the Teflon
impingers and bypassing all other sampling train components. A purge
rate of 2 liters/min for 10 minutes has been found to be sufficient to
obtain equilibrium. After the citrate scrubber has been conditioned,
assemble the sampling train, and conduct (optional) a leak-check as
described in Method 6, section 8.2.
8.3 Sample Collection. Same as in Method 6, section 8.3, except the
sampling rate is 2 liters/min (10 percent) for 1 or 3 hours. After the
sample is collected, remove the probe from the stack, and conduct
(mandatory) a post-test leak-check as described in Method 6, section
8.2. The 15-minute purge of the train following collection should not be
performed. After each 3-hour test run (or after three 1-hour samples),
conduct one system performance check (see section 8.5) to determine the
reduced sulfur recovery efficiency through the sampling train. After
this system performance check and before the next test run, rinse and
brush the probe with water, replace the filter, and change the citrate
scrubber (optional but recommended).

Note: In Method 16, a test run is composed of 16 individual analyses
(injects) performed over a period of not less than 3 hours or more than
6 hours. For Method 16A to be consistent with Method 16, the following
may be used to obtain a test run: (1) collect three 60-minute samples or
(2) collect one 3-hour sample. (Three test runs constitute a test.)

8.4 Sample Recovery. Disconnect the impingers. Quantitatively
transfer the contents of the midget impingers of the Method 6 part of
the train into a leak-free polyethylene bottle for shipment. Rinse the
three midget impingers and the connecting tubes with water and add the
washings to the same storage container. Mark the fluid level. Seal and
identify the sample container.
8.5 System Performance Check.
8.5.1 A system performance check is done (1) to validate the
sampling train components and procedure (prior to testing; optional) and
(2) to validate a test run (after a run). Perform a check in the field
prior to testing consisting of at least two samples (optional), and
perform an additional check after each 3 hour run or after three 1-hour
samples (mandatory).
8.5.2 The checks involve sampling a known concentration of
H2S and comparing the analyzed concentration with the known
concentration. Mix the H2S recovery check gas (Section 7.1.4)
and combustion gas in a dilution system such as that shown in Figure
16A-3. Adjust the flow rates to generate an H2S concentration
in the range of the stack gas or within 20 percent of the applicable
standard and an oxygen concentration greater than 1 percent at a total
flow rate of at least 2.5 liters/min (5.3 ft\3\/hr). Use Equation 16A-3
to calculate the concentration of recovery gas generated. Calibrate the
flow rate from both sources with a soap bubble flow meter so that the
diluted concentration of H2S can be accurately calculated.
8.5.3 Collect 30-minute samples, and analyze in the same manner as
the emission samples. Collect the sample through the probe of the
sampling train using a manifold or some other suitable device that will
ensure extraction of a representative sample.
8.5.4 The recovery check must be performed in the field prior to
replacing the SO2 scrubber and particulate filter and before
the probe is cleaned. Use Equation 16A-4 (see section 12.5) to calculate
the recovery efficiency. Report the recovery efficiency with the
emission data; do not correct the emission data for the recovery
efficiency. A sample recovery of 100 20 percent must be obtained for
the emission data to be valid. However, if the recovery efficiency is
not in the 100 20 percent range but the results do not affect the
compliance or noncompliance status of the affected facility, the
Administrator may decide to accept the results of the compliance test.

9.0 Quality Control

[[Page 425]]

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.5........................... System Ensure validity of
performance sampling train
check. components and
analytical
procedure.
8.2, 10.0..................... Sampling Ensure accurate
equipment leak- measurement of stack
check and gas flow rate,
calibration. sample volume.
10.0.......................... Barium standard Ensure precision of
solution normality
standardization. determination.
11.1.......................... Replicate Ensure precision of
titrations. titration
determinations.
------------------------------------------------------------------------

10.0 Calibration

Same as Method 6, section 10.0.

11.0 Analytical Procedure

11.1 Sample Loss Check and Sample Analysis. Same as Method 6,
sections 11.1 and 11.2, respectively, with the following exception: for
1-hour sampling, take a 40-ml aliquot, add 160 ml of 100 percent
isopropanol and four drops of thorin.

12.0 Data Analysis and Calculations

In the calculations, at least one extra decimal figure should be
retained beyond that of the acquired data. Figures should be rounded off
after final calculations.
12.1 Nomenclature.

CTRS = Concentration of TRS as SO2, dry basis
corrected to standard conditions, ppmv.
CRG(act) = Actual concentration of recovery check gas (after
dilution), ppm.
CRG(m) = Measured concentration of recovery check gas
generated, ppm.
CH2S = Verified concentration of H2S recovery gas.
N = Normality of barium perchlorate titrant, milliequivalents/ml.
Pbar = Barometric pressure at exit orifice of the dry gas
meter, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
QH2S = Calibrated flow rate of H2S recovery gas,
liters/min.
QCG = Calibrated flow rate of combustion gas, liters/min.
R = Recovery efficiency for the system performance check, percent.
Tm = Average dry gas meter absolute temperature, [deg]K
([deg]R).
Tstd = Standard absolute temperature, 293 [deg]K (528
[deg]R).
Va = Volume of sample aliquot titrated, ml.
Vm = Dry gas volume as measured by the dry gas meter, liters
(dcf).
Vm(std) = Dry gas volume measured by the dry gas meter,
corrected to standard conditions, liters (dscf).
Vsoln = Total volume of solution in which the sulfur dioxide
sample is contained, 100 ml.
Vt = Volume of barium perchlorate titrant used for the
sample, ml (average of replicate titrations).
Vtb = Volume of barium perchlorate titrant used for the
blank, ml.
Y = Dry gas meter calibration factor.
32.03 = Equivalent weight of sulfur dioxide, mg/meq.

12.2 Dry Sample Gas Volume, Corrected to Standard Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.283

Where:

K1 = 0.3855 [deg]K/mm Hg for metric units,
= 17.65 [deg]R/in. Hg for English units.

12.3 Concentration of TRS as ppm SO2.
[GRAPHIC] [TIFF OMITTED] TR17OC00.284

Where:

[[Page 426]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.285

12.4 Concentration of Recovery Gas Generated in the System
Performance Check.
[GRAPHIC] [TIFF OMITTED] TR17OC00.286

12.5 Recovery Efficiency for the System Performance Check.
[GRAPHIC] [TIFF OMITTED] TR17OC00.287

13.0 Method Performance

13.1 Analytical Range. The lower detectable limit is 0.1 ppmv
SO2 when sampling at 2 liters/min (4.2 ft\3\/hr) for 3 hours
or 0.3 ppmv when sampling at 2 liters/min (4.2 ft\3\/hr) for 1 hour. The
upper concentration limit of the method exceeds the TRS levels generally
encountered at kraft pulp mills.
13.2 Precision. Relative standard deviations of 2.0 and 2.6 percent
were obtained when sampling a recovery boiler for 1 and 3 hours,
respectively.
13.3 Bias.
13.3.1 No bias was found in Method 16A relative to Method 16 in a
separate study at a recovery boiler.
13.3.2 Comparison of Method 16A with Method 16 at a lime kiln
indicated that there was no bias in Method 16A. However, instability of
the source emissions adversely affected the comparison. The precision of
Method 16A at the lime kiln was similar to that obtained at the recovery
boiler (Section 13.2.1).
13.3.3 Relative standard deviations of 2.7 and 7.7 percent have been
obtained for system performance checks.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

As an alternative to the procedures specified in section 7.1.4, the
following procedure may be used to verify the H2S
concentration of the recovery check gas.
16.1 Summary. The H2S is collected from the calibration
gas cylinder and is absorbed in zinc acetate solution to form zinc
sulfide. The latter compound is then measured iodometrically.
16.2 Range. The procedure has been examined in the range of 5 to
1500 ppmv.
16.3 Interferences. There are no known interferences to this
procedure when used to analyze cylinder gases containing H2S
in nitrogen.
16.4 Precision and Bias. Laboratory tests have shown a relative
standard deviation of less than 3 percent. The procedure showed no bias
when compared to a gas chromatographic method that used gravimetrically
certified permeation tubes for calibration.
16.5 Equipment and Supplies.
16.5.1 Sampling Apparatus. The sampling train is shown in Figure
16A-4. Its component parts are discussed in sections 16.5.1.1 through
16.5.2.
16.5.1.1 Sampling Line. Teflon tubing (\1/4\-in.) to connect the
cylinder regulator to the sampling valve.
16.5.1.2 Needle Valve. Stainless steel or Teflon needle valve to
control the flow rate of gases to the impingers.
16.5.1.3 Impingers. Three impingers of approximately 100-ml
capacity, constructed to permit the addition of reagents through the gas
inlet stem. The impingers shall be connected in series with leak-free
glass or Teflon connectors. The impinger bottoms have a standard 24/25
ground-glass fitting. The stems are from standard 6.4-mm (\1/4\-in.)
ball joint midget impingers, custom lengthened by about 1 in. When
fitted together, the stem end should be approximately 1.27 cm (\1/2\
in.) from the bottom (Southern Scientific, Inc., Micanopy, Florida: Set
Number S6962-048). The third in-line impinger acts as a drop-out bottle.
16.5.1.4 Drying Tube, Rate Meter, and Barometer. Same as Method 11,
sections 6.1.5, 6.1.8, and 6.1.10, respectively.
16.5.1.5 Cylinder Gas Regulator. Stainless steel, to reduce the
pressure of the gas stream entering the Teflon sampling line to a safe
level.
16.5.1.6 Soap Bubble Meter. Calibrated for 100 and 500 ml, or two
separate bubble meters.
16.5.1.7 Critical Orifice. For volume and rate measurements. The
critical orifice may be fabricated according to section 16.7.3 and must
be calibrated as specified in section 16.12.4.
16.5.1.8 Graduated Cylinder. 50-ml size.
16.5.1.9 Volumetric Flask. 1-liter size.
16.5.1.10 Volumetric Pipette. 15-ml size.

[[Page 427]]

16.5.1.11 Vacuum Gauge. Minimum 20 in. Hg capacity.
16.5.1.12 Stopwatch.
16.5.2 Sample Recovery and Analysis.
16.5.2.1 Erlenmeyer Flasks. 125- and 250-ml sizes.
16.5.2.2 Pipettes. 2-, 10-, 20-, and 100-ml volumetric.
16.5.2.3 Burette. 50-ml size.
16.5.2.4 Volumetric Flask. 1-liter size.
16.5.2.5 Graduated Cylinder. 50-ml size.
16.5.2.6 Wash Bottle.
16.5.2.7 Stirring Plate and Bars.
16.6 Reagents and Standards. Unless otherwise indicated, all
reagents must conform to the specifications established by the Committee
on Analytical Reagents of the American Chemical Society, where such
specifications are available. Otherwise, use the best available grade.
16.6.1 Water. Same as Method 11, section 7.1.3.
16.6.2 Zinc Acetate Absorbing Solution. Dissolve 20 g zinc acetate
in water, and dilute to 1 liter.
16.6.3 Potassium Bi-iodate [KH(IO3)2]
Solution, Standard 0.100 N. Dissolve 3.249 g anhydrous
KH(IO3)2 in water, and dilute to 1 liter.
16.6.4 Sodium Thiosulfate (Na2S2O3)
Solution, Standard 0.1 N. Same as Method 11, section 7.3.2. Standardize
according to section 16.12.2.
16.6.5 Na2S2O3 Solution, Standard
0.01 N. Pipette 100.0 ml of 0.1 N
Na2S2O3 solution into a 1-liter
volumetric flask, and dilute to the mark with water.
16.6.6 Iodine Solution, 0.1 N. Same as Method 11, section 7.2.3.
16.6.7 Standard Iodine Solution, 0.01 N. Same as in Method 11,
section 7.2.4. Standardize according to section 16.12.3.
16.6.8 Hydrochloric Acid (HCl) Solution, 10 Percent by Weight. Add
230 ml concentrated HCl (specific gravity 1.19) to 770 ml water.
16.6.9 Starch Indicator Solution. To 5 g starch (potato, arrowroot,
or soluble), add a little cold water, and grind in a mortar to a thin
paste. Pour into 1 liter of boiling water, stir, and let settle
overnight. Use the clear supernatant. Preserve with 1.25 g salicylic
acid, 4 g zinc chloride, or a combination of 4 g sodium propionate and 2
g sodium azide per liter of starch solution. Some commercial starch
substitutes are satisfactory.
16.7 Pre-test Procedures.
16.7.1 Selection of Gas Sample Volumes. This procedure has been
validated for estimating the volume of cylinder gas sample needed when
the H2S concentration is in the range of 5 to 1500 ppmv. The
sample volume ranges were selected in order to ensure a 35 to 60 percent
consumption of the 20 ml of 0.01 N iodine (thus ensuring a 0.01 N
Na2S2O3 titer of approximately 7 to 12
ml). The sample volumes for various H2S concentrations can be
estimated by dividing the approximate ppm-liters desired for a given
concentration range by the H2S concentration stated by the
manufacturer. For example, for analyzing a cylinder gas containing
approximately 10 ppmv H2S, the optimum sample volume is 65
liters (650 ppm-liters/10 ppmv). For analyzing a cylinder gas containing
approximately 1000 ppmv H2S, the optimum sample volume is 1
liter (1000 ppm-liters/1000 ppmv).

------------------------------------------------------------------------
Approximate
Approximate cylinder gas H2S concentration (ppmv) ppm-liters
desired
------------------------------------------------------------------------
5 to <30................................................ 650
30 to <500.............................................. 800
500 to <1500............................................ 1000
------------------------------------------------------------------------

16.7.2 Critical Orifice Flow Rate Selection. The following table
shows the ranges of sample flow rates that are desirable in order to
ensure capture of H2S in the impinger solution. Slight
deviations from these ranges will not have an impact on measured
concentrations.

------------------------------------------------------------------------
Critical orifice flow rate
Cylinder gas H2S concentration (ppmv) (ml/min)
------------------------------------------------------------------------
5 to 50 ppmv............................. 1500 500
50 to 250 ppmv........................... 500 250
250 to <1000 ppmv........................ 200 50
>1000 ppmv............................... 75 25
------------------------------------------------------------------------

16.7.3 Critical Orifice Fabrication. Critical orifice of desired
flow rates may be fabricated by selecting an orifice tube of desired
length and connecting \1/16\-in. x \1/4\-in. (0.16 cm x 0.64 cm)
reducing fittings to both ends. The inside diameters and lengths of
orifice tubes needed to obtain specific flow rates are shown below.

----------------------------------------------------------------------------------------------------------------
Flowrate (ml/ Altech Catalog
Tube (in. OD) Tube (in. ID) Length (in.) min) No.
----------------------------------------------------------------------------------------------------------------
\1/16\.......................................... 0.007 1.2 85 301430
\1/16\.......................................... 0.01 3.2 215 300530
\1/16\.......................................... 0.01 1.2 350 300530
\1/16\.......................................... 0.02 1.2 1400 300230
----------------------------------------------------------------------------------------------------------------

16.7.4 Determination of Critical Orifice Approximate Flow Rate.
Connect the critical orifice to the sampling system as shown in Figure
16A-4 but without the H2S cylinder. Connect a rotameter in
the line to the first impinger. Turn on the pump, and adjust the

[[Page 428]]

valve to give a reading of about half atmospheric pressure. Observe the
rotameter reading. Slowly increase the vacuum until a stable flow rate
is reached, and record this as the critical vacuum. The measured flow
rate indicates the expected critical flow rate of the orifice. If this
flow rate is in the range shown in section 16.7.2, proceed with the
critical orifice calibration according to section 16.12.4.
16.7.5 Determination of Approximate Sampling Time. Determine the
approximate sampling time for a cylinder of known concentration. Use the
optimum sample volume obtained in section 16.7.1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.288

16.8 Sample Collection.
16.8.1 Connect the Teflon tubing, Teflon tee, and rotameter to the
flow control needle valve as shown in Figure 16A-4. Vent the rotameter
to an exhaust hood. Plug the open end of the tee. Five to 10 minutes
prior to sampling, open the cylinder valve while keeping the flow
control needle valve closed. Adjust the delivery pressure to 20 psi.
Open the needle valve slowly until the rotameter shows a flow rate
approximately 50 to 100 ml above the flow rate of the critical orifice
being used in the system.
16.8.2 Place 50 ml of zinc acetate solution in two of the impingers,
connect them and the empty third impinger (dropout bottle) and the rest
of the equipment as shown in Figure 16A-4. Make sure the ground-glass
fittings are tight. The impingers can be easily stabilized by using a
small cardboard box in which three holes have been cut, to act as a
holder. Connect the Teflon sample line to the first impinger. Cover the
impingers with a dark cloth or piece of plastic to protect the absorbing
solution from light during sampling.
16.8.3 Record the temperature and barometric pressure. Note the gas
flow rate through the rotameter. Open the closed end of the tee. Connect
the sampling tube to the tee, ensuring a tight connection. Start the
sampling pump and stopwatch simultaneously. Note the decrease in flow
rate through the excess flow rotameter. This decrease should equal the
known flow rate of the critical orifice being used. Continue sampling
for the period determined in section 16.7.5.
16.8.4 When sampling is complete, turn off the pump and stopwatch.
Disconnect the sampling line from the tee and plug it. Close the needle
valve followed by the cylinder valve. Record the sampling time.
16.9 Blank Analysis. While the sample is being collected, run a
blank as follows: To a 250-ml Erlenmeyer flask, add 100 ml of zinc
acetate solution, 20.0 ml of 0.01 N iodine solution, and 2 ml HCl
solution. Titrate, while stirring, with 0.01 N
Na2S2O3 until the solution is light
yellow. Add starch, and continue titrating until the blue color
disappears. Analyze a blank with each sample, as the blank titer has
been observed to change over the course of a day.

Note: Iodine titration of zinc acetate solutions is difficult to
perform because the solution turns slightly white in color near the end
point, and the disappearance of the blue color is hard to recognize. In
addition, a blue color may reappear in the solution about 30 to 45
seconds after the titration endpoint is reached. This should not be
taken to mean the original endpoint was in error. It is recommended that
persons conducting this test perform several titrations to be able to
correctly identify the endpoint. The importance of this should be
recognized because the results of this analytical procedure are
extremely sensitive to errors in titration.

16.10 Sample Analysis. Sample treatment is similar to the blank
treatment. Before detaching the stems from the bottoms of the impingers,
add 20.0 ml of 0.01 N iodine solution through the stems of the impingers
holding the zinc acetate solution, dividing it between the two (add
about 15 ml to the first impinger and the rest to the second). Add 2 ml
HCl solution through the stems, dividing it as with the iodine.
Disconnect the sampling line, and store the impingers for 30 minutes. At
the end of 30 minutes, rinse the impinger stems into the impinger
bottoms. Titrate the impinger contents with 0.01 N
Na2S2O3. Do not transfer the contents
of the impinger to a flask because this may result in a loss of iodine
and cause a positive bias.
16.11 Post-test Orifice Calibration. Conduct a post-test critical
orifice calibration run using the calibration procedures outlined in
section 16.12.4. If the Qstd obtained before and after the
test differs by more than 5 percent, void the sample; if not, proceed to
perform the calculations.
16.12 Calibrations and Standardizations.
16.12.1 Rotameter and Barometer. Same as Method 11, sections 10.1.3
and 10.1.4.
16.12.2 Na2S2O3 Solution, 0.1 N.
Standardize the 0.1 N Na2S2O3 solution
as follows: To 80 ml water, stirring constantly, add 1 ml concentrated
H2SO4, 10.0 ml of 0.100 N
KH(IO3)2

[[Page 429]]

and 1 g potassium iodide. Titrate immediately with 0.1 N
Na2S2O3 until the solution is light
yellow. Add 3 ml starch solution, and titrate until the blue color just
disappears. Repeat the titration until replicate analyses agree within
0.05 ml. Take the average volume of
Na2S2O3 consumed to calculate the
normality to three decimal figures using Equation 16A-5.
16.12.3 Iodine Solution, 0.01 N. Standardize the 0.01 N iodine
solution as follows: Pipet 20.0 ml of 0.01 N iodine solution into a 125-
ml Erlenmeyer flask. Titrate with standard 0.01 N
Na2S2O3 solution until the solution is
light yellow. Add 3 ml starch solution, and continue titrating until the
blue color just disappears. If the normality of the iodine tested is not
0.010, add a few ml of 0.1 N iodine solution if it is low, or a few ml
of water if it is high, and standardize again. Repeat the titration
until replicate values agree within 0.05 ml. Take the average volume to
calculate the normality to three decimal figures using Equation 16A-6.
16.12.4 Critical Orifice. Calibrate the critical orifice using the
sampling train shown in Figure 16A-4 but without the H2S
cylinder and vent rotameter. Connect the soap bubble meter to the Teflon
line that is connected to the first impinger. Turn on the pump, and
adjust the needle valve until the vacuum is higher than the critical
vacuum determined in section 16.7.4. Record the time required for gas
flow to equal the soap bubble meter volume (use the 100-ml soap bubble
meter for gas flow rates below 100 ml/min, otherwise use the 500-ml soap
bubble meter). Make three runs, and record the data listed in Table 16A-
1. Use these data to calculate the volumetric flow rate of the orifice.
16.13 Calculations.
16.13.1 Nomenclature.

Bwa = Fraction of water vapor in ambient air during orifice
calibration.
CH2S = H2S concentration in cylinder
gas, ppmv.
[GRAPHIC] [TIFF OMITTED] TR17OC00.289

Ma = Molecular weight of ambient air saturated at impinger
temperature, g/g-mole.
Ms = Molecular weight of sample gas (nitrogen) saturated at
impinger temperature, g/g-mole.

Note: (For tests carried out in a laboratory where the impinger
temperature is 25 [deg]C, Ma = 28.5 g/g-mole and
Ms = 27.7 g/g-mole.)

NI = Normality of standard iodine solution (0.01 N), g-eq/
liter.
NT = Normality of standard
Na2S2O3 solution (0.01 N), g-
eq/liter.
Pbar = Barometric pressure, mm Hg.
Pstd = Standard absolute pressure, 760 mm Hg.
Qstd = Average volumetric flow rate through critical orifice,
liters/min.
Tamb = Absolute ambient temperature, [deg]K.
Tstd = Standard absolute temperature, 293 [deg]K.
ks = Sampling time, min.
ksb = Time for soap bubble meter flow rate measurement, min.
Vm(std) = Sample gas volume measured by the critical orifice,
corrected to standard conditions, liters.
Vsb = Volume of gas as measured by the soap bubble meter, ml.
Vsb(std) = Volume of gas as measured by the soap bubble
meter, corrected to standard conditions, liters.
VI = Volume of standard iodine solution (0.01 N) used, ml.
VT = Volume of standard
Na2S2O3 solution (0.01 N)
used, ml.
VTB = Volume of standard
Na2S2O3 solution (0.01 N)
used for the blank, ml.

16.13.2 Normality of Standard
Na2S2O3 Solution (0.1 N).
[GRAPHIC] [TIFF OMITTED] TR17OC00.290

16.13.3 Normality of Standard Iodine Solution (0.01 N).

[[Page 430]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.291

16.13.4 Sample Gas Volume.
[GRAPHIC] [TIFF OMITTED] TR17OC00.292

16.13.5 Concentration of H2S in the Gas Cylinder.

17.0 References
[GRAPHIC] [TIFF OMITTED] TR17OC00.293

1. American Public Health Association, American Water Works
Association, and Water Pollution Control Federation. Standard Methods
for the Examination of Water and Wastewater. Washington, DC. American
Public Health Association. 1975. pp. 316-317.
2. American Society for Testing and Materials. Annual Book of ASTM
Standards. Part 31: Water, Atmospheric Analysis. Philadelphia, PA. 1974.
pp. 40-42.
3. Blosser, R.O. A Study of TRS Measurement Methods. National
Council of the Paper Industry for Air and Stream Improvement, Inc., New
York, NY. Technical Bulletin No. 434. May 1984. 14 pp.
4. Blosser, R.O., H.S. Oglesby, and A.K. Jain. A Study of Alternate
SO2 Scrubber Designs Used for TRS Monitoring. A Special
Report by the National Council of the Paper Industry for Air and Stream
Improvement, Inc., New York, NY. July 1977.
5. Curtis, F., and G.D. McAlister. Development and Evaluation of an
Oxidation/Method 6 TRS Emission Sampling Procedure. Emission Measurement
Branch, Emission Standards and Engineering Division, U.S. Environmental
Protection Agency, Research Triangle Park, NC 27711. February 1980.
6. Gellman, I. A Laboratory and Field Study of Reduced Sulfur
Sampling and Monitoring Systems. National Council of the Paper Industry
for Air and Stream Improvement, Inc., New York, NY. Atmospheric Quality
Improvement Technical Bulletin No. 81. October 1975.
7. Margeson, J.H., J.E. Knoll, and M.R. Midgett. A Manual Method for
TRS Determination. Source Branch, Quality Assurance Division, U.S.
Environmental Protection Agency, Research Triangle Park, NC 27711.
8. National Council of the Paper Industry for Air and Stream
Improvement. An Investigation of H2S and SO2.
Calibration Cylinder Gas Stability and Their Standardization Using Wet
Chemical Techniques. Special Report 76-06. New York, NY. August 1976.
9. National Council of the Paper Industry for Air and Stream
Improvement. Wet Chemical Method for Determining the H2S
Concentration of Calibration Cylinder Gases. Technical Bulletin Number
450. New York, NY. January 1985. 23 pp.
10. National Council of the Paper Industry for Air and Stream
Improvement. Modified Wet Chemical Method for Determining the
H2S Concentration of Calibration Cylinder Gases. Draft
Report. New York, NY. March 1987. 29 pp.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 431]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.294

[[Page 432]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.295

[[Page 433]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.296

[[Page 434]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.297

Date____________________________________________________________________
Critical orifice ID_____________________________________________________
Soap bubble meter volume, Vsb---- liters
Time, ksb
Run no. 1 ---- min ---- sec
Run no. 2 ---- min ---- sec
Run no. 3 ---- min ---- sec
Average ---- min ---- sec
Covert the seconds to fraction of minute:
Time=---- min + ---- Sec/60=---- min
Barometric pressure, Pbar=---- mm Hg
Ambient temperature, t amb = 273 + ---- [deg]C=---- [deg]K=--
-- mm Hg. (This should be approximately 0.4 times barometric
pressure.)
Pump vacuum,

[[Page 435]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.298

Table 16A-1. Critical Orifice Calibration Data

Method 16B--Determination of Total Reduced Sulfur Emissions From
Stationary Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a knowledge of at least the
following additional test methods: Method 6C, Method 16, and Method 16A.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Total reduced sulfur (TRS) including: N/A
Dimethyl disulfide (DMDS), [(CH3)2S2]............... 62-49-20
Dimethyl sulfide (DMS), [(CH3)2S]................... 75-18-3
Hydrogen sulfide (H2S).............................. 7783-06-4
Methyl mercaptan (MeSH), [CH4S]..................... 74-93-1
Reported as: Sulfur dioxide (SO2)....................... 7449-09-5
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for determining TRS
emissions from recovery furnaces (boilers), lime kilns, and smelt
dissolving tanks at kraft pulp mills, and from other sources when
specified in an applicable subpart of the regulations. The flue gas must
contain at least 1 percent oxygen for complete oxidation of all TRS to
SO2.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Reduced sulfur compounds other than those regulated by the
emission standards, if present, may be measured by this method.
Therefore, carbonyl sulfide, which is partially oxidized to
SO2 and may be present in a lime kiln exit stack, would be a
positive interferant.
4.2 Particulate matter from the lime kiln stack gas (primarily
calcium carbonate) can cause a negative bias if it is allowed to enter
the citrate scrubber; the particulate matter will cause the pH to rise
and H2S to be absorbed before oxidation. Proper use of the
particulate filter, described in section 6.1.3 of Method 16A, will
eliminate this interference.
4.3 Carbon monoxide (CO) and carbon dioxide (CO2) have
substantial desensitizing effects on the FPD even after dilution.
Acceptable systems must demonstrate that they have eliminated this
interference by some procedure such as eluting these compounds before
the SO2. Compliance with this requirement can be demonstrated
by submitting chromatograms of calibration gases with and without
CO2 in diluent gas. The CO2 level should be
approximately 10 percent for the case with CO2 present. The
two chromatograms should show agreement within the precision limits of
section 13.0.

5.0 Safety

[[Page 436]]

the mucous membranes and may cause nausea, dizziness, and headache after
exposure.

6.0 Equipment and Supplies

6.1 Sample Collection. The sampling train is shown in Figure 16B-1.
Modifications to the apparatus are accepted provided the system
performance check in section 8.4.1 is met.
6.1.1 Probe, Probe Brush, Particulate Filter, SO2
Scrubber, Combustion Tube, and Furnace. Same as in Method 16A, sections
6.1.1 to 6.1.6.
6.1.2 Sampling Pump. Leakless Teflon-coated diaphragm type or
equivalent.
6.2 Analysis.
6.2.1 Dilution System (optional), Gas Chromatograph, Oven,
Temperature Gauges, Flow System, Flame Photometric Detector,
Electrometer, Power Supply, Recorder, Calibration System, Tube Chamber,
Flow System, and Constant Temperature Bath. Same as in Method 16,
sections 6.2.1, 6.2.2, and 6.3.
6.2.2 Gas Chromatograph Columns. Same as in Method 16, section
6.2.3. Other columns with demonstrated ability to resolve SO2
and be free from known interferences are acceptable alternatives. Single
column systems such as a 7-ft Carbsorb B HT 100 column have been found
satisfactory in resolving SO2 from CO2.

7.0 Reagents and Standards

Same as in Method 16, section 7.0, except for the following:
7.1 Calibration Gas. SO2 permeation tube gravimetrically
calibrated and certified at some convenient operating temperature. These
tubes consist of hermetically sealed FEP Teflon tubing in which a
liquefied gaseous substance is enclosed. The enclosed gas permeates
through the tubing wall at a constant rate. When the temperature is
constant, calibration gases covering a wide range of known
concentrations can be generated by varying and accurately measuring the
flow rate of diluent gas passing over the tubes. In place of
SO2 permeation tubes, cylinder gases containing
SO2 in nitrogen may be used for calibration. The cylinder gas
concentration must be verified according to section 8.2.1 of Method 6C.
The calibration gas is used to calibrate the GC/FPD system and the
dilution system.
7.2 Recovery Check Gas.
7.2.1 Hydrogen sulfide [100 parts per million by volume (ppmv) or
less] in nitrogen, stored in aluminum cylinders. Verify the
concentration by Method 11, the procedure discussed in section 16.0 of
Method 16A, or gas chromatography where the instrument is calibrated
with an H2S permeation tube as described below. For the wet-
chemical methods, the standard deviation should not exceed 5 percent on
at least three 20-minute runs.
7.2.2 Hydrogen sulfide recovery gas generated from a permeation
device gravimetrically calibrated and certified at some convenient
operation temperature may be used. The permeation rate of the device
must be such that at a dilution gas flow rate of 3 liters/min (64 ft\3\/
hr), an H2S concentration in the range of the stack gas or
within 20 percent of the emission standard can be generated.
7.3 Combustion Gas. Gas containing less than 50 ppbv reduced sulfur
compounds and less than 10 ppmv total hydrocarbons. The gas may be
generated from a clean-air system that purifies ambient air and consists
of the following components: diaphragm pump, silica gel drying tube,
activated charcoal tube, and flow rate measuring device. Gas from a
compressed air cylinder is also acceptable.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Pretest Procedures. Same as in Method 15, section 8.1.
8.2 Sample Collection. Before any source sampling is performed,
conduct a system performance check as detailed in section 8.4.1 to
validate the sampling train components and procedures. Although this
test is optional, it would significantly reduce the possibility of
rejecting tests as a result of failing the post-test performance check.
At the completion of the pretest system performance check, insert the
sampling probe into the test port making certain that no dilution air
enters the stack though the port. Condition the entire system with
sample for a minimum of 15 minutes before beginning analysis. If the
sample is diluted, determine the dilution factor as in section 10.4 of
Method 15.
8.3 Analysis. Inject aliquots of the sample into the GC/FPD analyzer
for analysis. Determine the concentration of SO2 directly
from the calibration curves or from the equation for the least-squares
line.
8.4. Post-Test Procedures
8.4.1 System Performance Check. Same as in Method 16A, section 8.5.
A sufficient number of sample injections should be made so that the
precision requirements of section 13.2 are satisfied.
8.4.2 Determination of Calibration Drift. Same as in Method 15,
section 8.3.2.

9.0 Quality Control

[[Page 437]]

8.1........................... Sampling Ensure accurate
equipment leak- measurement of stack
check and gas flow rate,
calibration. sample volume.
10.0.......................... Analytical Ensure precision of
calibration. analytical results
within 5 percent.
------------------------------------------------------------------------

10.0 Calibration

Same as in Method 16, section 10, except SO2 is used
instead of H2S.

11.0 Analytical Procedure

11.1 Sample collection and analysis are concurrent for this method
(see section 8.3).
12.0 Data Analysis and Calculations
12.1 Nomenclature.

CSO2 = Sulfur dioxide concentration,
ppmv.
CTRS = Total reduced sulfur
concentration as determined by Equation 16B-1, ppmv.
d = Dilution factor, dimensionless.
N = Number of samples.

12.2 SO2 Concentration. Determine the concentration of
SO2, CSO2, directly from the
calibration curves. Alternatively, the concentration may be calculated
using the equation for the least-squares line.
12.3 TRS Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.299

12.4 Average TRS Concentration
[GRAPHIC] [TIFF OMITTED] TR17OC00.300

13.0 Method Performance.

13.1 Range and Sensitivity. Coupled with a GC using a 1-ml sample
size, the maximum limit of the FPD for SO2 is approximately
10 ppmv. This limit is extended by diluting the sample gas before
analysis or by reducing the sample aliquot size. For sources with
emission levels between 10 and 100 ppm, the measuring range can be best
extended by reducing the sample size.
13.2 GC/FPD Calibration and Precision. A series of three consecutive
injections of the sample calibration gas, at any dilution, must produce
results which do not vary by more than 5 percent from the mean of the
three injections.
13.3 Calibration Drift. The calibration drift determined from the
mean of the three injections made at the beginning and end of any run or
series of runs within a 24-hour period must not exceed 5 percent.
13.4 System Calibration Accuracy. Losses through the sample
transport system must be measured and a correction factor developed to
adjust the calibration accuracy to 100 percent.
13.5 Field tests between this method and Method 16A showed an
average difference of less than 4.0 percent. This difference was not
determined to be significant.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Same as in Method 16, section 16.0.
2. National Council of the Paper Industry for Air and Stream
Improvement, Inc, A Study of TRS Measurement Methods. Technical Bulletin
No. 434. New York, NY. May 1984. 12p.
3. Margeson, J.H., J.E. Knoll, and M.R. Midgett. A Manual Method for
TRS Determination. Draft available from the authors. Source Branch,
Quality Assurance Division, U.S. Environmental Protection Agency,
Research Triangle Park, NC 27711.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 438]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.301

Method 16C--Determination of Total Reduced Sulfur Emissions From
Stationary Sources

1.0 Scope and Application

What is Method 16C?

Method 16C is a procedure for measuring total reduced sulfur (TRS)
in stationary source emissions using a continuous instrumental analyzer.
Quality assurance and quality control requirements are included to
assure that you, the tester, collect data of known quality. You must
document your adherence to these specific requirements for equipment,
supplies, sample collection and analysis, calculations, and data
analysis. This method does not completely describe all equipment,
supplies, and sampling and analytical procedures you will need but
refers to

[[Page 439]]

other methods for some of the details. Therefore, to obtain reliable
results, you should also have a thorough knowledge of these additional
test methods which are found in appendix A to this part:
(a) Method 6C--Determination of Sulfur Dioxide Emissions from
Stationary Sources (Instrumental Analyzer Procedure)
(b) Method 7E--Determination of Nitrogen Oxides Emissions from
Stationary Sources (Instrumental Analyzer Procedure)
(c) Method 16A--Determination of Total Reduced Sulfur Emissions from
Stationary Sources (Impinger Technique)
1.1 Analytes. What does Method 16C determine?

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Total reduced sulfur including: N/A
Dimethyl disulfide (DMDS), [(CH3)2S2]..................... 62-49-20
Dimethyl sulfide (DMS), [(CH3)2S]......................... 75-18-3
Hydrogen sulfide (H2S).................................... 7783-06-4
Methyl mercaptan (MeSH), (CH4S)........................... 74-93-1
Reported as: Sulfur dioxide (SO2)........................... 7449-09-5
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for determining TRS
emissions from recovery furnaces (boilers), lime kilns, and smelt
dissolving tanks at kraft pulp mills, and from other sources when
specified in an applicable subpart of the regulations.
1.3 Data Quality Objectives. Adherence to the requirements described
in Method 16C will enhance the quality of the data obtained.

2.0 Summary of Method

2.1 An integrated gas sample is extracted from the stack. The
SO2 is removed selectively from the sample using a citrate
buffer solution. The TRS compounds are then thermally oxidized to
SO2 and determined as SO2 by an instrumental
analyzer. This method is a combination of the sampling procedures of
Method 16A and the analytical procedures of Method 6C (referenced in
Method 7E), with minor modifications to facilitate their use together.

3.0 Definitions

Analyzer calibration error, Calibration curve, Calibration gas, Low-
level gas, Mid-level gas, High-level gas, Calibration drift, Calibration
span, Data recorder, Direct calibration mode, Gas analyzer, Interference
check, Measurement system, Response time, Run, System calibration mode,
System performance check, and Test are the same as used in Methods 16A
and 6C.

4.0 Interferences

4.1 Reduced sulfur compounds other than those defined as TRS, if
present, may be measured by this method. Compounds like carbonyl
sulfide, which is partially oxidized to SO2 and may be
present in a lime kiln exit stack, would be a positive interferent.
Interferences may vary among instruments, and instrument-specific
interferences must be evaluated through the interference check.
4.2 Particulate matter from the lime kiln stack gas (primarily
calcium carbonate) can cause a negative bias if it is allowed to enter
the citrate scrubber; the particulate matter will cause the pH to rise
and H2S to be absorbed before oxidation. Proper use of the
particulate filter, described in section 6.1.3 of Method 16A, will
eliminate this interference.

5.0 Safety

5.1 Disclaimer. This method may involve hazardous materials,
operations, and equipment. This test method may not address all of the
safety problems associated with its use. It is the responsibility of the
user to establish appropriate safety and health practices before
performing this test method.
5.2 Hydrogen Sulfide. Hydrogen sulfide is a flammable, poisonous gas
with the odor of rotten eggs. Hydrogen sulfide is extremely hazardous
and can cause collapse, coma, and death within a few seconds of one or
two inhalations at sufficient concentrations. Low concentrations
irritate the mucous membranes and may cause nausea, dizziness, and
headache after exposure. It is the responsibility of the user of this
test method to establish appropriate safety and health practices.

6.0 Equipment and Supplies

What do I need for the measurement system?

The measurement system is similar to those applicable components in
Methods 16A and 6C. Modifications to the apparatus are accepted provided
the performance criteria in section 13.0 are met.
6.1 Probe. Teflon tubing, 6.4-mm (\1/4\ in.) diameter, sequentially
wrapped with heat-resistant fiber strips, a rubberized heat tape (plug
at one end), and heat-resistant adhesive tape. A flexible thermocouple
or other suitable temperature measuring device must be placed between
the Teflon tubing and the fiber strips so that the temperature can be
monitored to prevent softening of the probe. The probe must be sheathed
in stainless steel to provide in-stack rigidity. A series of bored-out
stainless steel fittings placed at the front of the sheath will prevent
moisture and particulate from entering between the probe and sheath. A
6.4-mm (\1/4\ in.) Teflon elbow (bored out) must be attached to the
inlet of the probe, and a 2.54 cm (1 in.) piece of Teflon tubing must be
attached at the open end of the elbow to permit the opening of the probe
to be turned away from the particulate stream; this will reduce the
amount of particulate drawn into the sampling train. The probe is
depicted in Figure 16A-2 of Method 16A.
6.2 Probe Brush. Nylon bristle brush with handle inserted into a
3.2-mm (\1/8\ in.) Teflon

[[Page 440]]

tubing. The Teflon tubing should be long enough to pass the brush
through the length of the probe.
6.3 Particulate Filter. 50-mm Teflon filter holder and a 1- to 2-
m porosity, Teflon filter (may be available through Savillex
Corporation, 5325 Highway 101, Minnetonka, Minnesota 55343, or other
suppliers of filters). The filter holder must be maintained in a hot box
at a temperature sufficient to prevent moisture condensation. A
temperature of 121 [deg]C (250 [deg]F) was found to be sufficient when
testing a lime kiln under sub-freezing ambient conditions.
6.4 SO2 Scrubber. Three 300-ml Teflon segmented impingers
connected in series with flexible, thick-walled, Teflon tubing.
(Impinger parts and tubing may be available through Savillex or other
suppliers.) The first two impingers contain 100 ml of citrate buffer,
and the third impinger is initially dry. The tip of the tube inserted
into the solution should be constricted to less than 3 mm (\1/8\ in.) ID
and should be immersed to a depth of at least 5 cm (2 in.).
6.5 Combustion Tube. Quartz glass tubing with an expanded combustion
chamber 2.54 cm (1 in.) in diameter and at least 30.5 cm (12 in.) long.
The tube ends should have an outside diameter of 0.6 cm (\1/4\ in.) and
be at least 15.3 cm (6 in.) long. This length is necessary to maintain
the quartz-glass connector near ambient temperature and thereby avoid
leaks. Alternative combustion tubes are acceptable provided they are
shown to combust TRS at concentrations encountered during tests.
6.6 Furnace. A furnace of sufficient size to enclose the combustion
chamber of the combustion tube with a temperature regulator capable of
maintaining the temperature at 800 100 [deg]C (1472 180 [deg]F). The
furnace operating temperature should be checked with a thermocouple to
ensure accuracy.
6.7 Sampling Pump. A leak-free pump is required to pull the sample
gas through the system at a flow rate sufficient to minimize the
response time of the measurement system and must be constructed of
material that is non-reactive to the gas it contacts. For dilution-type
measurement systems, an eductor pump may be used to create a vacuum that
draws the sample through a critical orifice at a constant rate.
6.8 Calibration Gas Manifold. The calibration gas manifold must
allow the introduction of calibration gases either directly to the gas
analyzer in direct calibration mode or into the measurement system, at
the probe, in system calibration mode, or both, depending upon the type
of system used. In system calibration mode, the system must be able to
flood the sampling probe and vent excess gas. Alternatively, calibration
gases may be introduced at the calibration valve following the probe.
Maintain a constant pressure in the gas manifold. For in-stack dilution-
type systems, a gas dilution subsystem is required to transport large
volumes of purified air to the sample probe, and a probe controller is
needed to maintain the proper dilution ratio.
6.9 Sample Gas Manifold. The sample gas manifold diverts a portion
of the sample to the analyzer, delivering the remainder to the by-pass
discharge vent. The manifold should also be able to introduce
calibration gases directly to the analyzer. The manifold must be made of
material that is non-reactive to SO2 and be configured to
safely discharge the bypass gas.
6.10 SO2 Analyzer. You must use an instrument that uses
an ultraviolet, non-dispersive infrared, fluorescence, or other
detection principle to continuously measure SO2 in the gas
stream provided it meets the performance specifications in section 13.0.
6.11 Data Recording. A strip chart recorder, computerized data
acquisition system, digital recorder, or data logger for recording
measurement data must be used.

7.0 Reagents and Standards

Note: Unless otherwise indicated, all reagents must conform to the
specifications established by the Committee on Analytical Reagents of
the American Chemical Society. When such specifications are not
available, the best available grade must be used.
7.1 Water. Deionized distilled water must conform to ASTM
Specification D 1193-77 or 91 Type 3 (incorporated by reference--see
Sec. 60.17). The KMnO4 test for oxidizable organic matter
may be omitted when high concentrations of organic matter are not
expected to be present.
7.2 Citrate Buffer. Dissolve 300 g of potassium citrate (or 284 g of
sodium citrate) and 41 g of anhydrous citric acid in 1 liter of water
(200 ml is needed per test). Adjust the pH to between 5.4 and 5.6 with
potassium citrate or citric acid, as required.
7.3 Calibration Gas. Refer to section 7.1 of Method 7E (as
applicable) for the calibration gas requirements. Example calibration
gas mixtures are listed below.
(a) SO2 in nitrogen (N2).
(b) SO2 in air.
(c) SO2 and carbon dioxide (CO2) in
N2.
(d) SO2 and oxygen (O2) in N2.
(e) SO2/CO2/O2 gas mixture in
N2.
(f) CO2/NOX gas mixture in N2.
(g) CO2/SO2/NOX gas mixture in
N2.

For fluorescence-based analyzers, the O2 and CO2
concentrations of the calibration gases as introduced to the analyzer
must be within 1.0 percent (absolute) O2 and 1.0 percent
(absolute) CO2 of the O2 and CO2
concentrations of the effluent samples as introduced to the analyzer.
Alternatively, for fluorescence-based analyzers, use calibration blends
of SO2 in air and the nomographs provided by

[[Page 441]]

the vendor to determine the quenching correction factor (the effluent
O2 and CO2 concentrations must be known). This
requirement does not apply to ambient-level fluorescence analyzers that
are used in conjunction with sample dilution systems. Alternatively,
H2S in O2 or air may be used to calibrate the
analyzer through the tube furnace.
7.4 System Performance Check Gas. You must use H2S (100
ppmv or less) stored in aluminum cylinders with the concentration
certified by the manufacturer. Hydrogen sulfide in nitrogen is more
stable than H2S in air, but air may be used as the balance
gas.

Note: Alternatively, H2S recovery gas generated from a
permeation device gravimetrically calibrated and certified at some
convenient operating temperature may be used. The permeation rate of the
device must be such that at the appropriate dilution gas flow rate, an
H2S concentration can be generated in the range of the stack
gas or within 20 percent of the emission standard.

7.5 Interference Check. Examples of test gases for the interference
check are listed in Table 7E-3 of Method 7E.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Pre-sampling Tests. Before measuring emissions, perform the
following procedures:
(a) Calibration gas verification,
(b) Calibration error test,
(c) System performance check,
(d) Verification that the interference check has been satisfied.
8.1.1 Calibration Gas Verification. Obtain a certificate from the
gas manufacturer documenting the quality of the gas. Confirm that the
manufacturer certification is complete and current. Ensure that your
calibration gas certifications have not expired. This documentation
should be available on-site for inspection. To the extent practicable,
select a high-level gas concentration that will result in the measured
emissions being between 20 and 100 percent of the calibration span.
8.1.2 Analyzer Calibration Error Test. After you have assembled,
prepared, and calibrated your sampling system and analyzer, you must
conduct a 3-point analyzer calibration error test before the first run
and again after any failed system performance check or failed drift test
to ensure the calibration is acceptable. Introduce the low-, mid-, and
high-level calibration gases sequentially to the analyzer in direct
calibration mode. For each calibration gas, calculate the analyzer
calibration error using Equation 16C-1 in section 12.2. The calibration
error for the low-, mid-, and high-level gases must not exceed 5.0
percent or 0.5 ppmv. If the calibration error specification is not met,
take corrective action and repeat the test until an acceptable 3-point
calibration is achieved.
8.1.3 System Performance Check. A system performance check is done
(1) to validate the sampling train components and procedure (prior to
testing), and (2) to validate a test run (after a run). You must conduct
a performance check in the field prior to testing, and after each 3-hour
run or after three 1-hour runs. A performance check consists of sampling
and analyzing a known concentration of H2S (system
performance check gas) and comparing the analyzed concentration to the
known concentration. To conduct the system performance check, mix the
system performance check gas (Section 7.4) and ambient air, that has
been conditioned to remove moisture and sulfur-containing gases, in a
dilution system such as that shown in Figure 16A-3 of Method 16A.
Alternatively, ultra-high purity (UHP) grade air may be used. Adjust the
gas flow rates to generate an H2S concentration in the range
of the stack gas or within 20 percent of the applicable standard and an
oxygen concentration greater than 1 percent at a total flow rate of at
least 2.5 liters/min (5.3 ft3/hr). Use Equation 16A-3 from Method 16A to
calculate the concentration of system performance check gas generated.
Calibrate the flow rate from both gas sources with a soap bubble flow
meter so that the diluted concentration of H2S can be
accurately calculated. Alternatively, mass flow controllers with
documented calibrations may be used if UHP grade air is being used.
Sample duration should be sufficiently long to ensure a stable response
from the analyzer. Analyze in the same manner as the emission samples.
Collect the sample through the probe of the sampling train using a
manifold or other suitable device that will ensure extraction of a
representative sample. The TRS sample concentration measured between
system performance checks is corrected by the average of the pre- and
post-system performance checks.
8.1.4 Interference Check. Same as in Method 7E, section 8.2.7.
8.2 Measurement System Preparation.
8.2.1 For the SO2 scrubber, measure 100 ml of citrate
buffer into the first and second impingers; leave the third impinger
empty. Immerse the impingers in an ice bath, and locate them as close as
possible to the filter heat box. The connecting tubing should be free of
loops. Maintain the probe and filter temperatures sufficiently high to
prevent moisture condensation, and monitor with a suitable temperature
sensor. Prepare the oxidation furnace and maintain at 800 100 [deg]C
(1472 180 [deg]F).
8.2.2 Citrate Scrubber Conditioning Procedure. Condition the citrate
buffer scrubbing solution by pulling stack gas through the Teflon
impingers as described in section 8.4.1.

[[Page 442]]

8.3 Pretest Procedures. After the complete measurement system has
been set up at the site and deemed to be operational, the following
procedures must be completed before sampling is initiated.
8.3.1 Leak-Check. Appropriate leak-check procedures must be employed
to verify the integrity of all components, sample lines, and
connections. For components upstream of the sample pump, attach the
probe end of the sample line to a manometer or vacuum gauge, start the
pump and pull a vacuum greater than 50 mm (2 in.) Hg, close off the pump
outlet, and then stop the pump and ascertain that there is no leak for 1
minute. For components after the pump, apply a slight positive pressure
and check for leaks by applying a liquid (detergent in water, for
example) at each joint. Bubbling indicates the presence of a leak.
8.3.2 Initial System Performance Check. A system performance check
using the test gas (Section 7.4) is performed prior to testing to
validate the sampling train components and procedure.
8.4 Sample Collection and Analysis.
8.4.1 After performing the required pretest procedures described in
section 8.1, insert the sampling probe into the test port ensuring that
no dilution air enters the stack through the port. Condition the
sampling system and citrate buffer solution for a minimum of 15 minutes
before beginning analysis. Begin sampling and analysis. A source test
consists of three test runs. A test run shall consist of a single sample
collected over a 3-hour period or three separate 1-hour samples
collected over a period not to exceed six hours.
8.5 Post-Run Evaluations.
8.5.1 System Performance Check. Perform a post-run system
performance check before replacing the citrate buffer solution and
particulate filter and before the probe is cleaned. The check results
must not exceed the 100 20 percent limit set forth in section 13.2. If
this limit is exceeded, the intervening run is considered invalid.
However, if the recovery efficiency is not in the 100 20 percent range,
but the results do not affect the compliance or noncompliance status of
the affected facility, the Administrator may decide to accept the
results of the compliance test.
8.5.2 Calibration Drift. After a run or series of runs, not to
exceed a 24-hour period after initial calibration, perform a calibration
drift test using a calibration gas (preferably the level that best
approximates the sample concentration) in direct calibration mode. This
drift must not differ from the initial calibration error percent by more
than 3.0 percent or 0.5 ppm. If the drift exceeds this limit, the
intervening run or runs are considered valid, but a new analyzer
calibration error test must be performed and passed before continuing
sampling.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.1.2......................... Analyzer Establishes initial
calibration error calibration
test. accuracy within
5.0%.
8.1.3, 8.5.1.................. System performance Ensures accuracy of
check. sampling/
analytical
procedure to 100
20%.
8.5.2......................... Calibration drift Ensures calibration
test. drift is within
3.0%.
8.1.4......................... Interference check. Checks for
analytical
interferences.
8.3........................... Sampling equipment Ensures accurate
leak-check. measurement of
sample gas flow
rate, sample
volume.
------------------------------------------------------------------------

10.0 Calibration

10.1 Calibrate the system using the gases described in section 7.3.
Perform the initial 3-point calibration error test as described in
section 8.1.2 before you start the test. The specification in section 13
must be met. Conduct an initial system performance test described in
section 8.1.3 as well before the test to validate the sampling
components and procedures before sampling. After the test commences, a
system performance check is required after each run. You must include a
copy of the manufacturer's certification of the calibration gases used
in the testing as part of the test report. This certification must
include the 13 documentation requirements in the EPA Traceability
Protocol for Assay and Certification of Gaseous Calibration Standards,
September 1997, as amended August 25, 1999.

11.0 Analytical Procedure

Because sample collection and analysis are performed together (see
section 8.0), additional discussion of the analytical procedure is not
necessary.

12.0 Calculations and Data Analysis

12.1 Nomenclature.

ACE = Analyzer calibration error, percent of calibration span.
CD = Calibration drift, percent.
CDir = Measured concentration of a calibration gas (low, mid,
or high) when introduced in direct calibration mode, ppmv.
CH2S = Concentration of the system performance check gas,
ppmv H2S.

[[Page 443]]

CS = Measured concentration of the system performance gas
when introduced in system calibration mode, ppmv
H2S.
CV = Manufacturer certified concentration of a calibration
gas (low, mid, or high), ppmv SO2.
CSO2 = Unadjusted sample SO2 concentration, ppmv.
CTRS = Total reduced sulfur concentration corrected for
system performance, ppmv.
DF = Dilution system (if used) dilution factor, dimensionless.
SP = System performance, percent.

12.2 Analyzer Calibration Error. Use Equation 16C-1 to calculate the
analyzer calibration error for the low-, mid-, and high-level
calibration gases.
[GRAPHIC] [TIFF OMITTED] TR30JY12.175

12.3 System Performance Check. Use Equation 16C-2 to calculate the
system performance.
[GRAPHIC] [TIFF OMITTED] TR30JY12.176

12.4 Calibration Drift. Use Equation 16C-3 to calculate the
calibration drift at a single concentration level after a run or series
of runs (not to exceed a 24-hr period) from initial calibration. Compare
the single-level calibration gas error (ACEn) to the original
error obtained for that gas in the initial analyzer calibration error
test (ACEi).
[GRAPHIC] [TIFF OMITTED] TR30JY12.177

12.5 TRS Concentration as SO2. For each sample or test
run, calculate the arithmetic average of SO2 concentration
values (e.g., 1-minute averages). Then calculate the sample TRS
concentration by adjusting the average value of CSO2 for
system performance using Equation 16C-4.
[GRAPHIC] [TIFF OMITTED] TR27FE14.016

13.0 Method Performance

13.1 Analyzer Calibration Error. At each calibration gas level (low,
mid, and high), the calibration error must either not exceed 5.0 percent
of the calibration gas concentration or CDir-Cv
must be 0.5 ppmv.
13.2 System Performance. Each system performance check must not
deviate from the system performance gas concentration by more than 20
percent. Alternatively, the results are acceptable if Cs-
CH2S is 0.5 ppmv.
13.3 Calibration Drift. The calibration drift at the end of any run
or series of runs within a 24-hour period must not differ by more than
3.0 percent from the original ACE at the test concentration level or
ACEi-ACEn must not exceed 0.5 ppmv.
13.4 Interference Check. For the analyzer, the total interference
response (i.e., the sum of the interference responses of all tested
gaseous components) must not be greater than 2.5 percent of the
calibration span. Any

[[Page 444]]

interference is also acceptable if the sum of the responses does not
exceed 0.5 ppmv for a calibration span of 5 to 10 ppmv, or 0.2 ppmv for
a calibration span <5 ppmv.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. The references are the same as in section 16.0 of Method 16, section
17.0 of Method 16A, and section 17.0 of Method 6C.
2. National Council of the Paper Industry for Air and Stream
Improvement, Inc,. A Study of TRS Measurement Methods.
Technical Bulletin No. 434. New York, NY. May 1984. 12p.
3. Margeson, J.H., J.E. Knoll, and M.R. Midgett. A Manual Method for TRS
Determination. Draft available from the authors. Source
Branch, Quality Assurance Division, U.S. Environmental
Protection Agency, Research Triangle Park, NC 27711.

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 17--Determination of Particulate Matter Emissions From Stationary
Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 5.

1.0 Scope and Application

1.1 Analyte. Particulate matter (PM). No CAS number assigned.

Note: Particulate matter is not an absolute quantity. It is a
function of temperature and pressure. Therefore, to prevent variability
in PM emission regulations and/or associated test methods, the
temperature and pressure at which PM is to be measured must be carefully
defined. Of the two variables (i.e., temperature and pressure),
temperature has the greater effect upon the amount of PM in an effluent
gas stream; in most stationary source categories, the effect of pressure
appears to be negligible. In Method 5, 120 [deg]C (248 [deg]F) is
established as a nominal reference temperature. Thus, where Method 5 is
specified in an applicable subpart of the standard, PM is defined with
respect to temperature. In order to maintain a collection temperature of
120 [deg]C (248 [deg]F), Method 5 employs a heated glass sample probe
and a heated filter holder. This equipment is somewhat cumbersome and
requires care in its operation. Therefore, where PM concentrations (over
the normal range of temperature associated with a specified source
category) are known to be independent of temperature, it is desirable to
eliminate the glass probe and the heating systems, and to sample at
stack temperature.

1.2 Applicability. This method is applicable for the determination
of PM emissions, where PM concentrations are known to be independent of
temperature over the normal range of temperatures characteristic of
emissions from a specified source category. It is intended to be used
only when specified by an applicable subpart of the standards, and only
within the applicable temperature limits (if specified), or when
otherwise approved by the Administrator. This method is not applicable
to stacks that contain liquid droplets or are saturated with water
vapor. In addition, this method shall not be used as written if the
projected cross-sectional area of the probe extension-filter holder
assembly covers more than 5 percent of the stack cross-sectional area
(see section 8.1.2).
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Particulate matter is withdrawn isokinetically from the source
and collected on a glass fiber filter maintained at stack temperature.
The PM mass is determined gravimetrically after the removal of
uncombined water.

3.0 Definitions

Same as Method 5, section 3.0.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Sampling Train. A schematic of the sampling train used in this
method is shown in Figure 17-1. The sampling train components and
operation and maintenance are very similar to Method 5, which should be
consulted for details.
6.1.1 Probe Nozzle, Differential Pressure Gauge, Metering System,
Barometer, Gas Density Determination Equipment. Same as in Method 5,
sections 6.1.1, 6.1.4, 6.1.8, 6.1.9, and 6.1.10, respectively.

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6.1.2 Filter Holder. The in-stack filter holder shall be constructed
of borosilicate or quartz glass, or stainless steel. If a gasket is
used, it shall be made of silicone rubber, Teflon, or stainless steel.
Other holder and gasket materials may be used, subject to the approval
of the Administrator. The filter holder shall be designed to provide a
positive seal against leakage from the outside or around the filter.
6.1.3 Probe Extension. Any suitable rigid probe extension may be
used after the filter holder.
6.1.4 Pitot Tube. Same as in Method 5, section 6.1.3.
6.1.4.1 It is recommended (1) that the pitot tube have a known
baseline coefficient, determined as outlined in section 10 of Method 2;
and (2) that this known coefficient be preserved by placing the pitot
tube in an interference-free arrangement with respect to the sampling
nozzle, filter holder, and temperature sensor (see Figure 17-1). Note
that the 1.9 cm (\3/4\-in.) free-space between the nozzle and pitot tube
shown in Figure 17-1, is based on a 1.3 cm (\1/2\-in.) ID nozzle. If the
sampling train is designed for sampling at higher flow rates than that
described in APTD-0581, thus necessitating the use of larger sized
nozzles, the free-space shall be 1.9 cm (\3/4\-in.) with the largest
sized nozzle in place.
6.1.4.2 Source-sampling assemblies that do not meet the minimum
spacing requirements of Figure 17-1 (or the equivalent of these
requirements, e.g., Figure 2-4 of Method 2) may be used; however, the
pitot tube coefficients of such assemblies shall be determined by
calibration, using methods subject to the approval of the Administrator.
6.1.5 Condenser. It is recommended that the impinger system or
alternatives described in Method 5 be used to determine the moisture
content of the stack gas. Flexible tubing may be used between the probe
extension and condenser. Long tubing lengths may affect the moisture
determination.
6.2 Sample Recovery. Probe-liner and probe-nozzle brushes, wash
bottles, glass sample storage containers, petri dishes, graduated
cylinder and/or balance, plastic storage containers, funnel and rubber
policeman, funnel. Same as in Method 5, sections 6.2.1 through 6.2.8,
respectively.
6.3 Sample Analysis. Glass weighing dishes, desiccator, analytical
balance, balance, beakers, hygrometer, temperature sensor. Same as in
Method 5, sections 6.3.1 through 6.3.7, respectively.

7.0 Reagents and Standards

7.1 Sampling. Filters, silica gel, water, crushed ice, stopcock
grease. Same as in Method 5, sections 7.1.1, 7.1.2, 7.1.3, 7.1.4, and
7.1.5, respectively. Thimble glass fiber filters may also be used.
7.2 Sample Recovery. Acetone (reagent grade). Same as in Method 5,
section 7.2.
7.3 Sample Analysis. Acetone and Desiccant. Same as in Method 5,
sections 7.3.1 and 7.3.2, respectively.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sampling.
8.1.1 Pretest Preparation. Same as in Method 5, section 8.1.1.
8.1.2 Preliminary Determinations. Same as in Method 5, section
8.1.2, except as follows: Make a projected-area model of the probe
extension-filter holder assembly, with the pitot tube face openings
positioned along the centerline of the stack, as shown in Figure 17-2.
Calculate the estimated cross-section blockage, as shown in Figure 17-2.
If the blockage exceeds 5 percent of the duct cross sectional area, the
tester has the following options exist: (1) a suitable out-of-stack
filtration method may be used instead of in-stack filtration; or (2) a
special in-stack arrangement, in which the sampling and velocity
measurement sites are separate, may be used; for details concerning this
approach, consult with the Administrator (see also Reference 1 in
section 17.0). Select a probe extension length such that all traverse
points can be sampled. For large stacks, consider sampling from opposite
sides of the stack to reduce the length of probes.
8.1.3 Preparation of Sampling Train. Same as in Method 5, section
8.1.3, except the following: Using a tweezer or clean disposable
surgical gloves, place a labeled (identified) and weighed filter in the
filter holder. Be sure that the filter is properly centered and the
gasket properly placed so as not to allow the sample gas stream to
circumvent the filter. Check filter for tears after assembly is
completed. Mark the probe extension with heat resistant tape or by some
other method to denote the proper distance into the stack or duct for
each sampling point. Assemble the train as in Figure 17-1, using a very
light coat of silicone grease on all ground glass joints and greasing
only the outer portion (see APTD-0576) to avoid possibility of
contamination by the silicone grease. Place crushed ice around the
impingers.
8.1.4 Leak-Check Procedures. Same as in Method 5, section 8.1.4,
except that the filter holder is inserted into the stack during the
sampling train leak-check. To do this, plug the inlet to the probe
nozzle with a material that will be able to withstand the stack
temperature. Insert the filter holder into the stack and wait
approximately 5 minutes (or longer, if necessary) to allow the system to
come to equilibrium with the temperature of the stack gas stream.
8.1.5 Sampling Train Operation. The operation is the same as in
Method 5. Use a data sheet such as the one shown in Figure 5-3 of Method
5, except that the filter holder temperature is not recorded.

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8.1.6 Calculation of Percent Isokinetic. Same as in Method 5,
section 12.11.
8.2 Sample Recovery.
8.2.1 Proper cleanup procedure begins as soon as the probe extension
assembly is removed from the stack at the end of the sampling period.
Allow the assembly to cool.
8.2.2 When the assembly can be safely handled, wipe off all external
particulate matter near the tip of the probe nozzle and place a cap over
it to prevent losing or gaining particulate matter. Do not cap off the
probe tip tightly while the sampling train is cooling down as this would
create a vacuum in the filter holder, forcing condenser water backward.
8.2.3 Before moving the sample train to the cleanup site, disconnect
the filter holder-probe nozzle assembly from the probe extension; cap
the open inlet of the probe extension. Be careful not to lose any
condensate, if present. Remove the umbilical cord from the condenser
outlet and cap the outlet. If a flexible line is used between the first
impinger (or condenser) and the probe extension, disconnect the line at
the probe extension and let any condensed water or liquid drain into the
impingers or condenser. Disconnect the probe extension from the
condenser; cap the probe extension outlet. After wiping off the silicone
grease, cap off the condenser inlet. Ground glass stoppers, plastic
caps, or serum caps (whichever are appropriate) may be used to close
these openings.
8.2.4 Transfer both the filter holder-probe nozzle assembly and the
condenser to the cleanup area. This area should be clean and protected
from the wind so that the chances of contaminating or losing the sample
will be minimized.
8.2.5 Save a portion of the acetone used for cleanup as a blank.
Take 200 ml of this acetone from the wash bottle being used and place it
in a glass sample container labeled ``acetone blank.'' Inspect the train
prior to and during disassembly and not any abnormal conditions. Treat
the sample as discussed in Method 5, section 8.2.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization

The calibrations of the probe nozzle, pitot tube, metering system,
temperature sensors, and barometer are the same as in Method 5, sections
10.1 through 10.3, 10.5, and 10.6, respectively.

11.0 Analytical Procedure

Same as in Method 5, section 11.0. Analytical data should be
recorded on a form similar to that shown in Figure 5-6 of Method 5.

12.0 Data Analysis and Calculations.

Same as in Method 5, section 12.0.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

Same as in Method 5, section 16.0.

17.0 References

Same as in Method 5, section 17.0, with the addition of the
following:

1. Vollaro, R.F. Recommended Procedure for Sample Traverses in Ducts
Smaller than 12 Inches in Diameter. U.S. Environmental Protection
Agency, Emission Measurement Branch. Research Triangle Park, NC.
November 1976.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

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[GRAPHIC] [TIFF OMITTED] TR17OC00.302

[[Page 448]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.303

Method 18--Measurement of Gaseous Organic Compound Emissions By Gas
Chromatography

[[Page 449]]

should be exercised in the area of safety concerning choice of equipment
and operation in potentially explosive atmospheres.

1.0 Scope and Application

1.1 Analyte. Total gaseous organic compounds.
1.2 Applicability.
1.2.1 This method is designed to measure gaseous organics emitted
from an industrial source. While designed for ppm level sources, some
detectors are quite capable of detecting compounds at ambient levels,
e.g., ECD, ELCD, and helium ionization detectors. Some other types of
detectors are evolving such that the sensitivity and applicability may
well be in the ppb range in only a few years.
1.2.2 This method will not determine compounds that (1) are
polymeric (high molecular weight), (2) can polymerize before analysis,
or (3) have very low vapor pressures at stack or instrument conditions.
1.3 Range. The lower range of this method is determined by the
sampling system; adsorbents may be used to concentrate the sample, thus
lowering the limit of detection below the 1 part per million (ppm)
typically achievable with direct interface or bag sampling. The upper
limit is governed by GC detector saturation or column overloading; the
upper range can be extended by dilution of sample with an inert gas or
by using smaller volume gas sampling loops. The upper limit can also be
governed by condensation of higher boiling compounds.
1.4 Sensitivity. The sensitivity limit for a compound is defined as
the minimum detectable concentration of that compound, or the
concentration that produces a signal-to-noise ratio of three to one. The
minimum detectable concentration is determined during the presurvey
calibration for each compound.

2.0 Summary of Method

The major organic components of a gas mixture are separated by gas
chromatography (GC) and individually quantified by flame ionization,
photoionization, electron capture, or other appropriate detection
principles. The retention times of each separated component are compared
with those of known compounds under identical conditions. Therefore, the
analyst confirms the identity and approximate concentrations of the
organic emission components beforehand. With this information, the
analyst then prepares or purchases commercially available standard
mixtures to calibrate the GC under conditions identical to those of the
samples. The analyst also determines the need for sample dilution to
avoid detector saturation, gas stream filtration to eliminate
particulate matter, and prevention of moisture condensation.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Resolution interferences that may occur can be eliminated by
appropriate GC column and detector choice or by shifting the retention
times through changes in the column flow rate and the use of temperature
programming.
4.2 The analytical system is demonstrated to be essentially free
from contaminants by periodically analyzing blanks that consist of
hydrocarbon-free air or nitrogen.
4.3 Sample cross-contamination that occurs when high-level and low-
level samples or standards are analyzed alternately is best dealt with
by thorough purging of the GC sample loop between samples.
4.4 To assure consistent detector response, calibration gases are
contained in dry air. To adjust gaseous organic concentrations when
water vapor is present in the sample, water vapor concentrations are
determined for those samples, and a correction factor is applied.
4.5 The gas chromatograph run time must be sufficient to clear all
eluting peaks from the column before proceeding to the next run (in
order to prevent sample carryover).

5.0 Safety

6.0 Equipment and Supplies

6.1 Equipment needed for the presurvey sampling procedure can be
found in section 16.1.1.
6.2 Equipment needed for the integrated bag sampling and analysis
procedure can be found in section 8.2.1.1.1.
6.3 Equipment needed for direct interface sampling and analysis can
be found in section 8.2.2.1.
6.4 Equipment needed for the dilution interface sampling and
analysis can be found in section 8.2.3.1.
6.5 Equipment needed for adsorbent tube sampling and analysis can be
found in section 8.2.4.1.

7.0 Reagents and Standards

7.1 Reagents needed for the presurvey sampling procedure can be
found in section 16.1.2.

[[Page 450]]

8.0 Sample Collection, Preservation, Storage, and Transport

8.2 Final Sampling and Analysis Procedure. Considering safety (flame
hazards) and the source conditions, select an appropriate sampling and
analysis procedure (Section 8.2.1, 8.2.2, 8.2.3 or 8.2.4). In situations
where a hydrogen flame is a hazard and no intrinsically safe GC is
suitable, use the flexible bag collection technique or an adsorption
technique.
8.2.1 Integrated Bag Sampling and Analysis.
8.2.1.1 Evacuated Container Sampling Procedure. In this procedure,
the bags are filled by evacuating the rigid air-tight container holding
the bags. Use a field sample data sheet as shown in Figure 18-10.
Collect triplicate samples from each sample location.
8.2.1.1.1 Apparatus.
8.2.1.1.1.1 Probe. Stainless steel, Pyrex glass, or Teflon tubing
probe, according to the duct temperature, with Teflon tubing of
sufficient length to connect to the sample bag. Use stainless steel or
Teflon unions to connect probe and sample line.
8.2.1.1.1.2 Quick Connects. Male (2) and female (2) of stainless
steel construction.
8.2.1.1.1.3 Needle Valve. To control gas flow.
8.2.1.1.1.4 Pump. Leakless Teflon-coated diaphragm-type pump or
equivalent. To deliver at least 1 liter/min.
8.2.1.1.1.5 Charcoal Adsorption Tube. Tube filled with activated
charcoal, with glass wool plugs at each end, to adsorb organic vapors.
8.2.1.1.1.6 Flowmeter. 0 to 500-ml flow range; with manufacturer's
calibration curve.
8.2.1.1.2 Sampling Procedure. To obtain a sample, assemble the
sample train as shown in Figure 18-9. Leak-check both the bag and the
container. Connect the vacuum line from the needle valve to the Teflon
sample line from the probe. Place the end of the probe at the centroid
of the stack or at a point no closer to the walls than 1 in., and start
the pump. Set the flow rate so that the final volume of the sample is
approximately 80 percent of the bag capacity. After allowing sufficient
time to purge the line several times, connect the vacuum line to the
bag, and evacuate until the rotameter indicates no flow. Then position
the sample and vacuum lines for sampling, and begin the actual sampling,
keeping the rate proportional to the stack velocity. As a precaution,
direct the gas exiting the rotameter away from sampling personnel. At
the end of the sample period, shut off the pump, disconnect the sample
line from the bag, and disconnect the vacuum line from the bag
container. Record the source temperature, barometric pressure, ambient
temperature, sampling flow rate, and initial and final sampling time on
the data sheet shown in Figure 18-10. Protect the bag and its container
from sunlight. Record the time lapsed between sample collection and
analysis, and then conduct the recovery procedure in Section 8.4.2.
8.2.1.2 Direct Pump Sampling Procedure. Follow 8.2.1.1, except place
the pump and needle valve between the probe and the bag. Use a pump and
needle valve constructed of inert material not affected by the stack
gas. Leak-check the system, and then purge with stack gas before
connecting to the previously evacuated bag.
8.2.1.3 Explosion Risk Area Bag Sampling Procedure. Follow 8.2.1.1
except replace the pump with another evacuated can (see Figure 18-9a).
Use this method whenever there is a possibility of an explosion due to
pumps, heated probes, or other flame producing equipment.
8.2.1.4 Other Modified Bag Sampling Procedures. In the event that
condensation is observed in the bag while collecting the sample and a
direct interface system cannot be used, heat the bag during collection
and maintain it at a suitably elevated temperature during all subsequent
operations. (Note: Take care to leak-check the system prior to the
dilutions so as not to create a potentially explosive atmosphere.) As an
alternative, collect the sample gas, and simultaneously dilute it in the
bag.
8.2.1.4.1 First Alternative Procedure. Heat the box containing the
sample bag to 120 [deg]C (5 [deg]C). Then transport the bag as rapidly
as possible to the analytical area while maintaining the heating, or
cover the box with an insulating blanket. In the analytical area, keep
the box heated to 120 [deg]C (5 [deg]C) until analysis. Be sure that
the method of heating the box and the control for the heating circuit
are compatible with the safety restrictions required in each area.
8.2.1.4.2 Second Alternative Procedure. Prefill the bag with a known
quantity of inert gas. Meter the inert gas into the bag according to the
procedure for the preparation of gas concentration standards of volatile
liquid materials (Section 10.1.2.2), but eliminate the midget impinger
section. Take the partly filled bag to the source, and meter the source
gas into the bag through heated sampling lines and a heated flowmeter,
or Teflon positive displacement pump. Verify the dilution factors before
sampling each bag through dilution and analysis of gases of known
concentration.
8.2.1.5 Analysis of Bag Samples.
8.2.1.5.1 Apparatus. Same as section 8.1. A minimum of three gas
standards are required.
8.2.1.5.2 Procedure.
8.2.1.5.2.1 Establish proper GC operating conditions as described in
section 10.2, and record all data listed in Figure 18-7. Prepare the GC
so that gas can be drawn through the sample valve. Flush the sample loop
with

[[Page 451]]

calibration gas mixture, and activate the valve (sample pressure at the
inlet to the GC introduction valve should be similar during calibration
as during actual sample analysis). Obtain at least three chromatograms
for the mixture. The results are acceptable when the peak areas for the
three injections agree to within 5 percent of their average. If they do
not agree, run additional samples or correct the analytical techniques
until this requirement is met. Then analyze the other two calibration
mixtures in the same manner. Prepare a calibration curve as described in
section 10.2.
8.2.1.5.2.2 Analyze the three source gas samples by connecting each
bag to the sampling valve with a piece of Teflon tubing identified with
that bag. Analyze each bag sample three times. Record the data in Figure
18-11. If certain items do not apply, use the notation ``N.A.'' If the
bag has been maintained at an elevated temperature as described in
section 8.2.1.4, determine the stack gas water content by Method 4.
After all samples have been analyzed, repeat the analysis of the mid-
level calibration gas for each compound. Compare the average response
factor of the pre- and post-test analysis for each compound. If they
differ by >5percent, analyze the other calibration gas levels for that
compound, and prepare a calibration curve using all the pre- and post-
test calibration gas mixture values. If the two response factor averages
(pre-and post-test) differ by less than 5 percent from their mean value,
the tester has the option of using only the pre-test calibration curve
to generate the concentration values.
8.2.1.5.2.3 Analyze the two field audit samples as described in
Section 9.2 by connecting each bag containing an audit gas mixture to
the sampling valve. Calculate the results; record and report the data to
the audit supervisor.
8.2.1.6 Determination of Bag Water Vapor Content. Measure the
ambient temperature and barometric pressure near the bag. From a water
saturation vapor pressure table, determine and record the water vapor
content of the bag as a decimal figure. (Assume the relative humidity to
be 100 percent unless a lesser value is known.) If the bag has been
maintained at an elevated temperature as described in section 8.2.1.4,
determine the stack gas water content by Method 4.
8.2.1.8 Emission Calculations. From the calibration curve described
in section 8.2.1.5, select the value of Cs that corresponds
to the peak area. Calculate the concentration Cc in ppm, dry
basis, of each organic in the sample using Equation 18-5 in section
12.6.
8.2.2 Direct Interface Sampling and Analysis Procedure. The direct
interface procedure can be used provided that the moisture content of
the gas does not interfere with the analysis procedure, the physical
requirements of the equipment can be met at the site, and the source gas
concentration falls within the linear range of the detector. Adhere to
all safety requirements with this method.
8.2.2.1 Apparatus.
8.2.2.1.1 Probe. Constructed of stainless steel, Pyrex glass, or
Teflon tubing as dictated by duct temperature and reactivity of target
compounds. A filter or glass wool plug may be needed if particulate is
present in the stack gas. If necessary, heat the probe with heating tape
or a special heating unit capable of maintaining a temperature greater
than 110 [deg]C.
8.2.2.1.2 Sample Lines. 6.4-mm OD (or other diameter as needed)
Teflon lines, heat-traced to prevent condensation of material (greater
than 110 [deg]C).
8.2.2.1.3 Quick Connects. To connect sample line to gas sampling
valve on GC instrument and to pump unit used to withdraw source gas. Use
a quick connect or equivalent on the cylinder or bag containing
calibration gas to allow connection of the calibration gas to the gas
sampling valve.
8.2.2.1.4 Thermocouple Readout Device. Potentiometer or digital
thermometer, to measure source temperature and probe temperature.
8.2.2.1.5 Heated Gas Sampling Valve. Of two-position, six-port
design, to allow sample loop to be purged with source gas or to direct
source gas into the GC instrument.
8.2.2.1.6 Needle Valve. To control gas sampling rate from the
source.
8.2.2.1.7 Pump. Leakless Teflon-coated diaphragm-type pump or
equivalent, capable of at least 1 liter/minute sampling rate.
8.2.2.1.8 Flowmeter. Of suitable range to measure sampling rate.
8.2.2.1.9 Charcoal Adsorber. To adsorb organic vapor vented from the
source to prevent exposure of personnel to source gas.
8.2.2.1.10 Gas Cylinders. Carrier gas, oxygen and fuel as needed to
run GC and detector.
8.2.2.1.11 Gas Chromatograph. Capable of being moved into the field,
with detector, heated gas sampling valve, column required to complete
separation of desired components, and option for temperature
programming.
8.2.2.1.12 Recorder/Integrator. To record results.
8.2.2.2 Procedure. Calibrate the GC using the procedures in section
8.2.1.5.2.1. To obtain a stack gas sample, assemble the sampling system
as shown in Figure 18-12. Make sure all connections are tight. Turn on
the probe and sample line heaters. As the temperature of the probe and
heated line approaches the target temperature as indicated on the
thermocouple readout device, control the heating to maintain a
temperature greater than 110 [deg]C. Conduct a 3-point calibration of
the GC by analyzing each gas mixture in triplicate. Generate a
calibration curve. Place the inlet of the probe at the

[[Page 452]]

centroid of the duct, or at a point no closer to the walls than 1 m, and
draw source gas into the probe, heated line, and sample loop. After
thorough flushing, analyze the stack gas sample using the same
conditions as for the calibration gas mixture. For each run, sample,
analyze, and record five consecutive samples. A test consists of three
runs (five samples per run times three runs, for a total of fifteen
samples). After all samples have been analyzed, repeat the analysis of
the mid-level calibration gas for each compound. For each calibration
standard, compare the pre- and post-test average response factors (RF)
for each compound. If the two calibration RF values (pre- and post-
analysis) differ by more than 5 percent from their mean value, then
analyze the other calibration gas levels for that compound and determine
the stack gas sample concentrations by comparison to both calibration
curves (this is done by preparing a calibration curve using all the pre-
and post-test calibration gas mixture values.) If the two calibration RF
values differ by less than 5 percent from their mean value, the tester
has the option of using only the pre-test calibration curve to generate
the concentration values. Record this calibration data and the other
required data on the data sheet shown in Figure 18-11, deleting the
dilution gas information.
Note: Take care to draw all samples and calibration mixtures through
the sample loop at the same pressure.
8.2.2.3 Determination of Stack Gas Moisture Content. Use Method 4 to
measure the stack gas moisture content.
8.2.2.5 Emission Calculations. Same as section 8.2.1.8.
8.2.3 Dilution Interface Sampling and Analysis Procedure. Source
samples that contain a high concentration of organic materials may
require dilution prior to analysis to prevent saturating the GC
detector. The apparatus required for this direct interface procedure is
basically the same as that described in the section 8.2.2, except a
dilution system is added between the heated sample line and the gas
sampling valve. The apparatus is arranged so that either a 10:1 or 100:1
dilution of the source gas can be directed to the chromatograph. A pump
of larger capacity is also required, and this pump must be heated and
placed in the system between the sample line and the dilution apparatus.
8.2.3.1 Apparatus. The equipment required in addition to that
specified for the direct interface system is as follows:
8.2.3.1.1 Sample Pump. Leakless Teflon-coated diaphragm-type that
can withstand being heated to 120 [deg]C and deliver 1.5 liters/minute.
8.2.3.1.2 Dilution Pumps. Two Model A-150 Komhyr Teflon positive
displacement type delivering 150 cc/minute, or equivalent. As an option,
calibrated flowmeters can be used in conjunction with Teflon-coated
diaphragm pumps.
8.2.3.1.3 Valves. Two Teflon three-way valves, suitable for
connecting to Teflon tubing.
8.2.3.1.4 Flowmeters. Two, for measurement of diluent gas.
8.2.3.1.5 Diluent Gas with Cylinders and Regulators. Gas can be
nitrogen or clean dry air, depending on the nature of the source gases.
8.2.3.1.6 Heated Box. Suitable for being heated to 120 [deg]C, to
contain the three pumps, three-way valves, and associated connections.
The box should be equipped with quick connect fittings to facilitate
connection of: (1) the heated sample line from the probe, (2) the gas
sampling valve, (3) the calibration gas mixtures, and (4) diluent gas
lines. A schematic diagram of the components and connections is shown in
Figure 18-13. The heated box shown in Figure 18-13 is designed to
receive a heated line from the probe. An optional design is to build a
probe unit that attaches directly to the heated box. In this way, the
heated box contains the controls for the probe heaters, or, if the box
is placed against the duct being sampled, it may be possible to
eliminate the probe heaters. In either case, a heated Teflon line is
used to connect the heated box to the gas sampling valve on the
chromatograph.

Note: Care must be taken to leak-check the system prior to the
dilutions so as not to create a potentially explosive atmosphere.

8.2.3.2 Procedure.
8.2.3.2.1 Assemble the apparatus by connecting the heated box, shown
in Figure 18-13, between the heated sample line from the probe and the
gas sampling valve on the chromatograph. Vent the source gas from the
gas sampling valve directly to the charcoal filter, eliminating the pump
and rotameter. Heat the sample probe, sample line, and heated box.
Insert the probe and source thermocouple at the centroid of the duct, or
to a point no closer to the walls than 1 m. Measure the source
temperature, and adjust all heating units to a temperature 0 to 3 [deg]C
above this temperature. If this temperature is above the safe operating
temperature of the Teflon components, adjust the heating to maintain a
temperature high enough to prevent condensation of water and organic
compounds (greater than 110 [deg]C). Calibrate the GC through the
dilution system by following the procedures in section 8.2.1.5.2.1.
Determine the concentration of the diluted calibration gas using the
dilution factor and the certified concentration of the calibration gas.
Record the pertinent data on the data sheet shown in Figure 18-11.
8.2.3.2.2 Once the dilution system and GC operations are
satisfactory, proceed with the analysis of source gas, maintaining the
same dilution settings as used for the standards.

[[Page 453]]

8.2.3.2.3 Analyze the audit samples using either the dilution
system, or directly connect to the gas sampling valve as required.
Record all data and report the results to the audit supervisor.
8.2.3.3 Determination of Stack Gas Moisture Content. Same as section
8.2.2.3.
8.2.3.4 Quality Assurance. Same as section 8.2.2.4.
8.2.3.5 Emission Calculations. Same as section 8.2.2.5, with the
dilution factor applied.
8.2.4 Adsorption Tube Procedure. Any commercially available
adsorbent is allowed for the purposes of this method, as long as the
recovery study criteria in section 8.4.3 are met. Help in choosing the
adsorbent may be found by calling the distributor, or the tester may
refer to National Institute for Occupational Safety and Health (NIOSH)
methods for the particular organics to be sampled. For some adsorbents,
the principal interferent will be water vapor. If water vapor is thought
to be a problem, the tester may place a midget impinger in an ice bath
before the adsorbent tubes. If this option is chosen, the water catch in
the midget impinger shall be analyzed for the target compounds. Also,
the spike for the recovery study (in section 8.4.3) shall be conducted
in both the midget impinger and the adsorbent tubes. The combined
recovery (add the recovered amount in the impinger and the adsorbent
tubes to calculate R) shall then meet the criteria in section 8.4.3.

Note: Post-test leak-checks are not allowed for this technique since
this can result in sample contamination.

8.2.4.1 Additional Apparatus. The following items (or equivalent)
are suggested.
8.2.4.1.1 Probe. Borosilicate glass or stainless steel,
approximately 6-mm ID, with a heating system if water condensation is a
problem, and a filter (either in-stack or out-of-stack, heated to stack
temperature) to remove particulate matter. In most instances, a plug of
glass wool is a satisfactory filter.
8.2.4.1.2 Flexible Tubing. To connect probe to adsorption tubes. Use
a material that exhibits minimal sample adsorption.
8.2.4.1.3 Leakless Sample Pump. Flow controlled, constant rate pump,
with a set of limiting (sonic) orifices.
8.2.4.1.4 Bubble-Tube Flowmeter. Volume accuracy within 1 percent,
to calibrate pump.
8.2.4.1.5 Stopwatch. To time sampling and pump rate calibration.
8.2.4.1.6 Adsorption Tubes. Precleaned adsorbent, with mass of
adsorbent to be determined by calculating breakthrough volume and
expected concentration in the stack.
8.2.4.1.7 Barometer. Accurate to 5 mm Hg, to measure atmospheric
pressure during sampling and pump calibration.
8.2.4.1.8 Rotameter. O to 100 cc/min, to detect changes in flow rate
during sampling.
8.2.4.2 Sampling and Analysis.
8.2.4.2.1 Calibrate the pump and limiting orifice flow rate through
adsorption tubes with the bubble tube flowmeter before sampling. The
sample system can be operated as a ``recirculating loop'' for this
operation. Record the ambient temperature and barometric pressure. Then,
during sampling, use the rotameter to verify that the pump and orifice
sampling rate remains constant.
8.2.4.2.2 Use a sample probe, if required, to obtain the sample at
the centroid of the duct or at a point no closer to the walls than 1 m.
Minimize the length of flexible tubing between the probe and adsorption
tubes. Several adsorption tubes can be connected in series, if the extra
adsorptive capacity is needed. Adsorption tubes should be maintained
vertically during the test in order to prevent channeling. Provide the
gas sample to the sample system at a pressure sufficient for the
limiting orifice to function as a sonic orifice. Record the total time
and sample flow rate (or the number of pump strokes), the barometric
pressure, and ambient temperature. Obtain a total sample volume
commensurate with the expected concentration(s) of the volatile
organic(s) present and recommended sample loading factors (weight sample
per weight adsorption media). Laboratory tests prior to actual sampling
may be necessary to predetermine this volume. If water vapor is present
in the sample at concentrations above 2 to 3 percent, the adsorptive
capacity may be severely reduced. Operate the gas chromatograph
according to the manufacturer's instructions. After establishing optimum
conditions, verify and document these conditions during all operations.
Calibrate the instrument and then analyze the emission samples.
8.2.4.3 Standards and Calibration. If using thermal desorption,
obtain calibration gases using the procedures in section 10.1. If using
solvent extraction, prepare liquid standards in the desorption solvent.
Use a minimum of three different standards; select the concentrations to
bracket the expected average sample concentration. Perform the
calibration before and after each day's sample analyses using the
procedures in section 8.2.1.5.2.1.
8.2.4.4 Quality Assurance.
8.2.4.4.1 Determine the recovery efficiency of the pollutants of
interest according to section 8.4.3.
8.2.4.4.2 Determination of Sample Collection Efficiency (Optional).
If sample breakthrough is thought to be a problem, a routine procedure
for determining breakthrough is to analyze the primary and backup
portions of the adsorption tubes separately. If the backup portion
exceeds 10 percent of the total amount (primary and back-up), it is
usually a sign of sample breakthrough. For the purposes of this method,
only the recovery efficiency value (Section 8.4.3) is used to

[[Page 454]]

determine the appropriateness of the sampling and analytical procedure.
8.2.4.4.3 Volume Flow Rate Checks. Perform this check immediately
after sampling with all sampling train components in place. Use the
bubble-tube flowmeter to measure the pump volume flow rate with the
orifice used in the test sampling, and record the result. If it has
changed by more than 5 but less than 20 percent, calculate an average
flow rate for the test. If the flow rate has changed by more than 20
percent, recalibrate the pump and repeat the sampling.
8.2.4.4.4 Calculations. Correct all sample volumes to standard
conditions. If a sample dilution system has been used, multiply the
results by the appropriate dilution ratio. Correct all results according
to the applicable procedure in section 8.4.3. Report results as ppm by
volume, dry basis.
8.3 Reporting of Results. At the completion of the field analysis
portion of the study, ensure that the data sheets shown in Figure 18-11
have been completed. Summarize this data on the data sheets shown in
Figure 18-15.
8.4 Recovery Study. After conducting the presurvey and identifying
all of the pollutants of interest, conduct the appropriate recovery
study during the test based on the sampling system chosen for the
compounds of interest.
8.4.1 Recovery Study for Direct Interface or Dilution Interface
Sampling. If the procedures in section 8.2.2 or 8.2.3 are to be used to
analyze the stack gas, conduct the calibration procedure as stated in
section 8.2.2.2 or 8.2.3.2, as appropriate. Upon successful completion
of the appropriate calibration procedure, attach the mid-level
calibration gas for at least one target compound to the inlet of the
probe or as close as possible to the inlet of the probe, but before the
filter. Repeat the calibration procedure by sampling and analyzing the
mid-level calibration gas through the entire sampling and analytical
system in triplicate. The mean of the calibration gas response sampled
through the probe shall be within 10 percent of the analyzer response.
If the difference in the two means is greater than 10 percent, check for
leaks throughout the sampling system and repeat the analysis of the
standard through the sampling system until this criterion is met.
8.4.2 Recovery Study for Bag Sampling.
8.4.2.1 Follow the procedures for the bag sampling and analysis in
section 8.2.1. After analyzing all three bag samples, choose one of the
bag samples and tag this bag as the spiked bag. Spike the chosen bag
sample with a known mixture (gaseous or liquid) of all of the target
pollutants. The theoretical concentration, in ppm, of each spiked
compound in the bag shall be 40 to 60 percent of the average
concentration measured in the three bag samples. If a target compound
was not detected in the bag samples, the concentration of that compound
to be spiked shall be 5 times the limit of detection for that compound.
Store the spiked bag for the same period of time as the bag samples
collected in the field. After the appropriate storage time has passed,
analyze the spiked bag three times. Calculate the average fraction
recovered (R) of each spiked target compound with the equation in
section 12.7.
8.4.2.2 For the bag sampling technique to be considered valid for a
compound, 0.70 R 1.30. If the R value does not
meet this criterion for a target compound, the sampling technique is not
acceptable for that compound, and therefore another sampling technique
shall be evaluated for acceptance (by repeating the recovery study with
another sampling technique). Report the R value in the test report and
correct all field measurements with the calculated R value for that
compound by using the equation in section 12.8.
8.4.3 Recovery Study for Adsorption Tube Sampling. If following the
adsorption tube procedure in section 8.2.4, conduct a recovery study of
the compounds of interest during the actual field test. Set up two
identical sampling trains. Collocate the two sampling probes in the
stack. The probes shall be placed in the same horizontal plane, where
the first probe tip is 2.5 cm from the outside edge of the other. One of
the sampling trains shall be designated the spiked train and the other
the unspiked train. Spike all of the compounds of interest (in gaseous
or liquid form) onto the adsorbent tube(s) in the spiked train before
sampling. The mass of each spiked compound shall be 40 to 60 percent of
the mass expected to be collected with the unspiked train. Sample the
stack gas into the two trains simultaneously. Analyze the adsorbents
from the two trains utilizing identical analytical procedures and
instrumentation. Determine the fraction of spiked compound recovered (R)
using the equations in section 12.9.
8.4.3.1 Repeat the procedure in section 8.4.3 twice more, for a
total of three runs. In order for the adsorbent tube sampling and
analytical procedure to be acceptable for a compound,
0.70R1.30 (R in this case is the average of three
runs). If the average R value does not meet this criterion for a target
compound, the sampling technique is not acceptable for that compound,
and therefore another sampling technique shall be evaluated for
acceptance (by repeating the recovery study with another sampling
technique). Report the R value in the test report and correct all field
measurements with the calculated R value for that compound by using the
equation in section 12.8.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures

[[Page 455]]

10.0 Calibration and Standardization.

10.1 Calibration Standards. Obtain calibration gas standards for
each target compound to be analyzed. Commercial cylinder gases certified
by the manufacturer to be accurate to within 1 percent of the certified
label value are preferable, although cylinder gases certified by the
manufacturer to 2 percent accuracy are allowed. Another option allowed
by this method is for the tester to obtain high concentration certified
cylinder gases and then use a dilution system meeting the requirements
of Test Method 205, 40 CFR Part 51, Appendix M to make multi-level
calibration gas standards. Prepare or obtain enough calibration
standards so that there are three different concentrations of each
organic compound expected to be measured in the source sample. For each
organic compound, select those concentrations that bracket the
concentrations expected in the source samples. A calibration standard
may contain more than one organic compound. If samples are collected in
adsorbent tubes and extracted using solvent extraction, prepare or
obtain standards in the same solvent used for the sample extraction
procedure. Verify the stability of all standards for the time periods
they are used.
10.2 Preparation of Calibration Curves.
10.2.1 Establish proper GC conditions, then flush the sampling loop
for 30 seconds. Allow the sample loop pressure to equilibrate to
atmospheric pressure, and activate the injection valve. Record the
standard concentration, attenuator factor, injection time, chart speed,
retention time, peak area, sample loop temperature, column temperature,
and carrier gas flow rate. Analyze each standard in triplicate.
10.2.2 Repeat this procedure for each standard. Prepare a graphical
plot of concentration (Cs) versus the calibration area
values. Perform a regression analysis, and draw the least square line.

11.0 Analytical Procedures

11.1 Analysis Development
11.1.1 Selection of GC Parameters
11.1.1.1 Column Choice. Based on the initial contact with plant
personnel concerning the plant process and the anticipated emissions,
choose a column that provides good resolution and rapid analysis time.
The choice of an appropriate column can be aided by a literature search,
contact with manufacturers of GC columns, and discussion with personnel
at the emission source.

Note: Most column manufacturers keep excellent records on their
products. Their technical service departments may be able to recommend
appropriate columns and detector type for separating the anticipated
compounds, and they may be able to provide information on interferences,
optimum operating conditions, and column limitations. Plants with
analytical laboratories may be able to provide information on their
analytical procedures.

11.1.1.2 Preliminary GC Adjustment. Using the standards and column
obtained in section 11.1.1.1, perform initial tests to determine
appropriate GC conditions that provide good resolution and minimum
analysis time for the compounds of interest.
11.1.1.3 Preparation of Presurvey Samples. If the samples were
collected on an adsorbent, extract the sample as recommended by the
manufacturer for removal of the compounds with a solvent suitable to the
type of GC analysis. Prepare other samples in an appropriate manner.
11.1.1.4 Presurvey Sample Analysis.
11.1.1.4.1 Before analysis, heat the presurvey sample to the duct
temperature to vaporize any condensed material. Analyze the samples by
the GC procedure, and compare the retention times against those of the
calibration samples that contain the components expected to be in the
stream. If any compounds cannot be identified with certainty by this
procedure, identify them by other means such as GC/mass spectroscopy
(GC/MS) or GC/infrared techniques. A GC/MS system is recommended.
11.1.1.4.2 Use the GC conditions determined by the procedure of
section 11.1.1.2 for the first injection. Vary the GC parameters during
subsequent injections to determine the optimum settings. Once the
optimum settings have been determined, perform repeat injections of the
sample to determine the retention time of each compound. To inject a
sample, draw sample through the loop at a constant rate (100 ml/min for
30 seconds). Be careful not to pressurize the gas in the loop. Turn off
the pump and allow the gas in the sample loop to come to ambient
pressure. Activate the sample valve, and record injection time, loop
temperature, column temperature, carrier flow rate, chart speed, and
attenuator setting. Calculate the retention

[[Page 456]]

time of each peak using the distance from injection to the peak maximum
divided by the chart speed. Retention times should be repeatable within
0.5 seconds.
11.1.1.4.3 If the concentrations are too high for appropriate
detector response, a smaller sample loop or dilutions may be used for
gas samples, and, for liquid samples, dilution with solvent is
appropriate. Use the standard curves (Section 10.2) to obtain an
estimate of the concentrations.
11.1.1.4.4 Identify all peaks by comparing the known retention times
of compounds expected to be in the retention times of peaks in the
sample. Identify any remaining unidentified peaks which have areas
larger than 5 percent of the total using a GC/MS, or estimation of
possible compounds by their retention times compared to known compounds,
with confirmation by further GC analysis.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

Bws = Water vapor content of the bag sample or stack gas,
proportion by volume.
Cs = Concentration of the organic from the calibration curve,
ppm.
Gv = Gas volume or organic compound injected, ml.
Lv = Liquid volume of organic injected, l.
M = Molecular weight of organic, g/g-mole.
ms = Total mass of compound measured on adsorbent with spiked
train (g).
mu = Total mass of compound measured on adsorbent with
unspiked train (g).
mv = Mass per volume of spiked compound measured (g/
L).
Pi = Barometric or absolute sample loop pressure at time of
sample analysis, mm Hg.
Pm = Absolute pressure of dry gas meter, mm Hg.
Pr = Reference pressure, the barometric pressure or absolute
sample loop pressure recorded during calibration, mm Hg.
Ps = Absolute pressure of syringe before injection, mm Hg.
qc = Flow rate of the calibration gas to be diluted.
qc1 = Flow rate of the calibration gas to be diluted in stage
1.
qc2 = Flow rate of the calibration gas to be diluted in stage
2.
qd = Diluent gas flow rate.
qd1 = Flow rate of diluent gas in stage 1.
qd2 = Flow rate of diluent gas in stage 2.
s = Theoretical concentration (ppm) of spiked target compound in the
bag.
S = Theoretical mass of compound spiked onto adsorbent in spiked train
(g).
t = Measured average concentration (ppm) of target compound and source
sample (analysis results subsequent to bag spiking)
Ti = Sample loop temperature at the time of sample analysis,
[deg]K.
Tm = Absolute temperature of dry gas meter, [deg]K.
Ts = Absolute temperature of syringe before injection,
[deg]K.
u = Source sample average concentration (ppm) of target compound in the
bag (analysis results before bag spiking).
Vm = Gas volume indicated by dry gas meter, liters.
vs = volume of stack gas sampled with spiked train (L).
vu = volume of stack gas sampled with unspiked train (L).
X = Mole or volume fraction of the organic in the calibration gas to be
diluted.
Y = Dry gas meter calibration factor, dimensionless.
l = Liquid organic density as determined, g/ml.

24.055 = Ideal gas molar volume at 293 [deg]K and 760 mm Hg, liters/g-
mole.

1000 = Conversion factor, ml/liter.
10\6\ = Conversion to ppm.

12.2 Calculate the concentration, Cs, in ppm using the
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.304

12.3 Calculate the concentration, Cs, in ppm of the
organic in the final gas mixture using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.305

12.4 Calculate each organic standard concentration, Cs,
in ppm using the following equation:

[[Page 457]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.306

12.5 Calculate each organic standard concentration, Cs,
in ppm using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.307

12.6 Calculate the concentration, Cc, in ppm, dry basis,
of each organic is the sample using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.308

12.7 Calculate the average fraction recovered (R) of each spiked
target compound using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.309

12.8 Correct all field measurements with the calculated R value for
that compound using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.310

[[Page 458]]

12.9 Determine the mass per volume of spiked compound measured using
the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.311

12.10 Calculate the fraction of spiked compound recovered, R, using
the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.312

13.0 Method Performance

13.1 Since a potential sample may contain a variety of compounds
from various sources, a specific precision limit for the analysis of
field samples is impractical. Precision in the range of 5 to 10 percent
relative standard deviation (RSD) is typical for gas chromatographic
techniques, but an experienced GC operator with a reliable instrument
can readily achieve 5 percent RSD. For this method, the following
combined GC/operator values are required.
(a) Precision. Triplicate analyses of calibration standards fall
within 5 percent of their mean value.
(c) Recovery. After developing an appropriate sampling and
analytical system for the pollutants of interest, conduct the procedure
in section 8.4. Conduct the appropriate recovery study in section 8.4 at
each sampling point where the method is being applied. Submit the data
and results of the recovery procedure with the reporting of results
under section 8.3.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 Optional Presurvey and Presurvey Sampling.

Note: Presurvey screening is optional. Presurvey sampling should be
conducted for sources where the target pollutants are not known from
previous tests and/or process knowledge.

Perform a presurvey for each source to be tested. Refer to Figure
18-1. Some of the information can be collected from literature surveys
and source personnel. Collect gas samples that can be analyzed to
confirm the identities and approximate concentrations of the organic
emissions.
16.1.1 Apparatus. This apparatus list also applies to sections 8.2
and 11.
16.1.1.1 Teflon Tubing. (Mention of trade names or specific products
does not constitute endorsement by the U.S. Environmental Protection
Agency.) Diameter and length determined by connection requirements of
cylinder regulators and the GC. Additional tubing is necessary to
connect the GC sample loop to the sample.
16.1.1.2 Gas Chromatograph. GC with suitable detector, columns,
temperature-controlled sample loop and valve assembly, and temperature
programmable oven, if necessary. The GC shall achieve sensitivity
requirements for the compounds under study.
16.1.1.3 Pump. Capable of pumping 100 ml/min. For flushing sample
loop.
16.1.1.4 Flow Meter. To measure flow rates.
16.1.1.5 Regulators. Used on gas cylinders for GC and for cylinder
standards.
16.1.1.6 Recorder. Recorder with linear strip chart is minimum
acceptable. Integrator (optional) is recommended.
16.1.1.7 Syringes. 0.5-ml, 1.0- and 10-microliter size, calibrated,
maximum accuracy (gas tight) for preparing calibration standards. Other
appropriate sizes can be used.
16.1.1.8 Tubing Fittings. To plumb GC and gas cylinders.
16.1.1.9 Septa. For syringe injections.
16.1.1.10 Glass Jars. If necessary, clean, colored glass jars with
Teflon-lined lids for condensate sample collection. Size depends on
volume of condensate.
16.1.1.11 Soap Film Flowmeter. To determine flow rates.
16.1.1.12 Flexible Bags. Tedlar or equivalent, 10- and 50-liter
capacity, for preparation of standards. (Verify through the manufacturer
that the Tedlar alternative is suitable for the compound of interest and
make this verifying information available for inspection.)
16.1.1.13 Dry Gas Meter with Temperature and Pressure Gauges.
Accurate to 2 percent, for preparation of gas standards.
16.1.1.14 Midget Impinger/Hot Plate Assembly. For preparation of gas
standards.
16.1.1.15 Sample Flasks. For presurvey samples, must have gas-tight
seals.
16.1.1.16 Adsorption Tubes. If necessary, blank tubes filled with
necessary adsorbent (charcoal, Tenax, XAD-2, etc.) for presurvey
samples.
16.1.1.17 Personnel Sampling Pump. Calibrated, for collecting
adsorbent tube presurvey samples.
16.1.1.18 Dilution System. Calibrated, the dilution system is to be
constructed following the specifications of an acceptable method.
16.1.1.19 Sample Probes. Pyrex or stainless steel, of sufficient
length to reach centroid of stack, or a point no closer to the walls
than 1 m.
16.1.1.20 Barometer. To measure barometric pressure.
16.1.2 Reagents.
16.1.2.1 Water. Deionized distilled.
16.1.2.2 Methylene chloride.

[[Page 459]]

16.1.2.3 Calibration Gases. A series of standards prepared for every
compound of interest.
16.1.2.4 Organic Compound Solutions. Pure (99.9 percent), or as pure
as can reasonably be obtained, liquid samples of all the organic
compounds needed to prepare calibration standards.
16.1.2.5 Extraction Solvents. For extraction of adsorbent tube
samples in preparation for analysis.
16.1.2.6 Fuel. As recommended by the manufacturer for operation of
the GC.
16.1.2.7 Carrier Gas. Hydrocarbon free, as recommended by the
manufacturer for operation of the detector and compatibility with the
column.
16.1.2.8 Zero Gas. Hydrocarbon free air or nitrogen, to be used for
dilutions, blank preparation, and standard preparation.
16.1.3 Sampling.
16.1.3.1 Collection of Samples with Glass Sampling Flasks. Presurvey
samples may be collected in precleaned 250-ml double-ended glass
sampling flasks. Teflon stopcocks, without grease, are preferred. Flasks
should be cleaned as follows: Remove the stopcocks from both ends of the
flasks, and wipe the parts to remove any grease. Clean the stopcocks,
barrels, and receivers with methylene chloride (or other non-target
pollutant solvent, or heat and humidified air). Clean all glass ports
with a soap solution, then rinse with tap and deionized distilled water.
Place the flask in a cool glass annealing furnace, and apply heat up to
500 [deg]C. Maintain at this temperature for 1 hour. After this time
period, shut off and open the furnace to allow the flask to cool. Return
the stopcocks to the flask receivers. Purge the assembly with high-
purity nitrogen for 2 to 5 minutes. Close off the stopcocks after
purging to maintain a slight positive nitrogen pressure. Secure the
stopcocks with tape. Presurvey samples can be obtained either by drawing
the gases into the previously evacuated flask or by drawing the gases
into and purging the flask with a rubber suction bulb.
16.1.3.1.1 Evacuated Flask Procedure. Use a high-vacuum pump to
evacuate the flask to the capacity of the pump; then close off the
stopcock leading to the pump. Attach a 6-mm outside diameter (OD) glass
tee to the flask inlet with a short piece of Teflon tubing. Select a 6-
mm OD borosilicate sampling probe, enlarged at one end to a 12-mm OD and
of sufficient length to reach the centroid of the duct to be sampled.
Insert a glass wool plug in the enlarged end of the probe to remove
particulate matter. Attach the other end of the probe to the tee with a
short piece of Teflon tubing. Connect a rubber suction bulb to the third
leg of the tee. Place the filter end of the probe at the centroid of the
duct, and purge the probe with the rubber suction bulb. After the probe
is completely purged and filled with duct gases, open the stopcock to
the grab flask until the pressure in the flask reaches duct pressure.
Close off the stopcock, and remove the probe from the duct. Remove the
tee from the flask and tape the stopcocks to prevent leaks during
shipment. Measure and record the duct temperature and pressure.
16.1.3.1.2 Purged Flask Procedure. Attach one end of the sampling
flask to a rubber suction bulb. Attach the other end to a 6-mm OD glass
probe as described in section 8.3.3.1.1. Place the filter end of the
probe at the centroid of the duct, or at a point no closer to the walls
than 1 m, and apply suction with the bulb to completely purge the probe
and flask. After the flask has been purged, close off the stopcock near
the suction bulb, and then close off the stopcock near the probe. Remove
the probe from the duct, and disconnect both the probe and suction bulb.
Tape the stopcocks to prevent leakage during shipment. Measure and
record the duct temperature and pressure.
16.1.3.2 Flexible Bag Procedure. Any leak-free plastic (e.g.,
Tedlar, Mylar, Teflon) or plastic-coated aluminum (e.g., aluminized
Mylar) bag, or equivalent, can be used to obtain the pre-survey sample.
Use new bags, and leak-check them before field use. In addition, check
the bag before use for contamination by filling it with nitrogen or air
and analyzing the gas by GC at high sensitivity. Experience indicates
that it is desirable to allow the inert gas to remain in the bag about
24 hours or longer to check for desorption of organics from the bag.
Follow the leak-check and sample collection procedures given in Section
8.2.1.
16.1.3.3 Determination of Moisture Content. For combustion or water-
controlled processes, obtain the moisture content from plant personnel
or by measurement during the presurvey. If the source is below 59
[deg]C, measure the wet bulb and dry bulb temperatures, and calculate
the moisture content using a psychrometric chart. At higher
temperatures, use Method 4 to determine the moisture content.
16.1.4 Determination of Static Pressure. Obtain the static pressure
from the plant personnel or measurement. If a type S pitot tube and an
inclined manometer are used, take care to align the pitot tube 90[deg]
from the direction of the flow. Disconnect one of the tubes to the
manometer, and read the static pressure; note whether the reading is
positive or negative.
16.1.5 Collection of Presurvey Samples with Adsorption Tube. Follow
section 8.2.4 for presurvey sampling.

17.0 References

1. American Society for Testing and Materials. C1 Through C5
Hydrocarbons in the Atmosphere by Gas Chromatography. ASTM D 2820-72,
Part 23. Philadelphia, Pa. 23:950-958. 1973.

[[Page 460]]

2. Corazon, V.V. Methodology for Collecting and Analyzing Organic
Air Pollutants. U.S. Environmental Protection Agency. Research Triangle
Park, N.C. Publication No. EPA-600/2-79-042. February 1979.
3. Dravnieks, A., B.K. Krotoszynski, J. Whitfield, A. O'Donnell, and
T. Burgwald. Environmental Science and Technology. 5(12):1200-1222.
1971.
4. Eggertsen, F.T., and F.M. Nelsen. Gas Chromatographic Analysis of
Engine Exhaust and Atmosphere. Analytical Chemistry. 30(6): 1040-1043.
1958.
5. Feairheller, W.R., P.J. Marn, D.H. Harris, and D.L. Harris.
Technical Manual for Process Sampling Strategies for Organic Materials.
U.S. Environmental Protection Agency. Research Triangle Park, N.C.
Publication No. EPA 600/2-76-122. April 1976. 172 p.
6. Federal Register, 39 FR 9319-9323. 1974.
7. Federal Register, 39 FR 32857-32860. 1974.
8. Federal Register, 23069-23072 and 23076-23090. 1976.
9. Federal Register, 46569-46571. 1976.
10. Federal Register, 41771-41776. 1977.
11. Fishbein, L. Chromatography of Environmental Hazards, Volume II.
Elesevier Scientific Publishing Company. New York, N.Y. 1973.
12. Hamersma, J.W., S.L. Reynolds, and R.F. Maddalone. EPA/IERL-RTP
Procedures Manual: Level 1 Environmental Assessment. U.S. Environmental
Protection Agency. Research Triangle Park, N.C. Publication No. EPA 600/
276-160a. June 1976. 130 p.
13. Harris, J.C., M.J. Hayes, P.L. Levins, and D.B. Lindsay. EPA/
IERL-RTP Procedures for Level 2 Sampling and Analysis of Organic
Materials. U.S. Environmental Protection Agency. Research Triangle Park,
N.C. Publication No. EPA 600/7-79-033. February 1979. 154 p.
14. Harris, W.E., H.W. Habgood. Programmed Temperature Gas
Chromatography. John Wiley and Sons, Inc. New York. 1966.
15. Intersociety Committee. Methods of Air Sampling and Analysis.
American Health Association. Washington, D.C. 1972.
16. Jones, P.W., R.D. Grammer, P.E. Strup, and T.B. Stanford.
Environmental Science and Technology. 10:806-810. 1976.
17. McNair Han Bunelli, E.J. Basic Gas Chromatography. Consolidated
Printers. Berkeley. 1969.
18. Nelson, G.O. Controlled Test Atmospheres, Principles and
Techniques. Ann Arbor. Ann Arbor Science Publishers. 1971. 247 p.
19. NIOSH Manual of Analytical Methods, Volumes 1, 2, 3, 4, 5, 6, 7.
U.S. Department of Health and Human Services, National Institute for
Occupational Safety and Health. Center for Disease Control. 4676
Columbia Parkway, Cincinnati, Ohio 45226. April 1977--August 1981. May
be available from the Superintendent of Documents, Government Printing
Office, Washington, D.C. 20402. Stock Number/Price:

Volume 1--O17-033-00267-3/$13
Volume 2--O17-033-00260-6/$11
Volume 3--O17-033-00261-4/$14
Volume 4--O17-033-00317-3/$7.25
Volume 5--O17-033-00349-1/$10
Volume 6--O17-033-00369-6/$9
Volume 7--O17-033-00396-5/$7

Prices subject to change. Foreign orders add 25 percent.
20. Schuetzle, D., T.J. Prater, and S.R. Ruddell. Sampling and
Analysis of Emissions from Stationary Sources; I. Odor and Total
Hydrocarbons. Journal of the Air Pollution Control Association. 25(9):
925-932. 1975.
21. Snyder, A.D., F.N. Hodgson, M.A. Kemmer and J.R. McKendree.
Utility of Solid Sorbents for Sampling Organic Emissions from Stationary
Sources. U.S. Environmental Protection Agency. Research Triangle Park,
N.C. Publication No. EPA 600/2-76-201. July 1976. 71 p.
22. Tentative Method for Continuous Analysis of Total Hydrocarbons
in the Atmosphere. Intersociety Committee, American Public Health
Association. Washington, D.C. 1972. p. 184-186.
23. Zwerg, G. CRC Handbook of Chromatography, Volumes I and II.
Sherma, Joseph (ed.). CRC Press. Cleveland. 1972.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

I. Name of company______________________________________________________
Date____________________________________________________________________
Address_________________________________________________________________
________________________________________________________________________
Contracts_______________________________________________________________
Phone___________________________________________________________________
Process to be sampled___________________________________________________
________________________________________________________________________
________________________________________________________________________
Duct or vent to be sampled______________________________________________
________________________________________________________________________
II. Process description_________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
Raw material____________________________________________________________
________________________________________________________________________
________________________________________________________________________
Products________________________________________________________________
________________________________________________________________________
________________________________________________________________________

Operating cycle
Check: Batch -------- Continuous -------- Cyclic --------
Timing of batch or cycle________________________________________________
Best time to test_______________________________________________________

III. Sampling site______________________________________________________
A. Description__________________________________________________________
Site decription_________________________________________________________
Duct shape and size_____________________________________________________
Material________________________________________________________________

[[Page 461]]

Wall thickness -------- inches
Upstream distance -------- inches -------- diameter
Downstream distance -------- inches -------- diameter
Size of port____________________________________________________________
Size of access area_____________________________________________________
Hazards -------- Ambient temp. -------- [deg]F

B. Properties of gas stream
Temperature -------- [deg]C -------- [deg]F, Data source --------
Velocity --------, Data source --------
Static pressure -------- inches H2O, Data source --------
Moisture content --------%, Data source --------
Particulate content --------, Data source--------

Gaseous components
N2 -------- % Hydrocarbons -------- ppm
O2 --------% --------
CO -------- % -------- --------
CO2 -------- % -------- --------
SO2 -------- % -------- --------

Hydrocarbon components
-------- -------- ppm
-------- -------- ppm
-------- -------- ppm
-------- -------- ppm
-------- -------- ppm
-------- -------- ppm

C. Sampling considerations
Location to set up GC___________________________________________________
________________________________________________________________________
Special hazards to be considered________________________________________
________________________________________________________________________
Power available at duct_________________________________________________
Power available for GC__________________________________________________
Plant safety requirements_______________________________________________
________________________________________________________________________
Vehicle traffic rules___________________________________________________
________________________________________________________________________
Plant entry requirements________________________________________________
________________________________________________________________________
Security agreements_____________________________________________________
________________________________________________________________________
Potential problems______________________________________________________
________________________________________________________________________

D. Site diagrams. (Attach additional sheets if required).

Figure 18-1. Preliminary Survey Data Sheet

Components to be analyzed and Expected concentration
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
Suggested chromatographic column________________________________________
________________________________________________________________________
Column flow rate -- ml/min
Head pressure -------- mm Hg

Column temperature: Isothermal -------- [deg]C, Programmed from --------
[deg]C to -------- [deg]C at -------- [deg]C/min
Injection port/sample loop temperature -------- [deg]C
Detector temperature -------- [deg]C
Detector flow rates: Hydrogen -------- ml/min., head pressure --------
mm Hg, Air/Oxygen -------- ml/min., head pressure -------- mm Hg.
Chart speed -------- inches/minute
Compound data:
Compound and Retention time and Attenuation
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________

Figure 18-2. Chromatographic Conditions Data Sheet

Figure 18-3. Preparation of Standards in Tedlar or Tedlar-Equlivalent Bags and Calibration Curve
----------------------------------------------------------------------------------------------------------------
Standards
-----------------------------------------------------
Mixture #1 Mixture #2 Mixture #3

----------------------------------------------------------------------------------------------------------------
Standards Preparation Data:
Organic:
Bag number or identification......................
Dry gas meter calibration factor..................
Final meter reading (liters)......................
Initial meter reading (liters)....................
Metered volume (liters)...........................
Average meter temperature ([deg]K)................
Average meter pressure, gauge (mm Hg).............
Average atmospheric perssure (mm Hg)..............
Average meter pressure, absolute (mm Hg)..........
Syringe temperature ([deg]K) (see section
10.1.2.1)........................................
Syringe pressure, absolute (mm Hg) (see section
10.1.2.1)........................................
Volume of gas in syringe (ml) (Section 10.1.2.1)..
Density of liquid organic (g/ml) (Section
10.1.2.1)........................................
Volume of liquid in syringe (ml) (Section
10.1.2.1)........................................
GC Operating Conditions:

[[Page 462]]

Sample loop volume (ml)...............................
Sample loop temperature ( [deg]C).....................
Carrier gas flow rate (ml/min)........................
Column temperature:
Initial ( [deg]C).....................................
Rate change ( [deg]C/min).............................
Final ( [deg]C).......................................
Organic Peak Identification and Calculated Concentrations:
Injection time (24 hour clock)........................
Distance to peak (cm).................................
Chart speed (cm/min)..................................
Organic retention time (min)..........................
Attenuation factor....................................
Peak height (mm)......................................
Peak area (mm2).......................................
Peak area * attenuation factor (mm2)..................
Calculated concentration (ppm) (Equation 18-3 or 18-4)
----------------------------------------------------------------------------------------------------------------
Plot peak area * attenuation factor against calculated concentration to obtain calibration curve.

Flowmeter number or identification______________________________________
Flowmeter Type__________________________________________________________
Method: Bubble meter---- Spirometer---- Wet test meter ----
Readings at laboratory conditions:
Laboratory temperature (Tlab) ---- [deg]K
Laboratory barometric pressure (Plab)---- mm Hg
Flow data:

Flowmeter
----------------------------------------------------------------------------------------------------------------
Reading (as marked) Temp. ([deg]K) Pressure (absolute)
----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------

Calibration Device
----------------------------------------------------------------------------------------------------------------
Time (min) Gas volume \a\ Flow rate \b\
----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------
\a\ Vol. of gas may be measured in milliliters, liters or cubic feet.
\b\ Convert to standard conditions (20 [deg]C and 760 mm Hg). Plot flowmeter reading against flow rate (standard
conditions), and draw a smooth curve. If the flowmeter being calibrated is a rotameter or other flow device
that is viscosity dependent, it may be necessary to generate a ``family'' of calibration curves that cover the
operating pressure and temperature ranges of the flowmeter. While the following technique should be verified
before application, it may be possible to calculate flow rate reading for rotameters at standard conditions
Qstd as follows:

[GRAPHIC] [TIFF OMITTED] TR17OC00.313

[[Page 463]]

------------------------------------------------------------------------
Flow rate (laboratory conditions) Flow rate (STD conditions)
------------------------------------------------------------------------

------------------------------------------------------------------------

Figure 18-4. Flowmeter Calibration
[GRAPHIC] [TIFF OMITTED] TR17OC00.314

[[Page 464]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.315

Preparation of Standards by Dilution of Cylinder Standard
[Cylinder Standard: Organic -------- Certified Concentration -------- ppm]
----------------------------------------------------------------------------------------------------------------
Date:
Standards preparation data: --------------------------------------------------------------------------
Mixture 1 Mixture 2 Mixture 3
----------------------------------------------------------------------------------------------------------------
Stage 1:
Standard gas flowmeter reading...
Diluent gas flowmeter reading
Laboratory temperature ([deg]K)
Barometric pressure (mm Hg)
Flowmeter gage pressure (mm Hg)
Flow rate cylinder gas at
standard conditions (ml/min)
Flow rate diluent gas at standard
conditions (ml/min)
Calculated concentration (ppm)
Stage 2 (if used):
Standard gas flowmeter reading
Diluent gas flowmeter reading
Flow rate Stage 1 gas at standard
conditions (ml/min)
Flow rate diluent gas at standard
conditions
Calculated concentration (ppm)
GC Operating Conditions:
Sample loop volume (ml)
Sample loop temperature ( [deg]C)
Carrier gas flow rate (ml/min)
Column temperature:
Initial ( [deg]C)

[[Page 465]]

Program rate ( [deg]C/min)
Final ( [deg]C)
Organic Peak Identification and
Calculated Concentrations:
Injection time (24-hour clock)
Distance to peak (cm)
Chart speed (cm/min)
Retention time (min)
Attenuation factor
Peak area (mm\2\)
Peak area *attenuation factor
----------------------------------------------------------------------------------------------------------------
Plot peak area *attenuation factor against calculated concentration to obtain calibration curve.

Figure 18-7. Standards Prepared by Dilution of Cylinder Standard
[GRAPHIC] [TIFF OMITTED] TR17OC00.316

[[Page 466]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.317

[[Page 467]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.318

Plant-------- Date-------- Site--------
----------------------------------------------------------------------------------------------------------------
Sample 1 Sample 2 Sample 3
----------------------------------------------------------------------------------------------------------------
Source temperature ( [deg]C).................................... .............. .............. ..............
Barometric pressure (mm Hg)..................................... .............. .............. ..............
Ambient temperature ( [deg]C)................................... .............. .............. ..............
Sample flow rate (appr.)........................................ .............. .............. ..............
Bag number...................................................... .............. .............. ..............
Start time...................................................... .............. .............. ..............
Finish time..................................................... .............. .............. ..............
----------------------------------------------------------------------------------------------------------------

Figure 18-10. Field Sample Data Sheet--Tedlar or Tedlar-Equivalent Bag
Collection Method

Plant ------------------ Date ---------------- Location
------------------------

1. General information:
Source temperature ( [deg]C)...................... ................
Probe temperature ( [deg]C)....................... ................
Ambient temperature ( [deg]C)..................... ................
Atmospheric pressure (mm)......................... ................
Source pressure ('Hg)............................. ................
Absolute source pressure (mm)..................... ................
Sampling rate (liter/min)......................... ................
Sample loop volume (ml)........................... ................
Sample loop temperature ( [deg]C)................. ................
Columnar temperature:
Initial ( [deg]C) time (min).................. ................
Program rate ( [deg]C/min).................... ................
Final ( [deg]C)/time (min).................... ................
Carrier gas flow rate (ml/min).................... ................

[[Page 468]]

Detector temperature ( [deg]C).................... ................
Injection time (24-hour basis).................... ................
Chart Speed (mm/min).............................. ................
Dilution gas flow rate (ml/min)................... ................
Dilution gas used (symbol)........................ ................
Dilution ratio.................................... ................

2. Field Analysis Data--Calibration Gas
2. [Run No. -------- Time ------------]
----------------------------------------------------------------------------------------------------------------
Components Area Attenuation A x A Factor Conc.-- (ppm)
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------

Figure 18-11. Field Analysis Data Sheets

[[Page 469]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.319

[[Page 470]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.320

Gaseous Organic Sampling and Analysis Check List
[Respond with initials or number as appropriate]

Date

1. Presurvey data:
A. Grab sample collected........................ } ------
B. Grab sample analyzed for composition..... } ------
Method GC................................... } ------
GC/MS................................... } ------
Other................................... } ------
C. GC-FID analysis performed.................... } ------
2. Laboratory calibration data:
A. Calibration curves prepared.................. } ------
Number of components........................ } ------
Number of concentrations/component (3 } ------
required).
B. Audit samples (optional):
Analysis completed.............................. } ------
Verified for concentration...................... } ------
OK obtained for field work...................... } ------
3. Sampling procedures:
A. Method:
Bag sample.................................. } ------
Direct interface............................ } ------
Dilution interface.......................... } ------
B. Number of samples collected.................. } ------
4. Field Analysis:
A. Total hydrocarbon analysis performed......... } ------
B. Calibration curve prepared................... } ------
Number of components........................ } ------
Number of concentrations per component (3 } ------
required).

[[Page 471]]

Gaseous Organic Sampling and Analysis Data

Plant___________________________________________________________________
Date____________________________________________________________________
Location________________________________________________________________

Gaseous Organic Sampling and Analysis Check List (Respond With Initials
or Number as Appropriate)
------------------------------------------------------------------------

------------------------------------------------------------------------
1. Pre-survey data.................. Date
A. Grab sample collected........ --------
B. Grab sample analyzed for --------
composition....................
Method GC................... --------
GC/MS....................... --------
Other----------------------- --------
-..........................
C. GC-FID analysis performed.... --------
2. Laboratory calibration curves --------
prepared...........................
A. Number of components......... --------
B. Number of concentrations per --------
component (3 required).........
C. OK obtained for field work... --------
3. Sampling procedures..............
A. Method.......................
Bag sample.................. --------
Direct interface............ --------
Dilution interface.......... --------
B. Number of samples collected.. --------
4. Field Analysis...................
A. Total hydrocarbon analysis --------
performed......................
B. Calibration curve prepared... --------
Number of components........ --------
Number of concentrations per --------
component (3 required).....
------------------------------------------------------------------------

Figure 18-14. Sampling and Analysis Sheet

[36 FR 24877, Dec. 23, 1971]

Editorial Note: For Federal Register citations affecting appendix A-
6 to part 60, see the List of CFR sections Affected, which appears in
the Finding Aids section of the printed volume and at www.fdsys.gov.

Sec. Appendix A-7 to Part 60--Test Methods 19 through 25E

Method 19--Determination of sulfur dioxide removal efficiency and
particulate, sulfur dioxide and nitrogen oxides emission rates
Method 20--Determination of nitrogen oxides, sulfur dioxide, and diluent
emissions from stationary gas turbines
Method 21--Determination of volatile organic compound leaks
Method 22--Visual determination of fugitive emissions from material
sources and smoke emissions from flares
Method 23--Determination of Polychlorinated Dibenzo-p-Dioxins and
Polychlorinated Dibenzofurans From Stationary Sources
Method 24--Determination of volatile matter content, water content,
density, volume solids, and weight solids of surface coatings
Method 24A--Determination of volatile matter content and density of
printing inks and related coatings
Method 25--Determination of total gaseous nonmethane organic emissions
as carbon
Method 25A--Determination of total gaseous organic concentration using a
flame ionization analyzer
Method 25B--Determination of total gaseous organic concentration using a
nondispersive infrared analyzer
Method 25C--Determination of nonmethane organic compounds (NMOC) in MSW
landfill gases
Method 25D--Determination of the Volatile Organic Concentration of Waste
Samples
Method 25E--Determination of Vapor Phase Organic Concentration in Waste
Samples

[[Page 472]]

The test methods in this appendix are referred to in Sec. 60.8
(Performance Tests) and Sec. 60.11 (Compliance With Standards and
Maintenance Requirements) of 40 CFR part 60, subpart A (General
Provisions). Specific uses of these test methods are described in the
standards of performance contained in the subparts, beginning with
Subpart D.
Within each standard of performance, a section title ``Test Methods
and Procedures'' is provided to: (1) Identify the test methods to be
used as reference methods to the facility subject to the respective
standard and (2) identify any special instructions or conditions to be
followed when applying a method to the respective facility. Such
instructions (for example, establish sampling rates, volumes, or
temperatures) are to be used either in addition to, or as a substitute
for procedures in a test method. Similarly, for sources subject to
emission monitoring requirements, specific instructions pertaining to
any use of a test method as a reference method are provided in the
subpart or in Appendix B.
Inclusion of methods in this appendix is not intended as an
endorsement or denial of their applicability to sources that are not
subject to standards of performance. The methods are potentially
applicable to other sources; however, applicability should be confirmed
by careful and appropriate evaluation of the conditions prevalent at
such sources.
The approach followed in the formulation of the test methods
involves specifications for equipment, procedures, and performance. In
concept, a performance specification approach would be preferable in all
methods because this allows the greatest flexibility to the user. In
practice, however, this approach is impractical in most cases because
performance specifications cannot be established. Most of the methods
described herein, therefore, involve specific equipment specifications
and procedures, and only a few methods in this appendix rely on
performance criteria.
Minor changes in the test methods should not necessarily affect the
validity of the results and it is recognized that alternative and
equivalent methods exist. section 60.8 provides authority for the
Administrator to specify or approve (1) equivalent methods, (2)
alternative methods, and (3) minor changes in the methodology of the
test methods. It should be clearly understood that unless otherwise
identified all such methods and changes must have prior approval of the
Administrator. An owner employing such methods or deviations from the
test methods without obtaining prior approval does so at the risk of
subsequent disapproval and retesting with approved methods.
Within the test methods, certain specific equipment or procedures
are recognized as being acceptable or potentially acceptable and are
specifically identified in the methods. The items identified as
acceptable options may be used without approval but must be identified
in the test report. The potentially approvable options are cited as
``subject to the approval of the Administrator'' or as ``or
equivalent.'' Such potentially approvable techniques or alternatives may
be used at the discretion of the owner without prior approval. However,
detailed descriptions for applying these potentially approvable
techniques or alternatives are not provided in the test methods. Also,
the potentially approvable options are not necessarily acceptable in all
applications. Therefore, an owner electing to use such potentially
approvable techniques or alternatives is responsible for: (1) assuring
that the techniques or alternatives are in fact applicable and are
properly executed; (2) including a written description of the
alternative method in the test report (the written method must be clear
and must be capable of being performed without additional instruction,
and the degree of detail should be similar to the detail contained in
the test methods); and (3) providing any rationale or supporting data
necessary to show the validity of the alternative in the particular
application. Failure to meet these requirements can result in the
Administrator's disapproval of the alternative.

Method 19--Determination of Sulfur Dioxide Removal Efficiency and
Particulate Matter, Sulfur Dioxide, and Nitrogen Oxide Emission Rates

1.0 Scope and Application

1.1 Analytes. This method provides data reduction procedures
relating to the following pollutants, but does not include any sample
collection or analysis procedures.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Nitrogen oxides (NOX),
including:
Nitric oxide (NO)......... 10102-43-9....... N/A
Nitrogen dioxide (NO2).... 10102-44-0.......
Particulate matter (PM)....... None assigned.... N/A
Sulfur dioxide (SO2).......... 7499-09-05....... N/A
------------------------------------------------------------------------

[[Page 473]]

1.2 Applicability. Where specified by an applicable subpart of the
regulations, this method is applicable for the determination of (a) PM,
SO2, and NOX emission rates; (b) sulfur removal
efficiencies of fuel pretreatment and SO2 control devices;
and (c) overall reduction of potential SO2 emissions.

2.0 Summary of Method

2.1 Emission Rates. Oxygen (O2) or carbon dioxide
(CO2) concentrations and appropriate F factors (ratios of
combustion gas volumes to heat inputs) are used to calculate pollutant
emission rates from pollutant concentrations.
2.2 Sulfur Reduction Efficiency and SO2 Removal
Efficiency. An overall SO2 emission reduction efficiency is
computed from the efficiency of fuel pretreatment systems, where
applicable, and the efficiency of SO2 control devices.
2.2.1 The sulfur removal efficiency of a fuel pretreatment system is
determined by fuel sampling and analysis of the sulfur and heat contents
of the fuel before and after the pretreatment system.
2.2.2 The SO2 removal efficiency of a control device is
determined by measuring the SO2 rates before and after the
control device.
2.2.2.1 The inlet rates to SO2 control systems (or, when
SO2 control systems are not used, SO2 emission
rates to the atmosphere) are determined by fuel sampling and analysis.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety [Reserved]

6.0 Equipment and Supplies [Reserved]

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection, Preservation, Storage, and Transport [Reserved]

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedures [Reserved]

12.0 Data Analysis and Calculations

12.1 Nomenclature

Bwa = Moisture fraction of ambient air, percent.
Bws = Moisture fraction of effluent gas, percent.
%C = Concentration of carbon from an ultimate analysis of fuel, weight
percent.
Cd = Pollutant concentration, dry basis, ng/scm (lb/scf)
%CO2d,%CO2w = Concentration of carbon dioxide on a
dry and wet basis, respectively, percent.
Cw = Pollutant concentration, wet basis, ng/scm (lb/scf).
D = Number of sampling periods during the performance test period.
E = Pollutant emission rate, ng/J (lb/million Btu).
Ea = Average pollutant rate for the specified performance
test period, ng/J (lb/million Btu).
Eao, Eai = Average pollutant rate of the control
device, outlet and inlet, respectively, for the performance
test period, ng/J (lb/million Btu).
Ebi = Pollutant rate from the steam generating unit, ng/J
(lb/million Btu)
Ebo = Pollutant emission rate from the steam generating unit,
ng/J (lb/million Btu).
Eci = Pollutant rate in combined effluent, ng/J (lb/million
Btu).
Eco = Pollutant emission rate in combined effluent, ng/J (lb/
million Btu).
Ed = Average pollutant rate for each sampling period (e.g.,
24-hr Method 6B sample or 24-hr fuel sample) or for each fuel
lot (e.g., amount of fuel bunkered), ng/J (lb/million Btu).
Edi = Average inlet SO2 rate for each sampling
period d, ng/J (lb/million Btu)
Eg = Pollutant rate from gas turbine, ng/J (lb/million Btu).
Ega = Daily geometric average pollutant rate, ng/J (lbs/
million Btu) or ppm corrected to 7 percent O2.
Ejo,Eji = Matched pair hourly arithmetic average
pollutant rate, outlet and inlet, respectively, ng/J (lb/
million Btu) or ppm corrected to 7 percent O2.
Eh = Hourly average pollutant, ng/J (lb/million Btu).
Ehj = Hourly arithmetic average pollutant rate for hour
``j,'' ng/J (lb/million Btu) or ppm corrected to 7 percent
O2.
EXP = Natural logarithmic base (2.718) raised to the value enclosed by
brackets.
Fd, Fw, Fc = Volumes of combustion
components per unit of heat content, scm/J (scf/million Btu).
GCV = Gross calorific value of the fuel consistent with the ultimate
analysis, kJ/kg (Btu/lb).
GCVp, GCVr = Gross calorific value for the product
and raw fuel lots, respectively, dry basis, kJ/kg (Btu/lb).
%H = Concentration of hydrogen from an ultimate analysis of fuel, weight
percent.
H = Total number of operating hours for which pollutant rates are
determined in the performance test period.
Hb = Heat input rate to the steam generating unit from fuels
fired in the steam generating unit, J/hr (million Btu/hr).
Hg = Heat input rate to gas turbine from all fuels fired in
the gas turbine, J/hr (million Btu/hr).

[[Page 474]]

%H2O = Concentration of water from an ultimate analysis of
fuel, weight percent.
Hr = Total numbers of hours in the performance test period
(e.g., 720 hours for 30-day performance test period).
K = Conversion factor, 10^-5 (kJ/J)/(%) [106 Btu/million Btu].
Kc = (9.57 scm/kg)/% [(1.53 scf/lb)/%].
Kcc = (2.0 scm/kg)/% [(0.321 scf/lb)/%].
Khd = (22.7 scm/kg)/% [(3.64 scf/lb)/%].
Khw = (34.74 scm/kg)/% [(5.57 scf/lb)/%].
Kn = (0.86 scm/kg)/% [(0.14 scf/lb)/%].
Ko = (2.85 scm/kg)/% [(0.46 scf/lb)/%].
Ks = (3.54 scm/kg)/% [(0.57 scf/lb)/%].
Kw = (1.30 scm/kg)/% [(0.21 scf/lb)/%].
ln = Natural log of indicated value.
Lp,Lr = Weight of the product and raw fuel lots,
respectively, metric ton (ton).
%N = Concentration of nitrogen from an ultimate analysis of fuel, weight
percent.
N = Number of fuel lots during the averaging period.
n = Number of fuels being burned in combination.
nd = Number of operating hours of the affected facility
within the performance test period for each Ed
determined.
nt = Total number of hourly averages for which paired inlet
and outlet pollutant rates are available within the 24-hr
midnight to midnight daily period.
%O = Concentration of oxygen from an ultimate analysis of fuel, weight
percent.
%O2d, %O2w = Concentration of oxygen on a dry and
wet basis, respectively, percent.
Ps = Potential SO2 emissions, percent.
%Rf = SO2 removal efficiency from fuel
pretreatment, percent.
%Rg = SO2 removal efficiency of the control
device, percent.
%Rga = Daily geometric average percent reduction.
%Ro = Overall SO2 reduction, percent.
%S = Sulfur content of as-fired fuel lot, dry basis, weight percent.
Se = Standard deviation of the hourly average pollutant rates
for each performance test period, ng/J (lb/million Btu).
%Sf = Concentration of sulfur from an ultimate analysis of
fuel, weight percent.
Si = Standard deviation of the hourly average inlet pollutant
rates for each performance test period, ng/J (lb/million Btu).
So = Standard deviation of the hourly average emission rates
for each performance test period, ng/J (lb/million Btu).
%Sp, %Sr = Sulfur content of the product and raw
fuel lots respectively, dry basis, weight percent.
t0.95 = Values shown in Table 19-3 for the indicated number
of data points n.
Xk = Fraction of total heat input from each type of fuel k.

12.2 Emission Rates of PM, SO2, and NOX.
Select from the following sections the applicable procedure to compute
the PM, SO2, or NOX emission rate (E) in ng/J (lb/
million Btu). The pollutant concentration must be in ng/scm (lb/scf) and
the F factor must be in scm/J (scf/million Btu). If the pollutant
concentration (C) is not in the appropriate units, use Table 19-1 in
section 17.0 to make the proper conversion. An F factor is the ratio of
the gas volume of the products of combustion to the heat content of the
fuel. The dry F factor (Fd) includes all components of
combustion less water, the wet F factor (Fw) includes all
components of combustion, and the carbon F factor (Fc)
includes only carbon dioxide.

Note: Since Fw factors include water resulting only from
the combustion of hydrogen in the fuel, the procedures using
Fw factors are not applicable for computing E from steam
generating units with wet scrubbers or with other processes that add
water (e.g., steam injection).

12.2.1 Oxygen-Based F Factor, Dry Basis. When measurements are on a
dry basis for both O (%O2d) and pollutant (Cd)
concentrations, use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.321

12.2.2 Oxygen-Based F Factor, Wet Basis. When measurements are on a
wet basis for both O2 (%O2w) and pollutant
(Cw) concentrations, use either of the following:
12.2.2.1 If the moisture fraction of ambient air (Bwa) is
measured:
[GRAPHIC] [TIFF OMITTED] TR17OC00.322

Instead of actual measurement, Bwa may be estimated
according to the procedure below.

Note: The estimates are selected to ensure that negative errors will
not be larger than -1.5 percent. However, positive errors, or over-
estimation of emissions by as much as 5 percent may be introduced
depending upon the geographic location of the facility and the
associated range of ambient moisture.

[[Page 475]]

12.2.2.1.1 Bwa = 0.027. This value may be used at any
location at all times.
12.2.2.1.2 Bwa = Highest monthly average of
Bwa that occurred within the previous calendar year at the
nearest Weather Service Station. This value shall be determined annually
and may be used as an estimate for the entire current calendar year.
12.2.2.1.3 Bwa = Highest daily average of Bwa that
occurred within a calendar month at the nearest Weather Service Station,
calculated from the data from the past 3 years. This value shall be
computed for each month and may be used as an estimate for the current
respective calendar month.
12.2.2.2 If the moisture fraction (Bws) of the effluent
gas is measured:
[GRAPHIC] [TIFF OMITTED] TR17OC00.323

12.2.3 Oxygen-Based F Factor, Dry/Wet Basis.
12.2.3.1 When the pollutant concentration is measured on a wet basis
(Cw) and O2 concentration is measured on a dry
basis (%O2d), use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.324

12.2.3.2 When the pollutant concentration is measured on a dry basis
(Cd) and the O2 concentration is measured on a wet
basis (%O2w), use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.325

12.2.4 Carbon Dioxide-Based F Factor, Dry Basis. When measurements
are on a dry basis for both CO2 (%CO2d) and
pollutant (Cd) concentrations, use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.326

12.2.5 Carbon Dioxide-Based F Factor, Wet Basis. When measurements
are on a wet basis for both CO2 (%CO2w) and
pollutant (Cw) concentrations, use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.327

12.2.6 Carbon Dioxide-Based F Factor, Dry/Wet Basis.
12.2.6.1 When the pollutant concentration is measured on a wet basis
(Cw) and CO2 concentration is measured on a dry
basis (%CO2d), use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.328

12.2.6.2 When the pollutant concentration is measured on a dry basis
(Cd) and CO2 concentration is measured on a wet
basis (%CO2w), use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.329

12.2.7 Direct-Fired Reheat Fuel Burning. The effect of direct-fired
reheat fuel burning (for the purpose of raising the temperature of the
exhaust effluent from wet scrubbers to above the moisture dew-point) on
emission rates will be less than 1.0 percent and, therefore, may be
ignored.
12.2.8 Combined Cycle-Gas Turbine Systems. For gas turbine-steam
generator combined cycle systems, determine the emissions from the steam
generating unit or the percent reduction in potential SO2
emissions as follows:
12.2.8.1 Compute the emission rate from the steam generating unit
using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.330

12.2.8.1.1 Use the test methods and procedures section of 40 CFR
Part 60, Subpart GG to obtain Eco and Eg. Do not
use Fw factors for determining Eg or
Eco. If an SO2 control device is used, measure
Eco after the control device.
12.2.8.1.2 Suitable methods shall be used to determine the heat
input rates to the steam generating units (Hb) and the gas
turbine (Hg).
12.2.8.2 If a control device is used, compute the percent of
potential SO2 emissions (Ps) using the following
equations:
[GRAPHIC] [TIFF OMITTED] TR17OC00.331

[[Page 476]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.332

Note: Use the test methods and procedures section of Subpart GG to
obtain Eci and Eg. Do not use Fw
factors for determining Eg or Eci.

12.3 F Factors. Use an average F factor according to section 12.3.1
or determine an applicable F factor according to section 12.3.2. If
combined fuels are fired, prorate the applicable F factors using the
procedure in section 12.3.3.
12.3.1 Average F Factors. Average F factors (Fd,
Fw, or Fc) from Table 19-2 in section 17.0 may be
used.
12.3.2 Determined F Factors. If the fuel burned is not listed in
Table 19-2 or if the owner or operator chooses to determine an F factor
rather than use the values in Table 19-2, use the procedure below:
12.3.2.1 Equations. Use the equations below, as appropriate, to
compute the F factors:
[GRAPHIC] [TIFF OMITTED] TR17OC00.333

[GRAPHIC] [TIFF OMITTED] TR17OC00.334

[GRAPHIC] [TIFF OMITTED] TR17OC00.335

Note: Omit the %H2O term in the equations for
Fw if %H and %O include the unavailable hydrogen and oxygen
in the form of H2O.)

12.3.2.2 Use applicable sampling procedures in section 12.5.2.1 or
12.5.2.2 to obtain samples for analyses.
12.3.2.3 Use ASTM D 3176-74 or 89 (all cited ASTM standards are
incorporated by reference--see Sec. 60.17) for ultimate analysis of the
fuel.
12.3.2.4 Use applicable methods in section 12.5.2.1 or 12.5.2.2 to
determine the heat content of solid or liquid fuels. For gaseous fuels,
use ASTM D 1826-77 or 94 (incorporated by reference--see Sec. 60.17) to
determine the heat content.
12.3.3 F Factors for Combination of Fuels. If combinations of fuels
are burned, use the following equations, as applicable unless otherwise
specified in an applicable subpart:
[GRAPHIC] [TIFF OMITTED] TR17OC00.336

[GRAPHIC] [TIFF OMITTED] TR17OC00.337

[GRAPHIC] [TIFF OMITTED] TR17OC00.338

12.4 Determination of Average Pollutant Rates.
12.4.1 Average Pollutant Rates from Hourly Values. When hourly
average pollutant rates (Eh), inlet or outlet, are obtained
(e.g., CEMS values), compute the average pollutant rate (Ea)
for the performance test period (e.g., 30 days) specified in the
applicable regulation using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.339

12.4.2 Average Pollutant Rates from Other than Hourly Averages. When
pollutant rates are determined from measured values representing longer
than 1-hour periods (e.g., daily fuel sampling and analyses or Method 6B
values), or when pollutant rates are determined from combinations of 1-
hour and longer than 1-hour periods (e.g., CEMS and Method 6B values),
compute the average pollutant rate (Ea) for the performance
test period (e.g., 30 days) specified in the applicable regulation using
the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.340

12.4.3 Daily Geometric Average Pollutant Rates from Hourly Values.
The geometric average pollutant rate (Ega) is computed using
the following equation:

[[Page 477]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.341

12.5 Determination of Overall Reduction in Potential Sulfur Dioxide
Emission.
12.5.1 Overall Percent Reduction. Compute the overall percent
SO2 reduction (%Ro) using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.342

12.5.2 Pretreatment Removal Efficiency (Optional). Compute the
SO2 removal efficiency from fuel pretreatment
(%Rf) for the averaging period (e.g., 90 days) as specified
in the applicable regulation using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.343

Note: In calculating %Rf, include %S and GCV values for
all fuel lots that are not pretreated and are used during the averaging
period.

12.5.2.1 Solid Fossil (Including Waste) Fuel/Sampling and Analysis.

Note: For the purposes of this method, raw fuel (coal or oil) is the
fuel delivered to the desulfurization (pretreatment) facility. For oil,
the input oil to the oil desulfurization process (e.g., hydrotreatment)
is considered to be the raw fuel.

12.5.2.1.1 Sample Increment Collection. Use ASTM D 2234-76, 96, 97a,
or 98 (incorporated by reference--see Sec. 60.17), Type I, Conditions
A, B, or C, and systematic spacing. As used in this method, systematic
spacing is intended to include evenly spaced increments in time or
increments based on equal weights of coal passing the collection area.
As a minimum, determine the number and weight of increments required per
gross sample representing each coal lot according to Table 2 or
Paragraph 7.1.5.2 of ASTM D 2234. Collect one gross sample for each lot
of raw coal and one gross sample for each lot of product coal.
12.5.2.1.2 ASTM Lot Size. For the purpose of section 12.5.2 (fuel
pretreatment), the lot size of product coal is the weight of product
coal from one type of raw coal. The lot size of raw coal is the weight
of raw coal used to produce one lot of product coal. Typically, the lot
size is the weight of coal processed in a 1-day (24-hour) period. If
more than one type of coal is treated and produced in 1 day, then gross
samples must be collected and analyzed for each type of coal. A coal lot
size equaling the 90-day quarterly fuel quantity for a steam generating
unit may be used if representative sampling can be conducted for each
raw coal and product coal.

Note: Alternative definitions of lot sizes may be used, subject to
prior approval of the Administrator.

12.5.2.1.3 Gross Sample Analysis. Use ASTM D 2013-72 or 86 to
prepare the sample, ASTM D 3177-75 or 89 or ASTM D 4239-85, 94, or 97 to
determine sulfur content (%S), ASTM D 3173-73 or 87 to determine
moisture content, and ASTM D 2015-77 (Reapproved 1978) or 96, D 3286-85
or 96, or D 5865-98 or 10 to determine gross calorific value (GCV) (all
standards cited are incorporated by reference--see Sec. 60.17 for
acceptable versions of the standards) on a dry basis for each gross
sample.
12.5.2.2 Liquid Fossil Fuel-Sampling and Analysis. See Note under
section 12.5.2.1.
12.5.2.2.1 Sample Collection. Follow the procedures for continuous
sampling in ASTM D 270 or D 4177-95 (incorporated by reference--see
Sec. 60.17) for each gross sample from each fuel lot.
12.5.2.2.2 Lot Size. For the purpose of section 12.5.2 (fuel
pretreatment), the lot size of a product oil is the weight of product
oil from one pretreatment facility and intended as one shipment (ship
load, barge load, etc.). The lot size of raw oil is the weight of each
crude liquid fuel type used to produce a lot of product oil.

[[Page 478]]

Note: Alternative definitions of lot sizes may be used, subject to
prior approval of the Administrator.

12.5.2.2.3 Sample Analysis. Use ASTM D 129-64, 78, or 95, ASTM D
1552-83 or 95, or ASTM D 4057-81 or 95 to determine the sulfur content
(%S) and ASTM D 240-76 or 92 (all standards cited are incorporated by
reference--see Sec. 60.17) to determine the GCV of each gross sample.
These values may be assumed to be on a dry basis. The owner or operator
of an affected facility may elect to determine the GCV by sampling the
oil combusted on the first steam generating unit operating day of each
calendar month and then using the lowest GCV value of the three GCV
values per quarter for the GCV of all oil combusted in that calendar
quarter.
12.5.2.3 Use appropriate procedures, subject to the approval of the
Administrator, to determine the fraction of total mass input derived
from each type of fuel.
12.5.3 Control Device Removal Efficiency. Compute the percent
removal efficiency (%Rg) of the control device using the
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.344

12.5.3.1 Use continuous emission monitoring systems or test methods,
as appropriate, to determine the outlet SO2 rates and, if
appropriate, the inlet SO2 rates. The rates may be determined
as hourly (Eh) or other sampling period averages
(Ed). Then, compute the average pollutant rates for the
performance test period (Eao and Eai) using the
procedures in section 12.4.
12.5.3.2 As an alternative, as-fired fuel sampling and analysis may
be used to determine inlet SO2 rates as follows:
12.5.3.2.1 Compute the average inlet SO2 rate
(Edi) for each sampling period using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.345

Where:
[GRAPHIC] [TIFF OMITTED] TR17OC00.346

After calculating Edi, use the procedures in section 12.4 to
determine the average inlet SO2 rate for the performance test
period (Eai).
12.5.3.2.2 Collect the fuel samples from a location in the fuel
handling system that provides a sample representative of the fuel
bunkered or consumed during a steam generating unit operating day. For
the purpose of as-fired fuel sampling under section 12.5.3.2 or section
12.6, the lot size for coal is the weight of coal bunkered or consumed
during each steam generating unit operating day. The lot size for oil is
the weight of oil supplied to the ``day'' tank or consumed during each
steam generating unit operating day. For reporting and calculation
purposes, the gross sample shall be identified with the calendar day on
which sampling began. For steam generating unit operating days when a
coal-fired steam generating unit is operated without coal being added to
the bunkers, the coal analysis from the previous ``as bunkered'' coal
sample shall be used until coal is bunkered again. For steam generating
unit operating days when an oil-fired steam generating unit is operated
without oil being added to the oil ``day'' tank, the oil analysis from
the previous day shall be used until the ``day'' tank is filled again.
Alternative definitions of fuel lot size may be used, subject to prior
approval of the Administrator.
12.5.3.2.3 Use ASTM procedures specified in section 12.5.2.1 or
12.5.2.2 to determine %S and GCV.
12.5.4 Daily Geometric Average Percent Reduction from Hourly Values.
The geometric average percent reduction (%Rga) is computed
using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.347

[[Page 479]]

Note: The calculation includes only paired data sets (hourly
average) for the inlet and outlet pollutant measurements.

12.6 Sulfur Retention Credit for Compliance Fuel. If fuel sampling
and analysis procedures in section 12.5.2.1 are being used to determine
average SO2 emission rates (Eas) to the atmosphere
from a coal-fired steam generating unit when there is no SO2
control device, the following equation may be used to adjust the
emission rate for sulfur retention credits (no credits are allowed for
oil-fired systems) (Edi) for each sampling period using the
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.348

Where:
[GRAPHIC] [TIFF OMITTED] TR17OC00.349

After calculating Edi, use the procedures in section
12.4.2 to determine the average SO2 emission rate to the
atmosphere for the performance test period (Eao).
12.7 Determination of Compliance When Minimum Data Requirement Is
Not Met.
12.7.1 Adjusted Emission Rates and Control Device Removal
Efficiency. When the minimum data requirement is not met, the
Administrator may use the following adjusted emission rates or control
device removal efficiencies to determine compliance with the applicable
standards.
12.7.1.1 Emission Rate. Compliance with the emission rate standard
may be determined by using the lower confidence limit of the emission
rate (Eao*) as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.350

12.7.1.2 Control Device Removal Efficiency. Compliance with the
overall emission reduction (%Ro) may be determined by using
the lower confidence limit of the emission rate (Eao*) and
the upper confidence limit of the inlet pollutant rate (Eai*)
in calculating the control device removal efficiency (%Rg) as
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.351

[GRAPHIC] [TIFF OMITTED] TR17OC00.352

12.7.2 Standard Deviation of Hourly Average Pollutant Rates. Compute
the standard deviation (Se) of the hourly average pollutant
rates using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.353

Equation 19-19 through 19-31 may be used to compute the standard
deviation for both the outlet (So) and, if applicable, inlet
(Si) pollutant rates.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References [Reserved]

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Table 19-1--Conversion Factors for Concentration
----------------------------------------------------------------------------------------------------------------
From To Multiply by
----------------------------------------------------------------------------------------------------------------
g/scm................................... ng/scm......................... 10\9\
mg/scm.................................. ng/scm......................... 10\6\
lb/scf.................................. ng/scm......................... 1.602 x 10\13\

[[Page 480]]

ppm SO2................................. ng/scm......................... 2.66 x 10\6\
ppm NOX................................. ng/scm......................... 1.912 x 10\6\
ppm SO2................................. lb/scf......................... 1.660 x 10 7
ppm NOX................................. lb/scf......................... 1.194 x 10 7
----------------------------------------------------------------------------------------------------------------

Table 19-2--F Factors for Various Fuels\1\
--------------------------------------------------------------------------------------------------------------------------------------------------------
Fd Fw Fc
Fuel Type -----------------------------------------------------------------------------------------------
dscm/J dscf/10\6\ Btu wscm/J wscf/10\6\ Btu scm/J scf/10\6\ Btu
--------------------------------------------------------------------------------------------------------------------------------------------------------
Coal:
Anthracite \2\...................................... 2.71 x 10 7 10,100 2.83 x 10 7 10,540 0.530 x 10 7 1,970
Bituminus \2\....................................... 2.63 x 10 7 9,780 2.86 x 10 7 10,640 0.484 x 10 7 1,800
Lignite............................................. 2.65 x 10 7 9,860 3.21 x 10 7 11,950 0.513 x 10 7 1,910
Oil \3\............................................. 2.47 x 10 7 9,190 2.77 x 10 7 10,320 0.383 x 10 7 1,420
Gas:....................................................
Natural............................................. 2.34 x 10 7 8,710 2.85 x 10 7 10,610 0.287 x 10 7 1,040
Propane............................................. 2.34 x 10 7 8,710 2.74 x 10 7 10,200 0.321 x 10 7 1,190
Butane.............................................. 2.34 x 10 7 8,710 2.79 x 10 7 10,390 0.337 x 10 7 1,250
Wood.................................................... 2.48 x 10 7 9,240 .............. .............. 0.492 x 10 7 1,830
Wood Bark............................................... 2.58 x 10 7 9,600 .............. .............. 0.516 x 10 7 1,920
Municipal............................................... 2.57 x 10 7 9,570 .............. .............. 0.488 x 10 7 1,820
Solid Waste............................................. .............. .............. .............. .............. .............. ..............
--------------------------------------------------------------------------------------------------------------------------------------------------------
\1\ Determined at standard conditions: 20 [deg]C (68 [deg]F) and 760 mm Hg (29.92 in Hg)
\2\ As classified according to ASTM D 388.
\3\ Crude, residual, or distillate.

Table 19-3--Values for T0.95*
----------------------------------------------------------------------------------------------------------------
n\1\ t0.95 n\1\ t0.95 n\1\ t0.95
----------------------------------------------------------------------------------------------------------------
2................................................. 6.31 8 1.89 22-26 1.71
3................................................. 2.42 9 1.86 27-31 1.70
4................................................. 2.35 10 1.83 32-51 1.68
5................................................. 2.13 11 1.81 52-91 1.67
6................................................. 2.02 12-16 1.77 92-151 1.66
7................................................. 1.94 17-21 1.73 152 or more 1.65
----------------------------------------------------------------------------------------------------------------
\1\The values of this table are corrected for n-1 degrees of freedom. Use n equal to the number (H) of hourly
average data points.

Method 20--Determination of Nitrogen Oxides, Sulfur Dioxide, and Diluent
Emissions From Stationary Gas Turbines

1.0 Scope and Application

What is Method 20?

Method 20 contains the details you must follow when using an
instrumental analyzer to determine concentrations of nitrogen oxides,
oxygen, carbon dioxide, and sulfur dioxide in the emissions from
stationary gas turbines. This method follows the specific instructions
for equipment and performance requirements, supplies, sample collection
and analysis, calculations, and data analysis in the methods listed in
section 2.0.
1.1 Analytes. What does this method determine?

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Nitrogen oxides (NOX) as 10102-43-9 Typically <2% of
nitrogen dioxide: Calibration Span.
Nitric oxide (NO).......... 10102-44-0
Nitrogen dioxide NO2.......
Diluent oxygen (O2) or carbon .............. Typically <2% of
dioxide (CO2). Calibration Span.
Sulfur dioxide (SOX)........... 7446-09-5 Typically <2% of
Calibration Span.
------------------------------------------------------------------------

1.2 Applicability. When is this method required? The use of Method
20 may be required by specific New Source Performance Standards, Clean
Air Marketing rules, and State Implementation Plans and permits where

[[Page 481]]

measuring SO2, NOX, CO2, and/or
O2 concentrations in stationary gas turbines emissions are
required. Other regulations may also require its use.
1.3 Data Quality Objectives. How good must my collected data be?
Refer to section 1.3 of Method 7E.

2.0 Summary of Method

In this method, NOX, O2 (or CO2),
and SOX are measured using the following methods found in
appendix A to this part:
(a) Method 1--Sample and Velocity Traverses for Stationary Sources.
(b) Method 3A--Determination of Oxygen and Carbon Dioxide Emissions
From Stationary Sources (Instrumental Analyzer Procedure).
(c) Method 6C--Determination of Sulfur Dioxide Emissions From
Stationary Sources (Instrumental Analyzer Procedure).
(d) Method 7E--Determination of Nitrogen Oxides Emissions From
Stationary Sources (Instrumental Analyzer Procedure).
(e) Method 19--Determination of Sulfur Dioxide Removal Efficiency
and Particulate Matter, Sulfur Dioxide, and Nitrogen Oxide Emission
Rates.

3.0 Definitions

Refer to section 3.0 of Method 7E for the applicable definitions.

4.0 Interferences

Refer to section 4.0 of Methods 3A, 6C, and 7E as applicable.

5.0 Safety

Refer to section 5.0 of Method 7E.

6.0 Equipment and Supplies

The measurement system design is shown in Figure 7E-1 of Method 7E.
Refer to the appropriate methods listed in section 2.0 for equipment and
supplies.

7.0 Reagents and Standards

Refer to the appropriate methods listed in section 2.0 for reagents
and standards.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sampling Site and Sampling Points. Follow the procedures of
section 8.1 of Method 7E. For the stratification test in section 8.1.2,
determine the diluent-corrected pollutant concentration at each traverse
point.
8.2 Initial Measurement System Performance Tests. You must refer to
the appropriate methods listed in section 2.0 for the measurement system
performance tests as applicable.
8.3 Interference Check. You must follow the procedures in section
8.3 of Method 3A or 6C, or section 8.2.7 of Method 7E (as appropriate).
8.4 Sample Collection. You must follow the procedures of section 8.4
of the appropriate methods listed in section 2.0. A test run must have a
duration of at least 21 minutes.
8.5 Post-Run System Bias Check, Drift Assessment, and Alternative
Dynamic Spike Procedure. You must follow the procedures of sections 8.5
and 8.6 of the appropriate methods listed in section 2.0. A test run
must have a duration of at least 21 minutes.

9.0 Quality Control

Follow quality control procedures in section 9.0 of Method 7E.

10.0 Calibration and Standardization

Follow the procedures for calibration and standardization in section
10.0 of Method 7E.

11.0 Analytical Procedures

Because sample collection and analysis are performed together (see
section 8), additional discussion of the analytical procedure is not
necessary.

12.0 Calculations and Data Analysis

You must follow the procedures for calculations and data analysis in
section 12.0 of the appropriate method listed in section 2.0. Follow the
procedures in section 12.0 of Method 19 for calculating fuel-specific F
factors, diluent-corrected pollutant concentrations, and emission rates.

13.0 Method Performance

The specifications for the applicable performance checks are the
same as in section 13.0 of Method 7E.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

Refer to section 16.0 of the appropriate method listed in section
2.0 for alternative procedures.

17.0 References

Refer to section 17.0 of the appropriate method listed in section
2.0 for references.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

Refer to section 18.0 of the appropriate method listed in section
2.0 for tables, diagrams, flowcharts, and validation data.

Method 21--Determination of Volatile Organic Compound Leaks

1.0 Scope and Application

1.1 Analytes.

[[Page 482]]

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Volatile Organic Compounds (VOC).......... No CAS number assigned.
------------------------------------------------------------------------

1.2 Scope. This method is applicable for the determination of VOC
leaks from process equipment. These sources include, but are not limited
to, valves, flanges and other connections, pumps and compressors,
pressure relief devices, process drains, open-ended valves, pump and
compressor seal system degassing vents, accumulator vessel vents,
agitator seals, and access door seals.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A portable instrument is used to detect VOC leaks from
individual sources. The instrument detector type is not specified, but
it must meet the specifications and performance criteria contained in
section 6.0. A leak definition concentration based on a reference
compound is specified in each applicable regulation. This method is
intended to locate and classify leaks only, and is not to be used as a
direct measure of mass emission rate from individual sources.

3.0 Definitions

3.1 Calibration gas means the VOC compound used to adjust the
instrument meter reading to a known value. The calibration gas is
usually the reference compound at a known concentration approximately
equal to the leak definition concentration.
3.2 Calibration precision means the degree of agreement between
measurements of the same known value, expressed as the relative
percentage of the average difference between the meter readings and the
known concentration to the known concentration.
3.3 Leak definition concentration means the local VOC concentration
at the surface of a leak source that indicates that a VOC emission
(leak) is present. The leak definition is an instrument meter reading
based on a reference compound.
3.4 No detectable emission means a local VOC concentration at the
surface of a leak source, adjusted for local VOC ambient concentration,
that is less than 2.5 percent of the specified leak definition
concentration. that indicates that a VOC emission (leak) is not present.
3.5 Reference compound means the VOC species selected as the
instrument calibration basis for specification of the leak definition
concentration. (For example, if a leak definition concentration is
10,000 ppm as methane, then any source emission that results in a local
concentration that yields a meter reading of 10,000 on an instrument
meter calibrated with methane would be classified as a leak. In this
example, the leak definition concentration is 10,000 ppm and the
reference compound is methane.)
3.6 Response factor means the ratio of the known concentration of a
VOC compound to the observed meter reading when measured using an
instrument calibrated with the reference compound specified in the
applicable regulation.
3.7 Response time means the time interval from a step change in VOC
concentration at the input of the sampling system to the time at which
90 percent of the corresponding final value is reached as displayed on
the instrument readout meter.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

A VOC monitoring instrument meeting the following specifications is
required:
6.1 The VOC instrument detector shall respond to the compounds being
processed. Detector types that may meet this requirement include, but
are not limited to, catalytic oxidation, flame ionization, infrared
absorption, and photoionization.
6.2 The instrument shall be capable of measuring the leak definition
concentration specified in the regulation.
6.3 The scale of the instrument meter shall be readable to 2.5
percent of the specified leak definition concentration.
6.4 The instrument shall be equipped with an electrically driven
pump to ensure that a sample is provided to the detector at a constant
flow rate. The nominal sample flow rate, as measured at the sample probe
tip, shall be 0.10 to 3.0 l/min (0.004 to 0.1 ft\3\/min) when the probe
is fitted with a glass wool plug or filter that may be used to prevent
plugging of the instrument.
6.5 The instrument shall be equipped with a probe or probe extension
or sampling not to exceed 6.4 mm (\1/4\ in) in outside diameter,

[[Page 483]]

with a single end opening for admission of sample.
6.6 The instrument shall be intrinsically safe for operation in
explosive atmospheres as defined by the National Electrical Code by the
National Fire Prevention Association or other applicable regulatory code
for operation in any explosive atmospheres that may be encountered in
its use. The instrument shall, at a minimum, be intrinsically safe for
Class 1, Division 1 conditions, and/or Class 2, Division 1 conditions,
as appropriate, as defined by the example code. The instrument shall not
be operated with any safety device, such as an exhaust flame arrestor,
removed.

7.0 Reagents and Standards

7.1 Two gas mixtures are required for instrument calibration and
performance evaluation:
7.1.1 Zero Gas. Air, less than 10 parts per million by volume (ppmv)
VOC.
7.1.2 Calibration Gas. For each organic species that is to be
measured during individual source surveys, obtain or prepare a known
standard in air at a concentration approximately equal to the applicable
leak definition specified in the regulation.
7.2 Cylinder Gases. If cylinder calibration gas mixtures are used,
they must be analyzed and certified by the manufacturer to be within 2
percent accuracy, and a shelf life must be specified. Cylinder standards
must be either reanalyzed or replaced at the end of the specified shelf
life.
7.3 Prepared Gases. Calibration gases may be prepared by the user
according to any accepted gaseous preparation procedure that will yield
a mixture accurate to within 2 percent. Prepared standards must be
replaced each day of use unless it is demonstrated that degradation does
not occur during storage.
7.4 Mixtures with non-Reference Compound Gases. Calibrations may be
performed using a compound other than the reference compound. In this
case, a conversion factor must be determined for the alternative
compound such that the resulting meter readings during source surveys
can be converted to reference compound results.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Instrument Performance Evaluation. Assemble and start up the
instrument according to the manufacturer's instructions for recommended
warmup period and preliminary adjustments.
8.1.1 Response Factor. A response factor must be determined for each
compound that is to be measured, either by testing or from reference
sources. The response factor tests are required before placing the
analyzer into service, but do not have to be repeated at subsequent
intervals.
8.1.1.1 Calibrate the instrument with the reference compound as
specified in the applicable regulation. Introduce the calibration gas
mixture to the analyzer and record the observed meter reading. Introduce
zero gas until a stable reading is obtained. Make a total of three
measurements by alternating between the calibration gas and zero gas.
Calculate the response factor for each repetition and the average
response factor.
8.1.1.2 The instrument response factors for each of the individual
VOC to be measured shall be less than 10 unless otherwise specified in
the applicable regulation. When no instrument is available that meets
this specification when calibrated with the reference VOC specified in
the applicable regulation, the available instrument may be calibrated
with one of the VOC to be measured, or any other VOC, so long as the
instrument then has a response factor of less than 10 for each of the
individual VOC to be measured.
8.1.1.3 Alternatively, if response factors have been published for
the compounds of interest for the instrument or detector type, the
response factor determination is not required, and existing results may
be referenced. Examples of published response factors for flame
ionization and catalytic oxidation detectors are included in References
1-3 of section 17.0.
8.1.2 Calibration Precision. The calibration precision test must be
completed prior to placing the analyzer into service and at subsequent
3-month intervals or at the next use, whichever is later.
8.1.2.1 Make a total of three measurements by alternately using zero
gas and the specified calibration gas. Record the meter readings.
Calculate the average algebraic difference between the meter readings
and the known value. Divide this average difference by the known
calibration value and multiply by 100 to express the resulting
calibration precision as a percentage.
8.1.2.2 The calibration precision shall be equal to or less than 10
percent of the calibration gas value.
8.1.3 Response Time. The response time test is required before
placing the instrument into service. If a modification to the sample
pumping system or flow configuration is made that would change the
response time, a new test is required before further use.
8.1.3.1 Introduce zero gas into the instrument sample probe. When
the meter reading has stabilized, switch quickly to the specified
calibration gas. After switching, measure the time required to attain 90
percent of the final stable reading. Perform this test sequence three
times and record the results. Calculate the average response time.
8.1.3.2 The instrument response time shall be equal to or less than
30 seconds. The instrument pump, dilution probe (if any), sample probe,
and probe filter that will be used

[[Page 484]]

during testing shall all be in place during the response time
determination.
8.2 Instrument Calibration. Calibrate the VOC monitoring instrument
according to section 10.0.
8.3 Individual Source Surveys.
8.3.1 Type I--Leak Definition Based on Concentration. Place the
probe inlet at the surface of the component interface where leakage
could occur. Move the probe along the interface periphery while
observing the instrument readout. If an increased meter reading is
observed, slowly sample the interface where leakage is indicated until
the maximum meter reading is obtained. Leave the probe inlet at this
maximum reading location for approximately two times the instrument
response time. If the maximum observed meter reading is greater than the
leak definition in the applicable regulation, record and report the
results as specified in the regulation reporting requirements. Examples
of the application of this general technique to specific equipment types
are:
8.3.1.1 Valves. The most common source of leaks from valves is the
seal between the stem and housing. Place the probe at the interface
where the stem exits the packing gland and sample the stem
circumference. Also, place the probe at the interface of the packing
gland take-up flange seat and sample the periphery. In addition, survey
valve housings of multipart assembly at the surface of all interfaces
where a leak could occur.
8.3.1.2 Flanges and Other Connections. For welded flanges, place the
probe at the outer edge of the flange-gasket interface and sample the
circumference of the flange. Sample other types of nonpermanent joints
(such as threaded connections) with a similar traverse.
8.3.1.3 Pumps and Compressors. Conduct a circumferential traverse at
the outer surface of the pump or compressor shaft and seal interface. If
the source is a rotating shaft, position the probe inlet within 1 cm of
the shaft-seal interface for the survey. If the housing configuration
prevents a complete traverse of the shaft periphery, sample all
accessible portions. Sample all other joints on the pump or compressor
housing where leakage could occur.
8.3.1.4 Pressure Relief Devices. The configuration of most pressure
relief devices prevents sampling at the sealing seat interface. For
those devices equipped with an enclosed extension, or horn, place the
probe inlet at approximately the center of the exhaust area to the
atmosphere.
8.3.1.5 Process Drains. For open drains, place the probe inlet at
approximately the center of the area open to the atmosphere. For covered
drains, place the probe at the surface of the cover interface and
conduct a peripheral traverse.
8.3.1.6 Open-ended Lines or Valves. Place the probe inlet at
approximately the center of the opening to the atmosphere.
8.3.1.7 Seal System Degassing Vents and Accumulator Vents. Place the
probe inlet at approximately the center of the opening to the
atmosphere.
8.3.1.8 Access door seals. Place the probe inlet at the surface of
the door seal interface and conduct a peripheral traverse.
8.3.2 Type II--``No Detectable Emission''. Determine the local
ambient VOC concentration around the source by moving the probe randomly
upwind and downwind at a distance of one to two meters from the source.
If an interference exists with this determination due to a nearby
emission or leak, the local ambient concentration may be determined at
distances closer to the source, but in no case shall the distance be
less than 25 centimeters. Then move the probe inlet to the surface of
the source and determine the concentration as outlined in section 8.3.1.
The difference between these concentrations determines whether there are
no detectable emissions. Record and report the results as specified by
the regulation. For those cases where the regulation requires a specific
device installation, or that specified vents be ducted or piped to a
control device, the existence of these conditions shall be visually
confirmed. When the regulation also requires that no detectable
emissions exist, visual observations and sampling surveys are required.
Examples of this technique are:
8.3.2.1 Pump or Compressor Seals. If applicable, determine the type
of shaft seal. Perform a survey of the local area ambient VOC
concentration and determine if detectable emissions exist as described
in section 8.3.2.
8.3.2.2 Seal System Degassing Vents, Accumulator Vessel Vents,
Pressure Relief Devices. If applicable, observe whether or not the
applicable ducting or piping exists. Also, determine if any sources
exist in the ducting or piping where emissions could occur upstream of
the control device. If the required ducting or piping exists and there
are no sources where the emissions could be vented to the atmosphere
upstream of the control device, then it is presumed that no detectable
emissions are present. If there are sources in the ducting or piping
where emissions could be vented or sources where leaks could occur, the
sampling surveys described in section 8.3.2 shall be used to determine
if detectable emissions exist.
8.3.3 Alternative Screening Procedure.
8.3.3.1 A screening procedure based on the formation of bubbles in a
soap solution that is sprayed on a potential leak source may be used for
those sources that do not have continuously moving parts, that do not
have surface temperatures greater than the boiling point or less than
the freezing point of the soap solution, that do not have open

[[Page 485]]

areas to the atmosphere that the soap solution cannot bridge, or that do
not exhibit evidence of liquid leakage. Sources that have these
conditions present must be surveyed using the instrument technique of
section 8.3.1 or 8.3.2.
8.3.3.2 Spray a soap solution over all potential leak sources. The
soap solution may be a commercially available leak detection solution or
may be prepared using concentrated detergent and water. A pressure
sprayer or squeeze bottle may be used to dispense the solution. Observe
the potential leak sites to determine if any bubbles are formed. If no
bubbles are observed, the source is presumed to have no detectable
emissions or leaks as applicable. If any bubbles are observed, the
instrument techniques of section 8.3.1 or 8.3.2 shall be used to
determine if a leak exists, or if the source has detectable emissions,
as applicable.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.1.2......................... Instrument Ensure precision and
calibration accuracy,
precision check. respectively, of
instrument response
to standard.
10.0.......................... Instrument
calibration.
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 Calibrate the VOC monitoring instrument as follows. After the
appropriate warmup period and zero internal calibration procedure,
introduce the calibration gas into the instrument sample probe. Adjust
the instrument meter readout to correspond to the calibration gas value.

Note: If the meter readout cannot be adjusted to the proper value, a
malfunction of the analyzer is indicated and corrective actions are
necessary before use.

11.0 Analytical Procedures [Reserved]

12.0 Data Analyses and Calculations [Reserved]

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Dubose, D.A., and G.E. Harris. Response Factors of VOC Analyzers
at a Meter Reading of 10,000 ppmv for Selected Organic Compounds. U.S.
Environmental Protection Agency, Research Triangle Park, NC. Publication
No. EPA 600/2-81051. September 1981.
2. Brown, G.E., et al. Response Factors of VOC Analyzers Calibrated
with Methane for Selected Organic Compounds. U.S. Environmental
Protection Agency, Research Triangle Park, NC. Publication No. EPA 600/
2-81-022. May 1981.
3. DuBose, D.A. et al. Response of Portable VOC Analyzers to
Chemical Mixtures. U.S. Environmental Protection Agency, Research
Triangle Park, NC. Publication No. EPA 600/2-81-110. September 1981.
4. Handbook of Hazardous Materials: Fire, Safety, Health. Alliance
of American Insurers. Schaumberg, IL. 1983.

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 22--Visual Determination of Fugitive Emissions From Material
Sources and Smoke Emissions From Flares

Note: This method is not inclusive with respect to observer
certification. Some material is incorporated by reference from Method 9.

1.0 Scope and Application

This method is applicable for the determination of the frequency of
fugitive emissions from stationary sources, only as specified in an
applicable subpart of the regulations. This method also is applicable
for the determination of the frequency of visible smoke emissions from
flares.

2.0 Summary of Method

2.1 Fugitive emissions produced during material processing,
handling, and transfer operations or smoke emissions from flares are
visually determined by an observer without the aid of instruments.
2.2 This method is used also to determine visible smoke emissions
from flares used for combustion of waste process materials.
2.3 This method determines the amount of time that visible emissions
occur during the observation period (i.e., the accumulated emission
time). This method does not require that the opacity of emissions be
determined. Since this procedure requires only the determination of
whether visible emissions occur and does not require the determination
of opacity levels, observer certification according to the procedures of
Method 9 is not required. However, it is necessary that the observer is
knowledgeable with respect to the general procedures for determining the
presence of visible emissions. At a minimum, the observer must be
trained and knowledgeable regarding the effects of background contrast,
ambient lighting, observer position relative

[[Page 486]]

to lighting, wind, and the presence of uncombined water (condensing
water vapor) on the visibility of emissions. This training is to be
obtained from written materials found in References 1 and 2 or from the
lecture portion of the Method 9 certification course.

3.0 Definitions

3.1 Emission frequency means the percentage of time that emissions
are visible during the observation period.
3.2 Emission time means the accumulated amount of time that
emissions are visible during the observation period.
3.3 Fugitive emissions means emissions generated by an affected
facility which is not collected by a capture system and is released to
the atmosphere. This includes emissions that (1) escape capture by
process equipment exhaust hoods; (2) are emitted during material
transfer; (3) are emitted from buildings housing material processing or
handling equipment; or (4) are emitted directly from process equipment.
3.4 Observation period means the accumulated time period during
which observations are conducted, not to be less than the period
specified in the applicable regulation.
3.5 Smoke emissions means a pollutant generated by combustion in a
flare and occurring immediately downstream of the flame. Smoke occurring
within the flame, but not downstream of the flame, is not considered a
smoke emission.

4.0 Interferences

4.1 Occasionally, fugitive emissions from sources other than the
affected facility (e.g., road dust) may prevent a clear view of the
affected facility. This may particularly be a problem during periods of
high wind. If the view of the potential emission points is obscured to
such a degree that the observer questions the validity of continuing
observations, then the observations shall be terminated, and the
observer shall clearly note this fact on the data form.

5.0 Safety

6.0 Equipment

6.1 Stopwatches (two). Accumulative type with unit divisions of at
least 0.5 seconds.
6.2 Light Meter. Light meter capable of measuring illuminance in the
50 to 200 lux range, required for indoor observations only.

7.0 Reagents and Supplies [Reserved]

8.0 Sample Collection, Preservation, Storage, and Transfer [Reserved]

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure

11.1 Selection of Observation Location. Survey the affected
facility, or the building or structure housing the process to be
observed, and determine the locations of potential emissions. If the
affected facility is located inside a building, determine an observation
location that is consistent with the requirements of the applicable
regulation (i.e., outside observation of emissions escaping the
building/structure or inside observation of emissions directly emitted
from the affected facility process unit). Then select a position that
enables a clear view of the potential emission point(s) of the affected
facility or of the building or structure housing the affected facility,
as appropriate for the applicable subpart. A position at least 4.6 m (15
feet), but not more than 400 m (0.25 miles), from the emission source is
recommended. For outdoor locations, select a position where the sunlight
is not shining directly in the observer's eyes.
11.2 Field Records.
11.2.1 Outdoor Location. Record the following information on the
field data sheet (Figure 22-1): Company name, industry, process unit,
observer's name, observer's affiliation, and date. Record also the
estimated wind speed, wind direction, and sky condition. Sketch the
process unit being observed, and note the observer location relative to
the source and the sun. Indicate the potential and actual emission
points on the sketch.
11.2.2 Indoor Location. Record the following information on the
field data sheet (Figure 22-2): Company name, industry, process unit,
observer's name, observer's affiliation, and date. Record as appropriate
the type, location, and intensity of lighting on the data sheet. Sketch
the process unit being observed, and note the observer location relative
to the source. Indicate the potential and actual fugitive emission
points on the sketch.
11.3 Indoor Lighting Requirements. For indoor locations, use a light
meter to measure the level of illumination at a location as close to the
emission source(s) as is feasible. An illumination of greater than 100
lux (10 foot candles) is considered necessary for proper application of
this method.
11.4 Observations.
11.4.1 Procedure. Record the clock time when observations begin. Use
one stopwatch to monitor the duration of the observation

[[Page 487]]

period. Start this stopwatch when the observation period begins. If the
observation period is divided into two or more segments by process
shutdowns or observer rest breaks (see section 11.4.3), stop the
stopwatch when a break begins and restart the stopwatch without
resetting it when the break ends. Stop the stopwatch at the end of the
observation period. The accumulated time indicated by this stopwatch is
the duration of observation period. When the observation period is
completed, record the clock time. During the observation period,
continuously watch the emission source. Upon observing an emission
(condensed water vapor is not considered an emission), start the second
accumulative stopwatch; stop the watch when the emission stops. Continue
this procedure for the entire observation period. The accumulated
elapsed time on this stopwatch is the total time emissions were visible
during the observation period (i.e., the emission time.)
11.4.2 Observation Period. Choose an observation period of
sufficient length to meet the requirements for determining compliance
with the emission standard in the applicable subpart of the regulations.
When the length of the observation period is specifically stated in the
applicable subpart, it may not be necessary to observe the source for
this entire period if the emission time required to indicate
noncompliance (based on the specified observation period) is observed in
a shorter time period. In other words, if the regulation prohibits
emissions for more than 6 minutes in any hour, then observations may
(optional) be stopped after an emission time of 6 minutes is exceeded.
Similarly, when the regulation is expressed as an emission frequency and
the regulation prohibits emissions for greater than 10 percent of the
time in any hour, then observations may (optional) be terminated after 6
minutes of emission are observed since 6 minutes is 10 percent of an
hour. In any case, the observation period shall not be less than 6
minutes in duration. In some cases, the process operation may be
intermittent or cyclic. In such cases, it may be convenient for the
observation period to coincide with the length of the process cycle.
11.4.3 Observer Rest Breaks. Do not observe emissions continuously
for a period of more than 15 to 20 minutes without taking a rest break.
For sources requiring observation periods of greater than 20 minutes,
the observer shall take a break of not less than 5 minutes and not more
than 10 minutes after every 15 to 20 minutes of observation. If
continuous observations are desired for extended time periods, two
observers can alternate between making observations and taking breaks.
11.5 Recording Observations. Record the accumulated time of the
observation period on the data sheet as the observation period duration.
Record the accumulated time emissions were observed on the data sheet as
the emission time. Record the clock time the observation period began
and ended, as well as the clock time any observer breaks began and
ended.

12.0 Data Analysis and Calculations

If the applicable subpart requires that the emission rate be
expressed as an emission frequency (in percent), determine this value as
follows: Divide the accumulated emission time (in seconds) by the
duration of the observation period (in seconds) or by any minimum
observation period required in the applicable subpart, if the actual
observation period is less than the required period, and multiply this
quotient by 100.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Missan, R., and A. Stein. Guidelines for Evaluation of Visible
Emissions Certification, Field Procedures, Legal Aspects, and Background
Material. EPA Publication No. EPA-340/1-75-007. April 1975.
2. Wohlschlegel, P., and D.E. Wagoner. Guideline for Development of
a Quality Assurance Program: Volume IX--Visual Determination of Opacity
Emissions from Stationary Sources. EPA Publication No. EPA-650/4-74-
005i. November 1975.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 488]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.354

[[Page 489]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.355

Method 23--Determination of Polychlorinated Dibenzo-p-Dioxins and
Polychlorinated Dibenzofurans From Stationary Sources

1. Applicability and Principle

1.1 Applicability. This method is applicable to the determination of
polychlorinated dibenzo-p-dioxins (PCDD's) and polychlorinated
dibenzofurans (PCDF's) from stationary sources.
1.2 Principle. A sample is withdrawn from the gas stream
isokinetically and collected in the sample probe, on a glass fiber
filter, and on a packed column of adsorbent material. The sample cannot
be separated into a particle vapor fraction. The PCDD's and

[[Page 490]]

PCDF's are extracted from the sample, separated by high resolution gas
chromatography, and measured by high resolution mass spectrometry.

2. Apparatus

2.1 Sampling. A schematic of the sampling train used in this method
is shown in Figure 23-1. Sealing greases may not be used in assembling
the train. The train is identical to that described in section 2.1 of
Method 5 of this appendix with the following additions:
[GRAPHIC] [TIFF OMITTED] TC01JN92.249

[[Page 491]]

2.1.1 Nozzle. The nozzle shall be made of nickel, nickel-plated
stainless steel, quartz, or borosilicate glass.
2.1.2 Sample Transfer Lines. The sample transfer lines, if needed,
shall be heat traced, heavy walled TFE (\1/2\ in. OD with \1/8\ in.
wall) with connecting fittings that are capable of forming leak-free,
vacuum-tight connections without using sealing greases. The line shall
be as short as possible and must be maintained at 120 [deg]C.
2.1.1 Filter Support. Teflon or Teflon-coated wire.
2.1.2 Condenser. Glass, coil type with compatible fittings. A
schematic diagram is shown in Figure 23-2.
2.1.3 Water Bath. Thermostatically controlled to maintain the gas
temperature exiting the condenser at <20 [deg]C (68 [deg]F).
2.1.4 Adsorbent Module. Glass container to hold the solid adsorbent.
A shematic diagram is shown in Figure 23-2. Other physical
configurations of the resin trap/condenser assembly are acceptable. The
connecting fittings shall form leak-free, vacuum tight seals. No sealant
greases shall be used in the sampling train. A coarse glass frit is
included to retain the adsorbent.
2.2 Sample Recovery.
2.2.1 Fitting Caps. Ground glass, Teflon tape, or aluminum foil
(Section 2.2.6) to cap off the sample exposed sections of the train.
2.2.2 Wash Bottles. Teflon, 500-ml.
2.2.3 Probe-Liner Probe-Nozzle, and Filter-Holder Brushes. Inert
bristle brushes with precleaned stainless steel or Teflon handles. The
probe brush shall have extensions of stainless steel or Teflon, at least
as long as the probe. The brushes shall be properly sized and shaped to
brush out the nozzle, probe liner, and transfer line, if used.

[[Page 492]]

[GRAPHIC] [TIFF OMITTED] TC01JN92.250

2.2.4 Filter Storage Container. Sealed filter holder, wide-mouth
amber glass jar with Teflon-lined cap, or glass petri dish.
2.2.5 Balance. Triple beam.
2.2.6 Aluminum Foil. Heavy duty, hexane-rinsed.
2.2.7 Storage Container. Air-tight container to store silica gel.

[[Page 493]]

2.2.8 Graduated Cylinder. Glass, 250-ml with 2-ml graduation.
2.2.9 Glass Sample Storage Container. Amber glass bottle for sample
glassware washes, 500- or 1000-ml, with leak free Teflon-lined caps.
2.3 Analysis.
2.3.1 Sample Container. 125- and 250-ml flint glass bottles with
Teflon-lined caps.
2.3.2 Test Tube. Glass.
2.3.3 Soxhlet Extraction Apparatus. Capable of holding 43 x 123 mm
extraction thimbles.
2.3.4 Extraction Thimble. Glass, precleaned cellulosic, or glass
fiber.
2.3.5 Pasteur Pipettes. For preparing liquid chromatographic
columns.
2.3.6 Reacti-vials. Amber glass, 2-ml, silanized prior to use.
2.3.7 Rotary Evaporator. Buchi/Brinkman RF-121 or equivalent.
2.3.8 Nitrogen Evaporative Concentrator. N-Evap Analytical
Evaporator Model III or equivalent.
2.3.9 Separatory Funnels. Glass, 2-liter.
2.3.10 Gas Chromatograph. Consisting of the following components:
2.3.10.1 Oven. Capable of maintaining the separation column at the
proper operating temperature [deg]C and performing programmed increases
in temperature at rates of at least 40 [deg]C/min.
2.3.10.2 Temperature Gauge. To monitor column oven, detector, and
exhaust temperatures 1 [deg]C.
2.3.10.3 Flow System. Gas metering system to measure sample, fuel,
combustion gas, and carrier gas flows.
2.3.10.4 Capillary Columns. A fused silica column, 60 x 0.25 mm
inside diameter (ID), coated with DB-5 and a fused silica column, 30 m x
0.25 mm ID coated with DB-225. Other column systems may be used provided
that the user is able to demonstrate using calibration and performance
checks that the column system is able to meet the specifications of
section 6.1.2.2.
2.3.11 Mass Spectrometer. Capable of routine operation at a
resolution of 1:10000 with a stability of 5 ppm.
2.3.12 Data System. Compatible with the mass spectrometer and
capable of monitoring at least five groups of 25 ions.
2.3.13 Analytical Balance. To measure within 0.1 mg.

3. Reagents

3.1 Sampling.
3.1.1 Filters. Glass fiber filters, without organic binder,
exhibiting at least 99.95 percent efficiency (<0.05 percent penetration)
on 0.3-micron dioctyl phthalate smoke particles. The filter efficiency
test shall be conducted in accordance with ASTM Standard Method D 2986-
71 (Reapproved 1978) (incorporated by reference--see Sec. 60.17).
3.1.1.1 Precleaning. All filters shall be cleaned before their
initial use. Place a glass extraction thimble and 1 g of silica gel and
a plug of glass wool into a Soxhlet apparatus, charge the apparatus with
toluene, and reflux for a minimum of 3 hours. Remove the toluene and
discard it, but retain the silica gel. Place no more than 50 filters in
the thimble onto the silica gel bed and top with the cleaned glass wool.
Charge the Soxhlet with toluene and reflux for 16 hours. After
extraction, allow the Soxhlet to cool, remove the filters, and dry them
under a clean N2 stream. Store the filters in a glass petri
dish sealed with Teflon tape.
3.1.2 Adsorbent Resin. Amberlite XAD-2 resin. Thoroughly cleaned
before initial use.
3.1.2.1 Cleaning Procedure. This procedure may be carried out in a
giant Soxhlet extractor. An all-glass filter thimble containing an
extra-course frit is used for extraction of XAD-2. The frit is recessed
10-15 mm above a crenelated ring at the bottom of the thimble to
facilitate drainage. The resin must be carefully retained in the
extractor cup with a glass wool plug and a stainless steel ring because
it floats on methylene chloride. This process involves sequential
extraction in the following order.

------------------------------------------------------------------------
Solvent Procedure
------------------------------------------------------------------------
Water..................................... Initial rinse: Place resin
in a beaker, rinse once
with water, and discard.
Fill with water a second
time, let stand overnight,
and discard.
Water..................................... Extract with water for 8
hours.
Methanol.................................. Extract for 22 hours.
Methylene Chloride........................ Extract for 22 hours.
Toluene................................... Extract for 22 hours.
------------------------------------------------------------------------

3.1.2.2 Drying.
3.1.2.2.1 Drying Column. Pyrex pipe, 10.2 cm ID by 0.6 m long, with
suitable retainers.
3.1.2.2.2 Procedure. The adsorbent must be dried with clean inert
gas. Liquid nitrogen from a standard commercial liquid nitrogen cylinder
has proven to be a reliable source of large volumes of gas free from
organic contaminants. Connect the liquid nitrogen cylinder to the column
by a length of cleaned copper tubing, 0.95 cm ID, coiled to pass through
a heat source. A convenient heat source is a water-bath heated from a
steam line. The final nitrogen temperature should only be warm to the
touch and not over 40 [deg]C. Continue flowing nitrogen through the
adsorbent until all the residual solvent is removed. The flow rate
should be sufficient to gently agitate the particles but not so
excessive as the cause the particles to fracture.
3.1.2.3 Quality Control Check. The adsorbent must be checked for
residual toluene.
3.1.2.3.1 Extraction. Weigh 1.0 g sample of dried resin into a small
vial, add 3 ml of toluene, cap the vial, and shake it well.

[[Page 494]]

3.1.2.3.2 Analysis. Inject a 2 l sample of the extract into
a gas chromatograph operated under the following conditions:

Column: 6 ft x \1/8\ in stainless steel containing 10 percent OV-101
on 100/120 Supelcoport.
Carrier Gas: Helium at a rate of 30 ml/min.
Detector: Flame ionization detector operated at a sensitivity of 4 x
10^-11 A/mV.
Injection Port Temperature: 250 [deg]C.
Detector Temperature: 305 [deg]C.
Oven Temperature: 30 [deg]C for 4 min; programmed to rise at 40
[deg]C/min until it reaches 250 [deg]C; return to 30 [deg]C after 17
minutes.

Compare the results of the analysis to the results from the
reference solution. Prepare the reference solution by injection 2.5
l of methylene chloride into 100 ml of toluene. This
corresponds to 100 g of methylene chloride per g of adsorbent.
The maximum acceptable concentration is 1000 g/g of adsorbent.
If the adsorbent exceeds this level, drying must be continued until the
excess methylene chloride is removed.
3.1.2.4 Storage. The adsorbent must be used within 4 weeks of
cleaning. After cleaning, it may be stored in a wide mouth amber glass
container with a Teflon-lined cap or placed in one of the glass
adsorbent modules tightly sealed with glass stoppers. If precleaned
adsorbent is purchased in sealed containers, it must be used within 4
weeks after the seal is broken.
3.1.3 Glass Wool. Cleaned by sequential immersion in three aliquots
of methylene chloride, dried in a 110 [deg]C oven, and stored in a
methylene chloride-washed glass jar with a Teflon-lined screw cap.
3.1.4 Water. Deionized distilled and stored in a methylene chloride-
rinsed glass container with a Teflon-lined screw cap.
3.1.5 Silica Gel. Indicating type, 6 to 16 mesh. If previously used,
dry at 175 [deg]C (350 [deg]F) for two hours. New silica gel may be used
as received. Alternately other types of desiccants (equivalent or
better) may be used, subject to the approval of the Administrator.
3.1.6 Chromic Acid Cleaning Solution. Dissolve 20 g of sodium
dichromate in 15 ml of water, and then carefully add 400 ml of
concentrated sulfuric acid.
3.2 Sample Recovery.
3.2.2 Acetone. Pesticide quality.
3.2.2 Methylene Chloride. Pesticide qualtity.
3.2.3 Toluene. Pesticide quality.
3.3 Analysis.
3.3.1 Potassium Hydroxide. ACS grade, 2-percent (weight/volume) in
water.
3.3.2 Sodium Sulfate. Granulated, reagent grade. Purify prior to use
by rinsing with methylene chloride and oven drying. Store the cleaned
material in a glass container with a Teflon-lined screw cap.
3.3.3 Sulfuric Acid. Reagent grade.
3.3.4 Sodium Hydroxide. 1.0 N. Weigh 40 g of sodium hydroxide into a
1-liter volumetric flask. Dilute to 1 liter with water.
3.3.5 Hexane. Pesticide grade.
3.3.6 Methylene Chloride. Pesticide grade.
3.3.7 Benzene. Pesticide Grade.
3.3.8 Ethyl Acetate.
3.3.9 Methanol. Pesticide Grade.
3.3.10 Toluene. Pesticide Grade.
3.3.11 Nonane. Pesticide Grade.
3.3.12 Cyclohexane. Pesticide Grade.
3.3.13 Basic Alumina. Activity grade 1, 100-200 mesh. Prior to use,
activate the alumina by heating for 16 hours at 130 [deg]C before use.
Store in a desiccator. Pre-activated alumina may be purchased from a
supplier and may be used as received.
3.3.14 Silica Gel. Bio-Sil A, 100-200 mesh. Prior to use, activate
the silica gel by heating for at least 30 minutes at 180 [deg]C. After
cooling, rinse the silica gel sequentially with methanol and methylene
chloride. Heat the rinsed silica gel at 50 [deg]C for 10 minutes, then
increase the temperature gradually to 180 [deg]C over 25 minutes and
maintain it at this temperature for 90 minutes. Cool at room temperature
and store in a glass container with a Teflon-lined screw cap.
3.3.15 Silica Gel Impregnated with Sulfuric Acid. Combine 100 g of
silica gel with 44 g of concentrated sulfuric acid in a screw capped
glass bottle and agitate thoroughly. Disperse the solids with a stirring
rod until a uniform mixture is obtained. Store the mixture in a glass
container with a Teflon-lined screw cap.
3.3.16 Silica Gel Impregnated with Sodium Hydroxide. Combine 39 g of
1 N sodium hydroxide with 100 g of silica gel in a screw capped glass
bottle and agitate thoroughly. Disperse solids with a stirring rod until
a uniform mixture is obtained. Store the mixture in glass container with
a Teflon-lined screw cap.
3.3.17 Carbon/Celite. Combine 10.7 g of AX-21 carbon with 124 g of
Celite 545 in a 250-ml glass bottle with a Teflon-lined screw cap.
Agitate the mixture thoroughly until a uniform mixture is obtained.
Store in the glass container.
3.3.18 Nitrogen. Ultra high purity.
3.3.19 Hydrogen. Ultra high purity.
3.3.20 Internal Standard Solution. Prepare a stock standard solution
containing the isotopically labelled PCDD's and PCDF's at the
concentrations shown in Table 1 under the heading ``Internal Standards''
in 10 ml of nonane.
3.3.21 Surrogate Standard Solution. Prepare a stock standard
solution containing the isotopically labelled PCDD's and PCDF's at the
concentrations shown in Table 1 under the heading ``Surrogate
Standards'' in 10 ml of nonane.
3.3.22 Recovery Standard Solution. Prepare a stock standard solution
containing the

[[Page 495]]

isotopically labelled PCDD's and PCDF's at the concentrations shown in
Table 1 under the heading ``Recovery Standards'' in 10 ml of nonane.

4. Procedure

4.1 Sampling. The complexity of this method is such that, in order
to obtain reliable results, testers should be trained and experienced
with the test procedures.
4.1.1 Pretest Preparation.
4.1.1.1 Cleaning Glassware. All glass components of the train
upstream of and including the adsorbent module, shall be cleaned as
described in section 3A of the ``Manual of Analytical Methods for the
Analysis of Pesticides in Human and Environmental Samples.'' Special
care shall be devoted to the removal of residual silicone grease
sealants on ground glass connections of used glassware. Any residue
shall be removed by soaking the glassware for several hours in a chromic
acid cleaning solution prior to cleaning as described above.
4.1.1.2 Adsorbent Trap. The traps must be loaded in a clean area to
avoid contamination. They may not be loaded in the field. Fill a trap
with 20 to 40 g of XAD-2. Follow the XAD-2 with glass wool and tightly
cap both ends of the trap. Add 100 l of the surrogate standard
solution (section 3.3.21) to each trap.
4.1.1.3 Sample Train. It is suggested that all components be
maintained according to the procedure described in APTD-0576.
Alternative mercury-free thermometers may be used if the thermometers
are, at a minimum, equivalent in terms of performance or suitably
effective for the specific temperature measurement application.
4.1.1.4 Silica Gel. Weigh several 200 to 300 g portions of silica
gel in an air tight container to the nearest 0.5 g. Record the total
weight of the silica gel plus container, on each container. As an
alternative, the silica gel may be weighed directly in its impinger or
sampling holder just prior to sampling.
4.1.1.5 Filter. Check each filter against light for irregularities
and flaws or pinhole leaks. Pack the filters flat in a clean glass
container.
4.1.2 Preliminary Determinations. Same as section 4.1.2 of Method 5.
4.1.3 Preparation of Collection Train.
4.1.3.1 During preparation and assembly of the sampling train, keep
all train openings where contamination can enter, sealed until just
prior to assembly or until sampling is about to begin.

Note: Do not use sealant grease in assembling the train.

4.1.3.2 Place approximately 100 ml of water in the second and third
impingers, leave the first and fourth impingers empty, and transfer
approximately 200 to 300 g of preweighed silica gel from its container
to the fifth impinger.
4.1.3.3 Place the silica gel container in a clean place for later
use in the sample recovery. Alternatively, the weight of the silica gel
plus impinger may be determined to the nearest 0.5 g and recorded.
4.1.3.4 Assemble the train as shown in Figure 23-1.
4.1.3.5 Turn on the adsorbent module and condenser coil
recirculating pump and begin monitoring the adsorbent module gas entry
temperature. Ensure proper sorbent temperature gas entry temperature
before proceeding and before sampling is initiated. It is extremely
important that the XAD-2 adsorbent resin temperature never exceed 50
[deg]C because thermal decomposition will occur. During testing, the
XAD-2 temperature must not exceed 20 [deg]C for efficient capture of the
PCDD's and PCDF's.
4.1.4 Leak-Check Procedure. Same as Method 5, section 4.1.4.
4.1.5 Sample Train Operation. Same as Method 5, section 4.1.5.
4.2 Sample Recovery. Proper cleanup procedure begins as soon as the
probe is removed from the stack at the end of the sampling period. Seal
the nozzle end of the sampling probe with Teflon tape or aluminum foil.
When the probe can be safely handled, wipe off all external
particulate matter near the tip of the probe. Remove the probe from the
train and close off both ends with aluminum foil. Seal off the inlet to
the train with Teflon tape, a ground glass cap, or aluminum foil.
Transfer the probe and impinger assembly to the cleanup area. This
area shall be clean and enclosed so that the chances of losing or
contaminating the sample are minimized. Smoking, which could contaminate
the sample, shall not be allowed in the cleanup area.
Inspect the train prior to and during disassembly and note any
abnormal conditions, e.g., broken filters, colored impinger liquid, etc.
Treat the samples as follows:
4.2.1 Container No. 1. Either seal the filter holder or carefully
remove the filter from the filter holder and place it in its identified
container. Use a pair of cleaned tweezers to handle the filter. If it is
necessary to fold the filter, do so such that the particulate cake is
inside the fold. Carefully transfer to the container any particulate
matter and filter fibers which adhere to the filter holder gasket, by
using a dry inert bristle brush and a sharp-edged blade. Seal the
container.
4.2.2 Adsorbent Module. Remove the module from the train, tightly
cap both ends, label it, cover with aluminum foil, and store it on ice
for transport to the laboratory.
4.2.3 Container No. 2. Quantitatively recover material deposited in
the nozzle, probe transfer lines, the front half of the filter holder,
and the cyclone, if used, first, by

[[Page 496]]

brushing while rinsing three times each with acetone and then, by
rinsing the probe three times with methylene chloride. Collect all the
rinses in Container No. 2.
Rinse the back half of the filter holder three times with acetone.
Rinse the connecting line between the filter and the condenser three
times with acetone. Soak the connecting line with three separate
portions of methylene chloride for 5 minutes each. If using a separate
condenser and adsorbent trap, rinse the condenser in the same manner as
the connecting line. Collect all the rinses in Container No. 2 and mark
the level of the liquid on the container.
4.2.4 Container No. 3. Repeat the methylene chloride-rinsing
described in section 4.2.3 using toluene as the rinse solvent. Collect
the rinses in Container No. 3 and mark the level of the liquid on the
container.
4.2.5 Impinger Water. Measure the liquid in the first three
impingers to within 1 ml by using a graduated cylinder or by weighing
it to within 0.5 g by using a balance. Record the volume or weight of
liquid present. This information is required to calculate the moisture
content of the effluent gas.
Discard the liquid after measuring and recording the volume or
weight.
4.2.7 Silica Gel. Note the color of the indicating silica gel to
determine if it has been completely spent and make a mention of its
condition. Transfer the silica gel from the fifth impinger to its
original container and seal. If a moisture determination is made, follow
the applicable procedures in sections 8.7.6.3 and 11.2.3 of Method 5 to
handle and weigh the silica gel. If moisture is not measured, the silica
gel may be disposed.

5. Analysis

All glassware shall be cleaned as described in section 3A of the
``Manual of Analytical Methods for the Analysis of Pesticides in Human
and Environmental Samples.'' All samples must be extracted within 30
days of collection and analyzed within 45 days of extraction.
5.1 Sample Extraction.
5.1.1 Extraction System. Place an extraction thimble (section
2.3.4), 1 g of silica gel, and a plug of glass wool into the Soxhlet
apparatus, charge the apparatus with toluene, and reflux for a minimum
of 3 hours. Remove the toluene and discard it, but retain the silica
gel. Remove the extraction thimble from the extraction system and place
it in a glass beaker to catch the solvent rinses.
5.1.2 Container No. 1 (Filter). Transfer the contents directly to
the glass thimble of the extraction system and extract them
simultaneously with the XAD-2 resin.
5.1.3 Adsorbent Cartridge. Suspend the adsorbent module directly
over the extraction thimble in the beaker (See section 5.1.1). The glass
frit of the module should be in the up position. Using a Teflon squeeze
bottle containing toluene, flush the XAD-2 into the thimble onto the bed
of cleaned silica gel. Thoroughly rinse the glass module catching the
rinsings in the beaker containing the thimble. If the resin is wet,
effective extraction can be accomplished by loosely packing the resin in
the thimble. Add the XAD-2 glass wool plug into the thimble.
5.1.4 Container No. 2 (Acetone and Methylene Chloride). Concentrate
the sample to a volume of about 1-5 ml using the rotary evaporator
apparatus, at a temperature of less than 37 [deg]C. Rinse the sample
container three times with small portions of methylene chloride and add
these to the concentrated solution and concentrate further to near
dryness. This residue contains particulate matter removed in the rinse
of the train probe and nozzle. Add the concentrate to the filter and the
XAD-2 resin in the Soxhlet apparatus described in section 5.1.1.
5.1.5 Extraction. Add 100 l of the internal standard
solution (Section 3.3.20) to the extraction thimble containing the
contents of the adsorbent cartridge, the contents of Container No. 1,
and the concentrate from section 5.1.4. Cover the contents of the
extraction thimble with the cleaned glass wool plug to prevent the XAD-2
resin from floating into the solvent reservoir of the extractor. Place
the thimble in the extractor, and add the toluene contained in the
beaker to the solvent reservoir. Pour additional toluene to fill the
reservoir approximately \2/3\ full. Add Teflon boiling chips and
assemble the apparatus. Adjust the heat source to cause the extractor to
cycle three times per hour. Extract the sample for 16 hours. After
extraction, allow the Soxhlet to cool. Transfer the toluene extract and
three 10-ml rinses to the rotary evaporator. Concentrate the extract to
approximately 10 ml. At this point the analyst may choose to split the
sample in half. If so, split the sample, store one half for future use,
and analyze the other according to the procedures in sections 5.2 and
5.3. In either case, use a nitrogen evaporative concentrator to reduce
the volume of the sample being analyzed to near dryness. Dissolve the
residue in 5 ml of hexane.
5.1.6 Container No. 3 (Toluene Rinse). Add 100 l of the
Internal Standard solution (section 3.3.2) to the contents of the
container. Concentrate the sample to a volume of about 1-5 ml using the
rotary evaporator apparatus at a temperature of less than 37 [deg]C.
Rinse the sample container apparatus at a temperature of less than 37
[deg]C. Rinse the sample container three times with small portions of
toluene and add these to the concentrated solution and concentrate
further to near dryness. Analyze the extract separately according to the
procedures in sections 5.2 and 5.3, but concentrate the solution in a
rotary evaporator apparatus rather than a nitrogen evaporative
concentrator.
5.2 Sample Cleanup and Fractionation.

[[Page 497]]

5.2.1 Silica Gel Column. Pack one end of a glass column, 20 mm x 230
mm, with glass wool. Add in sequence, 1 g silica gel, 2 g of sodium
hydroxide impregnated silica gel, 1 g silica gel, 4 g of acid-modified
silica gel, and 1 g of silica gel. Wash the column with 30 ml of hexane
and discard it. Add the sample extract, dissolved in 5 ml of hexane to
the column with two additional 5-ml rinses. Elute the column with an
additional 90 ml of hexane and retain the entire eluate. Concentrate
this solution to a volume of about 1 ml using the nitrogen evaporative
concentrator (section 2.3.7).
5.2.2 Basic Alumina Column. Shorten a 25-ml disposable Pasteur
pipette to about 16 ml. Pack the lower section with glass wool and 12 g
of basic alumina. Transfer the concentrated extract from the silica gel
column to the top of the basic alumina column and elute the column
sequentially with 120 ml of 0.5 percent methylene chloride in hexane
followed by 120 ml of 35 percent methylene chloride in hexane. Discard
the first 120 ml of eluate. Collect the second 120 ml of eluate and
concentrate it to about 0.5 ml using the nitrogen evaporative
concentrator.
5.2.3 AX-21 Carbon/Celite 545 Column. Remove the botton 0.5 in. from
the tip of a 9-ml disposable Pasteur pipette. Insert a glass fiber
filter disk in the top of the pipette 2.5 cm from the constriction. Add
sufficient carbon/celite mixture to form a 2 cm column. Top with a glass
wool plug. In some cases AX-21 carbon fines may wash through the glass
wool plug and enter the sample. This may be prevented by adding a celite
plug to the exit end of the column. Rinse the column in sequence with 2
ml of 50 percent benzene in ethyl acetate, 1 ml of 50 percent methylene
chloride in cyclohexane, and 2 ml of hexane. Discard these rinses.
Transfer the concentrate in 1 ml of hexane from the basic alumina column
to the carbon/celite column along with 1 ml of hexane rinse. Elute the
column sequentially with 2 ml of 50 percent methylene chloride in hexane
and 2 ml of 50 percent benzene in ethyl acetate and discard these
eluates. Invert the column and elute in the reverse direction with 13 ml
of toluene. Collect this eluate. Concentrate the eluate in a rotary
evaporator at 50 [deg]C to about 1 ml. Transfer the concentrate to a
Reacti-vial using a toluene rinse and concentrate to a volume of 200
l using a stream of N2. Store extracts at room
temperature, shielded from light, until the analysis is performed.
5.3 Analysis. Analyze the sample with a gas chromatograph coupled to
a mass spectrometer (GC/MS) using the instrumental parameters in
sections 5.3.1 and 5.3.2. Immediately prior to analysis, add a 20
l aliquot of the Recovery Standard solution from Table 1 to
each sample. A 2 l aliquot of the extract is injected into the
GC. Sample extracts are first analyzed using the DB-5 capillary column
to determine the concentration of each isomer of PCDD's and PCDF's
(tetra-through octa-). If tetra-chlorinated dibenzofurans are detected
in this analysis, then analyze another aliquot of the sample in a
separate run, using the DB-225 column to measure the 2,3,7,8 tetra-
chloro dibenzofuran isomer. Other column systems may be used, provided
that the user is able to demonstrate using calibration and performance
checks that the column system is able to meet the specifications of
section 6.1.2.2.
5.3.1 Gas Chromatograph Operating Conditions.
5.3.1.1 Injector. Configured for capillary column, splitless, 250
[deg]C.
5.3.1.2 Carrier Gas. Helium, 1-2 ml/min.
5.3.1.3 Oven. Initially at 150 [deg]C. Raise by at least 40 [deg]C/
min to 190 [deg]C and then at 3 [deg]C/min up to 300 [deg]C.
5.3.2 High Resolution Mass Spectrometer.
5.3.2.1 Resolution. 10000 m/e.
5.3.2.2 Ionization Mode. Electron impact.
5.3.2.3 Source Temperature 250 [deg]C.
5.3.2.4 Monitoring Mode. Selected ion monitoring. A list of the
various ions to be monitored is summarized in Table 3.
5.3.2.5 Identification Criteria. The following identification
criteria shall be used for the characterization of polychlorinated
dibenzodioxins and dibenzofurans.
1. The integrated ion-abundance ratio (M/M + 2 or M + 2/M + 4) shall
be within 15 percent of the theoretical value. The acceptable ion-
abundance ratio ranges for the identification of chlorine-containing
compounds are given in Table 4.
2. The retention time for the analytes must be within 3 seconds of
the corresponding \1\\3\ C-labeled internal standard, surrogate or
alternate standard.
3. The monitored ions, shown in Table 3 for a given analyte, shall
reach their maximum within 2 seconds of each other.
4. The identification of specific isomers that do not have
corresponding \1\\3\ C-labeled standards is done by comparison of the
relative retention time (RRT) of the analyte to the nearest internal
standard retention time with reference (i.e., within 0.005 RRT units) to
the comparable RRT's found in the continuing calibration.
5. The signal to noise ratio for all monitored ions must be greater
than 2.5.
6. The confirmation of 2, 3, 7, 8-TCDD and 2, 3, 7, 8-TCDF shall
satisfy all of the above identification criteria.
7. For the identification of PCDF's, no signal may be found in the
corresponding PCDPE channels.
5.3.2.6 Quantification. The peak areas for the two ions monitored
for each analyte are summed to yield the total response for each
analyte. Each internal standard is used to quantify the indigenous
PCDD's or PCDF's in its homologous series. For example, the \1\\3\ C
12-2,3,7,8-tetra chlorinated dibenzodioxin is used to
calculate the concentrations of all

[[Page 498]]

other tetra chlorinated isomers. Recoveries of the tetra- and penta-
internal standards are calculated using the \1\\3\ C 12-
1,2,3,4-TCDD. Recoveries of the hexa- through octa- internal standards
are calculated using \1\\3\ C 12-1,2,3,7,8,9-HxCDD.
Recoveries of the surrogate standards are calculated using the
corresponding homolog from the internal standard.

6. Calibration

Same as Method 5 with the following additions.
6.1 GC/MS System.
6.1.1 Initial Calibration. Calibrate the GC/MS system using the set
of five standards shown in Table 2. The relative standard deviation for
the mean response factor from each of the unlabeled analytes (Table 2)
and of the internal, surrogate, and alternate standards shall be less
than or equal to the values in Table 5. The signal to noise ratio for
the GC signal present in every selected ion current profile shall be
greater than or equal to 2.5. The ion abundance ratios shall be within
the control limits in Table 4.
6.1.2 Daily Performance Check.
6.1.2.1 Calibration Check. Inject on l of solution Number 3
from Table 2. Calculate the relative response factor (RRF) for each
compound and compare each RRF to the corresponding mean RRF obtained
during the initial calibration. The analyzer performance is acceptable
if the measured RRF's for the labeled and unlabeled compounds for the
daily run are within the limits of the mean values shown in Table 5. In
addition, the ion-abundance ratios shall be within the allowable control
limits shown in Table 4.
6.1.2.2 Column Separation Check. Inject a solution of a mixture of
PCDD's and PCDF's that documents resolution between 2,3,7,8-TCDD and
other TCDD isomers. Resolution is defined as a valley between peaks that
is less than 25 percent of the lower of the two peaks. Identify and
record the retention time windows for each homologous series.
Perform a similar resolution check on the confirmation column to
document the resolution between 2,3,7,8 TCDF and other TCDF isomers.
6.2 Lock Channels. Set mass spectrometer lock channels as specified
in Table 3. Monitor the quality control check channels specified in
Table 3 to verify instrument stability during the analysis.

7. Quality Control

7.1 Sampling Train Collection Efficiency Check. Add 100 l
of the surrogate standards in Table 1 to the absorbent cartridge of each
train before collecting the field samples.
7.2 Internal Standard Percent Recoveries. A group of nine carbon
labeled PCDD's and PCDF's representing, the tetra-through
octachlorinated homologues, is added to every sample prior to
extraction. The role of the internal standards is to quantify the native
PCDD's and PCDF's present in the sample as well as to determine the
overall method efficiency. Recoveries of the internal standards must be
between 40 to 130 percent for the tetra-through hexachlorinated
compounds while the range is 25 to 130 percent for the higher hepta- and
octachlorinated homologues.
7.3 Surrogate Recoveries. The five surrogate compounds in Table 2
are added to the resin in the adsorbent sampling cartridge before the
sample is collected. The surrogate recoveries are measured relative to
the internal standards and are a measure of collection efficiency. They
are not used to measure native PCDD's and PCDF's. All recoveries shall
be between 70 and 130 percent. Poor recoveries for all the surrogates
may be an indication of breakthrough in the sampling train. If the
recovery of all standards is below 70 percent, the sampling runs must be
repeated. As an alternative, the sampling runs do not have to be
repeated if the final results are divided by the fraction of surrogate
recovery. Poor recoveries of isolated surrogate compounds should not be
grounds for rejecting an entire set of the samples.
7.4 Toluene QA Rinse. Report the results of the toluene QA rinse
separately from the total sample catch. Do not add it to the total
sample.

8.0 [Reserved]

9. Calculations

Same as Method 5, section 6 with the following additions.
9.1 Nomenclature.

Aai = Integrated ion current of the noise at the retention
time of the analyte.
A*ci = Integrated ion current of the two ions characteristic
of the internal standard i in the calibration standard.
Acij = Integrated ion current of the two ions characteristic
of compound i in the jth calibration standard.
A*cij = Integrated ion current of the two ions characteristic
of the internal standard i in the jth calibration standard.
Acsi = Integrated ion current of the two ions characteristic
of surrogate compound i in the calibration standard.
Ai = Integrated ion current of the two ions characteristic of
compound i in the sample.
A*i = Integrated ion current of the two ions characteristic
of internal standard i in the sample.
Ars = Integrated ion current of the two ions characteristic
of the recovery standard.
Asi = Integrated ion current of the two ions characteristic
of surrogate compound i in the sample.
Ci = Concentration of PCDD or PCDF i in the sample, pg/M \3\.

[[Page 499]]

CT = Total concentration of PCDD's or PCDF's in the sample,
pg/M \3\.
mci = Mass of compound i in the calibration standard injected
into the analyzer, pg.
mrs = Mass of recovery standard in the calibration standard
injected into the analyzer, pg.
msi = Mass of surrogate compound in the calibration standard,
pg.
RRFi = Relative response factor.
RRFrs = Recovery standard response factor.
RRFs = Surrogate compound response factor.
9.2 Average Relative Response Factor.
[GRAPHIC] [TIFF OMITTED] TC16NO91.219

9.3 Concentration of the PCDD's and PCDF's.
[GRAPHIC] [TIFF OMITTED] TC16NO91.220

9.4 Recovery Standard Response Factor.
[GRAPHIC] [TIFF OMITTED] TC16NO91.221

9.5 Recovery of Internal Standards (R*).
[GRAPHIC] [TIFF OMITTED] TC16NO91.222

9.6 Surrogate Compound Response Factor.
[GRAPHIC] [TIFF OMITTED] TC16NO91.223

9.7 Recovery of Surrogate Compounds (Rs).
[GRAPHIC] [TIFF OMITTED] TC16NO91.224

9.8 Minimum Detectable Limit (MDL).
[GRAPHIC] [TIFF OMITTED] TC16NO91.225

9.9 Total Concentration of PCDD's and PCDF's in the Sample.
[GRAPHIC] [TIFF OMITTED] TC16NO91.226

Any PCDD's or PCDF's that are reported as nondetected (below the
MDL) shall be counted as zero for the purpose of calculating the total
concentration of PCDD's and PCDF's in the sample.

10. Bibliography

1. American Society of Mechanical Engineers. Sampling for the
Determination of Chlorinated Organic Compounds in Stack Emissions.
Prepared for U.S. Department of Energy and U.S. Environmental Protection
Agency. Washington DC. December 1984. 25 p.
2. American Society of Mechanical Engineers. Analytical Procedures
to Assay Stack Effluent Samples and Residual Combustion Products for
Polychlorinated Dibenzo-p-Dioxins (PCDD) and Polychlorinated
Dibenzofurans (PCDF). Prepared for the U.S. Department of Energy and
U.S. Environmental Protection Agency. Washington, DC. December 1984. 23
p.
3. Thompson, J. R. (ed.). Analysis of Pesticide Residues in Human
and Environmental Samples. U.S. Environmental Protection Agency.
Research Triangle Park, NC. 1974.
4. Triangle Laboratories. Case Study: Analysis of Samples for the
Presence of Tetra Through Octachloro-p-Dibenzodioxins and Dibenzofurans.
Research Triangle Park, NC. 1988. 26 p.
5. U.S. Environmental Protection Agency. Method 8290--The Analysis
of Polychlorinated Dibenzo-p-dioxin and Polychlorinated Dibenzofurans by
High-Resolution Gas Chromotography/High-Resolution Mass Spectrometry.
In: Test Methods for Evaluating Solid Waste. Washington, DC. SW-846.

Table 1--Composition of the Sample Fortification and Recovery Standards
Solutions
------------------------------------------------------------------------
Concentration
Analyte (pg/l)

------------------------------------------------------------------------
Internal Standards:
\13\ C12-2,3,7,8-TCDD................................ 100
\13\ C12-1,2,3,7,8-PeCDD............................. 100
\13\ C12-1,2,3,6,7,8-HxCDD........................... 100
\13\ C12-1,2,3,4,6,7,8-HpCDD......................... 100
\13\ C12-OCDD........................................ 100
\13\ C12-2,3,7,8-TCDF................................ 100
\13\ C12-1,2,3,7,8-PeCDF............................. 100
\13\ C12-1,2,3,6,7,8-HxCDF........................... 100
\13\ C12-1,2,3,4,6,7,8-HpCDF......................... 100
Surrogate Standards:
\37\ Cl4-2,3,7,8-TCDD................................ 100
\13\ C12-1,2,3,4,7,8-HxCDD........................... 100
\13\ C12-2,3,4,7,8-PeCDF............................. 100
\13\ C12-1,2,3,4,7,8-HxCDF........................... 100
\13\ C12-1,2,3,4,7,8,9-HpCDF......................... 100
Recovery Standards:
\13\ C12-1,2,3,4-TCDD................................ 500
\13\ C12-1,2,3,7,8,9-HxCDD........................... 500
------------------------------------------------------------------------

Table 2--Composition of the Initial Calibration Solutions
------------------------------------------------------------------------
Concentrations (pg/L)

----------------------------------
Compound Solution No.
----------------------------------
1 2 3 4 5
------------------------------------------------------------------------
Alternate Standard:
\13\ C12-1,2,3,7,8,9-HxCDF......... 2.5 5 25 250 500

[[Page 500]]

Recovery Standards:
\13\ C12-1,2,3,4-TCDD.............. 100 100 100 100 100
\13\ C12-1,2,3,7,8,9-HxCDD......... 100 100 100 100 100
------------------------------------------------------------------------

Table 3--Elemental Compositions and Exact Masses of the Ions Monitored by High Resolution Mass Spectrometry for
PCDD's and PCDF's
----------------------------------------------------------------------------------------------------------------
Descriptor
No. Accurate mass Ion type Elemental composition Analyte
----------------------------------------------------------------------------------------------------------------
2 292.9825 LOCK C7F11 PFK
303.9016 M C12H4\35\Cl4O TCDF
305.8987 M + 2 C12H4\35\Cl\37\O TCDF
315.9419 M \13\C12H4\35\Cl4O TCDF (S)
317.9389 M + 2 \13\C12H4\35\Cl3\37\ClO TCDF (S)
319.8965 M C12H4\35\ClO2 TCDD
321.8936 M + 2 C12H4\35\Cl3\37\ClO2 TCDD
327.8847 M C12H4\37\Cl4O2 TCDD (S)
330.9792 QC C7F13 PFK
331.9368 M \13\C12H4\35\Cl4O2 TCDD (S)
333.9339 M + 2 \13\C12H4\35\Cl\37\ClO2 TCDD (S)
339.8597 M + 2 C12H3\35\Cl4\37\ClO PECDF
341.8567 M + 4 C12H3\35\Cl3\37\Cl2O PeCDF
351.9000 M + 2 \13\C12H3\35\Cl4\37\ClO PeCDF (S)
353.8970 M + 4 \13\C12H3\35\Cl\35\\37\Cl2O PeCDF (S)
355.8546 M + 2 C12H3\35\Cl337ClO2 PeCDD
357.8516 M + 4 C12H3\35\Cl3\37\Cl2O2 PeCDD
367.8949 M + 2 \13\C12H3\35\Cl4\37\ClO2 PeCDD (S)
369.8919 M + 4 \13\C12H3\35\Cl3\37\ Cl2O2 PeCDD (S)
375.8364 M + 2 C12H4\35\Cl5\37\ClO HxCDPE
409.7974 M + 2 C12H3\35\Cl6\37\ClO HpCPDE
3 373.8208 M + 2 C12H235Cl5\37\ClO HxCDF
375.8178 M + 4 C12H2\35\Cl4\37\Cl2O HxCDF
383.8639 M \13\C12H2\35\Cl6O HxCDF (S)
385.8610 M + 2 \13\C12H2\35\Cl5\37\ClO HxCDF (S)
389.8157 M + 2 C12H2\35\Cl5\37\ClO2 HxCDD
391.8127 M + 4 C12H2\35\Cl4\37\Cl2O2 HxCDD
392.9760 LOCK C9F15 PFK
401.8559 M + 2 \13\C12H2\35\Cl5\37\ClO2 HxCDD (S)
403.8529 M + 4 \13\C12H2\35\Cl4\37\Cl2O HxCDD (S)
445.7555 M + 4 C12H2\35\Cl6\37\Cl2O OCDPE
430.9729 QC C9F17 PFK
4 407.7818 M + 2 C12H\35\Cl6\37\ClO HpCDF
409.7789 M + 4 C12H\35\Cl5\37\Cl2O HpCDF
417.8253 M \13\C12H\35\Cl7O HpCDF (S)
419.8220 M + 2 \13\C12H\35\Cl6\37\ClO HpCDF (S)
423.7766 M + 2 C12H\35\Cl6\37\ClO2 HpCDD
425.7737 M + 4 C12H\35\Cl5\37\Cl2O2 HpCDD
435.8169 M + 2 \13\C12H\35\Cl6\37\ClO2 HpCDD (S)
437.8140 M + 4 \13\C12H\35\Cl5\37\Cl2O2 HpCDD (S)
479.7165 M + 4 C12H\35\Cl7\37\Cl2O NCPDE
430.9729 LOCK C9F17 PFK
441.7428 M + 2 C12\35\Cl7\37\ClO OCDF
443.7399 M + 4 C12\35\Cl6\37\Cl2O OCDF
457.7377 M + 2 C12\35\Cl7\37\ClO2 OCDD
459.7348 M + 4 C12\35\Cl6\37\Cl2O2 OCDD
469.7779 M + 2 \13\C12\35\Cl7\37\ClO2 OCDD (S)
471.7750 M + 4 \13\C12\35\Cl6\37\Cl2O2 OCDD (S)
513.6775 M + 4 C12\35\Cl8\37\Cl2O2 DCDPE
442.9728 QC C10F17 PFK
----------------------------------------------------------------------------------------------------------------
(a) The following nuclidic masses were used:
H = 1.007825
C = 12.000000
\13\C = 13.003355
F = 18.9984
O = 15.994915
\35\Cl = 34.968853
\37\Cl = 36.965903

[[Page 501]]

S = Labeled Standard
QC = Ion selected for monitoring instrument stability during the GC/MS analysis.

Table 4--Acceptable Ranges for Ion-Abundance Ratios of PCDD's and PCDF's
------------------------------------------------------------------------
No. of Control limits
chlorine Ion type Theoretical -----------------
atoms ratio Lower Upper
------------------------------------------------------------------------
4 M/M + 2 0.77 0.65 0.89
5 M + 2/M + 4 1.55 1.32 1.78
6 M + 2/M + 4 1.24 1.05 1.43
6 \a\ M/M + 2 0.51 0.43 0.59
7 \b\ M/M + 2 0.44 0.37 0.51
7 M + 2/M + 4 1.04 0.88 1.20
8 M + 2/M + 4 0.89 0.76 1.02
------------------------------------------------------------------------
\a\ Used only for \13\C-HxCDF.
\b\ Used only for \13\C-HpCDF.

Table 5--Minimum Requirements for Initial and Daily Calibration Response
Factors
------------------------------------------------------------------------
Relative response factors
-------------------------------
Compound Initial Daily
calibration calibration %
RSD difference
------------------------------------------------------------------------
Unlabeled
Analytes:
2,3,7,8-TCDD.......................... 25 25
2,3,7,8-TCDF.......................... 25 25
1,2,3,7,8-PeCDD....................... 25 25
1,2,3,7,8-PeCDF....................... 25 25
2,3,4,7,8-PeCDF....................... 25 25
1,2,4,5,7,8-HxCDD..................... 25 25
1,2,3,6,7,8-HxCDD..................... 25 25
1,2,3,7,8,9-HxCDD..................... 25 25
1,2,3,4,7,8-HxCDF..................... 25 25
1,2,3,6,7,8-HxCDF..................... 25 25
1,2,3,7,8,9-HxCDF..................... 25 25
2,3,4,6,7,8-HxCDF..................... 25 25
1,2,3,4,6,7,8-HpCDD................... 25 25
1,2,3,4,6,7,8-HpCDF................... 25 25
OCDD.................................. 25 25
OCDF.................................. 30 30
Internal
Standards:
\13\C12-2,3,7,8-TCDD.................. 25 25
\13\C12-1,2,3,7,8-PeCDD............... 30 30
\13\C12-1,2,3,6,7,8-HxCDD............. 25 25
\13\C12-1,2,3,4,6,7,8-HpCDD........... 30 30
\13\C12-OCDD.......................... 30 30
\13\C12-2,3,7,8-TCDF.................. 30 30
\13\C12-1,2,3,7,8-PeCDF............... 30 30
\13\C12-1,2,3,6,7,8-HxCDF............. 30 30
\13\C12-1,2,3,4,6,7,8-HpCDF........... 30 30
Surrogate
Standards:
\37\Cl4-2,3,7,8-TCDD.................. 25 25
\13\C12-2,3,4,7,8-PeCDF............... 25 25
\13\C12-1,2,3,4,7,8-HxCDD............. 25 25
\13\C12-1,2,3,4,7,8-HxCDF............. 25 25
\13\C12-1,2,3,4,7,8,9-HpCDF........... 25 25
Alternate
Standard:
\13\C12-1,2,3,7,8,9-HxCDF............. 25 25
------------------------------------------------------------------------

Method 24--Determination of Volatile Matter Content, Water Content,
Density, Volume Solids, and Weight Solids of Surface Coatings

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Volatile organic compounds Water.......... No CAS Number assigned 7732-
18-5
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of volatile matter content, water content, density, volume solids, and
weight solids of paint, varnish, lacquer, or other related surface
coatings.
1.3 Precision and Bias. Intra-and inter-laboratory analytical
precision statements are presented in section 13.1. No bias has been
identified.

2.0 Summary of Method

2.1 Standard methods are used to determine the volatile matter
content, water content, density, volume solids, and weight solids of
paint, varnish, lacquer, or other related surface coatings.

3.0 Definitions

3.1 Waterborne coating means any coating which contains more than 5
percent water by weight in its volatile fraction.
3.2 Multicomponent coatings are coatings that are packaged in two or
more parts, which are combined before application. Upon combination a
coreactant from one part of the coating chemically reacts, at ambient
conditions, with a coreactant from another part of the coating.
3.3 Ultraviolet (UV) radiation-cured coatings are coatings which
contain unreacted monomers that are polymerized by exposure to
ultraviolet light.

4.0 Interferences [Reserved]

5.0 Safety

[[Page 502]]

Appropriate precautions can be found in reference documents, such as
Reference 3 of section 16.0.

6.0 Equipment and Supplies

The equipment and supplies specified in the ASTM methods listed in
sections 6.1 through 6.6 (incorporated by reference--see Sec. 60.17 for
acceptable versions of the methods) are required:
6.1 ASTM D 1475-60, 80, or 90, Standard Test Method for Density of
Paint, Varnish, Lacquer, and Related Products.
6.2 ASTM D 2369-81, 87, 90, 92, 93, or 95, Standard Test Method for
Volatile Content of Coatings.
6.3 ASTM D 3792-79 or 91, Standard Test Method for Water Content of
Water Reducible Paints by Direct Injection into a Gas Chromatograph.
6.4 ASTM D 4017-81, 90, or 96a, Standard Test Method for Water in
Paints and Paint Materials by the Karl Fischer Titration Method.
6.5 ASTM 4457-85 91, Standard Test Method for Determination of
Dichloromethane and 1,1,1-Trichloroethane in Paints and Coatings by
Direct Injection into a Gas Chromatograph.
6.6 ASTM D 5403-93, Standard Test Methods for Volatile Content of
Radiation Curable Materials.
6.7 ASTM D 6419-00, Test Method for Volatile Content of Sheet-Fed
and Coldset Web Offset Printing Inks.

7.0 Reagents and Standards

7.1 The reagents and standards specified in the ASTM methods listed
in sections 6.1 through 6.6 are required.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Follow the sample collection, preservation, storage, and
transport procedures described in Reference 1 of section 16.0.

9.0 Quality Control

9.1 Reproducibility

Note: Not applicable to UV radiation-cured coatings). The variety of
coatings that may be subject to analysis makes it necessary to verify
the ability of the analyst and the analytical procedures to obtain
reproducible results for the coatings tested. Verification is
accomplished by running duplicate analyses on each sample tested
(Sections 11.2 through 11.4) and comparing the results with the intra-
laboratory precision statements (Section 13.1) for each parameter.

9.2 Confidence Limits for Waterborne Coatings. Because of the
inherent increased imprecision in the determination of the VOC content
of waterborne coatings as the weight percent of water increases,
measured parameters for waterborne coatings are replaced with
appropriate confidence limits (Section 12.6). These confidence limits
are based on measured parameters and inter-laboratory precision
statements.

10.0 Calibration and Standardization

10.1 Perform the calibration and standardization procedures
specified in the ASTM methods listed in sections 6.1 through 6.6.

11.0 Analytical Procedure

Additional guidance can be found in Reference 2 of section 16.0.
11.1 Non Thin-film Ultraviolet Radiation-cured (UV radiation-cured)
Coatings.
11.1.1 Volatile Content. Use the procedure in ASTM D 5403 to
determine the volatile matter content of the coating except the curing
test described in NOTE 2 of ASTM D 5403 is required.
11.1.2 Water Content. To determine water content, follow section
11.3.2.
11.1.3 Coating Density. To determine coating density, follow section
11.3.3.
11.1.4 Solids Content. To determine solids content, follow section
11.3.4.
11.1.5 To determine if a coating or ink can be classified as a thin-
film UV cured coating or ink, use the equation in section 12.2. If C is
less than 0.2 g and A is greater than or equal to 225 cm\2\ (35 in\2\)
then the coating or ink is considered a thin-film UV radiation-cured
coating and ASTM D 5403 is not applicable.

Note: As noted in section 1.4 of ASTM D 5403, this method may not be
applicable to radiation curable materials wherein the volatile material
is water.

11.2 Multi-component Coatings.
11.2.1 Sample Preparation.
11.2.1.1 Prepare about 100 ml of sample by mixing the components in
a storage container, such as a glass jar with a screw top or a metal can
with a cap. The storage container should be just large enough to hold
the mixture. Combine the components (by weight or volume) in the ratio
recommended by the manufacturer. Tightly close the container between
additions and during mixing to prevent loss of volatile materials.
However, most manufacturers mixing instructions are by volume. Because
of possible error caused by expansion of the liquid when measuring the
volume, it is recommended that the components be combined by weight.
When weight is used to combine the components and the manufacturer's
recommended ratio is by volume, the density must be determined by
section 11.3.3.
11.2.1.2 Immediately after mixing, take aliquots from this 100 ml
sample for determination of the total volatile content, water content,
and density.
11.2.2 Volatile Content. To determine total volatile content, use
the apparatus and

[[Page 503]]

reagents described in ASTM D2369 (incorporated by reference; see Sec.
60.17 for the approved versions of the standard), respectively, and use
the following procedures:
11.2.2.1 Weigh and record the weight of an aluminum foil weighing
dish. Add 3 1 ml of suitable solvent as specified in ASTM D2369 to the
weighing dish. Using a syringe as specified in ASTM D2369, weigh to 1
mg, by difference, a sample of coating into the weighing dish. For
coatings believed to have a volatile content less than 40 weight
percent, a suitable size is 0.3 + 0.10 g, but for coatings believed to
have a volatile content greater than 40 weight percent, a suitable size
is 0.5 0.1 g.

Note: If the volatile content determined pursuant to section 12.4 is
not in the range corresponding to the sample size chosen repeat the test
with the appropriate sample size. Add the specimen dropwise, shaking
(swirling) the dish to disperse the specimen completely in the solvent.
If the material forms a lump that cannot be dispersed, discard the
specimen and prepare a new one. Similarly, prepare a duplicate. The
sample shall stand for a minimum of 1 hour, but no more than 24 hours
prior to being oven cured at 110 5 [deg]C (230 9 [deg]F) for 1 hour.

11.2.2.2 Heat the aluminum foil dishes containing the dispersed
specimens in the forced draft oven for 60 min at 110 5 [deg]C (230 9
[deg]F). Caution--provide adequate ventilation, consistent with accepted
laboratory practice, to prevent solvent vapors from accumulating to a
dangerous level.
11.2.2.3 Remove the dishes from the oven, place immediately in a
desiccator, cool to ambient temperature, and weigh to within 1 mg.
11.2.2.4 Run analyses in pairs (duplicate sets) for each coating
mixture until the criterion in section 11.4 is met. Calculate
WV following Equation 24-2 and record the arithmetic average.
11.2.3 Water Content. To determine water content, follow section
11.3.2.
11.2.4 Coating Density. To determine coating density, follow section
11.3.3.
11.2.5 Solids Content. To determine solids content, follow section
11.3.4.
11.2.6 Exempt Solvent Content. To determine the exempt solvent
content, follow section 11.3.5.

Note: For all other coatings (i.e., water-or solvent-borne coatings)
not covered by multicomponent or UV radiation-cured coatings, analyze as
shown below:

11.3 Water-or Solvent-borne coatings.
11.3.1 Volatile Content. Use the procedure in ASTM D 2369 to
determine the volatile matter content (may include water) of the
coating.
11.3.1.1 Record the following information:

W1 = weight of dish and sample before heating, g
W2 = weight of dish and sample after heating, g
W3 = sample weight, g.

11.3.1.2 Calculate the weight fraction of the volatile matter
(Wv) for each analysis as shown in section 12.3.
11.3.1.3 Run duplicate analyses until the difference between the two
values in a set is less than or equal to the intra-laboratory precision
statement in section 13.1.
11.3.1.4 Record the arithmetic average (Wv).
11.3.2 Water Content. For waterborne coatings only, determine the
weight fraction of water (Ww) using either ASTM D 3792 or
ASTM D 4017.
11.3.2.1 Run duplicate analyses until the difference between the two
values in a set is less than or equal to the intra-laboratory precision
statement in section 13.1.
11.3.2.2 Record the arithmetic average (ww).
11.3.3 Coating Density. Determine the density (Dc, kg/l) of the
surface coating using the procedure in ASTM D 1475.
11.3.3.1 Run duplicate analyses until each value in a set deviates
from the mean of the set by no more than the intra-laboratory precision
statement in section 13.1.
11.3.3.2 Record the arithmetic average (Dc).
11.3.4 Solids Content. Determine the volume fraction (Vs)
solids of the coating by calculation using the manufacturer's
formulation.
11.3.5 Exempt Solvent Content. Determine the weight fraction of
exempt solvents (WE) by using ASTM Method D4457. Run a
duplicate set of determinations and record the arithmetic average
(WE).
11.4 Sample Analysis Criteria. For Wv and Ww,
run duplicate analyses until the difference between the two values in a
set is less than or equal to the intra-laboratory precision statement
for that parameter. For Dc, run duplicate analyses until each
value in a set deviates from the mean of the set by no more than the
intra-laboratory precision statement. If, after several attempts, it is
concluded that the ASTM procedures cannot be used for the specific
coating with the established intra-laboratory precision (excluding UV
radiation-cured coatings), the U.S. Environmental Protection Agency
(EPA) will assume responsibility for providing the necessary procedures
for revising the method or precision statements upon written request to:
Director, Emissions, Monitoring, and Analysis Division, MD-14, Office of
Air Quality Planning and Standards, U.S. Environmental Protection
Agency, Research Triangle Park, NC 27711.

12.0 Calculations and Data Analysis

12.1 Nomenclature.

A = Area of substrate, cm\2\, (in\2\).
C = Amount of coating or ink added to the substrate, g.
Dc = Density of coating or ink, g/cm\3\ (g/in\3\).

[[Page 504]]

F = Manufacturer's recommended film thickness, cm (in).
Wo = Weight fraction of nonaqueous volatile matter, g/g.
Ws = Weight fraction of solids, g/g.
Wv = Weight fraction of the volatile matter, g/g.
Ww = Weight fraction of the water, g/g.

12.2 To determine if a coating or ink can be classified as a thin-
film UV cured coating or ink, use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.356

12.3 Calculate Wv for each analysis as shown below:
[GRAPHIC] [TIFF OMITTED] TR17OC00.357

12.4 Nonaqueous Volatile Matter.
12.4.1 Solvent-borne Coatings.
[GRAPHIC] [TIFF OMITTED] TR17OC00.358

12.4.2 Waterborne Coatings.
[GRAPHIC] [TIFF OMITTED] TR17OC00.359

12.4.3 Coatings Containing Exempt Solvents.
[GRAPHIC] [TIFF OMITTED] TR17OC00.360

12.5 Weight Fraction Solids.
[GRAPHIC] [TIFF OMITTED] TR17OC00.361

12.6 Confidence Limit Calculations for Waterborne Coatings. To
calculate the lower confidence limit, subtract the appropriate inter-
laboratory precision value from the measured mean value for that
parameter. To calculate the upper confidence limit, add the appropriate
inter-laboratory precision value to the measured mean value for that
parameter. For Wv and Dc, use the lower confidence
limits; for Ww, use the upper confidence limit. Because
Ws is calculated, there is no adjustment for this parameter.

13.0 Method Performance

13.1 Analytical Precision Statements. The intra-and inter-laboratory
precision statements are given in Table 24-1 in section 17.0.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as specified in section 6.0, with the addition of the
following:
1. Standard Procedure for Collection of Coating and Ink Samples for
Analysis by Reference Methods 24 and 24A. EPA-340/1-91-010. U.S.
Environmental Protection Agency, Stationary Source Compliance Division,
Washington, D.C. September 1991.
2. Standard Operating Procedure for Analysis of Coating and Ink
Samples by Reference Methods 24 and 24A.
EPA-340/1-91-011. U.S. Environmental Protection Agency, Stationary
Source Compliance Division, Washington, D.C. September 1991.
3. Handbook of Hazardous Materials: Fire, Safety, Health. Alliance
of American Insurers. Schaumberg, IL. 1983.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Table 24-1--Analytical Precision Statements
----------------------------------------------------------------------------------------------------------------
Intra-laboratory Inter-laboratory
----------------------------------------------------------------------------------------------------------------
Volatile matter content, Wv............ 0.015 Wv.......................... 0.047 Wv
Water content, Ww...................... 0.029 Ww.......................... 0.075 Ww
Density, Dc............................ 0.001 kg/l........................ 0.002 kg/l
----------------------------------------------------------------------------------------------------------------

Method 24A--Determination of Volatile Matter Content and Density of
Publication Rotogravure Inks and Related Publication Rotogravure
Coatings

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Volatile organic compounds (VOC).......... No CAS number assigned.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of the VOC content and density of solvent-borne (solvent-reducible)
publication rotogravure inks and related publication rotogravure
coatings.

2.0 Summary of Method

2.1 Separate procedures are used to determine the VOC weight
fraction and density of the ink or related coating and the density of
the solvent in the ink or related coating. The VOC weight fraction is
determined by measuring the weight loss of a known sample quantity which
has been heated for a specified length of time at a specified
temperature. The density of both the ink or related coating and solvent
are measured by a standard procedure. From this information, the VOC
volume fraction is calculated.

[[Page 505]]

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

5.1 Disclaimer. This method may involve hazardous materials,
operations, and equipment. This test method does not purport to address
all of the safety problems associated with its use. It is the
responsibility of the user of this test method to establish appropriate
safety and health practices and to determine the applicability of
regulatory limitations prior to performing this test method.
5.2 Hazardous Components. Some of the compounds that may be
contained in the inks or related coatings analyzed by this method may be
irritating or corrosive to tissues or may be toxic. Nearly all are fire
hazards. Appropriate precautions can be found in reference documents,
such as Reference 6 of section 16.0.

6.0 Equipment and Supplies

The following equipment and supplies are required for sample
analysis:
6.1 Weighing Dishes. Aluminum foil, 58 mm (2.3 in.) in diameter by
18 mm (0.7 in.) high, with a flat bottom. There must be at least three
weighing dishes per sample.
6.2 Disposable Syringe. 5 ml.
6.3 Analytical Balance. To measure to within 0.1 mg.
6.4 Oven. Vacuum oven capable of maintaining a temperature of 120 2
[deg]C (248 4 [deg]F) and an absolute pressure of 510 51 mm Hg (20 2
in. Hg) for 4 hours. Alternatively, a forced draft oven capable of
maintaining a temperature of 120 2 [deg]C (248 4 [deg]F) for 24 hours.
6.5 The equipment and supplies specified in ASTM D 1475-60, 80, or
90 (incorporated by reference--see Sec. 60.17).

7.0 Reagents and Standards

7.1 The reagents and standards specified in ASTM D 1475-60, 80, or
90 are required.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Follow the sample collection, preservation, storage, and
transport procedures described in Reference 4 of section 16.0.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure

Additional guidance can be found in Reference 5 of section 16.0.
11.1 VOC Weight Fraction. Shake or mix the ink or related coating
sample thoroughly to assure that all the solids are completely
suspended. Label and weigh to the nearest 0.1 mg a weighing dish and
record this weight (Mx1). Using a 5 ml syringe, without a
needle, extract an aliquot from the ink or related coating sample. Weigh
the syringe and aliquot to the nearest 0.1 mg and record this weight
(Mcy1). Transfer 1 to 3 g of the aliquot to the tared
weighing dish. Reweigh the syringe and remaining aliquot to the nearest
0.1 mg and record this weight (Mcy2). Heat the weighing dish
with the transferred aliquot in a vacuum oven at an absolute pressure of
510 51 mm Hg (20 2 in. Hg) and a temperature of 120 2 [deg]C (248 4
[deg]F) for 4 hours. Alternatively, heat the weighing dish with the
transferred aliquot in a forced draft oven at a temperature of 120 2
[deg]C for 24 hours. After the weighing dish has cooled, reweigh it to
the nearest 0.1 mg and record the weight (Mx2). Repeat this
procedure two times for each ink or related coating sample, for a total
of three samples.
11.2 Ink or Related Coating Density. Determine the density of the
ink or related coating (Dc) according to the procedure
outlined in ASTM D 1475. Make a total of three determinations for each
ink or related coating sample. Report the ink or related coating density
as the arithmetic average (Dc) of the three determinations.
11.3 Solvent Density. Determine the density of the solvent
(Do) according to the procedure outlined in ASTM D 1475. Make
a total of three determinations for each ink or related coating sample.
Report the solvent density as the arithmetic average (Do) of
the three determinations.

12.0 Calculations and Data Analysis

12.1 VOC Weight Fraction. For each determination, calculate the
volatile organic content weight fraction (Wo) using the
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.362

Make a total of three determinations. Report the VOC weight fraction as
the arithmetic average (Wo) of the three determinations.
12.2 VOC Volume Fraction. Calculate the volume fraction volatile
organic content (Vo) using the following equation:

[[Page 506]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.363

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Standard Test Method for Density of Paint, Varnish, Lacquer, and
Related Products. ASTM Designation D 1475.
2. Teleconversation. Wright, Chuck, Inmont Corporation with Reich,
R., A., Radian Corporation. September 25, 1979, Gravure Ink Analysis.
3. Teleconversation. Oppenheimer, Robert, Gravure Research Institute
with Burt, Rick, Radian Corporation, November 5, 1979, Gravure Ink
Analysis.
4. Standard Procedure for Collection of Coating and Ink Samples for
Analysis by Reference Methods 24 and 24A. EPA-340/1-91-010. U.S.
Environmental Protection Agency, Stationary Source Compliance Division,
Washington, D.C. September 1991.
5. Standard Operating Procedure for Analysis of Coating and Ink
Samples by Reference Methods 24 and 24A. EPA-340/1-91-011. U.S.
Environmental Protection Agency, Stationary Source Compliance Division,
Washington, D.C. September 1991.
6. Handbook of Hazardous Materials: Fire, Safety, Health. Alliance
of American Insurers. Schaumberg, IL. 1983.

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 25--Determination of Total Gaseous Nonmethane Organic Emissions
as Carbon

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total gaseous nonmethane organic N/A Dependent upon
compounds (TGNMO). analytical
equipment.
------------------------------------------------------------------------

1.2 Applicability.
1.2.1 This method is applicable for the determination of volatile
organic compounds (VOC) (measured as total gaseous nonmethane organics
(TGNMO) and reported as carbon) in stationary source emissions. This
method is not applicable for the determination of organic particulate
matter.
1.2.2 This method is not the only method that applies to the
measurement of VOC. Costs, logistics, and other practicalities of source
testing may make other test methods more desirable for measuring VOC
contents of certain effluent streams. Proper judgment is required in
determining the most applicable VOC test method. For example, depending
upon the molecular composition of the organics in the effluent stream, a
totally automated semicontinuous nonmethane organics (NMO) analyzer
interfaced directly to the source may yield accurate results. This
approach has the advantage of providing emission data semicontinuously
over an extended time period.
1.2.3 Direct measurement of an effluent with a flame ionization
detector (FID) analyzer may be appropriate with prior characterization
of the gas stream and knowledge that the detector responds predictably
to the organic compounds in the stream. If present, methane
(CH4) will, of course, also be measured. The FID can be used
under any of the following limited conditions: (1) Where only one
compound is known to exist; (2) when the organic compounds consist of
only hydrogen and carbon; (3) where the relative percentages of the
compounds are known or can be determined, and the FID responses to the
compounds are known; (4) where a consistent mixture of the compounds
exists before and after emission control and only the relative
concentrations are to be assessed; or (5) where the FID can be
calibrated against mass standards of the compounds emitted (solvent
emissions, for example).
1.2.4 Another example of the use of a direct FID is as a screening
method. If there is enough information available to provide a rough
estimate of the analyzer accuracy, the FID analyzer can be used to
determine the VOC content of an uncharacterized gas stream. With a
sufficient buffer to account for possible inaccuracies, the direct FID
can be a useful tool to obtain the desired results without costly exact
determination.
1.2.5 In situations where a qualitative/quantitative analysis of an
effluent stream is desired or required, a gas chromatographic FID system
may apply. However, for sources emitting numerous organics, the time and
expense of this approach will be formidable.

[[Page 507]]

2.0 Summary of Method

2.1 An emission sample is withdrawn from the stack at a constant
rate through a heated filter and a chilled condensate trap by means of
an evacuated sample tank. After sampling is completed, the TGNMO are
determined by independently analyzing the condensate trap and sample
tank fractions and combining the analytical results. The organic content
of the condensate trap fraction is determined by oxidizing the NMO to
carbon dioxide (CO2) and quantitatively collecting in the
effluent in an evacuated vessel; then a portion of the CO2 is
reduced to CH4 and measured by an FID. The organic content of
the sample tank fraction is measured by injecting a portion of the
sample into a gas chromatographic column to separate the NMO from carbon
monoxide (CO), CO2, and CH4; the NMO are oxidized
to CO2, reduced to CH4, and measured by an FID. In
this manner, the variable response of the FID associated with different
types of organics is eliminated.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Carbon Dioxide and Water Vapor. When carbon dioxide
(CO2) and water vapor are present together in the stack, they
can produce a positive bias in the sample. The magnitude of the bias
depends on the concentrations of CO2 and water vapor. As a
guideline, multiply the CO2 concentration, expressed as
volume percent, times the water vapor concentration. If this product
does not exceed 100, the bias can be considered insignificant. For
example, the bias is not significant for a source having 10 percent
CO2 and 10 percent water vapor, but it might be significant
for a source having 10 percent CO2 and 20 percent water
vapor.
4.2. Particulate Matter. Collection of organic particulate matter in
the condensate trap would produce a positive bias. A filter is included
in the sampling equipment to minimize this bias.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The sampling system consists of a heated
probe, heated filter, condensate trap, flow control system, and sample
tank (see Figure 25-1). The TGNMO sampling equipment can be constructed
from commercially available components and components fabricated in a
machine shop. The following equipment is required:
6.1.1 Heated Probe. 6.4-mm (\1/4\-in.) OD stainless steel tubing
with a heating system capable of maintaining a gas temperature at the
exit end of at least 129 [deg]C (265 [deg]F). The probe shall be
equipped with a temperature sensor at the exit end to monitor the gas
temperature. A suitable probe is shown in Figure 25-1. The nozzle is an
elbow fitting attached to the front end of the probe while the
temperature sensor is inserted in the side arm of a tee fitting attached
to the rear of the probe. The probe is wrapped with a suitable length of
high temperature heating tape, and then covered with two layers of glass
cloth insulation and one layer of aluminum foil or an equivalent
wrapping.

Note: If it is not possible to use a heating system for safety
reasons, an unheated system with an in-stack filter is a suitable
alternative.

6.1.2 Filter Holder. 25-mm (\15/16\-in.) ID Gelman filter holder
with 303 stainless steel body and 316 stainless steel support screen
with the Viton O-ring replaced by a Teflon O-ring.
6.1.3 Filter Heating System.
6.1.3.1 A metal box consisting of an inner and an outer shell
separated by insulating material with a heating element in the inner
shell capable of maintaining a gas temperature at the filter of 121 3
[deg]C (250 5 [deg]F). The heating box shall include temperature
sensors to monitor the gas temperature immediately upstream and
immediately downstream of the filter.
6.1.3.2 A suitable heating box is shown in Figure 25-2. The outer
shell is a metal box that measures 102 mm x 280 mm x 292 mm (4 in. x 11
in. x 11\1/2\ in.), while the inner shell is a metal box measuring 76 mm
x 229 mm x 241 mm (3 in. x 9 in. x 9\1/2\ in.). The inner box is
supported by 13-mm (\1/2\-in.) phenolic rods. The void space between the
boxes is filled with ceramic fiber insulation which is sealed in place
by means of a silicon rubber bead around the upper sides of the box. A
removable lid made in a similar manner, with a 25-mm (1-in.) gap between
the parts is used to cover the heating chamber. The inner box is heated
with a 250-watt cartridge heater, shielded by a stainless steel shroud.
The heater is regulated by a thermostatic temperature controller which
is set to maintain a gas temperature of 121 [deg]C (250 [deg]F) as
measured by the temperature sensor upstream of the filter.

Note: If it is not possible to use a heating system for safety
reasons, an unheated system with an in-stack filter is a suitable
alternative.

6.1.4 Condensate Trap. 9.5-mm (\3/8\-in.) OD 316 stainless steel
tubing bent into a U-shape. Exact dimensions are shown in Figure

[[Page 508]]

25-3. The tubing shall be packed with coarse quartz wool, to a density
of approximately 0.11 g/cm\3\ before bending. While the condensate trap
is packed with dry ice in the Dewar, an ice bridge may form between the
arms of the condensate trap making it difficult to remove the condensate
trap. This problem can be prevented by attaching a steel plate between
the arms of the condensate trap in the same plane as the arms to
completely fill the intervening space.
6.1.5 Valve. Stainless steel control valve for starting and stopping
sample flow.
6.1.6 Metering Valve. Stainless steel valve for regulating the
sample flow rate through the sample train.
6.1.7 Rate Meter. Rotameter, or equivalent, capable of measuring
sample flow in the range of 60 to 100 cm\3\/min (0.13 to 0.21 ft\3\/hr).
6.1.8 Sample Tank. Stainless steel or aluminum tank with a minimum
volume of 4 liters (0.14 ft\3\).

Note: Sample volumes greater than 4 liters may be required for
sources with low organic concentrations.

6.1.9 Mercury Manometer. U-tube manometer or absolute pressure gauge
capable of measuring pressure to within 1 mm Hg in the range of 0 to 900
mm.
6.1.10 Vacuum Pump. Capable of evacuating to an absolute pressure of
10 mm Hg.
6.2 Condensate Recovery. The system for the recovery of the organics
captured in the condensate trap consists of a heat source, an oxidation
catalyst, a nondispersive infrared (NDIR) analyzer, and an intermediate
collection vessel (ICV). Figure 25-4 is a schematic of a typical system.
The system shall be capable of proper oxidation and recovery, as
specified in section 10.1.1. The following major components are
required:
6.2.1 Heat Source. Sufficient to heat the condensate trap (including
probe) to a temperature of 200 [deg]C (390 [deg]F). A system using both
a heat gun and an electric tube furnace is recommended.
6.2.2 Heat Tape. Sufficient to heat the connecting tubing between
the water trap and the oxidation catalyst to 100 [deg]C (212 [deg]F).
6.2.3 Oxidation Catalyst. A suitable length of 9.5 mm (\3/8\-in.) OD
Inconel 600 tubing packed with 15 cm (6 in.) of 3.2 mm (\3/8\-in.)
diameter 19 percent chromia on alumina pellets. The catalyst material is
packed in the center of the catalyst tube with quartz wool packed on
either end to hold it in place.
6.2.4 Water Trap. Leak-proof, capable of removing moisture from the
gas stream.
6.2.5 Syringe Port. A 6.4-mm (\1/4\-in.) OD stainless steel tee
fitting with a rubber septum placed in the side arm.
6.2.6 NDIR Detector. Capable of indicating CO2
concentration in the range of zero to 5 percent, to monitor the progress
of combustion of the organic compounds from the condensate trap.
6.2.7 Flow-Control Valve. Stainless steel, to maintain the trap
conditioning system near atmospheric pressure.
6.2.8 Intermediate Collection Vessel. Stainless steel or aluminum,
equipped with a female quick connect. Tanks with nominal volumes of at
least 6 liters (0.2 ft\3\) are recommended.
6.2.9 Mercury Manometer. Same as described in section 6.1.9.
6.2.10 Syringe. 10-ml gas-tight glass syringe equipped with an
appropriate needle.
6.2.11 Syringes. 10-l and 50-l liquid injection
syringes.
6.2.12 Liquid Sample Injection Unit. 316 Stainless steel U-tube
fitted with an injection septum (see Figure 25-7).
6.3 Analysis.
6.3.1 NMO Analyzer. The NMO analyzer is a gas chromatograph (GC)
with backflush capability for NMO analysis and is equipped with an
oxidation catalyst, reduction catalyst, and FID. Figures 25-5 and 25-6
are schematics of a typical NMO analyzer. This semicontinuous GC/FID
analyzer shall be capable of: (1) Separating CO, CO2, and
CH4 from NMO, (2) reducing the CO2 to
CH4 and quantifying as CH4, and (3) oxidizing the
NMO to CO2, reducing the CO2 to CH4 and
quantifying as CH4, according to section 10.1.2. The analyzer
consists of the following major components:
6.3.1.1 Oxidation Catalyst. A suitable length of 9.5-mm (\3/8\-in.)
OD Inconel 600 tubing packed with 5.1 cm (2 in.) of 19 percent chromia
on 3.2-mm (\1/8\-in.) alumina pellets. The catalyst material is packed
in the center of the tube supported on either side by quartz wool. The
catalyst tube must be mounted vertically in a 650 [deg]C (1200 [deg]F)
furnace. Longer catalysts mounted horizontally may be used, provided
they can meet the specifications of section 10.1.2.1.
6.3.1.2 Reduction Catalyst. A 7.6-cm (3-in.) length of 6.4-mm (\1/
4\-in.) OD Inconel tubing fully packed with 100-mesh pure nickel powder.
The catalyst tube must be mounted vertically in a 400 [deg]C (750
[deg]F) furnace.
6.3.1.3 Separation Column(s). A 30-cm (1-ft) length of 3.2-mm (\1/
8\-in.) OD stainless steel tubing packed with 60/80 mesh Unibeads 1S
followed by a 61-cm (2-ft) length of 3.2-mm (\1/8\-in.) OD stainless
steel tubing packed with 60/80 mesh Carbosieve G. The Carbosieve and
Unibeads columns must be baked separately at 200 [deg]C (390 [deg]F)
with carrier gas flowing through them for 24 hours before initial use.
6.3.1.4 Sample Injection System. A single 10-port GC sample
injection valve or a group of valves with sufficient ports fitted with a
sample loop properly sized to interface with the NMO analyzer (1-cc loop
recommended).
6.3.1.5 FID. An FID meeting the following specifications is
required:

[[Page 509]]

6.3.1.5.1 Linearity. A linear response (5 percent) over the
operating range as demonstrated by the procedures established in section
10.1.2.3.
6.3.1.5.2 Range. A full scale range of 10 to 50,000 ppm
CH4. Signal attenuators shall be available to produce a
minimum signal response of 10 percent of full scale.
6.3.1.6 Data Recording System. Analog strip chart recorder or
digital integration system compatible with the FID for permanently
recording the analytical results.
6.3.2 Barometer. Mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 1 mm Hg.
6.3.3 Temperature Sensor. Capable of measuring the laboratory
temperature within 1 [deg]C (2 [deg]F).
6.3.4 Vacuum Pump. Capable of evacuating to an absolute pressure of
10 mm Hg.

7.0 Reagents and Standards

7.1 Sample Collection. The following reagents are required for
sample collection:
7.1.1 Dry Ice. Solid CO2, crushed.
7.1.2 Coarse Quartz Wool. 8 to 15 um.
7.1.3 Filters. Glass fiber filters, without organic binder,
exhibiting at least 99.95 percent efficiency (<0.05 percent penetration)
on 0.3 micron dioctyl phthalate smoke particles. The filter efficiency
test shall be conducted in accordance with ASTM Method D2986-71, 78, or
95a (incorporated by reference--see Sec. 60.17). Test data from the
supplier's quality control program are sufficient for this purpose.
7.2 NMO Analysis. The following gases are required for NMO analysis:
7.2.1 Carrier Gases. Helium (He) and oxygen (O2)
containing less than 1 ppm CO2 and less than 0.1 ppm
hydrocarbon.
7.2.2 Fuel Gas. Hydrogen (H2), at least 99.999 percent
pure.
7.2.3 Combustion Gas. Either air (less than 0.1 ppm total
hydrocarbon content) or O2 (purity 99.99 percent or greater),
as required by the detector.
7.3 Condensate Analysis. The following are required for condensate
analysis:
7.3.1 Gases. Containing less than 1 ppm carbon.
7.3.1.1 Air.
7.3.1.2 Oxygen.
7.3.2 Liquids. To conform to the specifications established by the
Committee on Analytical Reagents of the American Chemical Society.
7.3.2.1 Hexane.
7.3.2.2 Decane.
7.4 Calibration. For all calibration gases, the manufacturer must
recommend a maximum shelf life for each cylinder (i.e., the length of
time the gas concentration is not expected to change more than 5
percent from its certified value). The date of gas cylinder preparation,
certified organic concentration, and recommended maximum shelf life must
be affixed to each cylinder before shipment from the gas manufacturer to
the buyer. The following calibration gases are required:
7.4.1 Oxidation Catalyst Efficiency Check Calibration Gas. Gas
mixture standard with nominal concentration of 1 percent methane in air.
7.4.2 FID Linearity and NMO Calibration Gases. Three gas mixture
standards with nominal propane concentrations of 20 ppm, 200 ppm, and
3000 ppm, in air.
7.4.3 CO2 Calibration Gases. Three gas mixture standards
with nominal CO2 concentrations of 50 ppm, 500 ppm, and 1
percent, in air.

Note: Total NMO less than 1 ppm required for 1 percent mixture.

7.4.4 NMO Analyzer System Check Calibration Gases. Four calibration
gases are needed as follows:
7.4.4.1 Propane Mixture. Gas mixture standard containing (nominal)
50 ppm CO, 50 ppm CH4, 1 percent CO2, and 20 ppm
C3H8, prepared in air.
7.4.4.2 Hexane. Gas mixture standard containing (nominal) 50 ppm
hexane in air.
7.4.4.3 Toluene. Gas mixture standard containing (nominal) 20 ppm
toluene in air.
7.4.4.4 Methanol. Gas mixture standard containing (nominal) 100 ppm
methanol in air.

8.0 Sample Collection, Preservation, Transport, and Storage

8.1 Sampling Equipment Preparation.
8.1.1 Condensate Trap Cleaning. Before its initial use and after
each use, a condensate trap should be thoroughly cleaned and checked to
ensure that it is not contaminated. Both cleaning and checking can be
accomplished by installing the trap in the condensate recovery system
and treating it as if it were a sample. The trap should be heated as
described in section 11.1.3. A trap may be considered clean when the
CO2 concentration in its effluent gas drops below 10 ppm.
This check is optional for traps that most recently have been used to
collect samples which were then recovered according to the procedure in
section 11.1.3.
8.1.2 Sample Tank Evacuation and Leak-Check. Evacuate the sample
tank to 10 mm Hg absolute pressure or less. Then close the sample tank
valve, and allow the tank to sit for 60 minutes. The tank is acceptable
if a change in tank vacuum of less than 1 mm Hg is noted. The evacuation
and leak-check may be conducted either in the laboratory or the field.
8.1.3 Sampling Train Assembly. Just before assembly, measure the
tank vacuum using a mercury manometer. Record this vacuum, the ambient
temperature, and the barometric pressure at this time. Close the sample
tank valve and assemble the sampling

[[Page 510]]

system as shown in Figure 25-1. Immerse the condensate trap body in dry
ice at least 30 minutes before commencing sampling to improve collection
efficiency. The point where the inlet tube joins the trap body should be
2.5 to 5 cm (1 to 2 in.) above the top of the dry ice.
8.1.4 Pretest Leak-Check. A pretest leak-check is required.
Calculate or measure the approximate volume of the sampling train from
the probe tip to the sample tank valve. After assembling the sampling
train, plug the probe tip, and make certain that the sample tank valve
is closed. Turn on the vacuum pump, and evacuate the sampling system
from the probe tip to the sample tank valve to an absolute pressure of
10 mm Hg or less. Close the purge valve, turn off the pump, wait a
minimum period of 10 minutes, and recheck the indicated vacuum.
Calculate the maximum allowable pressure change based on a leak rate of
1 percent of the sampling rate using Equation 25-1, section 12.2. If the
measured pressure change exceeds the allowable, correct the problem and
repeat the leak-check before beginning sampling.
8.2 Sample Collection.
8.2.1 Unplug the probe tip, and place the probe into the stack such
that the probe is perpendicular to the duct or stack axis; locate the
probe tip at a single preselected point of average velocity facing away
from the direction of gas flow. For stacks having a negative static
pressure, seal the sample port sufficiently to prevent air in-leakage
around the probe. Set the probe temperature controller to 129 [deg]C
(265 [deg]F) and the filter temperature controller to 121 [deg]C (250
[deg]F). Allow the probe and filter to heat for about 30 minutes before
purging the sample train.
8.2.2 Close the sample valve, open the purge valve, and start the
vacuum pump. Set the flow rate between 60 and 100 cm\3\/min (0.13 and
0.21 ft\3\/hr), and purge the train with stack gas for at least 10
minutes.
8.2.3 When the temperatures at the exit ends of the probe and filter
are within the corresponding specified ranges, check the dry ice level
around the condensate trap, and add dry ice if necessary. Record the
clock time. To begin sampling, close the purge valve and stop the pump.
Open the sample valve and the sample tank valve. Using the flow control
valve, set the flow through the sample train to the proper rate. Adjust
the flow rate as necessary to maintain a constant rate (10 percent)
throughout the duration of the sampling period. Record the sample tank
vacuum and flowmeter setting at 5-minute intervals. (See Figure 25-8.)
Select a total sample time greater than or equal to the minimum sampling
time specified in the applicable subpart of the regulations; end the
sampling when this time period is reached or when a constant flow rate
can no longer be maintained because of reduced sample tank vacuum.

Note: If sampling had to be stopped before obtaining the minimum
sampling time (specified in the applicable subpart) because a constant
flow rate could not be maintained, proceed as follows: After closing the
sample tank valve, remove the used sample tank from the sampling train
(without disconnecting other portions of the sampling train). Take
another evacuated and leak-checked sample tank, measure and record the
tank vacuum, and attach the new tank to the sampling train. After the
new tank is attached to the sample train, proceed with the sampling
until the required minimum sampling time has been exceeded.

8.3 Sample Recovery. After sampling is completed, close the flow
control valve, and record the final tank vacuum; then record the tank
temperature and barometric pressure. Close the sample tank valve, and
disconnect the sample tank from the sample system. Disconnect the
condensate trap at the inlet to the rate meter, and tightly seal both
ends of the condensate trap. Do not include the probe from the stack to
the filter as part of the condensate sample.
8.4 Sample Storage and Transport. Keep the trap packed in dry ice
until the samples are returned to the laboratory for analysis. Ensure
that run numbers are identified on the condensate trap and the sample
tank(s).

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.1.1........................ Initial Ensure acceptable
performance condensate recovery
check of efficiency.
condensate
recovery
apparatus.
10.1.2, 10.2.................. NMO analyzer Ensure precision of
initial and analytical results.
daily
performance
checks.
------------------------------------------------------------------------

10.0 Calibration and Standardization

Note: Maintain a record of performance of each item.

10.1 Initial Performance Checks.
10.1.1 Condensate Recovery Apparatus. Perform these tests before the
system is first placed in operation, after any shutdown of 6 months or
more, and after any major modification of the system, or at the
frequency recommended by the manufacturer.
10.1.1.1 Carrier Gas and Auxiliary O2 Blank Check.
Analyze each new tank of carrier gas or auxiliary O2 with the
NMO analyzer to

[[Page 511]]

check for contamination. Treat the gas cylinders as noncondensible gas
samples, and analyze according to the procedure in section 11.2.3. Add
together any measured CH4, CO, CO2, or NMO. The
total concentration must be less than 5 ppm.
10.1.1.2 Oxidation Catalyst Efficiency Check.
10.1.1.2.1 With a clean condensate trap installed in the recovery
system or a \1/8\ stainless steel connector tube, replace the
carrier gas cylinder with the high level methane standard gas cylinder
(Section 7.4.1). Set the four-port valve to the recovery position, and
attach an ICV to the recovery system. With the sample recovery valve in
vent position and the flow-control and ICV valves fully open, evacuate
the manometer or gauge, the connecting tubing, and the ICV to 10 mm Hg
absolute pressure. Close the flow-control and vacuum pump valves.
10.1.1.2.2 After the NDIR response has stabilized, switch the sample
recovery valve from vent to collect. When the manometer or pressure
gauge begins to register a slight positive pressure, open the flow-
control valve. Keep the flow adjusted such that the pressure in the
system is maintained within 10 percent of atmospheric pressure. Continue
collecting the sample in a normal manner until the ICV is filled to a
nominal gauge pressure of 300 mm Hg. Close the ICV valve, and remove the
ICV from the system. Place the sample recovery valve in the vent
position, and return the recovery system to its normal carrier gas and
normal operating conditions. Analyze the ICV for CO2 using
the NMO analyzer; the catalyst efficiency is acceptable if the
CO2 concentration is within 2 percent of the methane standard
concentration.
10.1.1.3 System Performance Check. Construct a liquid sample
injection unit similar in design to the unit shown in Figure 25-7.
Insert this unit into the condensate recovery and conditioning system in
place of a condensate trap, and set the carrier gas and auxiliary
O2 flow rates to normal operating levels. Attach an evacuated
ICV to the system, and switch from system vent to collect. With the
carrier gas routed through the injection unit and the oxidation
catalyst, inject a liquid sample (see sections 10.1.1.3.1 to 10.1.1.3.4)
into the injection port. Operate the trap recovery system as described
in section 11.1.3. Measure the final ICV pressure, and then analyze the
vessel to determine the CO2 concentration. For each
injection, calculate the percent recovery according to section 12.7.
Calculate the relative standard deviation for each set of triplicate
injections according to section 12.8. The performance test is acceptable
if the average percent recovery is 100 5 percent and the relative
standard deviation is less than 2 percent for each set of triplicate
injections.
10.1.1.3.1 50 l hexane.
10.1.1.3.2 10 l hexane.
10.1.1.3.3 50 l decane.
10.1.1.3.4 10 l decane.
10.1.2 NMO Analyzer. Perform these tests before the system is first
placed in operation, after any shutdown longer than 6 months, and after
any major modification of the system.
10.1.2.1 Oxidation Catalyst Efficiency Check. Turn off or bypass the
NMO analyzer reduction catalyst. Make triplicate injections of the high
level methane standard (Section 7.4.1). The oxidation catalyst operation
is acceptable if the FID response is less than 1 percent of the injected
methane concentration.
10.1.2.2 Reduction Catalyst Efficiency Check. With the oxidation
catalyst unheated or bypassed and the heated reduction catalyst
bypassed, make triplicate injections of the high level methane standard
(Section 7.4.1). Repeat this procedure with both catalysts operative.
The reduction catalyst operation is acceptable if the responses under
both conditions agree within 5 percent of their average.
10.1.2.3 NMO Analyzer Linearity Check Calibration. While operating
both the oxidation and reduction catalysts, conduct a linearity check of
the analyzer using the propane standards specified in section 7.4.2.
Make triplicate injections of each calibration gas. For each gas (i.e.,
each set of triplicate injections), calculate the average response
factor (area/ppm C) for each gas, as well as and the relative standard
deviation (according to section 12.8). Then calculate the overall mean
of the response factor values. The instrument linearity is acceptable if
the average response factor of each calibration gas is within 2.5
percent of the overall mean value and if the relative standard deviation
gas is less than 2 percent of the overall mean value. Record the overall
mean of the propane response factor values as the NMO calibration
response factor (RFNMO). Repeat the linearity check using the
CO2 standards specified in section 7.4.3. Make triplicate
injections of each gas, and then calculate the average response factor
(area/ppm C) for each gas, as well as the overall mean of the response
factor values. Record the overall mean of the response factor values as
the CO2 calibration response factor (RFCO2). The
RFCO2 must be within 10 percent of the RFNMO.
10.1.2.4 System Performance Check. Check the column separation and
overall performance of the analyzer by making triplicate injections of
the calibration gases listed in section 7.4.4. The analyzer performance
is acceptable if the measured NMO value for each gas (average of
triplicate injections) is within 5 percent of the expected value.
10.2 NMO Analyzer Daily Calibration. The following calibration
procedures shall be performed before and immediately after the

[[Page 512]]

analysis of each set of samples, or on a daily basis, whichever is more
stringent:
10.2.1 CO2 Response Factor. Inject triplicate samples of
the high level CO2 calibration gas (Section 7.4.3), and
calculate the average response factor. The system operation is adequate
if the calculated response factor is within 5 percent of the
RFCO2 calculated during the initial performance test (Section
10.1.2.3). Use the daily response factor (DRFCO2) for
analyzer calibration and the calculation of measured CO2
concentrations in the ICV samples.
10.2.2 NMO Response Factors. Inject triplicate samples of the mixed
propane calibration cylinder gas (Section 7.4.4.1), and calculate the
average NMO response factor. The system operation is adequate if the
calculated response factor is within 10 percent of the RFNMO
calculated during the initial performance test (Section 10.1.2.4). Use
the daily response factor (DRFNMO) for analyzer calibration
and calculation of NMO concentrations in the sample tanks.
10.3 Sample Tank and ICV Volume. The volume of the gas sampling
tanks used must be determined. Determine the tank and ICV volumes by
weighing them empty and then filled with deionized distilled water;
weigh to the nearest 5 g, and record the results. Alternatively, measure
the volume of water used to fill them to the nearest 5 ml.

11.0 Analytical Procedure

11.1 Condensate Recovery. See Figure 25-9. Set the carrier gas flow
rate, and heat the catalyst to its operating temperature to condition
the apparatus.
11.1.1 Daily Performance Checks. Each day before analyzing any
samples, perform the following tests:
11.1.1.1 Leak-Check. With the carrier gas inlets and the sample
recovery valve closed, install a clean condensate trap in the system,
and evacuate the system to 10 mm Hg absolute pressure or less. Monitor
the system pressure for 10 minutes. The system is acceptable if the
pressure change is less than 2 mm Hg.
11.1.1.2 System Background Test. Adjust the carrier gas and
auxiliary oxygen flow rate to their normal values of 100 cc/min and 150
cc/min, respectively, with the sample recovery valve in vent position.
Using a 10-ml syringe, withdraw a sample from the system effluent
through the syringe port. Inject this sample into the NMO analyzer, and
measure the CO2 content. The system background is acceptable
if the CO2 concentration is less than 10 ppm.
11.1.1.3 Oxidation Catalyst Efficiency Check. Conduct a catalyst
efficiency test as specified in section 10.1.1.2. If the criterion of
this test cannot be met, make the necessary repairs to the system before
proceeding.
11.1.2 Condensate Trap CO2 Purge and Sample Tank
Pressurization.
11.1.2.1 After sampling is completed, the condensate trap will
contain condensed water and organics and a small volume of sampled gas.
This gas from the stack may contain a significant amount of
CO2 which must be removed from the condensate trap before the
sample is recovered. This is accomplished by purging the condensate trap
with zero air and collecting the purged gas in the original sample tank.
11.1.2.2 Begin with the sample tank and condensate trap from the
test run to be analyzed. Set the four-port valve of the condensate
recovery system in the CO2 purge position as shown in Figure
25-9. With the sample tank valve closed, attach the sample tank to the
sample recovery system. With the sample recovery valve in the vent
position and the flow control valve fully open, evacuate the manometer
or pressure gauge to the vacuum of the sample tank. Next, close the
vacuum pump valve, open the sample tank valve, and record the tank
pressure.
11.1.2.3 Attach the dry ice-cooled condensate trap to the recovery
system, and initiate the purge by switching the sample recovery valve
from vent to collect position. Adjust the flow control valve to maintain
atmospheric pressure in the recovery system. Continue the purge until
the CO2 concentration of the trap effluent is less than 5
ppm. CO2 concentration in the trap effluent should be
measured by extracting syringe samples from the recovery system and
analyzing the samples with the NMO analyzer. This procedure should be
used only after the NDIR response has reached a minimum level. Using a
10-ml syringe, extract a sample from the syringe port prior to the NDIR,
and inject this sample into the NMO analyzer.
11.1.2.4 After the completion of the CO2 purge, use the
carrier gas bypass valve to pressurize the sample tank to approximately
1,060 mm Hg absolute pressure with zero air.
11.1.3 Recovery of the Condensate Trap Sample (See Figure 25-10).
11.1.3.1 Attach the ICV to the sample recovery system. With the
sample recovery valve in a closed position, between vent and collect,
and the flow control and ICV valves fully open, evacuate the manometer
or gauge, the connecting tubing, and the ICV to 10 mm Hg absolute
pressure. Close the flow-control and vacuum pump valves.
11.1.3.2 Begin auxiliary oxygen flow to the oxidation catalyst at a
rate of 150 cc/min, then switch the four-way valve to the trap recovery
position and the sample recovery valve to collect position. The system
should now be set up to operate as indicated in Figure 25-10. After the
manometer or pressure gauge begins to register a slight positive
pressure, open the flow control valve. Adjust the flow-control valve to
maintain atmospheric pressure in the system within 10 percent.

[[Page 513]]

11.1.3.3 Remove the condensate trap from the dry ice, and allow it
to warm to ambient temperature while monitoring the NDIR response. If,
after 5 minutes, the CO2 concentration of the catalyst
effluent is below 10,000 ppm, discontinue the auxiliary oxygen flow to
the oxidation catalyst. Begin heating the trap by placing it in a
furnace preheated to 200 [deg]C (390 [deg]F). Once heating has begun,
carefully monitor the NDIR response to ensure that the catalyst effluent
concentration does not exceed 50,000 ppm. Whenever the CO2
concentration exceeds 50,000 ppm, supply auxiliary oxygen to the
catalyst at the rate of 150 cc/min. Begin heating the tubing that
connected the heated sample box to the condensate trap only after the
CO2 concentration falls below 10,000 ppm. This tubing may be
heated in the same oven as the condensate trap or with an auxiliary heat
source such as a heat gun. Heating temperature must not exceed 200
[deg]C (390 [deg]F). If a heat gun is used, heat the tubing slowly along
its entire length from the upstream end to the downstream end, and
repeat the pattern for a total of three times. Continue the recovery
until the CO2 concentration drops to less than 10 ppm as
determined by syringe injection as described under the condensate trap
CO2 purge procedure (Section 11.1.2).
11.1.3.4 After the sample recovery is completed, use the carrier gas
bypass valve to pressurize the ICV to approximately 1060 mm Hg absolute
pressure with zero air.
11.2 Analysis. Once the initial performance test of the NMO analyzer
has been successfully completed (see section 10.1.2) and the daily
CO2 and NMO response factors have been determined (see
section 10.2), proceed with sample analysis as follows:
11.2.1 Operating Conditions. The carrier gas flow rate is 29.5 cc/
min He and 2.2 cc/min O2. The column oven is heated to 85
[deg]C (185 [deg]F). The order of elution for the sample from the column
is CO, CH4, CO2, and NMO.
11.2.2 Analysis of Recovered Condensate Sample. Purge the sample
loop with sample, and then inject the sample. Under the specified
operating conditions, the CO2 in the sample will elute in
approximately 100 seconds. As soon as the detector response returns to
baseline following the CO2 peak, switch the carrier gas flow
to backflush, and raise the column oven temperature to 195 [deg]C (380
[deg]F) as rapidly as possible. A rate of 30 [deg]C/min (90 [deg]F) has
been shown to be adequate. Record the value obtained for the condensible
organic material (Ccm) measured as CO2 and any
measured NMO. Return the column oven temperature to 85 [deg]C (185
[deg]F) in preparation for the next analysis. Analyze each sample in
triplicate, and report the average Ccm.
11.2.3 Analysis of Sample Tank. Perform the analysis as described in
section 11.2.2, but record only the value measured for NMO
(Ctm).

12.0 Data Analysis and Calculations

Carry out the calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after final
calculations. All equations are written using absolute pressure;
absolute pressures are determined by adding the measured barometric
pressure to the measured gauge or manometer pressure.
12.1 Nomenclature.

C = TGNMO concentration of the effluent, ppm C equivalent.
Cc = Calculated condensible organic (condensate trap)
concentration of the effluent, ppm C equivalent.
Ccm = Measured concentration (NMO analyzer) for the
condensate trap ICV, ppm CO2.
Ct = Calculated noncondensible organic concentration (sample
tank) of the effluent, ppm C equivalent.
Ctm = Measured concentration (NMO analyzer) for the sample
tank, ppm NMO.
F = Sampling flow rate, cc/min.
L = Volume of liquid injected, l.
M = Molecular weight of the liquid injected, g/g-mole.
Mc = TGNMO mass concentration of the effluent, mg C/dsm\3\.
N = Carbon number of the liquid compound injected (N = 12 for decane, N
= 6 for hexane).
n = Number of data points.
Pf = Final pressure of the intermediate collection vessel, mm
Hg absolute.
Pb = Barometric pressure, cm Hg.
Pti = Gas sample tank pressure before sampling, mm Hg
absolute.
Pt = Gas sample tank pressure after sampling, but before
pressurizing, mm Hg absolute.
Ptf = Final gas sample tank pressure after pressurizing, mm
Hg absolute.
q = Total number of analyzer injections of intermediate collection
vessel during analysis (where k = injection number, 1 * * *
q).
r = Total number of analyzer injections of sample tank during analysis
(where j = injection number, 1 * * * r).
r = Density of liquid injected, g/cc.
Tf = Final temperature of intermediate collection vessel,
[deg]K.
Tti = Sample tank temperature before sampling, [deg]K.
Tt = Sample tank temperature at completion of sampling,
[deg]K.
Ttf = Sample tank temperature after pressurizing, [deg]K.
V = Sample tank volume, m\3\.
Vt = Sample train volume, cc.
Vv = Intermediate collection vessel volume, m\3\.
Vs = Gas volume sampled, dsm\3\.
xi = Individual measurements.
x = Mean value.

[[Page 514]]

FP = Allowable pressure change, cm Hg.
K = Leak-check period, min.

12.2 Allowable Pressure Change. For the pretest leak-check,
calculate the allowable pressure change using Equation 25-1:
[GRAPHIC] [TIFF OMITTED] TR17OC00.364

12.3 Sample Volume. For each test run, calculate the gas volume
sampled using Equation 25-2:
[GRAPHIC] [TIFF OMITTED] TR17OC00.365

12.4 Noncondensible Organics. For each sample tank, determine the
concentration of nonmethane organics (ppm C) using Equation 25-3:
[GRAPHIC] [TIFF OMITTED] TR17OC00.366

12.5 Condensible Organics. For each condensate trap determine the
concentration of organics (ppm C) using Equation 25-4:
[GRAPHIC] [TIFF OMITTED] TR17OC00.367

12.6 TGNMO Mass Concentration. Determine the TGNMO mass
concentration as carbon for each test run, using Equation 25-5:
[GRAPHIC] [TIFF OMITTED] TR17OC00.368

12.7 Percent Recovery. Calculate the percent recovery for the liquid
injections to the condensate recovery and conditioning system using
Equation 25-6:
[GRAPHIC] [TIFF OMITTED] TR17OC00.369

where K = 1.604 ([deg]K)(g-mole)(%)/(mm Hg)(ml)(m\3\)(ppm).

12.8 Relative Standard Deviation. Use Equation 25-7 to calculate the
relative standard deviation (RSD) of percent recovery and analyzer
linearity.
[GRAPHIC] [TIFF OMITTED] TR17OC00.370

13.0 Method Performance

13.1 Range. The minimum detectable limit of the method has been
determined to be 50 parts per million by volume (ppm). No upper limit
has been established.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Salo, A.E., S. Witz, and R.D. MacPhee. Determination of Solvent
Vapor Concentrations by Total Combustion Analysis: A Comparison of
Infrared with Flame Ionization Detectors. Paper No. 75-33.2. (Presented
at the 68th Annual Meeting of the Air Pollution Control Association.
Boston, MA. June 15-20, 1975.) 14 p.

[[Page 515]]

2. Salo, A.E., W.L. Oaks, and R.D. MacPhee. Measuring the Organic
Carbon Content of Source Emissions for Air Pollution Control. Paper No.
74-190. (Presented at the 67th Annual Meeting of the Air Pollution
Control Association. Denver, CO. June 9-13, 1974.) 25 p.

17.0 Tables, Diagrams, Flowcharts, and Validation Data
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[[Page 524]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.380

Method 25A--Determination of Total Gaseous Organic Concentration Using a
Flame Ionization Analyzer

1.0 Scope and Application

1.1 Analytes.

[[Page 525]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total Organic Compounds........ N/A <2% of span.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of total gaseous organic concentration of vapors consisting primarily of
alkanes, alkenes, and/or arenes (aromatic hydrocarbons). The
concentration is expressed in terms of propane (or other appropriate
organic calibration gas) or in terms of carbon.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted from the source through a heated
sample line and glass fiber filter to a flame ionization analyzer (FIA).
Results are reported as volume concentration equivalents of the
calibration gas or as carbon equivalents.

3.0 Definitions

3.1 Calibration drift means the difference in the measurement system
response to a mid-level calibration gas before and after a stated period
of operation during which no unscheduled maintenance, repair, or
adjustment took place.
3.2 Calibration error means the difference between the gas
concentration indicated by the measurement system and the know
concentration of the calibration gas.
3.3 Calibration gas means a known concentration of a gas in an
appropriate diluent gas.
3.4 Measurement system means the total equipment required for the
determination of the gas concentration. The system consists of the
following major subsystems:
3.4.1 Sample interface means that portion of a system used for one
or more of the following: sample acquisition, sample transportation,
sample conditioning, or protection of the analyzer(s) from the effects
of the stack effluent.
3.4.2 Organic analyzer means that portion of the measurement system
that senses the gas to be measured and generates an output proportional
to its concentration.
3.5 Response time means the time interval from a step change in
pollutant concentration at the inlet to the emission measurement system
to the time at which 95 percent of the corresponding final value is
reached as displayed on the recorder.
3.6 Span Value means the upper limit of a gas concentration
measurement range that is specified for affected source categories in
the applicable part of the regulations. The span value is established in
the applicable regulation and is usually 1.5 to 2.5 times the applicable
emission limit. If no span value is provided, use a span value
equivalent to 1.5 to 2.5 times the expected concentration. For
convenience, the span value should correspond to 100 percent of the
recorder scale.
3.7 Zero drift means the difference in the measurement system
response to a zero level calibration gas before or after a stated period
of operation during which no unscheduled maintenance, repair, or
adjustment took place.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Measurement System. Any measurement system for total organic
concentration that meets the specifications of this method. A schematic
of an acceptable measurement system is shown in Figure 25A-1. All
sampling components leading to the analyzer shall be heated
110 [deg]C (220 [deg]F) throughout the sampling period,
unless safety reasons are cited (Section 5.2) The essential components
of the measurement system are described below:
6.1.1 Organic Concentration Analyzer. A flame ionization analyzer
(FIA) capable of meeting or exceeding the specifications of this method.
The flame ionization detector block shall be heated >120 [deg]C (250
[deg]F).
6.1.2 Sample Probe. Stainless steel, or equivalent, three-hole rake
type. Sample holes shall be 4 mm (0.16-in.) in diameter or smaller and
located at 16.7, 50, and 83.3 percent of the equivalent stack diameter.
Alternatively, a single opening probe may be used so that a gas sample
is collected from the centrally located 10 percent area of the stack
cross-section.
6.1.3 Heated Sample Line. Stainless steel or Teflon'' tubing to
transport the sample gas

[[Page 526]]

to the analyzer. The sample line should be heated (110
[deg]C) to prevent any condensation.
6.1.4 Calibration Valve Assembly. A three-way valve assembly to
direct the zero and calibration gases to the analyzers is recommended.
Other methods, such as quick-connect lines, to route calibration gas to
the analyzers are applicable.
6.1.5 Particulate Filter. An in-stack or an out-of-stack glass fiber
filter is recommended if exhaust gas particulate loading is significant.
An out-of-stack filter should be heated to prevent any condensation.
6.1.6 Recorder. A strip-chart recorder, analog computer, or digital
recorder for recording measurement data. The minimum data recording
requirement is one measurement value per minute.

7.0 Reagents and Standards

7.1 Calibration Gases. The calibration gases for the gas analyzer
shall be propane in air or propane in nitrogen. Alternatively, organic
compounds other than propane can be used; the appropriate corrections
for response factor must be made. Calibration gases shall be prepared in
accordance with the procedure listed in Citation 2 of section 16.
Additionally, the manufacturer of the cylinder should provide a
recommended shelf life for each calibration gas cylinder over which the
concentration does not change more than 2 percent from the certified
value. For calibration gas values not generally available (i.e.,
organics between 1 and 10 percent by volume), alternative methods for
preparing calibration gas mixtures, such as dilution systems (Test
Method 205, 40 CFR Part 51, Appendix M), may be used with prior approval
of the Administrator.
7.1.1 Fuel. A 40 percent H2/60 percent N2 gas
mixture is recommended to avoid an oxygen synergism effect that
reportedly occurs when oxygen concentration varies significantly from a
mean value.
7.1.2 Zero Gas. High purity air with less than 0.1 part per million
by volume (ppmv) of organic material (propane or carbon equivalent) or
less than 0.1 percent of the span value, whichever is greater.
7.1.3 Low-level Calibration Gas. An organic calibration gas with a
concentration equivalent to 25 to 35 percent of the applicable span
value.
7.1.4 Mid-level Calibration Gas. An organic calibration gas with a
concentration equivalent to 45 to 55 percent of the applicable span
value.
7.1.5 High-level Calibration Gas. An organic calibration gas with a
concentration equivalent to 80 to 90 percent of the applicable span
value.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Selection of Sampling Site. The location of the sampling site is
generally specified by the applicable regulation or purpose of the test
(i.e., exhaust stack, inlet line, etc.). The sample port shall be
located to meet the testing requirements of Method 1.
8.2 Location of Sample Probe. Install the sample probe so that the
probe is centrally located in the stack, pipe, or duct and is sealed
tightly at the stack port connection.
8.3 Measurement System Preparation. Prior to the emission test,
assemble the measurement system by following the manufacturer's written
instructions for preparing sample interface and the organic analyzer.
Make the system operable (Section 10.1).
8.4 Calibration Error Test. Immediately prior to the test series
(within 2 hours of the start of the test), introduce zero gas and high-
level calibration gas at the calibration valve assembly. Adjust the
analyzer output to the appropriate levels, if necessary. Calculate the
predicted response for the low-level and mid-level gases based on a
linear response line between the zero and high-level response. Then
introduce low-level and mid-level calibration gases successively to the
measurement system. Record the analyzer responses for low-level and mid-
level calibration gases and determine the differences between the
measurement system responses and the predicted responses. These
differences must be less than 5 percent of the respective calibration
gas value. If not, the measurement system is not acceptable and must be
replaced or repaired prior to testing. No adjustments to the measurement
system shall be conducted after the calibration and before the drift
check (Section 8.6.2). If adjustments are necessary before the
completion of the test series, perform the drift checks prior to the
required adjustments and repeat the calibration following the
adjustments. If multiple electronic ranges are to be used, each
additional range must be checked with a mid-level calibration gas to
verify the multiplication factor.
8.5 Response Time Test. Introduce zero gas into the measurement
system at the calibration valve assembly. When the system output has
stabilized, switch quickly to the high-level calibration gas. Record the
time from the concentration change to the measurement system response
equivalent to 95 percent of the step change. Repeat the test three times
and average the results.
8.6 Emission Measurement Test Procedure.
8.6.1 Organic Measurement. Begin sampling at the start of the test
period, recording time and any required process information as
appropriate. In particulate, note on the recording chart, periods of
process interruption or cyclic operation.

[[Page 527]]

8.6.2 Drift Determination. Immediately following the completion of
the test period and hourly during the test period, reintroduce the zero
and mid-level calibration gases, one at a time, to the measurement
system at the calibration valve assembly. (Make no adjustments to the
measurement system until both the zero and calibration drift checks are
made.) Record the analyzer response. If the drift values exceed the
specified limits, invalidate the test results preceding the check and
repeat the test following corrections to the measurement system.
Alternatively, recalibrate the test measurement system as in section 8.4
and report the results using both sets of calibration data (i.e., data
determined prior to the test period and data determined following the
test period).

Note: Note on the recording chart periods of process interruption or
cyclic operation.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Method section measure Effect
------------------------------------------------------------------------
8.4........................... Zero and Ensures that bias
calibration introduced by drift
drift tests. in the measurement
system output during
the run is no
greater than 3
percent of span.
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 FIA equipment can be calibrated for almost any range of total
organic concentrations. For high concentrations of organics (>1.0
percent by volume as propane), modifications to most commonly available
analyzers are necessary. One accepted method of equipment modification
is to decrease the size of the sample to the analyzer through the use of
a smaller diameter sample capillary. Direct and continuous measurement
of organic concentration is a necessary consideration when determining
any modification design.

11.0 Analytical Procedure

The sample collection and analysis are concurrent for this method
(see section 8.0).

12.0 Calculations and Data Analysis

12.1 Determine the average organic concentration in terms of ppmv as
propane or other calibration gas. The average shall be determined by
integration of the output recording over the period specified in the
applicable regulation. If results are required in terms of ppmv as
carbon, adjust measured concentrations using Equation 25A-1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.381

Where:

Cc = Organic concentration as carbon, ppmv.
Cmeas = Organic concentration as measured, ppmv.
K = Carbon equivalent correction factor.
= 2 for ethane.
= 3 for propane.
= 4 for butane.
= Appropriate response factor for other organic calibration gases.

13.0 Method Performance

13.1 Measurement System Performance Specifications.
13.1.1 Zero Drift. Less than 3 percent of the span value.
13.1.2 Calibration Drift. Less than 3 percent of span value.
13.1.3 Calibration Error. Less than 5 percent of the calibration
gas value.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Measurement of Volatile Organic Compounds--Guideline Series. U.S.
Environmental Protection Agency. Research Triangle Park, NC. Publication
No. EPA-450/2-78-041. June 1978. p. 46-54.
2. EPA Traceability Protocol for Assay and Certification of Gaseous
Calibration Standards. U.S. Environmental Protection Agency, Quality
Assurance and Technical Support Division. Research Triangle Park, N.C.
September 1993.
3. Gasoline Vapor Emission Laboratory Evaluation--Part 2. U.S.
Environmental Protection Agency, Office of Air Quality Planning and
Standards. Research Triangle Park, NC. EMB Report No. 75-GAS-6. August
1975.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 528]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.382

Method 25B--Determination of Total Gaseous Organic Concentration Using a
Nondispersive Infrared Analyzer

1.0 Scope and Application

1.1 Analytes.

[[Page 529]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total Organic Compounds........... N/A <2% of span.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of total gaseous organic concentration of vapors consisting primarily of
alkanes. Other organic materials may be measured using the general
procedure in this method, the appropriate calibration gas, and an
analyzer set to the appropriate absorption band.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

A gas sample is extracted from the source through a heated sample
line, if necessary, and glass fiber filter to a nondispersive infrared
analyzer (NDIR). Results are reported as volume concentration
equivalents of the calibration gas or as carbon equivalents.

3.0 Definitions

Same as Method 25A, section 3.0.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Same as Method 25A, section 6.0, with the exception of the
following:
6.1 Organic Concentration Analyzer. A nondispersive infrared
analyzer designed to measure alkane organics and capable of meeting or
exceeding the specifications in this method.

7.0 Reagents and Standards

Same as Method 25A, section 7.1. No fuel gas is required for an
NDIR.

8.0 Sample Collection, Preservation, Storage, and Transport

Same as Method 25A, section 8.0.

9.0 Quality Control

Same as Method 25A, section 9.0.

10.0 Calibration and Standardization

Same as Method 25A, section 10.0.

11.0 Analytical Procedure

The sample collection and analysis are concurrent for this method
(see section 8.0).

12.0 Calculations and Data Analysis

Same as Method 25A, section 12.0.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as Method 25A, section 16.0.

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 25C--Determination of Nonmethane Organic Compounds (NMOC) in
Landfill Gases

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Nonmethane organic compounds (NMOC)....... No CAS number assigned.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable to the sampling and
measurement of NMOC as carbon in landfill gases (LFG).
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A sample probe that has been perforated at one end is driven or
augured to a depth of 0.9 m (3 ft) below the bottom of the landfill
cover. A sample of the landfill gas is extracted with an evacuated
cylinder. The NMOC content of the gas is determined by

[[Page 530]]

injecting a portion of the gas into a gas chromatographic column to
separate the NMOC from carbon monoxide (CO), carbon dioxide
(CO2), and methane (CH4); the NMOC are oxidized to
CO2, reduced to CH4, and measured by a flame
ionization detector (FID). In this manner, the variable response of the
FID associated with different types of organics is eliminated.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

5.1 Since this method is complex, only experienced personnel should
perform this test. LFG contains methane, therefore explosive mixtures
may exist on or near the landfill. It is advisable to take appropriate
safety precautions when testing landfills, such as refraining from
smoking and installing explosion-proof equipment.

6.0 Equipment and Supplies

6.1 Sample Probe. Stainless steel, with the bottom third perforated.
Teflon probe liners and sampling lines are also allowed. Non-perforated
probes are allowed as long as they are withdrawn to create a gap
equivalent to having the bottom third perforated. The sample probe must
be capped at the bottom and must have a threaded cap with a sampling
attachment at the top. The sample probe must be long enough to go
through and extend no less than 0.9 m (3 ft) below the landfill cover.
If the sample probe is to be driven into the landfill, the bottom cap
should be designed to facilitate driving the probe into the landfill.
6.2 Sampling Train.
6.2.1 Rotameter with Flow Control Valve. Capable of measuring a
sample flow rate of 100 10 ml/min. The control valve must be made of
stainless steel.
6.2.2 Sampling Valve. Stainless steel.
6.2.3 Pressure Gauge. U-tube mercury manometer, or equivalent,
capable of measuring pressure to within 1 mm Hg (0.5 in H2O)
in the range of 0 to 1,100 mm Hg (0 to 590 in H2O).
6.2.4 Sample Tank. Stainless steel or aluminum cylinder, equipped
with a stainless steel sample tank valve.
6.3 Vacuum Pump. Capable of evacuating to an absolute pressure of 10
mm Hg (5.4 in H2O).
6.4 Purging Pump. Portable, explosion proof, and suitable for
sampling NMOC.
6.5 Pilot Probe Procedure. The following are needed only if the
tester chooses to use the procedure described in section 8.2.1.
6.5.1 Pilot Probe. Tubing of sufficient strength to withstand being
driven into the landfill by a post driver and an outside diameter of at
least 6 mm (0.25 in.) smaller than the sample probe. The pilot probe
shall be capped on both ends and long enough to go through the landfill
cover and extend no less than 0.9 m (3 ft) into the landfill.
6.5.2 Post Driver and Compressor. Capable of driving the pilot probe
and the sampling probe into the landfill. The Kitty Hawk portable post
driver has been found to be acceptable.
6.6 Auger Procedure. The following are needed only if the tester
chooses to use the procedure described in section 8.2.2.
6.6.1 Auger. Capable of drilling through the landfill cover and to a
depth of no less than 0.9 m (3 ft) into the landfill.
6.6.2 Pea Gravel.
6.6.3 Bentonite.
6.7 NMOC Analyzer, Barometer, Thermometer, and Syringes. Same as in
sections 6.3.1, 6.3.2, 6.33, and 6.2.10, respectively, of Method 25.

7.0 Reagents and Standards

7.1 NMOC Analysis. Same as in Method 25, section 7.2.
7.2 Calibration. Same as in Method 25, section 7.4, except omit
section 7.4.3.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sample Tank Evacuation and Leak-Check. Conduct the sample tank
evacuation and leak-check either in the laboratory or the field. Connect
the pressure gauge and sampling valve to the sample tank. Evacuate the
sample tank to 10 mm Hg (5.4 in H2O) absolute pressure or
less. Close the sampling valve, and allow the tank to sit for 30
minutes. The tank is acceptable if no change more than 2 mm is noted.
Include the results of the leak-check in the test report.
8.2 Sample Probe Installation. The tester may use the procedure in
section 8.2.1 or 8.2.2.
8.2.1 Pilot Probe Procedure. Use the post driver to drive the pilot
probe at least 0.9 m (3 ft) below the landfill cover. Alternative
procedures to drive the probe into the landfill may be used subject to
the approval of the Administrator's designated representative.
8.2.1.1 Remove the pilot probe and drive the sample probe into the
hole left by the pilot probe. The sample probe shall extend at least 0.9
m (3 ft) below the landfill cover and shall protrude about 0.3 m (1 ft)
above the landfill cover. Seal around the sampling probe with bentonite
and cap the sampling probe with the sampling probe cap.
8.2.2 Auger Procedure. Use an auger to drill a hole to at least 0.9
m (3 ft) below the landfill cover. Place the sample probe in the hole
and backfill with pea gravel to a level 0.6 m (2 ft) from the surface.
The sample probe shall protrude at least 0.3 m (1 ft) above the landfill
cover. Seal the remaining area around the probe with bentonite. Allow 24

[[Page 531]]

hours for the landfill gases to equilibrate inside the augured probe
before sampling.
8.2.3 Driven Probes. Closed-point probes may be driven directly into
the landfill in a single step. This method may not require backfilling
if the probe is adequately sealed by its insertion. Unperforated probes
that are inserted in this manner and withdrawn at a distance from a
detachable tip to create an open space are also acceptable.
8.3 Sample Train Assembly. Just before assembling the sample train,
measure the sample tank vacuum using the pressure gauge. Record the
vacuum, the ambient temperature, and the barometric pressure at this
time. Assemble the sampling probe purging system as shown in Figure 25C-
1.
8.4 Sampling Procedure. Open the sampling valve and use the purge
pump and the flow control valve to evacuate at least two sample probe
volumes from the system at a flow rate of 500 ml/min or less. Close the
sampling valve and replace the purge pump with the sample tank apparatus
as shown in Figure 25C-2. Open the sampling valve and the sample tank
valve and, using the flow control valve, sample at a flow rate of 500
ml/min or less until either a constant flow rate can no longer be
maintained because of reduced sample tank vacuum or the appropriate
composite volume is attained. Disconnect the sampling tank apparatus and
pressurize the sample cylinder to approximately 1,060 mm Hg (567 in.
H2O) absolute pressure with helium, and record the final
pressure. Alternatively, the sample tank may be pressurized in the lab.
8.4.1 The following restrictions apply to compositing samples from
different probe sites into a single cylinder: (1) Individual composite
samples per cylinder must be of equal volume; this must be verified by
recording the flow rate, sampling time, vacuum readings, or other
appropriate volume measuring data, (2) individual composite samples must
have a minimum volume of 1 liter unless data is provided showing smaller
volumes can be accurately measured, and (3) composite samples must not
be collected using the final cylinder vacuum as it diminishes to ambient
pressure.
8.4.2 Use Method 3C to determine the percent N2 in each
cylinder. The presence of N2 indicates either infiltration of
ambient air into the landfill gas sample or an inappropriate testing
site has been chosen where anaerobic decomposition has not begun. The
landfill gas sample is acceptable if the concentration of N2
is less than 20 percent. Alternatively, Method 3C may be used to
determine the oxygen content of each cylinder as an air infiltration
test. With this option, the oxygen content of each cylinder must be less
than 5 percent.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

10.0 Calibration and Standardization

Note: Maintain a record of performance of each item.

10.1 Initial NMOC Analyzer Performance Test. Same as in Method 25,
section 10.1, except omit the linearity checks for CO2
standards.
10.2 NMOC Analyzer Daily Calibration.
10.2.1 NMOC Response Factors. Same as in Method 25, section 10.2.2.
10.3 Sample Tank Volume. The volume of the gas sampling tanks must
be determined. Determine the tank volumes by weighing them empty and
then filled with deionized water; weigh to the nearest 5 g, and record
the results. Alternatively, measure the volume of water used to fill
them to the nearest 5 ml.

11.0 Analytical Procedures

11.1 The oxidation, reduction, and measurement of NMOC's is similar
to Method 25. Before putting the NMOC analyzer into routine operation,
conduct an initial performance test. Start the analyzer, and perform all
the necessary functions in order to put the analyzer into proper working
order. Conduct the performance test according to the procedures
established in section 10.1. Once the performance test has been
successfully completed and the NMOC calibration response factor has been
determined, proceed with sample analysis as follows:
11.1.1 Daily Operations and Calibration Checks. Before and
immediately after the analysis of each set of samples or on a daily
basis (whichever occurs first), conduct a calibration test according to
the procedures established in section 10.2. If the criteria of the daily
calibration test cannot be met, repeat

[[Page 532]]

the NMOC analyzer performance test (Section 10.1) before proceeding.
11.1.2 Operating Conditions. Same as in Method 25, section 11.2.1.
11.1.3 Analysis of Sample Tank. Purge the sample loop with sample,
and then inject the sample. Under the specified operating conditions,
the CO2 in the sample will elute in approximately 100
seconds. As soon as the detector response returns to baseline following
the CO2 peak, switch the carrier gas flow to backflush, and
raise the column oven temperature to 195 [deg]C (383 [deg]F) as rapidly
as possible. A rate of 30 [deg]C/min (54 [deg]F/min) has been shown to
be adequate. Record the value obtained for any measured NMOC. Return the
column oven temperature to 85 [deg]C (185 [deg]F) in preparation for the
next analysis. Analyze each sample in triplicate, and report the average
as Ctm.
11.2 Audit Sample Analysis. When the method is used to analyze
samples to demonstrate compliance with a source emission regulation, an
audit sample, if available, must be analyzed.

12.0 Data Analysis and Calculations

Note: All equations are written using absolute pressure; absolute
pressures are determined by adding the measured barometric pressure to
the measured gauge or manometer pressure.

12.1 Nomenclature.

Bw = Moisture content in the sample, fraction.
CN2 = Reported N2 concentration
(CN2Corr by Method 3C), fraction.
Ct = Calculated NMOC concentration, ppmv C equivalent.
Ctm = Measured NMOC concentration, ppmv C equivalent.
Pb = Barometric pressure, mm Hg.
Pt = Gas sample tank pressure after sampling, but before
pressurizing, mm Hg absolute.
Ptf = Final gas sample tank pressure after pressurizing, mm
Hg absolute.
Pti = Gas sample tank pressure after evacuation, mm Hg
absolute.
Pw = Vapor pressure of H2O (from Table 25C-1), mm
Hg.
r = Total number of analyzer injections of sample tank during analysis
(where j = injection number, 1 . . . r).
Tt = Sample tank temperature at completion of sampling,
[deg]K.
Tti = Sample tank temperature before sampling, [deg]K.
Ttf = Sample tank temperature after pressurizing, [deg]K.

12.2 Water Correction. Use Table 25C-1 (Section 17.0), the LFG
temperature, and barometric pressure at the sampling site to calculate
Bw.
[GRAPHIC] [TIFF OMITTED] TR17OC00.383

12.3 NMOC Concentration. Use the following equation to calculate the
concentration of NMOC for each sample tank.
[GRAPHIC] [TIFF OMITTED] TR17OC00.384

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Salo, Albert E., Samuel Witz, and Robert D. MacPhee.
Determination of Solvent Vapor Concentrations by Total Combustion
Analysis: A Comparison of Infrared with Flame Ionization Detectors.
Paper No. 75-33.2. (Presented at the 68th Annual Meeting of the Air
Pollution Control Association. Boston, Massachusetts. June 15-20, 1975.)
14 p.
2. Salo, Albert E., William L. Oaks, and Robert D. MacPhee.
Measuring the Organic Carbon Content of Source Emissions for Air
Pollution Control. Paper No. 74-190. (Presented at the 67th Annual
Meeting of the Air Pollution Control Association. Denver, Colorado. June
9-13, 1974.) 25 p.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 533]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.385

Table 25C-1--Moisture Correction
------------------------------------------------------------------------
Vapor Vapor
Pressure Temperature, Pressure
Temperature, [deg]C of H2O, [deg]C of H2O,
mm Hg mm Hg
------------------------------------------------------------------------
4................................... 6.1 18 15.5
6................................... 7.0 20 17.5
8................................... 8.0 22 19.8
10.................................. 9.2 24 22.4
12.................................. 10.5 26 25.2
14.................................. 12.0 28 28.3
16.................................. 13.6 30 31.8
------------------------------------------------------------------------

[[Page 534]]

Method 25D--Determination of the Volatile Organic Concentration of Waste
Samples

Note: Performance of this method should not be attempted by persons
unfamiliar with the operation of a flame ionization detector (FID) or an
electrolytic conductivity detector (ELCD) because knowledge beyond the
scope of this presentation is required.

1.0 Scope and Application

1.1 Analyte. Volatile Organic Compounds. No CAS No. assigned.
1.2 Applicability. This method is applicable for determining the
volatile organic (VO) concentration of a waste sample.

2.0 Summary of Method

2.1 Principle. A sample of waste is obtained at a point which is
most representative of the unexposed waste (where the waste has had
minimum opportunity to volatilize to the atmosphere). The sample is
suspended in an organic/aqueous matrix, then heated and purged with
nitrogen for 30 min. in order to separate certain organic compounds.
Part of the sample is analyzed for carbon concentration, as methane,
with an FID, and part of the sample is analyzed for chlorine
concentration, as chloride, with an ELCD. The VO concentration is the
sum of the carbon and chlorine content of the sample.

3.0 Definitions

3.1 Well-mixed in the context of this method refers to turbulent
flow which results in multiple-phase waste in effect behaving as single-
phase waste due to good mixing.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Note: Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.

6.1 Sampling. The following equipment is required:
6.1.1 Sampling Tube. Flexible Teflon, 0.25 in. ID (6.35 mm).
6.1.2 Sample Container. Borosilicate glass, 40-mL, and a Teflon-
lined screw cap capable of forming an air tight seal.
6.1.3 Cooling Coil. Fabricated from 0.25 in (6.35 mm). ID 304
stainless steel tubing with a thermocouple at the coil outlet.
6.2 Analysis. The following equipment is required.
6.2.1 Purging Apparatus. For separating the VO from the waste
sample. A schematic of the system is shown in Figure 25D-1. The purging
apparatus consists of the following major components.
6.2.1.1 Purging Flask. A glass container to hold the sample while it
is heated and purged with dry nitrogen. The cap of the purging flask is
equipped with three fittings: one for a purging lance (fitting with the
#7 Ace-thread), one for the Teflon exit tubing (side fitting, also a #7
Ace-thread), and a third (a 50-mm Ace-thread) to attach the base of the
purging flask as shown in Figure 25D-2. The base of the purging flask is
a 50-mm ID (2 in) cylindrical glass tube. One end of the tube is open
while the other end is sealed. Exact dimensions are shown in Figure 25D-
2.
6.2.1.2 Purging Lance. Glass tube, 6-mm OD (0.2 in) by 30 cm (12 in)
long. The purging end of the tube is fitted with a four-arm bubbler with
each tip drawn to an opening 1 mm (0.04 in) in diameter. Details and
exact dimensions are shown in Figure 25D-2.
6.2.1.3 Coalescing Filter. Porous fritted disc incorporated into a
container with the same dimensions as the purging flask. The details of
the design are shown in Figure 25D-3.
6.2.1.4 Constant Temperature Chamber. A forced draft oven capable of
maintaining a uniform temperature around the purging flask and
coalescing filter of 75 2 [deg]C (167 3.6 [deg]F).
6.2.1.5 Three-way Valve. Manually operated, stainless steel. To
introduce calibration gas into system.
6.2.1.6 Flow Controllers. Two, adjustable. One capable of
maintaining a purge gas flow rate of 6 0.06 L/min (0.2 0.002 ft\3\/
min) The other capable of maintaining a calibration gas flow rate of 1-
100 mL/min (0.00004-0.004 ft\3\/min).
6.2.1.7 Rotameter. For monitoring the air flow through the purging
system (0-10 L/min)(0-0.4 ft\3\/min).
6.2.1.8 Sample Splitters. Two heated flow restrictors (placed inside
oven or heated to 120 10 [deg]C (248 18 [deg]F) ). At a purge rate of
6 L/min (0.2 ft\3\/min), one will supply a constant flow to the first
detector (the rest of the flow will be directed to the second sample
splitter). The second splitter will split the analytical flow between
the second detector and the flow restrictor. The approximate flow to the
FID will be 40 mL/min (0.0014 ft\3\/min) and to the ELCD will be 15 mL/
min (0.0005 ft\3\/min), but the exact flow must be adjusted to be
compatible with the individual detector and to meet its linearity
requirement. The two sample splitters will be connected to each other by
1/8[foot] OD (3.175 mm) stainless steel tubing.

[[Page 535]]

6.2.1.9 Flow Restrictor. Stainless steel tubing, 1/8[foot] OD (3.175
mm), connecting the second sample splitter to the ice bath. Length is
determined by the resulting pressure in the purging flask (as measured
by the pressure gauge). The resulting pressure from the use of the flow
restrictor shall be 6-7 psig.
6.2.1.10 Filter Flask. With one-hole stopper. Used to hold ice bath.
Excess purge gas is vented through the flask to prevent condensation in
the flowmeter and to trap volatile organic compounds.
6.2.1.11 Four-way Valve. Manually operated, stainless steel. Placed
inside oven, used to bypass purging flask.
6.2.1.12 On/Off Valves. Two, stainless steel. One heat resistant up
to 130 [deg]C (266 [deg]F) and placed between oven and ELCD. The other a
toggle valve used to control purge gas flow.
6.2.1.13 Pressure Gauge. Range 0-40 psi. To monitor pressure in
purging flask and coalescing filter.
6.2.1.14 Sample Lines. Teflon, 1/4[foot] OD (6.35 mm), used inside
the oven to carry purge gas to and from purging chamber and to and from
coalescing filter to four-way valve. Also used to carry sample from
four-way valve to first sample splitter.
6.2.1.15 Detector Tubing. Stainless steel, 1/8[foot] OD (3.175 mm),
heated to 120 10 [deg]C (248 18 [deg]F) . Used to carry sample gas
from each sample splitter to a detector. Each piece of tubing must be
wrapped with heat tape and insulating tape in order to insure that no
cold spots exist. The tubing leading to the ELCD will also contain a
heat-resistant on-off valve (Section 6.2.1.12) which shall also be
wrapped with heat-tape and insulation.
6.2.2 Volatile Organic Measurement System. Consisting of an FID to
measure the carbon concentration of the sample and an ELCD to measure
the chlorine concentration.
6.2.2.1 FID. A heated FID meeting the following specifications is
required.
6.2.2.1.1 Linearity. A linear response (5 percent) over the
operating range as demonstrated by the procedures established in section
10.1.1.
6.2.2.1.2 Range. A full scale range of 50 pg carbon/sec to 50
g carbon/sec. Signal attenuators shall be available to produce
a minimum signal response of 10 percent of full scale.
6.2.2.1.3 Data Recording System. A digital integration system
compatible with the FID for permanently recording the output of the
detector. The recorder shall have the capability to start and stop
integration at points selected by the operator or it shall be capable of
the ``integration by slices'' technique (this technique involves
breaking down the chromatogram into smaller increments, integrating the
area under the curve for each portion, subtracting the background for
each portion, and then adding all of the areas together for the final
area count).
6.2.2.2 ELCD. An ELCD meeting the following specifications is
required. 1-propanol must be used as the electrolyte. The electrolyte
flow through the conductivity cell shall be 1 to 2 mL/min (0.00004 to
0.00007 ft\3\/min).

Note: A \1/4\-in. ID (6.35 mm) quartz reactor tube is strongly
recommended to reduce carbon buildup and the resulting detector
maintenance.

6.2.2.2.1 Linearity. A linear response (10 percent) over the
response range as demonstrated by the procedures in section 10.1.2.
6.2.2.2.2 Range. A full scale range of 5.0 pg/sec to 500 ng/sec
chloride. Signal attenuators shall be available to produce a minimum
signal response of 10 percent of full scale.
6.2.2.2.3 Data Recording System. A digital integration system
compatible with the output voltage range of the ELCD. The recorder must
have the capability to start and stop integration at points selected by
the operator or it shall be capable of performing the ``integration by
slices'' technique.

7.0 Reagents and Standards

7.1 Sampling.
7.1.1 Polyethylene Glycol (PEG). Ninety-eight percent pure with an
average molecular weight of 400. Before using the PEG, remove any
organic compounds that might be detected as volatile organics by heating
it to 120 [deg]C (248 [deg]F) and purging it with nitrogen at a flow
rate of 1 to 2 L/min (0.04 to 0.07 ft\3\/min) for 2 hours. The cleaned
PEG must be stored under a 1 to 2 L/min (0.04 to 0.07 ft\3\/min)
nitrogen purge until use. The purge apparatus is shown in Figure 25D-4.
7.2 Analysis.
7.2.1 Sample Separation. The following are required for the sample
purging step.
7.2.1.1 PEG. Same as section 7.1.1.
7.2.1.2 Purge Gas. Zero grade nitrogen (N2), containing
less than 1 ppm carbon.
7.2.2 Volatile Organics Measurement. The following are required for
measuring the VO concentration.
7.2.2.1 Hydrogen (H2). Zero grade H2, 99.999
percent pure.
7.2.2.2 Combustion Gas. Zero grade air or oxygen as required by the
FID.
7.2.2.3 Calibration Gas. Pressurized gas cylinder containing 10
percent propane and 1 percent 1,1-dichloroethylene by volume in
nitrogen.
7.2.2.4 Water. Deionized distilled water that conforms to American
Society for Testing and Materials Specification D 1193-74, Type 3, is
required for analysis. At the option of the analyst, the
KMnO4 test for oxidizable organic matter may be omitted when
high concentrations are not expected to be present.
7.2.2.5 1-Propanol. ACS grade or better. Electrolyte Solution. For
use in the ELCD.

[[Page 536]]

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sampling.
8.1.1 Sampling Plan Design and Development. Use the procedures in
chapter nine of Reference 1 in section 16 as guidance in developing a
sampling plan.
8.1.2 Single Phase or Well-mixed Waste.
8.1.2.1 Install a sampling tap to obtain the sample at a point which
is most representative of the unexposed waste (where the waste has had
minimum opportunity to volatilize to the atmosphere). Assemble the
sampling apparatus as shown in Figure 25D-5.
8.1.2.2 Prepare the sampling containers as follows: Pour 30 mL of
clean PEG into the container. PEG will reduce but not eliminate the loss
of organics during sample collection. Weigh the sample container with
the screw cap, the PEG, and any labels to the nearest 0.01 g and record
the weight (mst). Store the containers in an ice bath until 1
hour before sampling (PEG will solidify at ice bath temperatures; allow
the containers to reach room temperature before sampling).
8.1.2.3 Begin sampling by purging the sample lines and cooling coil
with at least four volumes of waste. Collect the purged material in a
separate container and dispose of it properly.
8.1.2.4 After purging, stop the sample flow and direct the sampling
tube to a preweighed sample container, prepared as described in section
8.1.2.2. Keep the tip of the tube below the surface of the PEG during
sampling to minimize contact with the atmosphere. Sample at a flow rate
such that the temperature of the waste is less than 10 [deg]C (50
[deg]F). Fill the sample container and immediately cap it (within 5
seconds) so that a minimum headspace exists in the container. Store
immediately in a cooler and cover with ice.
8.1.3 Multiple-phase Waste. Collect a 10 g sample of each phase of
waste generated using the procedures described in section 8.1.2 or
8.1.5. Each phase of the waste shall be analyzed as a separate sample.
Calculate the weighted average VO concentration of the waste using
Equation 25D-13 (Section 12.14).
8.1.4 Solid waste. Add approximately 10 g of the solid waste to a
container prepared in the manner described in section 8.1.2.2,
minimizing headspace. Cap and chill immediately.
8.1.5 Alternative to Tap Installation. If tap installation is
impractical or impossible, fill a large, clean, empty container by
submerging the container into the waste below the surface of the waste.
Immediately fill a container prepared in the manner described in section
8.1.2.2 with approximately 10 g of the waste collected in the large
container. Minimize headspace, cap and chill immediately.
8.1.6 Alternative sampling techniques may be used upon the approval
of the Administrator.
8.2 Sample Recovery.
8.2.1 Assemble the purging apparatus as shown in Figures 25D-1 and
25D-2. The oven shall be heated to 75 2 [deg]C (167 3.6 [deg]F). The
sampling lines leading from the oven to the detectors shall be heated to
120 10 [deg]C (248 18 [deg]F) with no cold spots. The flame ionization
detector shall be operated with a heated block. Adjust the purging lance
so that it reaches the bottom of the chamber.
8.2.2 Remove the sample container from the cooler, and wipe the
exterior of the container to remove any extraneous ice, water, or other
debris. Reweigh the sample container to the nearest 0.01 g, and record
the weight (msf). Pour the contents of the sample container
into the purging flask, rinse the sample container three times with a
total of 20 mL of PEG (since the sample container originally held 30 mL
of PEG, the total volume of PEG added to the purging flask will be 50
mL), transferring the rinsings to the purging flask after each rinse.
Cap purging flask between rinses. The total volume of PEG in the purging
flask shall be 50 mL. Add 50 mL of water to the purging flask.

9.0 Quality Control

9.1 Quality Control Samples. If audit samples are not available,
prepare and analyze the two types of quality control samples (QCS)
listed in Sections 9.1.1 and 9.1.2. Before placing the system in
operation, after a shutdown of greater than six months, and after any
major modifications, analyze each QCS in triplicate. For each detector,
calculate the percent recovery by dividing measured concentration by
theoretical concentration and multiplying by 100. Determine the mean
percent recovery for each detector for each QCS triplicate analysis. The
RSD for any triplicate analysis shall be 10 percent. For QCS
1 (methylene chloride), the percent recovery shall be 90
percent for carbon as methane, and 55 percent for chlorine as
chloride. For QCS 2 (1,3-dichloro-2-propanol), the percent recovery
shall be 15 percent for carbon as methane, and 6
percent for chlorine as chloride. If the analytical system does not meet
the above-mentioned criteria for both detectors, check the system
parameters (temperature, system pressure, purge rate, etc.), correct the
problem, and repeat the triplicate analysis of each QCS.
9.1.1 QCS 1, Methylene Chloride. Prepare a stock solution by
weighing, to the nearest 0.1 mg, 55 L of HPLC grade methylene
chloride in a tared 5 mL volumetric flask. Record the weight in
milligrams, dilute to 5 mL with cleaned PEG, and inject 100 L
of the stock solution into a sample prepared as a water blank (50 mL of
cleaned PEG and 60 mL of water in the purging flask). Analyze

[[Page 537]]

the QCS according to the procedures described in sections 10.2 and 10.3,
excluding section 10.2.2. To calculate the theoretical carbon
concentration (in mg) in QCS 1, multiply mg of methylene chloride in the
stock solution by 3.777 x 10^-3. To calculate the theoretical
chlorine concentration (in mg) in QCS 1, multiply mg of methylene
chloride in the stock solution by 1.670 x 10^-2.
9.1.2 QCS 2, 1,3-dichloro-2-propanol. Prepare a stock solution by
weighing, to the nearest 0.1 mg, 60 L of high purity grade 1,3-
dichloro-2-propanol in a tared 5 mL volumetric flask. Record the weight
in milligrams, dilute to 5 mL with cleaned PEG, and inject 100
L of the stock solution into a sample prepared as a water blank
(50 mL of cleaned PEG and 60 mL of water in the purging flask). Analyze
the QCS according to the procedures described in sections 10.2 and 10.3,
excluding section 10.2.2. To calculate the theoretical carbon
concentration (in mg) in QCS 2, multiply mg of 1,3-dichloro-2-propanol
in the stock solution by 7.461 x 10^-3. To calculate the
theoretical chlorine concentration (in mg) in QCS 2, multiply mg of 1,3-
dichloro-2-propanol in the stock solution by 1.099 x 10^-2.
9.1.3 Routine QCS Analysis. For each set of compliance samples (in
this context, set is per facility, per compliance test), analyze one QCS
1 and one QCS 2 sample. The percent recovery for each sample for each
detector shall be 13 percent of the mean recovery established for the
most recent set of QCS triplicate analysis (Section 9.4). If the sample
does not meet this criteria, check the system components and analyze
another QCS 1 and 2 until a single set of QCS meet the 13 percent
criteria.

10.0 Calibration and Standardization

10.1 Initial Performance Check of Purging System. Before placing the
system in operation, after a shutdown of greater than six months, after
any major modifications, and at least once per month during continuous
operation, conduct the linearity checks described in sections 10.1.1 and
10.1.2. Install calibration gas at the three-way calibration gas valve.
See Figure 25D-1.
10.1.1 Linearity Check Procedure. Using the calibration standard
described in section 7.2.2.3 and by varying the injection time, it is
possible to calibrate at multiple concentration levels. Use Equation
25D-3 to calculate three sets of calibration gas flow rates and run
times needed to introduce a total mass of carbon, as methane,
(mc) of 1, 5, and 10 mg into the system (low, medium and high
FID calibration, respectively). Use Equation 25D-4 to calculate three
sets of calibration gas flow rates and run times needed to introduce a
total chloride mass (mch) of 1, 5, and 10 mg into the system
(low, medium and high ELCD calibration, respectively). With the system
operating in standby mode, allow the FID and the ELCD to establish a
stable baseline. Set the secondary pressure regulator of the calibration
gas cylinder to the same pressure as the purge gas cylinder and set the
proper flow rate with the calibration flow controller (see Figure 25D-
1). The calibration gas flow rate can be measured with a flowmeter
attached to the vent position of the calibration gas valve. Set the
four-way bypass valve to standby position so that the calibration gas
flows through the coalescing filter only. Inject the calibration gas by
turning the calibration gas valve from vent position to inject position.
Continue the calibration gas flow for the appropriate period of time
before switching the calibration valve to vent position. Continue
recording the response of the FID and the ELCD for 5 min after switching
off calibration gas flow. Make triplicate injections of all six levels
of calibration.
10.1.2 Linearity Criteria. Calculate the average response factor
(Equations 25D-5 and 25D-6) and the relative standard deviation (RSD)
(Equation 25D-10) at each level of the calibration curve for both
detectors. Calculate the overall mean of the three response factor
averages for each detector. The FID linearity is acceptable if each
response factor is within 5 percent of the overall mean and if the RSD
for each set of triplicate injections is less than 5 percent. The ELCD
linearity is acceptable if each response factor is within 10 percent of
the overall mean and if the RSD for each set of triplicate injections is
less than 10 percent. Record the overall mean value of the response
factors for the FID and the ELCD. If the calibration for either the FID
or the ELCD does not meet the criteria, correct the detector/system
problem and repeat sections 10.1.1 and 10.1.2.
10.2 Daily Calibrations.
10.2.1 Daily Linearity Check. Follow the procedures outlined in
section 10.1.1 to analyze the medium level calibration for both the FID
and the ELCD in duplicate at the start of the day. Calculate the
response factors and the RSDs for each detector. For the FID, the
calibration is acceptable if the average response factor is within 5
percent of the overall mean response factor (Section 10.1.2) and if the
RSD for the duplicate injection is less than 5 percent. For the ELCD,
the calibration is acceptable if the average response factor is within
10 percent of the overall mean response factor (Section 10.1.2) and if
the RSD for the duplicate injection is less than 10 percent. If the
calibration for either the FID or the ELCD does not meet the criteria,
correct the detector/system problem and repeat sections 10.1.1 and
10.1.2.
10.2.2 Calibration Range Check.
10.2.2.1 If the waste concentration for either detector falls below
the range of calibration for that detector, use the procedure outlined
in section 10.1.1 to choose two calibration points that bracket the new
target

[[Page 538]]

concentration. Analyze each of these points in triplicate (as outlined
in section 10.1.1) and use the criteria in section 10.1.2 to determine
the linearity of the detector in this ``mini-calibration'' range.
10.2.2.2 After the initial linearity check of the mini-calibration
curve, it is only necessary to test one of the points in duplicate for
the daily calibration check (in addition to the points specified in
section 10.2.1). The average daily mini-calibration point should fit the
linearity criteria specified in section 10.2.1. If the calibration for
either the FID or the ELCD does not meet the criteria, correct the
detector/system problem and repeat the calibration procedure mentioned
in the first paragraph of section 10.2.2. A mini-calibration curve for
waste concentrations above the calibration curve for either detector is
optional.
10.3 Analytical Balance. Calibrate against standard weights.

11.0 Analysis

11.1 Sample Analysis.
11.1.1 Turn on the constant temperature chamber and allow the
temperature to equilibrate at 75 2 [deg]C (167 3.6 [deg]F). Turn the
four-way valve so that the purge gas bypasses the purging flask, the
purge gas flowing through the coalescing filter and to the detectors
(standby mode). Turn on the purge gas. Allow both the FID and the ELCD
to warm up until a stable baseline is achieved on each detector. Pack
the filter flask with ice. Replace ice after each run and dispose of the
waste water properly. When the temperature of the oven reaches 75 2
[deg]C (167 3.6 [deg]F), start both integrators and record baseline.
After 1 min, turn the four-way valve so that the purge gas flows through
the purging flask, to the coalescing filter and to the sample splitters
(purge mode). Continue recording the response of the FID and the ELCD.
Monitor the readings of the pressure gauge and the rotameter. If the
readings fall below established setpoints, stop the purging, determine
the source of the leak, and resolve the problem before resuming. Leaks
detected during a sampling period invalidate that sample.
11.1.2 As the purging continues, monitor the output of the detectors
to make certain that the analysis is proceeding correctly and that the
results are being properly recorded. Every 10 minutes read and record
the purge flow rate, the pressure and the chamber temperature. Continue
the purging for 30 minutes.
11.1.3 For each detector output, integrate over the entire area of
the peak starting at 1 minute and continuing until the end of the run.
Subtract the established baseline area from the peak area. Record the
corrected area of the peak. See Figure 25D-6 for an example integration.
11.2 Water Blank. A water blank shall be analyzed for each batch of
cleaned PEG prepared. Transfer about 60 mL of water into the purging
flask. Add 50 mL of the cleaned PEG to the purging flask. Treat the
blank as described in sections 8.2 and 8.3, excluding section 8.2.2.
Calculate the concentration of carbon and chlorine in the blank sample
(assume 10 g of waste as the mass). A VO concentration equivalent to
10 percent of the applicable standard may be subtracted from
the measured VO concentration of the waste samples. Include all blank
results and documentation in the test report.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

Ab = Area under the water blank response curve, counts.
Ac = Area under the calibration response curve, counts.
As = Area under the sample response curve, counts.
C = Concentration of volatile organics in the sample, ppmw.
Cc = Concentration of carbon, as methane, in the calibration
gas, mg/L.
Cch = Concentration of chloride in the calibration gas, mg/L.
Cj = VO concentration of phase j, ppmw.
DRt = Average daily response factor of the FID, mg
CH4/counts.
Drth = Average daily response factor of the ELCD, mg
Cl^-/counts.
Fj = Weight fraction of phase j present in the waste.
mc = Mass of carbon, as methane, in a calibration run, mg.
mch = Mass of chloride in a calibration run, mg.
ms = Mass of the waste sample, g.
msc = Mass of carbon, as methane, in the sample, mg.
msf = Mass of sample container and waste sample, g.
msh = Mass of chloride in the sample, mg.
mst = Mass of sample container prior to sampling, g.
mVO = Mass of volatile organics in the sample, mg.
n = Total number of phases present in the waste.
Pp = Percent propane in calibration gas (L/L).
Pvc = Percent 1,1-dichloroethylene in calibration gas (L/L).
Qc = Flow rate of calibration gas, L/min.
tc = Length of time standard gas is delivered to the
analyzer, min.
W = Weighted average VO concentration, ppmw.

12.2 Concentration of Carbon, as Methane, in the Calibration Gas.

[[Page 539]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.386

12.3 Concentration of Chloride in the Calibration Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.387

12.4 Mass of Carbon, as Methane, in a Calibration Run.
[GRAPHIC] [TIFF OMITTED] TR17OC00.388

12.5 Mass of Chloride in a Calibration Run.
[GRAPHIC] [TIFF OMITTED] TR17OC00.389

12.6 FID Response Factor, mg/counts.
[GRAPHIC] [TIFF OMITTED] TR17OC00.390

12.7 ELCD Response Factor, mg/counts.
[GRAPHIC] [TIFF OMITTED] TR17OC00.391

12.8 Mass of Carbon in the Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.392

12.9 Mass of Chloride in the Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.393

12.10 Mass of Volatile Organics in the Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.394

12.11 Relative Standard Deviation.
[GRAPHIC] [TIFF OMITTED] TR17OC00.395

12.12 Mass of Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.396

12.13 Concentration of Volatile Organics in Waste.
[GRAPHIC] [TIFF OMITTED] TR17OC00.397

12.14 Weighted Average VO Concentration of Multi-phase Waste.
[GRAPHIC] [TIFF OMITTED] TR17OC00.398

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. ``Test Methods for Evaluating Solid Waste, Physical/Chemistry
Methods'', U.S. Environmental Protection Agency. Publication SW-846, 3rd
Edition, November 1986 as amended by Update I, November 1990.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 540]]

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[[Page 541]]

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[[Page 542]]

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[GRAPHIC] [TIFF OMITTED] TR17OC00.402

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[GRAPHIC] [TIFF OMITTED] TR17OC00.403

[[Page 545]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.404

Method 25E--Determination of Vapor Phase Organic Concentration in Waste
Samples

Note: Performance of this method should not be attempted by persons
unfamiliar with the operation of a flame ionization detector (FID) nor
by those who are unfamiliar with source sampling because knowledge
beyond the scope of this presentation is required. This method is not
inclusive with respect to specifications (e.g., reagents and standards)
and calibration procedures. Some material is incorporated by reference
from other methods. Therefore, to obtain reliable results, persons using
this method should have a thorough knowledge of at least the following
additional test methods: Method 106, part 61, Appendix B, and Method 18,
part 60, Appendix A.

[[Page 546]]

1.0 Scope and Application

1.1 Applicability. This method is applicable for determining the
vapor pressure of waste cited by an applicable regulation.
1.2 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 The headspace vapor of the sample is analyzed for carbon content
by a headspace analyzer, which uses an FID.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 The analyst shall select the operating parameters best suited to
the requirements for a particular analysis. The analyst shall produce
confirming data through an adequate supplemental analytical technique
and have the data available for review by the Administrator.

5.0 Safety [Reserved]

6.0 Equipment and Supplies

6.1 Sampling. The following equipment is required:
6.1.1 Sample Containers. Vials, glass, with butyl rubber septa,
Perkin-Elmer Corporation Numbers 0105-0129 (glass vials), B001-0728
(gray butyl rubber septum, plug style), 0105-0131 (butyl rubber septa),
or equivalent. The seal must be made from butyl rubber. Silicone rubber
seals are not acceptable.
6.1.2 Vial Sealer. Perkin-Elmer Number 105-0106, or equivalent.
6.1.3 Gas-Tight Syringe. Perkin-Elmer Number 00230117, or
equivalent.
6.1.4 The following equipment is required for sampling.
6.1.4.1 Tap.
6.1.4.2 Tubing. Teflon, 0.25-in. ID.

Note: Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.

6.1.4.3 Cooling Coil. Stainless steel (304), 0.25 in.-ID, equipped
with a thermocouple at the coil outlet.
6.2 Analysis. The following equipment is required.
6.2.1 Balanced Pressure Headspace Sampler. Perkin-Elmer HS-6, HS-
100, or equivalent, equipped with a glass bead column instead of a
chromatographic column.
6.2.2 FID. An FID meeting the following specifications is required.
6.2.2.1 Linearity. A linear response (5 percent) over the operating
range as demonstrated by the procedures established in section 10.2.
6.2.2.2 Range. A full scale range of 1 to 10,000 parts per million
(ppm) propane (C3H8). Signal attenuators shall be
available to produce a minimum signal response of 10 percent of full
scale.
6.2.3 Data Recording System. Analog strip chart recorder or digital
integration system compatible with the FID for permanently recording the
output of the detector.
6.2.4 Temperature Sensor. Capable of reading temperatures in the
range of 30 to 60 [deg]C (86 to 140 [deg]F) with an accuracy of 0.1
[deg]C (0.2 [deg]F).

7.0 Reagents and Standards

7.1 Analysis. The following items are required for analysis.
7.1.1 Hydrogen (H2). Zero grade hydrogen, as required by
the FID.
7.1.2 Carrier Gas. Zero grade nitrogen, containing less than 1 ppm
carbon (C) and less than 1 ppm carbon dioxide.
7.1.3 Combustion Gas. Zero grade air or oxygen as required by the
FID.
7.2 Calibration and Linearity Check.
7.2.1 Stock Cylinder Gas Standard. 100 percent propane. The
manufacturer shall: (a) Certify the gas composition to be accurate to 3
percent or better (see section 7.2.1.1); (b) recommend a maximum shelf
life over which the gas concentration does not change by greater than 5
percent from the certified value; and (c) affix the date of gas cylinder
preparation, certified propane concentration, and recommended maximum
shelf life to the cylinder before shipment to the buyer.
7.2.1.1 Cylinder Standards Certification. The manufacturer shall
certify the concentration of the calibration gas in the cylinder by (a)
directly analyzing the cylinder and (b) calibrating his analytical
procedure on the day of cylinder analysis. To calibrate his analytical
procedure, the manufacturer shall use, as a minimum, a three-point
calibration curve.
7.2.1.2 Verification of Manufacturer's Calibration Standards. Before
using, the manufacturer shall verify each calibration standard by (a)
comparing it to gas mixtures prepared in accordance with the procedure
described in section 7.1 of Method 106 of Part 61, Appendix B, or by (b)
calibrating it against Standard Reference Materials (SRM's) prepared by
the National Bureau of Standards, if such SRM's are available. The
agreement between the initially determined concentration value and the
verification concentration value must be within 5 percent. The
manufacturer must reverify all calibration standards on a time interval
consistent with the shelf life of the cylinder standards sold.

8.0 Sampling Collection, Preservation, Storage, and Transport

8.1 Install a sampling tap to obtain a sample at a point which is
most representative of the unexposed waste (where the waste has had
minimum opportunity to volatilize to

[[Page 547]]

the atmosphere). Assemble the sampling apparatus as shown in Figure 25E-
1.
8.2 Begin sampling by purging the sample lines and cooling coil with
at least four volumes of waste. Collect the purged material in a
separate container and dispose of it properly.
8.3 After purging, stop the sample flow and transfer the Teflon
sampling tube to a sample container. Sample at a flow rate such that the
temperature of the waste is <10 [deg]C (<50 [deg]F). Fill the sample
container halfway (5 percent) and cap it within 5 seconds. Store
immediately in a cooler and cover with ice.
8.4 Alternative sampling techniques may be used upon the approval of
the Administrator.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.2, 10.3.................... FID calibration Ensure precision of
and response analytical results.
check.
------------------------------------------------------------------------

10.0 Calibration and Standardization

Note: Maintain a record of performance of each item.

10.1 Use the procedures in sections 10.2 to calibrate the headspace
analyzer and FID and check for linearity before the system is first
placed in operation, after any shutdown longer than 6 months, and after
any modification of the system.
10.2 Calibration and Linearity. Use the procedures in section 10 of
Method 18 of Part 60, Appendix A, to prepare the standards and calibrate
the flowmeters, using propane as the standard gas. Fill the calibration
standard vials halfway (5 percent) with deionized water. Purge and fill
the airspace with calibration standard. Prepare a minimum of three
concentrations of calibration standards in triplicate at concentrations
that will bracket the applicable cutoff. For a cutoff of 5.2 kPa (0.75
psi), prepare nominal concentrations of 30,000, 50,000, and 70,000 ppm
as propane. For a cutoff of 27.6 kPa (4.0 psi), prepare nominal
concentrations of 200,000, 300,000, and 400,000 ppm as propane.
10.2.1 Use the procedures in section 11.3 to measure the FID
response of each standard. Use a linear regression analysis to calculate
the values for the slope (k) and the y-intercept (b). Use the procedures
in sections 12.3 and 12.2 to test the calibration and the linearity.
10.3 Daily FID Calibration Check. Check the calibration at the
beginning and at the end of the daily runs by using the following
procedures. Prepare 2 calibration standards at the nominal cutoff
concentration using the procedures in section 10.2. Place one at the
beginning and one at the end of the daily run. Measure the FID response
of the daily calibration standard and use the values for k and b from
the most recent calibration to calculate the concentration of the daily
standard. Use an equation similar to 25E-2 to calculate the percent
difference between the daily standard and Cs. If the
difference is within 5 percent, then the previous values for k and b can
be used. Otherwise, use the procedures in section 10.2 to recalibrate
the FID.

11.0 Analytical Procedures

11.1 Allow one hour for the headspace vials to equilibrate at the
temperature specified in the regulation. Allow the FID to warm up until
a stable baseline is achieved on the detector.
11.2 Check the calibration of the FID daily using the procedures in
section 10.3.
11.3 Follow the manufacturer's recommended procedures for the normal
operation of the headspace sampler and FID.
11.4 Use the procedures in sections 12.4 and 12.5 to calculate the
vapor phase organic vapor pressure in the samples.
11.5 Monitor the output of the detector to make certain that the
results are being properly recorded.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

A = Measurement of the area under the response curve, counts.
b = y-intercept of the linear regression line.
Ca = Measured vapor phase organic concentration of sample,
ppm as propane.
Cma = Average measured vapor phase organic concentration of
standard, ppm as propane.
Cm = Measured vapor phase organic concentration of standard,
ppm as propane.
Cs = Calculated standard concentration, ppm as propane.
k = Slope of the linear regression line.
Pbar = Atmospheric pressure at analysis conditions, mm Hg
(in. Hg).
P* = Organic vapor pressure in the sample, kPa (psi).
PD = Percent difference between the average measured vapor phase organic
concentration (Cm) and the calculated standard
concentration (Cs).
RSD = Relative standard deviation.
= 1.333 x 10^-7 kPa/[(mm Hg)(ppm)], (4.91 x
10^-7 psi/[(in. Hg)(ppm)])

[[Page 548]]

12.2 Linearity. Use the following equation to calculate the measured
standard concentration for each standard vial.
[GRAPHIC] [TIFF OMITTED] TR17OC00.405

12.2.1 Calculate the average measured standard concentration
(Cma) for each set of triplicate standards and use the
following equation to calculate PD between Cma and
Cs. The instrument linearity is acceptable if the PD is
within five for each standard.
[GRAPHIC] [TIFF OMITTED] TR17OC00.406

12.3. Relative Standard Deviation (RSD). Use the following equation
to calculate the RSD for each triplicate set of standards.
[GRAPHIC] [TIFF OMITTED] TR17OC00.407

The calibration is acceptable if the RSD is within five for each
standard concentration.
12.4 Concentration of organics in the headspace. Use the following
equation to calculate the concentration of vapor phase organics in each
sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.408

12.5 Vapor Pressure of Organics in the Headspace Sample. Use the
following equation to calculate the vapor pressure of organics in the
sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.409

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Salo, Albert E., Samuel Witz, and Robert D. MacPhee.
``Determination of Solvent Vapor Concentrations by Total Combustion
Analysis: a Comparison of Infared with Flame Ionization Detectors. Paper
No. 75-33.2. (Presented at the 68th Annual Meeting of the Air Pollution
Control Association. Boston, Massachusetts.
2. Salo, Albert E., William L. Oaks, and Robert D. MacPhee.
``Measuring the Organic Carbon Content of Source Emissions for Air
Pollution Control. Paper No. 74-190. (Presented at the 67th Annual
Meeting of the Air Pollution Control Association. Denver, Colorado. June
9-13, 1974.) p. 25.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 549]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.412

[36 FR 24877, Dec. 23, 1971]

Editorial Note: For Federal Register citations affecting appendix A-
7 to part 60, see the List of CFR sections Affected, which appears in
the Finding Aids section of the printed volume and at www.fdsys.gov.

Sec. Appendix A-8 to Part 60--Test Methods 26 through 30B

Method 26--Determination of Hydrogen Chloride Emissions From Stationary
Sources
Method 26A--Determination of hydrogen halide and halogen emissions from
stationary sources--isokinetic method

[[Page 550]]

Method 27--Determination of vapor tightness of gasoline delivery tank
using pressure-vacuum test
Method 28--Certification and auditing of wood heaters
Method 28A--Measurement of air to fuel ratio and minimum achievable burn
rates for wood-fired appliances
Method 29--Determination of metals emissions from stationary sources
The test methods in this appendix are referred to in Sec. 60.8
(Performance Tests) and Sec. 60.11 (Compliance With Standards and
Maintenance Requirements) of 40 CFR part 60, subpart A (General
Provisions). Specific uses of these test methods are described in the
standards of performance contained in the subparts, beginning with
Subpart D.
Within each standard of performance, a section title ``Test Methods
and Procedures'' is provided to: (1) Identify the test methods to be
used as reference methods to the facility subject to the respective
standard and (2) identify any special instructions or conditions to be
followed when applying a method to the respective facility. Such
instructions (for example, establish sampling rates, volumes, or
temperatures) are to be used either in addition to, or as a substitute
for procedures in a test method. Similarly, for sources subject to
emission monitoring requirements, specific instructions pertaining to
any use of a test method as a reference method are provided in the
subpart or in Appendix B.
Inclusion of methods in this appendix is not intended as an
endorsement or denial of their applicability to sources that are not
subject to standards of performance. The methods are potentially
applicable to other sources; however, applicability should be confirmed
by careful and appropriate evaluation of the conditions prevalent at
such sources.
The approach followed in the formulation of the test methods
involves specifications for equipment, procedures, and performance. In
concept, a performance specification approach would be preferable in all
methods because this allows the greatest flexibility to the user. In
practice, however, this approach is impractical in most cases because
performance specifications cannot be established. Most of the methods
described herein, therefore, involve specific equipment specifications
and procedures, and only a few methods in this appendix rely on
performance criteria.
Minor changes in the test methods should not necessarily affect the
validity of the results and it is recognized that alternative and
equivalent methods exist. section 60.8 provides authority for the
Administrator to specify or approve (1) equivalent methods, (2)
alternative methods, and (3) minor changes in the methodology of the
test methods. It should be clearly understood that unless otherwise
identified all such methods and changes must have prior approval of the
Administrator. An owner employing such methods or deviations from the
test methods without obtaining prior approval does so at the risk of
subsequent disapproval and retesting with approved methods.
Within the test methods, certain specific equipment or procedures
are recognized as being acceptable or potentially acceptable and are
specifically identified in the methods. The items identified as
acceptable options may be used without approval but must be identified
in the test report. The potentially approvable options are cited as
``subject to the approval of the Administrator'' or as ``or
equivalent.'' Such potentially approvable techniques or alternatives may
be used at the discretion of the owner without prior approval. However,
detailed descriptions for applying these potentially approvable
techniques or alternatives are not provided in the test methods. Also,
the potentially approvable options are not necessarily acceptable in all
applications. Therefore, an owner electing to use such potentially
approvable techniques or alternatives is responsible for: (1) assuring
that the techniques or alternatives are in fact applicable and are
properly executed; (2) including a written description of the
alternative method in the test report (the written method must be clear
and must be capable of being performed without additional instruction,
and the degree of detail should be similar to the detail contained in
the test methods); and (3) providing any rationale or supporting data
necessary to show the validity of the alternative in the particular
application. Failure to meet these requirements can result in the
Administrator's disapproval of the alternative.

Method 26--Determination of Hydrogen Halide and Halogen Emissions From
Stationary Sources Non-Isokinetic Method

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analytes CAS No.
------------------------------------------------------------------------
Hydrogen Chloride (HCl)................................. 7647-01-0
Hydrogen Bromide (HBr).................................. 10035-10-6
Hydrogen Fluoride (HF).................................. 7664-39-3
Chlorine (Cl2).......................................... 7882-50-5
Bromine (Br2)........................................... 7726-95-6
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for determining
emissions of hydrogen halides (HX) (HCl, HBr, and HF) and halogens
(X2) (Cl2 and Br2) from stationary
sources when specified by the applicable subpart. Sources, such as those
controlled by wet scrubbers, that emit acid particulate matter must be
sampled using Method 26A.

[[Page 551]]

1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 An integrated sample is extracted from the source and passed
through a prepurged heated probe and filter into dilute sulfuric acid
and dilute sodium hydroxide solutions which collect the gaseous hydrogen
halides and halogens, respectively. The filter collects particulate
matter including halide salts but is not routinely recovered and
analyzed. The hydrogen halides are solubilized in the acidic solution
and form chloride (Cl^-), bromide (Br^-), and
fluoride (F^-) ions. The halogens have a very low solubility
in the acidic solution and pass through to the alkaline solution where
they are hydrolyzed to form a proton (H\ + \), the halide ion, and the
hypohalous acid (HClO or HBrO). Sodium thiosulfate is added in excess to
the alkaline solution to assure reaction with the hypohalous acid to
form a second halide ion such that 2 halide ions are formed for each
molecule of halogen gas. The halide ions in the separate solutions are
measured by ion chromatography (IC).

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Volatile materials, such as chlorine dioxide (ClO2)
and ammonium chloride (NH4Cl), which produce halide ions upon
dissolution during sampling are potential interferents. Interferents for
the halide measurements are the halogen gases which disproportionate to
a hydrogen halide and a hydrohalous acid upon dissolution in water.
However, the use of acidic rather than neutral or basic solutions for
collection of the hydrogen halides greatly reduces the dissolution of
any halogens passing through this solution.
4.2 The simultaneous presence of HBr and CL2 may cause a
positive bias in the HCL result with a corresponding negative bias in
the Cl2 result as well as affecting the HBr/Br2
split.
4.3 High concentrations of nitrogen oxides (NOX) may
produce sufficient nitrate (NO3^- to interfere with
measurements of very low Br^- levels.
4.4 A glass wool plug should not be used to remove particulate
matter since a negative bias in the data could result.
4.5 There is anecdotal evidence that HF may be outgassed from new
teflon components. If HF is a target analyte, then preconditioning of
new teflon components, by heating should be considered.

5.0 Safety

6.0 Equipment and Supplies

Note: Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.

6.1 Sampling. The sampling train is shown in Figure 26-1, and
component parts are discussed below.
6.1.1 Probe. Borosilicate glass, approximately 3/8-in. (9-mm) I.D.
with a heating system capable of maintaining a probe gas temperature
during sampling between 120 and 134 [deg]C (248 and 273 [deg]F) to
prevent moisture condensation; or Teflon where stack probes are below
210 [deg]C. If HF is a target analyte, then preconditioning of new
teflon components by heating should be considered to prevent potential
HF outgassing. A Teflon-glass filter in a mat configuration should be
installed to remove particulate matter from the gas stream.
6.1.2 Three-way Stopcock. A borosilicate-glass three-way stopcock
with a heating system to prevent moisture condensation. The heated
stopcock should connect to the outlet of the heated filter and the inlet
of the first impinger. The heating system should be capable of
preventing condensation up to the inlet of the first impinger. Silicone
grease may be used, if necessary, to prevent leakage.

[[Page 552]]

6.1.3 Impingers. Four 30-ml midget impingers with leak-free glass
connectors. Silicone grease may be used, if necessary, to prevent
leakage. For sampling at high moisture sources or for sampling times
greater than one hour, a midget impinger with a shortened stem (such
that the gas sample does not bubble through the collected condensate)
should be used in front of the first impinger.
6.1.4 Drying Tube or Impinger. Tube or impinger, of Mae West design,
filled with 6- to 16-mesh indicating type silica gel, or equivalent, to
dry the gas sample and to protect the dry gas meter and pump. If the
silica gel has been used previously, dry at 175 [deg]C (350 [deg]F) for
2 hours. New silica gel may be used as received. Alternatively, other
types of desiccants (equivalent or better) may be used.
6.1.5 Heating System. Any heating system capable of maintaining a
temperature around the probe and filter holder between 120 and 134
[deg]C (248 and 273 [deg]F) during sampling, or such other temperature
as specified by an applicable subpart of the standards or approved by
the Administrator for a particular application.
6.1.6 Filter Holder and Support. The filter holder shall be made of
Teflon or quartz. The filter support shall be made of Teflon. All Teflon
filter holders and supports are available from Savillex Corp., 5325 Hwy
101, Minnetonka, MN 55345.
6.1.7 Sample Line. Leak-free, with compatible fittings to connect
the last impinger to the needle valve.
6.1.8 Rate Meter. Rotameter, or equivalent, capable of measuring
flow rate to within 2 percent of the selected flow rate of 2 liters/min
(0.07 ft\3\/min).
6.1.9 Purge Pump, Purge Line, Drying Tube, Needle Valve, and Rate
Meter. Pump capable of purging the sampling probe at 2 liters/min, with
drying tube, filled with silica gel or equivalent, to protect pump, and
a rate meter capable of measuring 0 to 5 liters/min (0.2 ft\3\/min).
6.1.10 Stopcock Grease, Valve, Pump, Volume Meter, Barometer, and
Vacuum Gauge. Same as in Method 6, sections 6.1.1.4, 6.1.1.7, 6.1.1.8,
6.1.1.10, 6.1.2, and 6.1.3.
6.1.11 Temperature Measuring Devices. Temperature sensors to monitor
the temperature of the probe and to monitor the temperature of the
sampling system from the outlet of the probe to the inlet of the first
impinger.
6.1.12 Ice Water Bath. To minimize loss of absorbing solution.
6.2 Sample Recovery.
6.2.1 Wash Bottles. Polyethylene or glass, 500-ml or larger, two.
6.2.2 Storage Bottles. 100- or 250-ml, high-density polyethylene
bottles with Teflon screw cap liners to store impinger samples.
6.3 Sample Preparation and Analysis. The materials required for
volumetric dilution and chromatographic analysis of samples are
described below.
6.3.1 Volumetric Flasks. Class A, 100-ml size.
6.3.2 Volumetric Pipets. Class A, assortment. To dilute samples to
the calibration range of the ion chromatograph.
6.3.3 Ion Chromatograph (IC). Suppressed or non-suppressed, with a
conductivity detector and electronic integrator operating in the peak
area mode. Other detectors, strip chart recorders, and peak height
measurements may be used.

7.0 Reagents and Standards

Note: Unless otherwise indicated, all reagents must conform to the
specifications established by the Committee on Analytical Reagents of
the American Chemical Society (ACS reagent grade). When such
specifications are not available, the best available grade shall be
used.

7.1 Sampling.
7.1.1 Filter. A 25-mm (1 in) (or other size) Teflon glass mat,
Pallflex TX40HI75 (Pallflex Inc., 125 Kennedy Drive, Putnam, CT 06260).
This filter is in a mat configuration to prevent fine particulate matter
from entering the sampling train. Its composition is 75% Teflon/25%
borosilicate glass. Other filters may be used, but they must be in a mat
(as opposed to a laminate) configuration and contain at least 75%
Teflon. For practical rather than scientific reasons, when the stack gas
temperature exceeds 210 [deg]C (410 [deg]F) and the HCl concentration is
greater than 20 ppm, a quartz-fiber filter may be used since Teflon
becomes unstable above this temperature.
7.1.2 Water. Deionized, distilled water that conforms to American
Society of Testing and Materials (ASTM) Specification D 1193-77 or 91,
Type 3 (incorporated by reference--see Sec. 60.17).
7.1.3 Acidic Absorbing Solution, 0.1 N Sulfuric Acid
(H2SO4). To prepare 100 ml of the absorbing
solution for the front impinger pair, slowly add 0.28 ml of concentrated
H2SO4 to about 90 ml of water while stirring, and
adjust the final volume to 100 ml using additional water. Shake well to
mix the solution.
7.1.4 Silica Gel. Indicating type, 6 to 16 mesh. If previously used,
dry at 180 [deg]C (350 [deg]F) for 2 hours. New silica gel may be used
as received. Alternatively, other types of desiccants may be used,
subject to the approval of the Administrator.
7.1.5 Alkaline Adsorbing Solution, 0.1 N Sodium Hydroxide (NaOH). To
prepare 100 ml of the scrubber solution for the third and fourth
impinger, dissolve 0.40 g of solid NaOH in about 90 ml of water, and
adjust the final

[[Page 553]]

solution volume to 100 ml using additional water. Shake well to mix the
solution.
7.1.6 Sodium Thiosulfate (Na2S2O3 5
H2O)
7.2 Sample Preparation and Analysis.
7.2.1 Water. Same as in section 7.1.2.
7.2.2 Absorbing Solution Blanks. A separate blank solution of each
absorbing reagent should be prepared for analysis with the field
samples. Dilute 30 ml of each absorbing solution to approximately the
same final volume as the field samples using the blank sample of rinse
water.
7.2.3 Halide Salt Stock Standard Solutions. Prepare concentrated
stock solutions from reagent grade sodium chloride (NaCl), sodium
bromide (NaBr), and sodium fluoride (NaF). Each must be dried at 110
[deg]C (230 [deg]F) for two or more hours and then cooled to room
temperature in a desiccator immediately before weighing. Accurately
weigh 1.6 to 1.7 g of the dried NaCl to within 0.1 mg, dissolve in
water, and dilute to 1 liter. Calculate the exact Cl^-
concentration using Equation 26-1 in section 12.2. In a similar manner,
accurately weigh and solubilize 1.2 to 1.3 g of dried NaBr and 2.2 to
2.3 g of NaF to make 1-liter solutions. Use Equations 26-2 and 26-3 in
section 12.2, to calculate the Br^- and F^-
concentrations. Alternately, solutions containing a nominal certified
concentration of 1000 mg/l NaCl are commercially available as convenient
stock solutions from which standards can be made by appropriate
volumetric dilution. Refrigerate the stock standard solutions and store
no longer than one month.
7.2.4 Chromatographic Eluent. Effective eluents for nonsuppressed IC
using a resin-or silica-based weak ion exchange column are a 4 mM
potassium hydrogen phthalate solution, adjusted to pH 4.0 using a
saturated sodium borate solution, and a 4 mM 4-hydroxy benzoate
solution, adjusted to pH 8.6 using 1 N NaOH. An effective eluent for
suppressed ion chromatography is a solution containing 3 mM sodium
bicarbonate and 2.4 mM sodium carbonate. Other dilute solutions buffered
to a similar pH and containing no interfering ions may be used. When
using suppressed ion chromatography, if the ``water dip'' resulting from
sample injection interferes with the chloride peak, use a 2 mM NaOH/2.4
mM sodium bicarbonate eluent.

8.0 Sample Collection, Preservation, Storage, and Transport

Note: Because of the complexity of this method, testers and analyst
should be trained and experienced with the procedure to ensure reliable
results.

8.1 Sampling.
8.1.1 Preparation of Collection Train. Prepare the sampling train as
follows: Pour 15 ml of the acidic absorbing solution into each one of
the first pair of impingers, and 15 ml of the alkaline absorbing
solution into each one of the second pair of impingers. Connect the
impingers in series with the knockout impinger first, if used, followed
by the two impingers containing the acidic absorbing solution and the
two impingers containing the alkaline absorbing solution. Place a fresh
charge of silica gel, or equivalent, in the drying tube or impinger at
the end of the impinger train.
8.1.2 Adjust the probe temperature and the temperature of the filter
and the stopcock (i.e., the heated area in Figure 26-1) to a temperature
sufficient to prevent water condensation. This temperature must be
maintained between 120 and 134 [deg]C (248 and 273 [deg]F). The
temperature should be monitored throughout a sampling run to ensure that
the desired temperature is maintained. It is important to maintain a
temperature around the probe and filter in this range since it is
extremely difficult to purge acid gases off these components. (These
components are not quantitatively recovered and, hence, any collection
of acid gases on these components would result in potential
undereporting of these emissions. The applicable subparts may specify
alternative higher temperatures.)
8.1.3 Leak-Check Procedure.
8.1.3.1 Sampling Train. A leak-check prior to the sampling run is
optional; however, a leak-check after the sampling run is mandatory. The
leak-check procedure is as follows: Temporarily attach a suitable [e.g.,
0-40 cc/min (0-2.4 in\3\/min)] rotameter to the outlet of the dry gas
meter and place a vacuum gauge at or near the probe inlet. Plug the
probe inlet, pull a vacuum of at least 250 mm Hg (10 in. Hg), and note
the flow rate as indicated by the rotameter. A leakage rate not in
excess of 2 percent of the average sampling rate is acceptable.

Note: Carefully release the probe inlet plug before turning off the
pump.

8.1.3.2 Pump. It is suggested (not mandatory) that the pump be leak-
checked separately, either prior to or after the sampling run. If done
prior to the sampling run, the pump leak-check shall precede the leak-
check of the sampling train described immediately above; if done after
the sampling run, the pump leak-check shall follow the train leak-check.
To leak-check the pump, proceed as follows: Disconnect the drying tube
from the probe-impinger assembly. Place a vacuum gauge at the inlet to
either the drying tube or pump, pull a vacuum of 250 mm (10 in) Hg, plug
or pinch off the outlet of the flow meter, and then turn off the pump.
The vacuum should remain stable for at least 30 sec. Other leak-check
procedures may be used, subject to the approval of the Administrator,
U.S. Environmental Protection Agency.

[[Page 554]]

8.1.4 Purge Procedure. Immediately before sampling, connect the
purge line to the stopcock, and turn the stopcock to permit the purge
pump to purge the probe (see Figure 1A of Figure 26-1). Turn on the
purge pump, and adjust the purge rate to 2 liters/min (0.07 ft\3\/min).
Purge for at least 5 minutes before sampling.
8.1.5 Sample Collection. Turn on the sampling pump, pull a slight
vacuum of approximately 25 mm Hg (1 in Hg) on the impinger train, and
turn the stopcock to permit stack gas to be pulled through the impinger
train (see Figure 1C of Figure 26-1). Adjust the sampling rate to 2
liters/min, as indicated by the rate meter, and maintain this rate to
within 10 percent during the entire sampling run. Take readings of the
dry gas meter volume and temperature, rate meter, and vacuum gauge at
least once every five minutes during the run. A sampling time of one
hour is recommended. Shorter sampling times may introduce a significant
negative bias in the HCl concentration. At the conclusion of the
sampling run, remove the train from the stack, cool, and perform a leak-
check as described in section 8.1.3.1.
8.2 Sample Recovery.
8.2.1 Disconnect the impingers after sampling. Quantitatively
transfer the contents of the acid impingers and the knockout impinger,
if used, to a leak-free storage bottle. Add the water rinses of each of
these impingers and connecting glassware to the storage bottle.
8.2.2 Repeat this procedure for the alkaline impingers and
connecting glassware using a separate storage bottle. Add 25 mg of
sodium thiosulfate per the product of ppm of halogen anticipated to be
in the stack gas times the volume (dscm) of stack gas sampled (0.7 mg
per ppm-dscf).

Note: This amount of sodium thiosulfate includes a safety factor of
approximately 5 to assure complete reaction with the hypohalous acid to
form a second Cl^- ion in the alkaline solution.

8.2.3 Save portions of the absorbing reagents (0.1 N
H2SO4 and 0.1 N NaOH) equivalent to the amount
used in the sampling train (these are the absorbing solution blanks
described in section 7.2.2); dilute to the approximate volume of the
corresponding samples using rinse water directly from the wash bottle
being used. Add the same amount of sodium thiosulfate solution to the
0.1 N NaOH absorbing solution blank. Also, save a portion of the rinse
water used to rinse the sampling train. Place each in a separate,
prelabeled storage bottle. The sample storage bottles should be sealed,
shaken to mix, and labeled. Mark the fluid level.
8.3 Sample Preparation for Analysis. Note the liquid levels in the
storage bottles and confirm on the analysis sheet whether or not leakage
occurred during transport. If a noticeable leakage has occurred, either
void the sample or use methods, subject to the approval of the
Administrator, to correct the final results. Quantitatively transfer the
sample solutions to 100-ml volumetric flasks, and dilute to 100 ml with
water.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.

10.1 Volume Metering System, Temperature Sensors, Rate Meter, and
Barometer. Same as in Method 6, sections 10.1, 10.2, 10.3, and 10.4.
10.2 Ion Chromatograph.
10.2.1 To prepare the calibration standards, dilute given amounts
(1.0 ml or greater) of the stock standard solutions to convenient
volumes, using 0.1 N H2SO4 or 0.1 N NaOH, as
appropriate. Prepare at least four calibration standards for each
absorbing reagent containing the appropriate stock solutions such that
they are within the linear range of the field samples.
10.2.2 Using one of the standards in each series, ensure adequate
baseline separation for the peaks of interest.
10.2.3 Inject the appropriate series of calibration standards,
starting with the lowest concentration standard first both before and
after injection of the quality control check sample, reagent blanks, and
field samples. This allows compensation for any instrument drift
occurring during sample analysis. The values from duplicate injections
of these calibration samples should agree within 5 percent of their mean
for the analysis to be valid.
10.2.4 Determine the peak areas, or heights, for the standards and
plot individual values versus halide ion concentrations in g/
ml.
10.2.5 Draw a smooth curve through the points. Use linear regression
to calculate a formula describing the resulting linear curve.

11.0 Analytical Procedures

[[Page 555]]

procedure until they are no longer present. Analysis of the acid and
alkaline absorbing solution samples requires separate standard
calibration curves; prepare each according to section 10.2. Ensure
adequate baseline separation of the analyses.
11.1.3 Between injections of the appropriate series of calibration
standards, inject in duplicate the reagent blanks, quality control
sample, and the field samples. Measure the areas or heights of the
Cl^-, Br^-, and F^- peaks. Use the mean
response of the duplicate injections to determine the concentrations of
the field samples and reagent blanks using the linear calibration curve.
The values from duplicate injections should agree within 5 percent of
their mean for the analysis to be valid. If the values of duplicate
injections are not within 5 percent of the mean, the duplicate
injections shall be repeated and all four values used to determine the
average response. Dilute any sample and the blank with equal volumes of
water if the concentration exceeds that of the highest standard.

12.0 Data Analysis and Calculations

Note: Retain at least one extra decimal figure beyond those
contained in the available data in intermediate calculations, and round
off only the final answer appropriately.

12.1 Nomenclature.

BX^- = Mass concentration of applicable absorbing
solution blank, g halide ion (Cl^-,
Br^-, F^-) /ml, not to exceed 1
g/ml which is 10 times the published analytical
detection limit of 0.1 g/ml.
C = Concentration of hydrogen halide (HX) or halogen (X2),
dry basis, mg/dscm.
K = 10^-3 mg/g.
KHCl = 1.028 (g HCl/g-mole)/(g
Cl^-/g-mole).
KHBr = 1.013 (g HBr/g-mole)/(g
Br^-/g-mole).
KHF = 1.053 (g HF/g-mole)/(g
F^-/g-mole).
mHX = Mass of HCl, HBr, or HF in sample, g.
mX2 = Mass of Cl2 or Br2 in sample,
g.
SX^- = Analysis of sample, g halide ion
(Cl^-, Br^-, F^-)/ml.
Vm(std) = Dry gas volume measured by the dry gas meter,
corrected to standard conditions, dscm.
Vs = Volume of filtered and diluted sample, ml.

12.2 Calculate the exact Cl^-, Br^-, and
F^- concentration in the halide salt stock standard solutions
using the following equations.
[GRAPHIC] [TIFF OMITTED] TR17OC00.413

12.3 Sample Volume, Dry Basis, Corrected to Standard Conditions.
Calculate the sample volume using Eq. 6-1 of Method 6.
12.4 Total g HCl, HBr, or HF Per Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.414

12.5 Total g Cl2 or Br2 Per Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.415

12.6 Concentration of Hydrogen Halide or Halogen in Flue Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.416

13.0 Method Performance

13.1 Precision and Bias. The within-laboratory relative standard
deviations are 6.2 and 3.2 percent at HCl concentrations of 3.9 and 15.3
ppm, respectively. The method does not

[[Page 556]]

exhibit a bias to Cl2 when sampling at concentrations less
than 50 ppm.
13.2 Sample Stability. The collected Cl^-samples can be
stored for up to 4 weeks.
13.3 Detection Limit. A typical IC instrumental detection limit for
Cl^- is 0.2 g/ml. Detection limits for the other
analyses should be similar. Assuming 50 ml liquid recovered from both
the acidified impingers, and the basic impingers, and 0.06 dscm of stack
gas sampled, then the analytical detection limit in the stack gas would
be about 0.1 ppm for HCl and Cl2, respectively.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

Method 26A. Method 26A, which uses isokinetic sampling equipment, is
an acceptable alternative to Method 26.

17.0 References

1. Steinsberger, S. C. and J. H. Margeson, ``Laboratory and Field
Evaluation of a Methodology for Determination of Hydrogen Chloride
Emissions from Municipal and Hazardous Waste Incinerators,'' U.S.
Environmental Protection Agency, Office of Research and Development,
Report No. 600/3-89/064, April 1989. Available from the National
Technical Information Service, Springfield, VA 22161 as PB89220586/AS.
2. State of California, Air Resources Board, Method 421,
``Determination of Hydrochloric Acid Emissions from Stationary
Sources,'' March 18, 1987.
3. Cheney, J.L. and C.R. Fortune. Improvements in the Methodology
for Measuring Hydrochloric Acid in Combustion Source Emissions. J.
Environ. Sci. Health. A19(3): 337-350. 1984.
4. Stern, D. A., B. M. Myatt, J. F. Lachowski, and K. T. McGregor.
Speciation of Halogen and Hydrogen Halide Compounds in Gaseous
Emissions. In: Incineration and Treatment of Hazardous Waste:
Proceedings of the 9th Annual Research Symposium, Cincinnati, Ohio, May
2-4, 1983. Publication No. 600/9-84-015. July 1984. Available from
National Technical Information Service, Springfield, VA 22161 as PB84-
234525.
5. Holm, R. D. and S. A. Barksdale. Analysis of Anions in Combustion
Products. In: Ion Chromatographic Analysis of Environmental Pollutants.
E. Sawicki, J. D. Mulik, and E. Wittgenstein (eds.). Ann Arbor,
Michigan, Ann Arbor Science Publishers. 1978. pp. 99-110.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 557]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.417

[[Page 558]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.418

Method 26A--Determination of Hydrogen Halide and Halogen Emissions From
Stationary Sources Isokinetic Method

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 2, Method 5, and Method
26.

1.0 Scope and Application

1.1 Analytes.

1.2 This method is applicable for determining emissions of hydrogen
halides (HX) [HCl, HBr, and HF] and halogens (X2)
[Cl2 and Br2] from stationary sources when
specified by the applicable subpart. This method collects the emission
sample isokinetically and is therefore particularly suited for sampling
at sources, such as those controlled by wet scrubbers, emitting acid
particulate matter (e.g., hydrogen halides dissolved in water droplets).
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Principle. Gaseous and particulate pollutants are withdrawn
isokinetically from the source and collected in an optional cyclone, on
a filter, and in absorbing solutions. The cyclone collects any liquid
droplets and is not necessary if the source emissions do not contain
them; however, it is preferable to include the cyclone in the sampling
train to protect the filter from any liquid present. The filter collects
particulate matter including halide salts but is not routinely recovered
or analyzed. Acidic and alkaline absorbing solutions collect the gaseous
hydrogen halides and halogens, respectively. Following sampling of
emissions containing liquid droplets, any halides/halogens dissolved in
the liquid in the cyclone and on the filter are vaporized to gas and
collected in the impingers by pulling conditioned ambient air through
the sampling train. The hydrogen halides are solubilized in the acidic
solution and form chloride (Cl^-), bromide (Br^-),

[[Page 559]]

and fluoride (F^-) ions. The halogens have a very low
solubility in the acidic solution and pass through to the alkaline
solution where they are hydrolyzed to form a proton (H\ + \), the halide
ion, and the hypohalous acid (HClO or HBrO). Sodium thiosulfate is added
to the alkaline solution to assure reaction with the hypohalous acid to
form a second halide ion such that 2 halide ions are formed for each
molecule of halogen gas. The halide ions in the separate solutions are
measured by ion chromatography (IC). If desired, the particulate matter
recovered from the filter and the probe is analyzed following the
procedures in Method 5.

Note: If the tester intends to use this sampling arrangement to
sample concurrently for particulate matter, the alternative Teflon probe
liner, cyclone, and filter holder should not be used. The Teflon filter
support must be used. The tester must also meet the probe and filter
temperature requirements of both sampling trains.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Volatile materials, such as chlorine dioxide (ClO2)
and ammonium chloride (NH4Cl), which produce halide ions upon
dissolution during sampling are potential interferents. Interferents for
the halide measurements are the halogen gases which disproportionate to
a hydrogen halide and a hypohalous acid upon dissolution in water. The
use of acidic rather than neutral or basic solutions for collection of
the hydrogen halides greatly reduces the dissolution of any halogens
passing through this solution.
4.2 The simultaneous presence of both HBr and Cl2 may
cause a positive bias in the HCl result with a corresponding negative
bias in the Cl2 result as well as affecting the HBr/
Br2 split.
4.3 High concentrations of nitrogen oxides (NOX) may
produce sufficient nitrate (NO3^-) to interfere
with measurements of very low Br^-levels.
4.4 There is anecdotal evidence that HF may be outgassed from new
Teflon components. If HF is a target analyte then preconditioning of new
Teflon components, by heating, should be considered.

5.0 Safety

6.0. Equipment and Supplies

Note: Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.

6.1 Sampling. The sampling train is shown in Figure 26A-1; the
apparatus is similar to the Method 5 train where noted as follows:
6.1.1 Probe Nozzle. Borosilicate or quartz glass; constructed and
calibrated according to Method 5, sections 6.1.1.1 and 10.1, and coupled
to the probe liner using a Teflon union; a stainless steel nut is
recommended for this union. When the stack temperature exceeds 210
[deg]C (410 [deg]F), a one-piece glass nozzle/liner assembly must be
used.
6.1.2 Probe Liner. Same as Method 5, section 6.1.1.2, except metal
liners shall not be used. Water-cooling of the stainless steel sheath is
recommended at temperatures exceeding 500 [deg]C (932 [deg]F). Teflon
may be used in limited applications where the minimum stack temperature
exceeds 120 [deg]C (250 [deg]F) but never exceeds the temperature where
Teflon is estimated to become unstable [approximately 210 [deg]C (410
[deg]F)].
6.1.3 Pitot Tube, Differential Pressure Gauge, Filter Heating
System, Metering System, Barometer, Gas Density Determination Equipment.
Same as Method 5, sections 6.1.1.3, 6.1.1.4, 6.1.1.6, 6.1.1.9, 6.1.2,
and 6.1.3.
6.1.4 Cyclone (Optional). Glass or Teflon. Use of the cyclone is
required only when the sample gas stream is saturated with moisture;
however, the cyclone is recommended to protect the filter from any
liquid droplets present.
6.1.5 Filter Holder. Borosilicate or quartz glass, or Teflon filter
holder, with a Teflon filter support and a sealing gasket. The sealing
gasket shall be constructed of Teflon or equivalent materials. The
holder design shall provide a positive seal against leakage at any point
along the filter circumference. The

[[Page 560]]

holder shall be attached immediately to the outlet of the cyclone.
6.1.6 Impinger Train. The following system shall be used to
determine the stack gas moisture content and to collect the hydrogen
halides and halogens: five or six impingers connected in series with
leak-free ground glass fittings or any similar leak-free
noncontaminating fittings. The first impinger shown in Figure 26A-1
(knockout or condensate impinger) is optional and is recommended as a
water knockout trap for use under high moisture conditions. If used,
this impinger should be constructed as described below for the alkaline
impingers, but with a shortened stem, and should contain 50 ml of 0.1 N
H2SO4. The following two impingers (acid impingers
which each contain 100 ml of 0.1 N H2SO4) shall be
of the Greenburg-Smith design with the standard tip (Method 5, section
6.1.1.8). The next two impingers (alkaline impingers which each contain
100 ml of 0.1 N NaOH) and the last impinger (containing silica gel)
shall be of the modified Greenburg-Smith design (Method 5, section
6.1.1.8). The condensate, acid, and alkaline impingers shall contain
known quantities of the appropriate absorbing reagents. The last
impinger shall contain a known weight of silica gel or equivalent
desiccant. Teflon impingers are an acceptable alternative.
6.1.7 Heating System. Any heating system capable of maintaining a
temperature around the probe and filter holder between 120 and 134
[deg]C (248 to 273 [deg]F) during sampling, or such other temperature as
specified by an applicable subpart of the standards or approved by the
Administrator for a particular application.
6.1.8 Ambient Air Conditioning Tube (Optional). Tube tightly packed
with approximately 150 g of fresh 8 to 20 mesh sodium hydroxide-coated
silica, or equivalent, (Ascarite II has been found suitable) to dry and
remove acid gases from the ambient air used to remove moisture from the
filter and cyclone, when the cyclone is used. The inlet and outlet ends
of the tube should be packed with at least 1-cm thickness of glass wool
or filter material suitable to prevent escape of fines. Fit one end with
flexible tubing, etc. to allow connection to probe nozzle following the
test run.
6.2 Sample Recovery.
6.2.1 Probe-Liner and Probe-Nozzle Brushes, Wash Bottles, Glass
Sample Storage Containers, Petri Dishes, Graduated Cylinder and/or
Balance, and Rubber Policeman. Same as Method 5, sections 6.2.1, 6.2.2,
6.2.3, 6.2.4, 6.2.5, and 6.2.7.
6.2.2 Plastic Storage Containers. Screw-cap polypropylene or
polyethylene containers to store silica gel. High-density polyethylene
bottles with Teflon screw cap liners to store impinger reagents, 1-
liter.
6.2.3 Funnels. Glass or high-density polyethylene, to aid in sample
recovery.
6.3 Sample Preparation and Analysis.
6.3.1 Volumetric Flasks. Class A, various sizes.
6.3.2 Volumetric Pipettes. Class A, assortment. To dilute samples to
calibration range of the ion chromatograph (IC).
6.3.3 Ion Chromatograph (IC). Suppressed or nonsuppressed, with a
conductivity detector and electronic integrator operating in the peak
area mode. Other detectors, a strip chart recorder, and peak heights may
be used.

7.0 Reagents and Standards

7.1 Sampling.
7.1.1 Filter. Teflon mat (e.g., Pallflex TX40HI45) filter. When the
stack gas temperature exceeds 210 [deg]C (410 [deg]F) a quartz fiber
filter may be used.
7.1.2 Water. Deionized, distilled water that conforms to American
Society of Testing and Materials (ASTM) Specification D 1193-77 or 91,
Type 3 (incorporated by reference--see Sec. 60.17).
7.1.3 Acidic Absorbing Solution, 0.1 N Sulfuric Acid
(H2SO4). To prepare 1 L, slowly add 2.80 ml of
concentrated 17.9 M H2SO4 to about 900 ml of water while stirring, and
adjust the final volume to 1 L using additional water. Shake well to mix
the solution.
7.1.4 Silica Gel, Crushed Ice, and Stopcock Grease. Same as Method
5, sections 7.1.2, 7.1.4, and 7.1.5, respectively.
7.1.5 Alkaline Absorbing Solution, 0.1 N Sodium Hydroxide (NaOH). To
prepare 1 L, dissolve 4.00 g of solid NaOH in about 900 ml of water and
adjust the final volume to 1 L using additional water. Shake well to mix
the solution.
7.1.6 Sodium Thiosulfate,
(Na2S2O33.5 H2O).
7.2 Sample Preparation and Analysis.
7.2.1 Water. Same as in section 7.1.2.
7.2.2 Absorbing Solution Blanks. A separate blank solution of each
absorbing reagent should be prepared for analysis with the field
samples. Dilute 200 ml of each absorbing solution (250 ml of the acidic
absorbing solution, if a condensate impinger is used) to the same final
volume as the field samples using the blank sample of rinse water. If a
particulate determination is conducted, collect a blank sample of
acetone.
7.2.3 Halide Salt Stock Standard Solutions. Prepare concentrated
stock solutions from reagent grade sodium chloride (NaCl), sodium
bromide (NaBr), and sodium fluoride (NaF). Each must be dried at 110
[deg]C (230 [deg]F) for two or more hours and then cooled to

[[Page 561]]

room temperature in a desiccator immediately before weighing. Accurately
weigh 1.6 to 1.7 g of the dried NaCl to within 0.1 mg, dissolve in
water, and dilute to 1 liter. Calculate the exact
Cl^-concentration using Equation 26A-1 in section 12.2. In a
similar manner, accurately weigh and solubilize 1.2 to 1.3 g of dried
NaBr and 2.2 to 2.3 g of NaF to make 1-liter solutions. Use Equations
26A-2 and 26A-3 in section 12.2, to calculate the Br^-and
F^-concentrations. Alternately, solutions containing a nominal
certified concentration of 1000 mg/L NaCl are commercially available as
convenient stock solutions from which standards can be made by
appropriate volumetric dilution. Refrigerate the stock standard
solutions and store no longer than one month.
7.2.4 Chromatographic Eluent. Same as Method 26, section 7.2.4.
7.2.5 Water. Same as section 7.1.1.
7.2.6 Acetone. Same as Method 5, section 7.2.

8.0 Sample Collection, Preservation, Storage, and Transport

Note: Because of the complexity of this method, testers and analysts
should be trained and experienced with the procedures to ensure reliable
results.

8.1 Sampling.
8.1.1 Pretest Preparation. Follow the general procedure given in
Method 5, section 8.1, except the filter need only be desiccated and
weighed if a particulate determination will be conducted.
8.1.2 Preliminary Determinations. Same as Method 5, section 8.2.
8.1.3 Preparation of Sampling Train. Follow the general procedure
given in Method 5, section 8.1.3, except for the following variations:
Add 50 ml of 0.1 N H2SO4 to the condensate
impinger, if used. Place 100 ml of 0.1 N H2SO4 in
each of the next two impingers. Place 100 ml of 0.1 N NaOH in each of
the following two impingers. Finally, transfer approximately 200-300 g
of preweighed silica gel from its container to the last impinger. Set up
the train as in Figure 26A-1. When used, the optional cyclone is
inserted between the probe liner and filter holder and located in the
heated filter box.
8.1.4 Leak-Check Procedures. Follow the leak-check procedures given
in Method 5, sections 8.4.2 (Pretest Leak-Check), 8.4.3 (Leak-Checks
During the Sample Run), and 8.4.4 (Post-Test Leak-Check).
8.1.5 Sampling Train Operation. Follow the general procedure given
in Method 5, Section 8.5. It is important to maintain a temperature
around the probe, filter (and cyclone, if used) between 120 and 134
[deg]C (248 and 273 [deg]F) since it is extremely difficult to purge
acid gases off these components. (These components are not
quantitatively recovered and hence any collection of acid gases on these
components would result in potential undereporting these emissions. The
applicable subparts may specify alternative higher temperatures.) For
each run, record the data required on a data sheet such as the one shown
in Method 5, Figure 5-3. If the condensate impinger becomes too full, it
may be emptied, recharged with 50 ml of 0.1 N H2SO4, and replaced during
the sample run. The condensate emptied must be saved and included in the
measurement of the volume of moisture collected and included in the
sample for analysis. The additional 50 ml of absorbing reagent must also
be considered in calculating the moisture. Before the sampling train
integrity is compromised by removing the impinger, conduct a leak-check
as described in Method 5, Section 8.4.2.
8.1.6 Post-Test Moisture Removal (Optional). When the optional
cyclone is included in the sampling train or when liquid is visible on
the filter at the end of a sample run even in the absence of a cyclone,
perform the following procedure. Upon completion of the test run,
connect the ambient air conditioning tube at the probe inlet and operate
the train with the filter heating system between 120 and 134 [deg]C (248
and 275 [deg]F) at a low flow rate (e.g., FH = 1 in. H2O) to
vaporize any liquid and hydrogen halides in the cyclone or on the filter
and pull them through the train into the impingers. After 30 minutes,
turn off the flow, remove the conditioning tube, and examine the cyclone
and filter for any visible liquid. If liquid is visible, repeat this
step for 15 minutes and observe again. Keep repeating until the cyclone
is dry.

Note: It is critical that this is repeated until the cyclone is
completely dry.

8.2 Sample Recovery. Allow the probe to cool. When the probe can be
handled safely, wipe off all the external surfaces of the tip of the
probe nozzle and place a cap loosely over the tip to prevent gaining or
losing particulate matter. Do not cap the probe tip tightly while the
sampling train is cooling down because this will create a vacuum in the
filter holder, drawing water from the impingers into the holder. Before
moving the sampling train to the cleanup site, remove the probe from the
sample train, wipe off any silicone grease, and cap the open outlet of
the impinger train, being careful not to lose any condensate that might
be present. Wipe off any silicone grease and cap the filter or cyclone
inlet. Remove the umbilical cord from the last impinger and cap the
impinger. If a flexible line is used between the first impinger and the
filter holder, disconnect it at the filter holder and let any condensed
water drain into the first impinger. Wipe off any silicone grease and
cap the filter holder outlet and the impinger inlet. Ground glass
stoppers, plastic caps, serum caps, Teflon tape, Parafilm, or aluminum
foil may be

[[Page 562]]

used to close these openings. Transfer the probe and filter/impinger
assembly to the cleanup area. This area should be clean and protected
from the weather to minimize sample contamination or loss. Inspect the
train prior to and during disassembly and note any abnormal conditions.
Treat samples as follows:
8.2.1 Container No. 1 (Optional; Filter Catch for Particulate
Determination). Same as Method 5, section 8.7.6.1, Container No. 1.
8.2.2 Container No. 2 (Optional; Front-Half Rinse for Particulate
Determination). Same as Method 5, section 8.7.6.2, Container No. 2.
8.2.3 Container No. 3 (Knockout and Acid Impinger Catch for Moisture
and Hydrogen Halide Determination). Disconnect the impingers. Measure
the liquid in the acid and knockout impingers to 1 ml by using a
graduated cylinder or by weighing it to 0.5 g by using a balance.
Record the volume or weight of liquid present. This information is
required to calculate the moisture content of the effluent gas.
Quantitatively transfer this liquid to a leak-free sample storage
container. Rinse these impingers and connecting glassware including the
back portion of the filter holder (and flexible tubing, if used) with
water and add these rinses to the storage container. Seal the container,
shake to mix, and label. The fluid level should be marked so that if any
sample is lost during transport, a correction proportional to the lost
volume can be applied. Retain rinse water and acidic absorbing solution
blanks to be analyzed with the samples.
8.2.4 Container No. 4 (Alkaline Impinger Catch for Halogen and
Moisture Determination). Measure and record the liquid in the alkaline
impingers as described in section 8.2.3. Quantitatively transfer this
liquid to a leak-free sample storage container. Rinse these two
impingers and connecting glassware with water and add these rinses to
the container. Add 25 mg of sodium thiosulfate per ppm halogen
anticipated to be in the stack gas multiplied by the volume (dscm) of
stack gas sampled (0.7 mg/ppm-dscf). Seal the container, shake to mix,
and label; mark the fluid level. Retain alkaline absorbing solution
blank to be analyzed with the samples.

Note: 25 mg per sodium thiosulfate per ppm halogen anticipated to be
in the stack includes a safety factor of approximately 5 to assure
complete reaction with the hypohalous acid to form a second
Cl^- ion in the alkaline solution.

8.2.5 Container No. 5 (Silica Gel for Moisture Determination). Same
as Method 5, section 8.7.6.3, Container No. 3.
8.2.6 Container Nos. 6 through 9 (Reagent Blanks). Save portions of
the absorbing reagents (0.1 N H2SO4 and 0.1 N
NaOH) equivalent to the amount used in the sampling train; dilute to the
approximate volume of the corresponding samples using rinse water
directly from the wash bottle being used. Add the same ratio of sodium
thiosulfate solution used in container No. 4 to the 0.1 N NaOH absorbing
reagent blank. Also, save a portion of the rinse water alone and a
portion of the acetone equivalent to the amount used to rinse the front
half of the sampling train. Place each in a separate, prelabeled sample
container.
8.2.7 Prior to shipment, recheck all sample containers to ensure
that the caps are well-secured. Seal the lids of all containers around
the circumference with Teflon tape. Ship all liquid samples upright and
all particulate filters with the particulate catch facing upward.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

9.2 Volume Metering System Checks. Same as Method 5, section 9.2.

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.

10.1 Probe Nozzle, Pitot Tube Assembly, Dry Gas Metering System,
Probe Heater, Temperature Sensors, Leak-Check of Metering System, and
Barometer. Same as Method 5, sections 10.1, 10.2, 10.3, 10.4, 10.5,
8.4.1, and 10.6, respectively.
10.2 Ion Chromatograph.
10.2.1 To prepare the calibration standards, dilute given amounts
(1.0 ml or greater) of the stock standard solutions to convenient
volumes, using 0.1 N H2SO4 or 0.1 N NaOH, as
appropriate. Prepare at least four calibration standards for each
absorbing reagent containing the three stock solutions such that they
are within the linear range of the field samples.
10.2.2 Using one of the standards in each series, ensure adequate
baseline separation for the peaks of interest.
10.2.3 Inject the appropriate series of calibration standards,
starting with the lowest concentration standard first both before and
after injection of the quality control check sample, reagent blanks, and
field samples.

[[Page 563]]

This allows compensation for any instrument drift occurring during
sample analysis. The values from duplicate injections of these
calibration samples should agree within 5 percent of their mean for the
analysis to be valid.
10.2.4 Determine the peak areas, or height, of the standards and
plot individual values versus halide ion concentrations in g/
ml.
10.2.5 Draw a smooth curve through the points. Use linear regression
to calculate a formula describing the resulting linear curve.

11.0 Analytical Procedures

Note: The liquid levels in the sample containers and confirm on the
analysis sheet whether or not leakage occurred during transport. If a
noticeable leakage has occurred, either void the sample or use methods,
subject to the approval of the Administrator, to correct the final
results.

11.1 Sample Analysis.
11.1.1 The IC conditions will depend upon analytical column type and
whether suppressed or non-suppressed IC is used. An example chromatogram
from a non-suppressed system using a 150-mm Hamilton PRP-X100 anion
column, a 2 ml/min flow rate of a 4 mM 4-hydroxy benzoate solution
adjusted to a pH of 8.6 using 1 N NaOH, a 50 l sample loop, and
a conductivity detector set on 1.0 S full scale is shown in
Figure 26-2.
11.1.2 Before sample analysis, establish a stable baseline. Next,
inject a sample of water, and determine if any Cl^-,
Br^-, or F^- appears in the chromatogram. If any of
these ions are present, repeat the load/injection procedure until they
are no longer present. Analysis of the acid and alkaline absorbing
solution samples requires separate standard calibration curves; prepare
each according to section 10.2. Ensure adequate baseline separation of
the analyses.
11.1.3 Between injections of the appropriate series of calibration
standards, inject in duplicate the reagent blanks, quality control
sample, and the field samples. Measure the areas or heights of the
Cl^-, Br^-, and F^- peaks. Use the mean
response of the duplicate injections to determine the concentrations of
the field samples and reagent blanks using the linear calibration curve.
The values from duplicate injections should agree within 5 percent of
their mean for the analysis to be valid. If the values of duplicate
injections are not within 5 percent of the mean, the duplicator
injections shall be repeated and all four values used to determine the
average response. Dilute any sample and the blank with equal volumes of
water if the concentration exceeds that of the highest standard.
11.2 Container Nos. 1 and 2 and Acetone Blank (Optional; Particulate
Determination). Same as Method 5, sections 11.2.1 and 11.2.2,
respectively.
11.3 Container No. 5. Same as Method 5, section 11.2.3 for silica
gel.

12.0 Data Analysis and Calculations

Note: Retain at least one extra decimal figure beyond those
contained in the available data in intermediate calculations, and round
off only the final answer appropriately.

12.1 Nomenclature. Same as Method 5, section 12.1. In addition:

BX- = Mass concentration of applicable absorbing solution
blank, g halide ion (Cl^-, Br^-,
F^-)/ml, not to exceed 1 g/ml which is 10
times the published analytical detection limit of 0.1
g/ml. (It is also approximately 5 percent of the mass
concentration anticipated to result from a one hour sample at
10 ppmv HCl.)
C = Concentration of hydrogen halide (HX) or halogen (X2),
dry basis, mg/dscm.
K = 10^-3 mg/g.
KHCl = 1.028 (g HCl/g-mole)/(g
Cl^-/g-mole).
KHBr = 1.013 (g HBr/g-mole)/(g
Br^-/g-mole).
KHF = 1.053 (g HF/g-mole)/(g
F^-/g-mole).
mHX = Mass of HCl, HBr, or HF in sample, ug.
mX2 = Mass of Cl2 or Br2 in sample, ug.
SX- = Analysis of sample, ug halide ion (Cl^-,
Br^-, F^-)/ml.
Vs = Volume of filtered and diluted sample, ml.

12.2 Calculate the exact Cl^-, Br^-, and
F^- concentration in the halide salt stock standard solutions
using the following equations.
[GRAPHIC] [TIFF OMITTED] TR17OC00.419

[GRAPHIC] [TIFF OMITTED] TR17OC00.420

[[Page 564]]

12.3 Average Dry Gas Meter Temperature and Average Orifice Pressure
Drop. See data sheet (Figure 5-3 of Method 5).
12.4 Dry Gas Volume. Calculate Vm(std) and adjust for
leakage, if necessary, using the equation in section 12.3 of Method 5.
12.5 Volume of Water Vapor and Moisture Content. Calculate the
volume of water vapor Vw(std) and moisture content
Bws from the data obtained in this method (Figure 5-3 of
Method 5); use Equations 5-2 and 5-3 of Method 5.
12.6 Isokinetic Variation and Acceptable Results. Use Method 5,
section 12.11.
12.7 Acetone Blank Concentration, Acetone Wash Blank Residue Weight,
Particulate Weight, and Particulate Concentration. For particulate
determination.
12.8 Total g HCl, HBr, or HF Per Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.421

12.9 Total g Cl2 or Br2 Per Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.422

12.10 Concentration of Hydrogen Halide or Halogen in Flue Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.423

12.11 Stack Gas Velocity and Volumetric Flow Rate. Calculate the
average stack gas velocity and volumetric flow rate, if needed, using
data obtained in this method and the equations in sections 12.3 and 12.4
of Method 2.

13.0 Method Performance

13.1 Precision and Bias. The method has a possible measurable
negative bias below 20 ppm HCl perhaps due to reaction with small
amounts of moisture in the probe and filter. Similar bias for the other
hydrogen halides is possible.
13.2 Sample Stability. The collected Cl-samples can be stored for up
to 4 weeks for analysis for HCl and Cl2.
13.3 Detection Limit. A typical analytical detection limit for HCl
is 0.2 g/ml. Detection limits for the other analyses should be
similar. Assuming 300 ml of liquid recovered for the acidified impingers
and a similar amounts recovered from the basic impingers, and 1 dscm of
stack gas sampled, the analytical detection limits in the stack gas
would be about 0.04 ppm for HCl and Cl2, respectively.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Steinsberger, S. C. and J. H. Margeson. Laboratory and Field
Evaluation of a Methodology for Determination of Hydrogen Chloride
Emissions from Municipal and Hazardous Waste Incinerators. U.S.
Environmental Protection Agency, Office of Research and Development.
Publication No. 600/3-89/064. April 1989. Available from National
Technical Information Service, Springfield, VA 22161 as PB89220586/AS.
2. State of California Air Resources Board. Method 421--
Determination of Hydrochloric Acid Emissions from Stationary Sources.
March 18, 1987.
3. Cheney, J.L. and C.R. Fortune. Improvements in the Methodology
for Measuring Hydrochloric Acid in Combustion Source Emissions. J.
Environ. Sci. Health. A19(3): 337-350. 1984.
4. Stern, D.A., B.M. Myatt, J.F. Lachowski, and K.T. McGregor.
Speciation of Halogen and Hydrogen Halide Compounds in Gaseous
Emissions. In: Incineration and Treatment of Hazardous Waste:
Proceedings of the 9th Annual Research Symposium, Cincinnati, Ohio, May
2-4, 1983. Publication No. 600/9-84-015. July 1984. Available from
National Technical Information Service, Springfield, VA 22161 as PB84-
234525.
5. Holm, R.D. and S.A. Barksdale. Analysis of Anions in Combustion
Products. In: Ion Chromatographic Analysis of Environmental Pollutants,
E. Sawicki, J.D. Mulik, and E. Wittgenstein (eds.). Ann Arbor, Michigan,
Ann Arbor Science Publishers. 1978. pp. 99-110.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 565]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.424

Method 27--Determination of Vapor Tightness of Gasoline Delivery Tank
Using Pressure Vaccuum Test

1.0 Scope and Application

1.1 Applicability. This method is applicable for the determination
of vapor tightness of a gasoline delivery collection equipment.

2.0 Summary of Method

2.1 Pressure and vacuum are applied alternately to the compartments
of a gasoline delivery tank and the change in pressure or vacuum is
recorded after a specified period of time.

[[Page 566]]

3.0 Definitions

3.1 Allowable pressure change (Fp) means the allowable amount of
decrease in pressure during the static pressure test, within the time
period t, as specified in the appropriate regulation, in mm
H2O.
3.2 Allowable vacuum change (Fv) means the allowable amount of
decrease in vacuum during the static vacuum test, within the time period
t, as specified in the appropriate regulation, in mm H2O.
3.3 Compartment means a liquid-tight division of a delivery tank.
3.4 Delivery tank means a container, including associated pipes and
fittings, that is attached to or forms a part of any truck, trailer, or
railcar used for the transport of gasoline.
3.5 Delivery tank vapor collection equipment means any piping,
hoses, and devices on the delivery tank used to collect and route
gasoline vapors either from the tank to a bulk terminal vapor control
system or from a bulk plant or service station into the tank.
3.6 Gasoline means a petroleum distillate or petroleum distillate/
alcohol blend having a Reid vapor pressure of 27.6 kilopascals or
greater which is used as a fuel for internal combustion engines.
3.7 Initial pressure (Pi) means the pressure applied to the delivery
tank at the beginning of the static pressure test, as specified in the
appropriate regulation, in mm H2O.
3.8 Initial vacuum (Vi) means the vacuum applied to the delivery
tank at the beginning of the static vacuum test, as specified in the
appropriate regulation, in mm H3.
3.9 Time period of the pressure or vacuum test (t) means the time
period of the test, as specified in the appropriate regulation, during
which the change in pressure or vacuum is monitored, in minutes.

4.0 Interferences [Reserved]

5.0 Safety

5.1 Gasoline contains several volatile organic compounds (e.g.,
benzene and hexane) which presents a potential for fire and/or
explosions. It is advisable to take appropriate precautions when testing
a gasoline vessel's vapor tightness, such as refraining from smoking and
using explosion-proof equipment.
5.2 This method may involve hazardous materials, operations, and
equipment. This test method may not address all of the safety problems
associated with its use. It is the responsibility of the user of this
test method to establish appropriate safety and health practices and
determine the applicability of regulatory limitations prior to
performing this test method

6.0 Equipment and Supplies

The following equipment and supplies are required for testing:
6.1 Pressure Source. Pump or compressed gas cylinder of air or inert
gas sufficient to pressurize the delivery tank to 500 mm (20 in.)
H2O above atmospheric pressure.
6.2 Regulator. Low pressure regulator for controlling pressurization
of the delivery tank.
6.3 Vacuum Source. Vacuum pump capable of evacuating the delivery
tank to 250 mm (10 in.) H2O below atmospheric pressure.
6.4 Pressure-Vacuum Supply Hose.
6.5 Manometer. Liquid manometer, or equivalent instrument, capable
of measuring up to 500 mm (20 in.) H2O gauge pressure with
2.5 mm (0.1 in.) H2O precision.
6.6 Pressure-Vacuum Relief Valves. The test apparatus shall be
equipped with an inline pressure-vacuum relief valve set to activate at
675 mm (26.6 in.) H2O above atmospheric pressure or 250 mm
(10 in.) H2O below atmospheric pressure, with a capacity equal to the
pressurizing or evacuating pumps.
6.7 Test Cap for Vapor Recovery Hose. This cap shall have a tap for
manometer connection and a fitting with shut-off valve for connection to
the pressure-vacuum supply hose.
6.8 Caps for Liquid Delivery Hoses.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Pretest Preparations.
8.1.1 Summary. Testing problems may occur due to the presence of
volatile vapors and/or temperature fluctuations inside the delivery
tank. Under these conditions, it is often difficult to obtain a stable
initial pressure at the beginning of a test, and erroneous test results
may occur. To help prevent this, it is recommended that prior to
testing, volatile vapors be removed from the tank and the temperature
inside the tank be allowed to stabilize. Because it is not always
possible to completely attain these pretest conditions, a provision to
ensure reproducible results is included. The difference in results for
two consecutive runs must meet the criteria in sections 8.2.2.5 and
8.2.3.5.
8.1.2 Emptying of Tank. The delivery tank shall be emptied of all
liquid.
8.1.3 Purging of Vapor. As much as possible the delivery tank shall
be purged of all volatile vapors by any safe, acceptable method. One
method is to carry a load of non-volatile liquid fuel, such as diesel or
heating oil, immediately prior to the test, thus flushing out all the
volatile gasoline vapors. A second method is to remove the volatile
vapors by blowing ambient air into each tank compartment for at least 20
minutes. This second method is usually not as effective and often causes
stabilization problems, requiring a

[[Page 567]]

much longer time for stabilization during the testing.
8.1.4 Temperature Stabilization. As much as possible, the test shall
be conducted under isothermal conditions. The temperature of the
delivery tank should be allowed to equilibrate in the test environment.
During the test, the tank should be protected from extreme environmental
and temperature variability, such as direct sunlight.
8.2 Test Procedure.
8.2.1 Preparations.
8.2.1.1 Open and close each dome cover.
8.2.1.2 Connect static electrical ground connections to the tank.
Attach the liquid delivery and vapor return hoses, remove the liquid
delivery elbows, and plug the liquid delivery fittings.

Note: The purpose of testing the liquid delivery hoses is to detect
tears or holes that would allow liquid leakage during a delivery. Liquid
delivery hoses are not considered to be possible sources of vapor
leakage, and thus, do not have to be attached for a vapor leakage test.
Instead, a liquid delivery hose could be either visually inspected, or
filled with water to detect any liquid leakage.

8.2.1.3 Attach the test cap to the end of the vapor recovery hose.
8.2.1.4 Connect the pressure-vacuum supply hose and the pressure-
vacuum relief valve to the shut-off valve. Attach a manometer to the
pressure tap.
8.2.1.5 Connect compartments of the tank internally to each other if
possible. If not possible, each compartment must be tested separately,
as if it were an individual delivery tank.
8.2.2 Pressure Test.
8.2.2.1 Connect the pressure source to the pressure-vacuum supply
hose.
8.2.2.2 Open the shut-off valve in the vapor recovery hose cap.
Apply air pressure slowly, pressurize the tank to Pi, the
initial pressure specified in the regulation.
8.2.2.3 Close the shut-off and allow the pressure in the tank to
stabilize, adjusting the pressure if necessary to maintain pressure of
Pi. When the pressure stabilizes, record the time and initial
pressure.
8.2.2.4 At the end of the time period (t) specified in the
regulation, record the time and final pressure.
8.2.2.5 Repeat steps 8.2.2.2 through 8.2.2.4 until the change in
pressure for two consecutive runs agrees within 12.5 mm (0.5 in.)
H2O. Calculate the arithmetic average of the two results.
8.2.2.6 Compare the average measured change in pressure to the
allowable pressure change, Fp, specified in the regulation. If the
delivery tank does not satisfy the vapor tightness criterion specified
in the regulation, repair the sources of leakage, and repeat the
pressure test until the criterion is met.
8.2.2.7 Disconnect the pressure source from the pressure-vacuum
supply hose, and slowly open the shut-off valve to bring the tank to
atmospheric pressure.
8.2.3 Vacuum Test.
8.2.3.1 Connect the vacuum source to the pressure-vacuum supply
hose.
8.2.3.2 Open the shut-off valve in the vapor recovery hose cap.
Slowly evacuate the tank to Vi, the initial vacuum specified
in the regulation.
8.2.3.3 Close the shut-off valve and allow the pressure in the tank
to stabilize, adjusting the pressure if necessary to maintain a vacuum
of Vi. When the pressure stabilizes, record the time and
initial vacuum.
8.2.3.4 At the end of the time period specified in the regulation
(t), record the time and final vacuum.
8.2.3.5 Repeat steps 8.2.3.2 through 8.2.3.4 until the change in
vacuum for two consecutive runs agrees within 12.5 mm (0.5 in.)
H2O. Calculate the arithmetic average of the two results.
8.2.3.6 Compare the average measured change in vacuum to the
allowable vacuum change, Fv, as specified in the regulation. If the
delivery tank does not satisfy the vapor tightness criterion specified
in the regulation, repair the sources of leakage, and repeat the vacuum
test until the criterion is met.
8.2.3.7 Disconnect the vacuum source from the pressure-vacuum supply
hose, and slowly open the shut-off valve to bring the tank to
atmospheric pressure.
8.2.4 Post-Test Clean-up. Disconnect all test equipment and return
the delivery tank to its pretest condition.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section(s) measure Effect
------------------------------------------------------------------------
8.2.2.5, 8.3.3.5.............. Repeat test Ensures data
procedures until precision.
change in
pressure or
vacuum for two
consecutive runs
agrees within
12.5 mm (0.5
in.) H2O.
------------------------------------------------------------------------

[[Page 568]]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedures [Reserved]

12.0 Data Analysis and Calculations [Reserved]

13.0 Method Performance

13.1 Precision. The vapor tightness of a gasoline delivery tank
under positive or negative pressure, as measured by this method, is
precise within 12.5 mm (0.5 in.) H2O
13.2 Bias. No bias has been identified.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 The pumping of water into the bottom of a delivery tank is an
acceptable alternative to the pressure source described above. Likewise,
the draining of water out of the bottom of a delivery tank may be
substituted for the vacuum source. Note that some of the specific step-
by-step procedures in the method must be altered slightly to accommodate
these different pressure and vacuum sources.
16.2 Techniques other than specified above may be used for purging
and pressurizing a delivery tank, if prior approval is obtained from the
Administrator. Such approval will be based upon demonstrated equivalency
with the above method.

17.0 References [Reserved]

18.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 28--Certification and Auditing of Wood Heaters

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 4, Method 5, Method 5G, Method 5H, Method 6, Method 6C, and
Method 16A.

1.0 Scope and Application

1.1 Analyte. Particulate matter (PM). No CAS number assigned.
1.2 Applicability. This method is applicable for the certification
and auditing of wood heaters, including pellet burning wood heaters.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Particulate matter emissions are measured from a wood heater
burning a prepared test fuel crib in a test facility maintained at a set
of prescribed conditions. Procedures for determining burn rates and
particulate emission rates and for reducing data are provided.

3.0 Definitions

3.1 2 x 4 or 4 x 4 means two inches by four inches or four inches by
four inches (50 mm by 100 mm or 100 mm by 100 mm), as nominal dimensions
for lumber.
3.2 Burn rate means the rate at which test fuel is consumed in a
wood heater. Measured in kilograms or lbs of wood (dry basis) per hour
(kg/hr or lb/hr).
3.3 Certification or audit test means a series of at least four test
runs conducted for certification or audit purposes that meets the burn
rate specifications in section 8.4.
3.4 Firebox means the chamber in the wood heater in which the test
fuel charge is placed and combusted.
3.5 Height means the vertical distance extending above the loading
door, if fuel could reasonably occupy that space, but not more than 2
inches above the top (peak height) of the loading door, to the floor of
the firebox (i.e., below a permanent grate) if the grate allows a 1-inch
diameter piece of wood to pass through the grate, or, if not, to the top
of the grate. Firebox height is not necessarily uniform but must account
for variations caused by internal baffles, air channels, or other
permanent obstructions.
3.6 Length means the longest horizontal fire chamber dimension that
is parallel to a wall of the chamber.
3.7 Pellet burning wood heater means a wood heater which meets the
following criteria: (1) The manufacturer makes no reference to burning
cord wood in advertising or other literature, (2) the unit is safety
listed for pellet fuel only, (3) the unit operating and instruction
manual must state that the use of cordwood is prohibited by law, and (4)
the unit must be manufactured and sold including the hopper and auger
combination as integral parts.
3.8 Secondary air supply means an air supply that introduces air to
the wood heater such that the burn rate is not altered by more than 25
percent when the secondary air supply is adjusted during the test run.
The wood heater manufacturer can document this through design drawings
that show the secondary air is introduced only into a mixing chamber or
secondary chamber outside the firebox.
3.9 Test facility means the area in which the wood heater is
installed, operated, and sampled for emissions.

[[Page 569]]

3.10 Test fuel charge means the collection of test fuel pieces
placed in the wood heater at the start of the emission test run.
3.11 Test fuel crib means the arrangement of the test fuel charge
with the proper spacing requirements between adjacent fuel pieces.
3.12 Test fuel loading density means the weight of the as-fired test
fuel charge per unit volume of usable firebox.
3.13 Test fuel piece means the 2 x 4 or 4 x 4 wood piece cut to the
length required for the test fuel charge and used to construct the test
fuel crib.
3.14 Test run means an individual emission test which encompasses
the time required to consume the mass of the test fuel charge.
3.15 Usable firebox volume means the volume of the firebox
determined using its height, length, and width as defined in this
section.
3.16 Width means the shortest horizontal fire chamber dimension that
is parallel to a wall of the chamber.
3.17 Wood heater means an enclosed, woodburning appliance capable of
and intended for space heating or domestic water heating, as defined in
the applicable regulation.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Same as section 6.0 of either Method 5G or Method 5H, with the
addition of the following:
6.1 Insulated Solid Pack Chimney. For installation of wood heaters.
Solid pack insulated chimneys shall have a minimum of 2.5 cm (1 in.)
solid pack insulating material surrounding the entire flue and possess a
label demonstrating conformance to U.L. 103 (incorporated by reference--
see Sec. 60.17).
6.2 Platform Scale and Monitor. For monitoring of fuel load weight
change. The scale shall be capable of measuring weight to within 0.05 kg
(0.1 lb) or 1 percent of the initial test fuel charge weight, whichever
is greater.
6.3 Wood Heater Temperature Monitors. Seven, each capable of
measuring temperature to within 1.5 percent of expected absolute
temperatures.
6.4 Test Facility Temperature Monitor. A thermocouple located
centrally in a vertically oriented 150 mm (6 in.) long, 50 mm (2 in.)
diameter pipe shield that is open at both ends, capable of measuring
temperature to within 1.5 percent of expected temperatures.
6.5 Balance (optional). Balance capable of weighing the test fuel
charge to within 0.05 kg (0.1 lb).
6.6 Moisture Meter. Calibrated electrical resistance meter for
measuring test fuel moisture to within 1 percent moisture content.
6.7 Anemometer. Device capable of detecting air velocities less than
0.10 m/sec (20 ft/min), for measuring air velocities near the test
appliance.
6.8 Barometer. Mercury, aneroid or other barometer capable of
measuring atmospheric pressure to within 2.5 mm Hg (0.1 in. Hg).
6.9 Draft Gauge. Electromanometer or other device for the
determination of flue draft or static pressure readable to within 0.50
Pa (0.002 in. H2O).
6.10 Humidity Gauge. Psychrometer or hygrometer for measuring room
humidity.
6.11 Wood Heater Flue.
6.11.1 Steel flue pipe extending to 2.6 0.15 m (8.5 0.5 ft) above
the top of the platform scale, and above this level, insulated solid
pack type chimney extending to 4.6 0.3 m (15 1 ft) above the platform
scale, and of the size specified by the wood heater manufacturer. This
applies to both freestanding and insert type wood heaters.
6.11.2 Other chimney types (e.g., solid pack insulated pipe) may be
used in place of the steel flue pipe if the wood heater manufacturer's
written appliance specifications require such chimney for home
installation (e.g., zero clearance wood heater inserts). Such
alternative chimney or flue pipe must remain and be sealed with the wood
heater following the certification test.
6.12 Test Facility. The test facility shall meet the following
requirements during testing:
6.12.1 The test facility temperature shall be maintained between 18
and 32 [deg]C (65 and 90 [deg]F) during each test run.
6.12.2 Air velocities within 0.6 m (2 ft) of the test appliance and
exhaust system shall be less than 0.25 m/sec (50 ft/min) without fire in
the unit.
6.12.3 The flue shall discharge into the same space or into a space
freely communicating with the test facility. Any hood or similar device
used to vent combustion products shall not induce a draft greater than
1.25 Pa (0.005 in. H2O) on the wood heater measured when the
wood heater is not operating.
6.12.4 For test facilities with artificially induced barometric
pressures (e.g., pressurized chambers), the barometric pressure in the
test facility shall not exceed 775 mm Hg (30.5 in. Hg) during any test
run.

[[Page 570]]

7.0 Reagents and Standards

Same as section 6.0 of either Method 5G or Method 5H, with the
addition of the following:
7.1 Test Fuel. The test fuel shall conform to the following
requirements:
7.1.1 Fuel Species. Untreated, air-dried, Douglas fir lumber. Kiln-
dried lumber is not permitted. The lumber shall be certified C grade
(standard) or better Douglas fir by a lumber grader at the mill of
origin as specified in the West Coast Lumber Inspection Bureau Standard
No. 16 (incorporated by reference--see Sec. 60.17).
7.1.2 Fuel Moisture. The test fuel shall have a moisture content
range between 16 to 20 percent on a wet basis (19 to 25 percent dry
basis). Addition of moisture to previously dried wood is not allowed. It
is recommended that the test fuel be stored in a temperature and
humidity-controlled room.
7.1.3 Fuel Temperature. The test fuel shall be at the test facility
temperature of 18 to 32 [deg]C (65 to 90 [deg]F).
7.1.4 Fuel Dimensions. The dimensions of each test fuel piece shall
conform to the nominal measurements of 2 x 4 and 4 x 4 lumber. Each
piece of test fuel (not including spacers) shall be of equal length,
except as necessary to meet requirements in section 8.8, and shall
closely approximate \5/6\ the dimensions of the length of the usable
firebox. The fuel piece dimensions shall be determined in relation to
the appliance's firebox volume according to guidelines listed below:
7.1.4.1 If the usable firebox volume is less than or equal to 0.043
m\3\ (1.5 ft\3\), use 2 x 4 lumber.
7.1.4.2 If the usable firebox volume is greater than 0.043 m\3\ (1.5
ft\3\) and less than or equal to 0.085 m\3\ (3.0 ft\3\), use 2 x 4 and 4
x 4 lumber. About half the weight of the test fuel charge shall be 2 x 4
lumber, and the remainder shall be 4 x 4 lumber.
7.1.4.3 If the usable firebox volume is greater than 0.085 m\3\ (3.0
ft\3\), use 4 x 4 lumber.
7.2 Test Fuel Spacers. Air-dried, Douglas fir lumber meeting the
requirements outlined in sections 7.1.1 through 7.1.3. The spacers shall
be 130 x 40 x 20 mm (5 x 1.5 x 0.75 in.).

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Test Run Requirements.
8.1.1 Burn Rate Categories. One emission test run is required in
each of the following burn rate categories:

Burn Rate Categories
[Average kg/hr (lb/hr), dry basis]
----------------------------------------------------------------------------------------------------------------
Category 1 Category 2 Category 3 Category 4
----------------------------------------------------------------------------------------------------------------
<0.80................................ 0.80 to 1.25........... 1.25 to 1.90........... Maximum.
(<1.76).............................. (1.76 to 2.76)......... (2.76 to 4.19)......... burn rate.
----------------------------------------------------------------------------------------------------------------

8.1.1.1 Maximum Burn Rate. For Category 4, the wood heater shall be
operated with the primary air supply inlet controls fully open (or, if
thermostatically controlled, the thermostat shall be set at maximum heat
output) during the entire test run, or the maximum burn rate setting
specified by the manufacturer's written instructions.
8.1.1.2 Other Burn Rate Categories. For burn rates in Categories 1
through 3, the wood heater shall be operated with the primary air supply
inlet control, or other mechanical control device, set at a
predetermined position necessary to obtain the average burn rate
required for the category.
8.1.1.3 Alternative Burn Rates for Burn Rate Categories 1 and 2.
8.1.1.3.1 If a wood heater cannot be operated at a burn rate below
0.80 kg/hr (1.76 lb/hr), two test runs shall be conducted with burn
rates within Category 2. If a wood heater cannot be operated at a burn
rate below 1.25 kg/hr (2.76 lb/hr), the flue shall be dampered or the
air supply otherwise controlled in order to achieve two test runs within
Category 2.
8.1.1.3.2 Evidence that a wood heater cannot be operated at a burn
rate less than 0.80 kg/hr shall include documentation of two or more
attempts to operate the wood heater in burn rate Category 1 and fuel
combustion has stopped, or results of two or more test runs
demonstrating that the burn rates were greater than 0.80 kg/hr when the
air supply controls were adjusted to the lowest possible position or
settings. Stopped fuel combustion is evidenced when an elapsed time of
30 minutes or more has occurred without a measurable (<0.05 kg (0.1 lb)
or 1.0 percent, whichever is greater) weight change in the test fuel
charge. See also section 8.8.3. Report the evidence and the reasoning
used to determine that a test in burn rate Category 1 cannot be
achieved; for example, two unsuccessful attempts to operate at a burn
rate of 0.4 kg/hr are not sufficient evidence that burn rate Category 1
cannot be achieved.

Note: After July 1, 1990, if a wood heater cannot be operated at a
burn rate less than 0.80 kg/hr, at least one test run with an average
burn rate of 1.00 kg/hr or less shall be conducted. Additionally, if
flue dampering must be used to achieve burn rates below 1.25

[[Page 571]]

kg/hr (or 1.0 kg/hr), results from a test run conducted at burn rates
below 0.90 kg/hr need not be reported or included in the test run
average provided that such results are replaced with results from a test
run meeting the criteria above.

8.2 Catalytic Combustor and Wood Heater Aging. The catalyst-equipped
wood heater or a wood heater of any type shall be aged before the
certification test begins. The aging procedure shall be conducted and
documented by a testing laboratory accredited according to procedures in
Sec. 60.535 of 40 CFR part 60.
8.2.1 Catalyst-equipped Wood Heater. Operate the catalyst-equipped
wood heater using fuel meeting the specifications outlined in sections
7.1.1 through 7.1.3, or cordwood with a moisture content between 15 and
25 percent on a wet basis. Operate the wood heater at a medium burn rate
(Category 2 or 3) with a new catalytic combustor in place and in
operation for at least 50 hours. Record and report hourly catalyst exit
temperature data (Section 8.6.2) and the hours of operation.
8.2.2 Non-Catalyst Wood Heater. Operate the wood heater using the
fuel described in section 8.4.1 at a medium burn rate for at least 10
hours. Record and report the hours of operation.
8.3 Pretest Recordkeeping. Record the test fuel charge dimensions
and weights, and wood heater and catalyst descriptions as shown in the
example in Figure 28-1.
8.4 Wood Heater Installation. Assemble the wood heater appliance and
parts in conformance with the manufacturer's written installation
instructions. Place the wood heater centrally on the platform scale and
connect the wood heater to the flue described in section 6.11. Clean the
flue with an appropriately sized, wire chimney brush before each
certification test.
8.5 Wood Heater Temperature Monitors.
8.5.1 For catalyst-equipped wood heaters, locate a temperature
monitor (optional) about 25 mm (1 in.) upstream of the catalyst at the
centroid of the catalyst face area, and locate a temperature monitor
(mandatory) that will indicate the catalyst exhaust temperature. This
temperature monitor is centrally located within 25 mm (1 in.) downstream
at the centroid of catalyst face area. Record these locations.
8.5.2 Locate wood heater surface temperature monitors at five
locations on the wood heater firebox exterior surface. Position the
temperature monitors centrally on the top surface, on two sidewall
surfaces, and on the bottom and back surfaces. Position the monitor
sensing tip on the firebox exterior surface inside of any heat shield,
air circulation walls, or other wall or shield separated from the
firebox exterior surface. Surface temperature locations for unusual
design shapes (e.g., spherical, etc.) shall be positioned so that there
are four surface temperature monitors in both the vertical and
horizontal planes passing at right angles through the centroid of the
firebox, not including the fuel loading door (total of five temperature
monitors).
8.6 Test Facility Conditions.
8.6.1 Locate the test facility temperature monitor on the horizontal
plane that includes the primary air intake opening for the wood heater.
Locate the temperature monitor 1 to 2 m (3 to 6 ft) from the front of
the wood heater in the 90[deg] sector in front of the wood heater.
8.6.2 Use an anemometer to measure the air velocity. Measure and
record the room air velocity before the pretest ignition period (Section
8.7) and once immediately following the test run completion.
8.6.3 Measure and record the test facility's ambient relative
humidity, barometric pressure, and temperature before and after each
test run.
8.6.4 Measure and record the flue draft or static pressure in the
flue at a location no greater than 0.3 m (1 ft) above the flue connector
at the wood heater exhaust during the test run at the recording
intervals (Section 8.8.2).
8.7 Wood Heater Firebox Volume.
8.7.1 Determine the firebox volume using the definitions for height,
width, and length in section 3. Volume adjustments due to presence of
firebrick and other permanent fixtures may be necessary. Adjust width
and length dimensions to extend to the metal wall of the wood heater
above the firebrick or permanent obstruction if the firebrick or
obstruction extending the length of the side(s) or back wall extends
less than one-third of the usable firebox height. Use the width or
length dimensions inside the firebrick if the firebrick extends more
than one-third of the usable firebox height. If a log retainer or grate
is a permanent fixture and the manufacturer recommends that no fuel be
placed outside the retainer, the area outside of the retainer is
excluded from the firebox volume calculations.
8.7.2 In general, exclude the area above the ash lip if that area is
less than 10 percent of the usable firebox volume. Otherwise, take into
account consumer loading practices. For instance, if fuel is to be
loaded front-to-back, an ash lip may be considered usable firebox
volume.
8.7.3 Include areas adjacent to and above a baffle (up to two inches
above the fuel loading opening) if four inches or more horizontal space
exist between the edge of the baffle and a vertical obstruction (e.g.,
sidewalls or air channels).
8.8 Test Fuel Charge.
8.8.1 Prepare the test fuel pieces in accordance with the
specifications outlined in sections 7.1 and 7.2. Determine the test fuel
moisture content with a calibrated electrical

[[Page 572]]

resistance meter or other equivalent performance meter. If necessary,
convert fuel moisture content values from dry basis (%Md) to
wet basis (%Mw) in section 12.2 using Equation 28-1.
Determine fuel moisture for each fuel piece (not including spacers) by
averaging at least three moisture meter readings, one from each of three
sides, measured parallel to the wood grain. Average all the readings for
all the fuel pieces in the test fuel charge. If an electrical resistance
type meter is used, penetration of insulated electrodes shall be one-
fourth the thickness of the test fuel piece or 19 mm (0.75 in.),
whichever is greater. Measure the moisture content within a 4-hour
period prior to the test run. Determine the fuel temperature by
measuring the temperature of the room where the wood has been stored for
at least 24 hours prior to the moisture determination.
8.8.2 Attach the spacers to the test fuel pieces with uncoated,
ungalvanized nails or staples as illustrated in Figure 28-2. Attachment
of spacers to the top of the test fuel piece(s) on top of the test fuel
charge is optional.
8.8.3 To avoid stacking difficulties, or when a whole number of test
fuel pieces does not result, all piece lengths shall be adjusted
uniformly to remain within the specified loading density. The shape of
the test fuel crib shall be geometrically similar to the shape of the
firebox volume without resorting to special angular or round cuts on the
individual fuel pieces.
8.8.4 The test fuel loading density shall be 112 11.2 kg/m\3\ (7
0.7 lb/ft3) of usable firebox volume on a wet basis.
8.9 Sampling Equipment. Prepare the sampling equipment as defined by
the selected method (i.e., either Method 5G or Method 5H). Collect one
particulate emission sample for each test run.
8.10 Secondary Air Adjustment Validation.
8.10.1 If design drawings do not show the introduction of secondary
air into a chamber outside the firebox (see ``secondary air supply''
under section 3.0, Definitions), conduct a separate test of the wood
heater's secondary air supply. Operate the wood heater at a burn rate in
Category 1 (Section 8.1.1) with the secondary air supply operated
following the manufacturer's written instructions. Start the secondary
air validation test run as described in section 8.8.1, except no
emission sampling is necessary and burn rate data shall be recorded at
5-minute intervals.
8.10.2 After the start of the test run, operate the wood heater with
the secondary air supply set as per the manufacturer's instructions, but
with no adjustments to this setting. After 25 percent of the test fuel
has been consumed, adjust the secondary air supply controls to another
setting, as per the manufacturer's instructions. Record the burn rate
data (5-minute intervals) for 20 minutes following the air supply
adjustment.
8.10.3 Adjust the air supply control(s) to the original position(s),
operate at this condition for at least 20 minutes, and repeat the air
supply adjustment procedure above. Repeat the procedure three times at
equal intervals over the entire burn period as defined in section 8.8.
If the secondary air adjustment results in a burn rate change of more
than an average of 25 percent between the 20-minute periods before and
after the secondary adjustments, the secondary air supply shall be
considered a primary air supply, and no adjustment to this air supply is
allowed during the test run.
8.10.4 The example sequence below describes a typical secondary air
adjustment validation check. The first cycle begins after at least 25
percent of the test fuel charge has been consumed.

Cycle 1
Part 1, sec air adjusted to final position--20 min
Part 2, sec air adjusted to final position--20 min
Part 3, sec air adjusted to final position--20 min
Cycle 2
Part 1, sec air adjusted to final position--20 min
Part 2, sec air adjusted to final position--20 min
Part 3, sec air adjusted to final position--20 min
Cycle 3
Part 1, sec air adjusted to final position--20 min
Part 2, sec air adjusted to final position--20 min
Part 3, sec air adjusted to final position--20 min

Note that the cycles may overlap; that is, Part 3 of Cycle 1 may
coincide in part or in total with Part 1 of Cycle 2. The calculation of
the secondary air percent effect for this example is as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.425

[[Page 573]]

8.11 Pretest Ignition. Build a fire in the wood heater in accordance
with the manufacturer's written instructions.
8.11.1 Pretest Fuel Charge. Crumpled newspaper loaded with kindling
may be used to help ignite the pretest fuel. The pretest fuel, used to
sustain the fire, shall meet the same fuel requirements prescribed in
section 7.1. The pretest fuel charge shall consist of whole 2 x 4's that
are no less than \1/3\ the length of the test fuel pieces. Pieces of 4 x
4 lumber in approximately the same weight ratio as for the test fuel
charge may be added to the pretest fuel charge.
8.11.2 Wood Heater Operation and Adjustments. Set the air inlet
supply controls at any position that will maintain combustion of the
pretest fuel load. At least one hour before the start of the test run,
set the air supply controls at the approximate positions necessary to
achieve the burn rate desired for the test run. Adjustment of the air
supply controls, fuel addition or subtractions, and coalbed raking shall
be kept to a minimum but are allowed up to 15 minutes prior to the start
of the test run. For the purposes of this method, coalbed raking is the
use of a metal tool (poker) to stir coals, break burning fuel into
smaller pieces, dislodge fuel pieces from positions of poor combustion,
and check for the condition of uniform charcoalization. Record all
adjustments made to the air supply controls, adjustments to and
additions or subtractions of fuel, and any other changes to wood heater
operations that occur during pretest ignition period. Record fuel weight
data and wood heater temperature measurements at 10-minute intervals
during the hour of the pretest ignition period preceding the start of
the test run. During the 15-minute period prior to the start of the test
run, the wood heater loading door shall not be open more than a total of
1 minute. Coalbed raking is the only adjustment allowed during this
period.

Note: One purpose of the pretest ignition period is to achieve
uniform charcoalization of the test fuel bed prior to loading the test
fuel charge. Uniform charcoalization is a general condition of the test
fuel bed evidenced by an absence of large pieces of burning wood in the
coal bed and the remaining fuel pieces being brittle enough to be broken
into smaller charcoal pieces with a metal poker. Manipulations to the
fuel bed prior to the start of the test run should be done to achieve
uniform charcoalization while maintaining the desired burn rate. In
addition, some wood heaters (e.g., high mass units) may require extended
pretest burn time and fuel additions to reach an initial average surface
temperature sufficient to meet the thermal equilibrium criteria in
section 8.3.

8.11.3 The weight of pretest fuel remaining at the start of the test
run is determined as the difference between the weight of the wood
heater with the remaining pretest fuel and the tare weight of the
cleaned, dry wood heater with or without dry ash or sand added
consistent with the manufacturer's instructions and the owner's manual.
The tare weight of the wood heater must be determined with the wood
heater (and ash, if added) in a dry condition.
8.12 Test Run. Complete a test run in each burn rate category, as
follows:
8.12.1 Test Run Start.
8.12.1.1 When the kindling and pretest fuel have been consumed to
leave a fuel weight between 20 and 25 percent of the weight of the test
fuel charge, record the weight of the fuel remaining and start the test
run. Record and report any other criteria, in addition to those
specified in this section, used to determine the moment of the test run
start (e.g., firebox or catalyst temperature), whether such criteria are
specified by the wood heater manufacturer or the testing laboratory.
Record all wood heater individual surface temperatures, catalyst
temperatures, any initial sampling method measurement values, and begin
the particulate emission sampling. Within 1 minute following the start
of the test run, open the wood heater door, load the test fuel charge,
and record the test fuel charge weight. Recording of average, rather
than individual, surface temperatures is acceptable for tests conducted
in accordance with Sec. 60.533(o)(3)(i) of 40 CFR part 60.
8.12.1.2 Position the fuel charge so that the spacers are parallel
to the floor of the firebox, with the spacer edges abutting each other.
If loading difficulties result, some fuel pieces may be placed on edge.
If the usable firebox volume is between 0.043 and 0.085 m\3\ (1.5 and
3.0 ft\3\), alternate the piece sizes in vertical stacking layers to the
extent possible. For example, place 2 x 4's on the bottom layer in
direct contact with the coal bed and 4 x 4's on the next layer, etc.
(See Figure 28-3). Position the fuel pieces parallel to each other and
parallel to the longest wall of the firebox to the extent possible
within the specifications in section 8.8.
8.12.1.3 Load the test fuel in appliances having unusual or
unconventional firebox design maintaining air space intervals between
the test fuel pieces and in conformance with the manufacturer's written
instructions. For any appliance that will not accommodate the loading
arrangement specified in the paragraph above, the test facility
personnel shall contact the Administrator for an alternative loading
arrangement.
8.12.1.4 The wood heater door may remain open and the air supply
controls adjusted up to five minutes after the start of the test run in
order to make adjustments to the test fuel charge and to ensure ignition
of the test fuel charge has occurred. Within the five minutes after the
start of the test run, close the wood heater door and adjust the air
supply controls to the position determined to produce

[[Page 574]]

the desired burn rate. No other adjustments to the air supply controls
or the test fuel charge are allowed (except as specified in sections
8.12.3 and 8.12.4) after the first five minutes of the test run. Record
the length of time the wood heater door remains open, the adjustments to
the air supply controls, and any other operational adjustments.
8.12.2 Data Recording. Record on a data sheet similar to that shown
in Figure 28-4, at intervals no greater than 10 minutes, fuel weight
data, wood heater individual surface and catalyst temperature
measurements, other wood heater operational data (e.g., draft), test
facility temperature and sampling method data.
8.12.3 Test Fuel Charge Adjustment. The test fuel charge may be
adjusted (i.e., repositioned) once during a test run if more than 60
percent of the initial test fuel charge weight has been consumed and
more than 10 minutes have elapsed without a measurable (<0.05 kg (0.1
lb) or 1.0 percent, whichever is greater) weight change. The time used
to make this adjustment shall be less than 15 seconds.
8.12.4 Air Supply Adjustment. Secondary air supply controls may be
adjusted once during the test run following the manufacturer's written
instructions (see section 8.10). No other air supply adjustments are
allowed during the test run. Recording of wood heater flue draft during
the test run is optional for tests conducted in accordance with Sec.
60.533(o)(3)(i) of 40 CFR part 60.
8.12.5 Auxiliary Wood Heater Equipment Operation. Heat exchange
blowers sold with the wood heater shall be operated during the test run
following the manufacturer's written instructions. If no manufacturer's
written instructions are available, operate the heat exchange blower in
the ``high'' position. (Automatically operated blowers shall be operated
as designed.) Shaker grates, by-pass controls, or other auxiliary
equipment may be adjusted only one time during the test run following
the manufacturer's written instructions.
Record all adjustments on a wood heater operational written record.

Note: If the wood heater is sold with a heat exchange blower as an
option, test the wood heater with the heat exchange blower operating as
described in sections 8.1 through 8.12 and report the results. As an
alternative to repeating all test runs without the heat exchange blower
operating, one additional test run may be without the blower operating
as described in section 8.12.5 at a burn rate in Category 2 (Section
8.1.1). If the emission rate resulting from this test run without the
blower operating is equal to or less than the emission rate plus 1.0 g/
hr (0.0022 lb/hr) for the test run in burn rate Category 2 with the
blower operating, the wood heater may be considered to have the same
average emission rate with or without the blower operating. Additional
test runs without the blower operating are unnecessary.

8.13 Test Run Completion. Continue emission sampling and wood heater
operation for 2 hours. The test run is completed when the remaining
weight of the test fuel charge is 0.00 kg (0.0 lb). End the test run
when the scale has indicated a test fuel charge weight of 0.00 kg (0.0
lb) or less for 30 seconds. At the end of the test run, stop the
particulate sampling, and record the final fuel weight, the run time,
and all final measurement values.
8.14 Wood Heater Thermal Equilibrium. The average of the wood heater
surface temperatures at the end of the test run shall agree with the
average surface temperature at the start of the test run to within 70
[deg]C (126 [deg]F).
8.15 Consecutive Test Runs. Test runs on a wood heater may be
conducted consecutively provided that a minimum one-hour interval occurs
between test runs.
8.16 Additional Test Runs. The testing laboratory may conduct more
than one test run in each of the burn rate categories specified in
section 8.1.1. If more than one test run is conducted at a specified
burn rate, the results from at least two-thirds of the test runs in that
burn rate category shall be used in calculating the weighted average
emission rate (see section 12.2). The measurement data and results of
all test runs shall be reported regardless of which values are used in
calculating the weighted average emission rate (see note in section
8.1).

9.0 Quality Control

Same as section 9.0 of either Method 5G or Method 5H.

10.0 Calibration and Standardizations

Same as section 10.0 of either Method 5G or Method 5H, with the
addition of the following:
10.1 Platform Scale. Perform a multi-point calibration (at least
five points spanning the operational range) of the platform scale before
its initial use. The scale manufacturer's calibration results are
sufficient for this purpose. Before each certification test, audit the
scale with the wood heater in place by weighing at least one calibration
weight (Class F) that corresponds to between 20 percent and 80 percent
of the expected test fuel charge weight. If the scale cannot reproduce
the value of the calibration weight within 0.05 kg (0.1 lb) or 1 percent
of the expected test fuel charge weight, whichever is greater,
recalibrate the scale before use with at least five calibration weights
spanning the operational range of the scale.
10.2 Balance (optional). Calibrate as described in section 10.1.

[[Page 575]]

10.3 Temperature Monitor. Calibrate as in Method 2, section 4.3,
before the first certification test and semiannually thereafter.
10.4 Moisture Meter. Calibrate as per the manufacturer's
instructions before each certification test.
10.5 Anemometer. Calibrate the anemometer as specified by the
manufacturer's instructions before the first certification test and
semiannually thereafter.
10.6 Barometer. Calibrate against a mercury barometer before the
first certification test and semiannually thereafter.
10.7 Draft Gauge. Calibrate as per the manufacturer's instructions;
a liquid manometer does not require calibration.
10.8 Humidity Gauge. Calibrate as per the manufacturer's
instructions before the first certification test and semiannually
thereafter.

11.0 Analytical Procedures

Same as section 11.0 of either Method 5G or Method 5H.

12.0 Data Analysis and Calculations

Same as section 12.0 of either Method 5G or Method 5H, with the
addition of the following:
12.1 Nomenclature.

BR = Dry wood burn rate, kg/hr (lb/hr)
Ei = Emission rate for test run, i, from Method 5G or 5H, g/
hr (lb/hr)
Ew = Weighted average emission rate, g/hr (lb/hr)
ki = Test run weighting factor = Pi + 1 -
Pi-1
%Md = Fuel moisture content, dry basis, percent.
%Mw = Average moisture in test fuel charge, wet basis,
percent.
n = Total number of test runs.
Pi = Probability for burn rate during test run, i, obtained
from Table 28-1. Use linear interpolation to determine
probability values for burn rates between those listed on the
table.
Wwd = Total mass of wood burned during the test run, kg (lb).

12.2 Wet Basis Fuel Moisture Content.
[GRAPHIC] [TIFF OMITTED] TR17OC00.426

12.3 Weighted Average Emission Rate. Calculate the weighted average
emission rate (Ew) using Equation 28-1:
[GRAPHIC] [TIFF OMITTED] TR17OC00.427

Note: Po always equals 0, P(n + 1) always
equals 1, P1 corresponds to the probability of the lowest
recorded burn rate, P2 corresponds to the probability of the
next lowest burn rate, etc. An example calculation is in section 12.3.1.

12.3.1 Example Calculation of Weighted Average Emission Rate.

------------------------------------------------------------------------
Burn rate Emissions
Burn rate category Test No. (Dry-kg/hr) (g/hr)
------------------------------------------------------------------------
1................................ 1 0.65 5.0
2\1\............................. 2 0.85 6.7
2................................ 3 0.90 4.7
2................................ 4 1.00 5.3
3................................ 5 1.45 3.8
4................................ 6 2.00 5.1
------------------------------------------------------------------------
\1\ As permitted in section 6.6, this test run may be omitted from the
calculation of the weighted average emission rate because three runs
were conducted for this burn rate category.

----------------------------------------------------------------------------------------------------------------
Test No. Burn rate Pi Ei Ki
----------------------------------------------------------------------------------------------------------------
0........................................................... ........... 0.000 ........... ...........
1........................................................... 0.65 0.121 5.0 0.300
2........................................................... 0.90 0.300 4.7 0.259
3........................................................... 1.00 0.380 5.3 0.422
4........................................................... 1.45 0.722 3.8 0.532
5........................................................... 2.00 0.912 5.1 0.278
6........................................................... ........... 1.000 ........... ...........
----------------------------------------------------------------------------------------------------------------
K1 = P2 - P0 = 0.300 - 0 = 0.300
K2 = P3 - P1 = 0.381 - 0.121 = 0.259
K3 = P4 - P2 = 0.722 - 0.300 = 0.422
K4 = P5 - P3 = 0.912 - 0.380 = 0.532
K5 = P6 - P4 = 1.000 - 0.722 = 0.278

Weighted Average Emission Rate, Ew, Calculation

[[Page 576]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.428

12.4 Average Wood Heater Surface Temperatures. Calculate the average
of the wood heater surface temperatures for the start of the test run
(Section 8.12.1) and for the test run completion (Section 8.13). If the
two average temperatures do not agree within 70 [deg]C (125 [deg]F),
report the test run results, but do not include the test run results in
the test average. Replace such test run results with results from
another test run in the same burn rate category.
12.5 Burn Rate. Calculate the burn rate (BR) using Equation 28-3:
[GRAPHIC] [TIFF OMITTED] TR17OC00.429

12.6 Reporting Criteria. Submit both raw and reduced test data for
wood heater tests.
12.6.1 Suggested Test Report Format.
12.6.1.1 Introduction.
12.6.1.1.1 Purpose of test-certification, audit, efficiency,
research and development.
12.6.1.1.2 Wood heater identification-manufacturer, model number,
catalytic/noncatalytic, options.
12.6.1.1.3 Laboratory-name, location (altitude), participants.
12.6.1.1.4 Test information-date wood heater received, date of
tests, sampling methods used, number of test runs.
12.6.1.2 Summary and Discussion of Results
12.6.1.2.1 Table of results (in order of increasing burn rate)-test
run number, burn rate, particulate emission rate, efficiency (if
determined), averages (indicate which test runs are used).
12.6.1.2.2 Summary of other data-test facility conditions, surface
temperature averages, catalyst temperature averages, pretest fuel
weights, test fuel charge weights, run times.
12.6.1.2.3 Discussion-Burn rate categories achieved, test run result
selection, specific test run problems and solutions.
12.6.1.3 Process Description.
12.6.1.3.1 Wood heater dimensions-volume, height, width, lengths (or
other linear dimensions), weight, volume adjustments.
12.6.1.3.2 Firebox configuration-air supply locations and operation,
air supply introduction location, refractory location and dimensions,
catalyst location, baffle and by-pass location and operation (include
line drawings or photographs).
12.6.1.3.3 Process operation during test-air supply settings and
adjustments, fuel bed adjustments, draft.
12.6.1.3.4 Test fuel-test fuel properties (moisture and
temperature), test fuel crib description (include line drawing or
photograph), test fuel loading density.
12.6.1.4 Sampling Locations.
12.6.1.4.1 Describe sampling location relative to wood heater.
Include drawing or photograph.
12.6.1.5 Sampling and Analytical Procedures
12.6.1.5.1 Sampling methods-brief reference to operational and
sampling procedures and optional and alternative procedures used.
12.6.1.5.2 Analytical methods-brief description of sample recovery
and analysis procedures.
12.6.1.6 Quality Control and Assurance Procedures and Results
12.6.1.6.1 Calibration procedures and results-certification
procedures, sampling and analysis procedures.
12.6.1.6.2 Test method quality control procedures-leak-checks,
volume meter checks, stratification (velocity) checks, proportionality
results.
12.6.1.7 Appendices
12.6.1.7.1 Results and Example Calculations. Complete summary tables
and accompanying examples of all calculations.
12.6.1.7.2 Raw Data. Copies of all uncorrected data sheets for
sampling measurements, temperature records and sample recovery data.
Copies of all pretest burn rate and wood heater temperature data.

[[Page 577]]

12.6.1.7.3 Sampling and Analytical Procedures. Detailed description
of procedures followed by laboratory personnel in conducting the
certification test, emphasizing particular parts of the procedures
differing from the methods (e.g., approved alternatives).
12.6.1.7.4 Calibration Results. Summary of all calibrations, checks,
and audits pertinent to certification test results with dates.
12.6.1.7.5 Participants. Test personnel, manufacturer
representatives, and regulatory observers.
12.6.1.7.6 Sampling and Operation Records. Copies of uncorrected
records of activities not included on raw data sheets (e.g., wood heater
door open times and durations).
12.6.1.7.7 Additional Information. Wood heater manufacturer's
written instructions for operation during the certification test.
12.6.2.1 Wood Heater Identification. Report wood heater
identification information. An example data form is shown in Figure 28-
4.
12.6.2.2 Test Facility Information. Report test facility
temperature, air velocity, and humidity information. An example data
form is shown on Figure 28-4.
12.6.2.3 Test Equipment Calibration and Audit Information. Report
calibration and audit results for the platform scale, test fuel balance,
test fuel moisture meter, and sampling equipment including volume
metering systems and gaseous analyzers.
12.6.2.4 Pretest Procedure Description. Report all pretest
procedures including pretest fuel weight, burn rates, wood heater
temperatures, and air supply settings. An example data form is shown on
Figure 28-4.
12.6.2.5 Particulate Emission Data. Report a summary of test results
for all test runs and the weighted average emission rate. Submit copies
of all data sheets and other records collected during the testing.
Submit examples of all calculations.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 Pellet Burning Heaters. Certification testing requirements and
procedures for pellet burning wood heaters are identical to those for
other wood heaters, with the following exceptions:
16.1.1 Test Fuel Properties. The test fuel shall be all wood pellets
with a moisture content no greater than 20 percent on a wet basis (25
percent on a dry basis). Determine the wood moisture content with either
ASTM D 2016-74 or 83, (Method A), ASTM D 4444-92, or ASTM D 4442-84 or
92 (all noted ASTM standards are incorporated by reference--see Sec.
60.17).
16.1.2 Test Fuel Charge Specifications. The test fuel charge size
shall be as per the manufacturer's written instructions for maintaining
the desired burn rate.
16.1.3 Wood Heater Firebox Volume. The firebox volume need not be
measured or determined for establishing the test fuel charge size. The
firebox dimensions and other heater specifications needed to identify
the heater for certification purposes shall be reported.
16.1.4 Heater Installation. Arrange the heater with the fuel supply
hopper on the platform scale as described in section 8.6.1.
16.1.5 Pretest Ignition. Start a fire in the heater as directed by
the manufacturer's written instructions, and adjust the heater controls
to achieve the desired burn rate. Operate the heater at the desired burn
rate for at least 1 hour before the start of the test run.
16.1.6 Test Run. Complete a test run in each burn rate category as
follows:
16.1.6.1 Test Run Start. When the wood heater has operated for at
least 1 hour at the desired burn rate, add fuel to the supply hopper as
necessary to complete the test run, record the weight of the fuel in the
supply hopper (the wood heater weight), and start the test run. Add no
additional fuel to the hopper during the test run.
Record all the wood heater surface temperatures, the initial
sampling method measurement values, the time at the start of the test,
and begin the emission sampling. Make no adjustments to the wood heater
air supply or wood supply rate during the test run.
16.1.6.2 Data Recording. Record the fuel (wood heater) weight data,
wood heater temperature and operational data, and emission sampling data
as described in section 8.12.2.
16.1.6.3 Test Run Completion. Continue emission sampling and wood
heater operation for 2 hours. At the end of the test run, stop the
particulate sampling, and record the final fuel weight, the run time,
and all final measurement values, including all wood heater individual
surface temperatures.
16.1.7 Calculations. Determine the burn rate using the difference
between the initial and final fuel (wood heater) weights and the
procedures described in section 12.4. Complete the other calculations as
described in section 12.0.

17.0 References

Same as Method 5G, with the addition of the following:

1. Radian Corporation. OMNI Environmental Services, Inc., Cumulative
Probability for a Given Burn Rate Based on Data Generated in the CONEG
and BPA Studies. Package of materials submitted to the Fifth Session of
the Regulatory Negotiation Committee, July 16-17, 1986.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 578]]

Table 28-1--Burn Rate Weighted Probabilities for Calculating Weighted Average Emission Rates
----------------------------------------------------------------------------------------------------------------
Cumulative Cumulative Cumulative
Burn rate (kg/hr-dry) probability Burn rate (kg/ probability Burn rate (kg/ probability
(P) hr-dry) (P) hr-dry) (P)
----------------------------------------------------------------------------------------------------------------
0.00............................ 0.000 1.70 0.840 3.40 0.989
0.05............................ 0.002 1.75 0.857 3.45 0.989
0.10............................ 0.007 1.80 0.875 3.50 0.990
0.15............................ 0.012 1.85 0.882 3.55 0.991
0.20............................ 0.016 1.90 0.895 3.60 0.991
0.25............................ 0.021 1.95 0.906 3.65 0.992
0.30............................ 0.028 2.00 0.912 3.70 0.992
0.35............................ 0.033 2.05 0.920 3.75 0.992
0.40............................ 0.041 2.10 0.925 3.80 0.993
0.45............................ 0.054 2.15 0.932 3.85 0.994
0.50............................ 0.065 2.20 0.936 3.90 0.994
0.55............................ 0.086 2.25 0.940 3.95 0.994
0.60............................ 0.100 2.30 0.945 4.00 0.994
0.65............................ 0.121 2.35 0.951 4.05 0.995
0.70............................ 0.150 2.40 0.956 4.10 0.995
0.75............................ 0.185 2.45 0.959 4.15 0.995
0.80............................ 0.220 2.50 0.964 4.20 0.995
0.85............................ 0.254 2.55 0.968 4.25 0.995
0.90............................ 0.300 2.60 0.972 4.30 0.996
0.95............................ 0.328 2.65 0.975 4.35 0.996
1.00............................ 0.380 2.70 0.977 4.40 0.996
1.05............................ 0.407 2.75 0.979 4.45 0.996
1.10............................ 0.460 2.80 0.980 4.50 0.996
1.15............................ 0.490 2.85 0.981 4.55 0.996
1.20............................ 0.550 2.90 0.982 4.60 0.996
1.25............................ 0.572 2.95 0.984 4.65 0.996
1.30............................ 0.620 3.00 0.984 4.70 0.996
1.35............................ 0.654 3.05 0.985 4.75 0.997
1.40............................ 0.695 3.10 0.986 4.80 0.997
1.45............................ 0.722 3.15 0.987 4.85 0.997
1.50............................ 0.750 3.20 0.987 4.90 0.997
1.55............................ 0.779 3.25 0.988 4.95 0.997
1.60............................ 0.800 3.30 0.988 5.0 1.000
0
1.65............................ 0.825 3.35 0.989 .............. ..............
----------------------------------------------------------------------------------------------------------------

[[Page 579]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.430

[[Page 580]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.431

[[Page 581]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.432

Method 28A--Measurement of Air- to-Fuel Ratio and Mimimum Achievable
Burn Rates for Wood-Fired Appliances

Note: This method does not include all or the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should also have a thorough knowledge of at
least the following additional test methods: Method 3, Method 3A, Method
5H, Method 6C, and Method 28.

1.0 Scope and Application

1.1 Analyte. Particulate matter (PM). No CAS number assigned.

[[Page 582]]

1.2 Applicability. This method is applicable for the measurement of
air-to-fuel ratios and minimum achievable burn rates, for determining
whether a wood-fired appliance is an affected facility, as specified in
40 CFR 60.530.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted from a location in the stack of a
wood-fired appliance while the appliance is operating at a prescribed
set of conditions. The gas sample is analyzed for carbon dioxide
(CO2), oxygen (O2), and carbon monoxide (CO).
These stack gas components are measured for determining the dry
molecular weight of the exhaust gas. Total moles of exhaust gas are
determined stoichiometrically. Air-to-fuel ratio is determined by
relating the mass of dry combustion air to the mass of dry fuel
consumed.

3.0 Definitions

Same as Method 28, section 3.0, with the addition of the following:
3.1 Air-to-fuel ratio means the ratio of the mass of dry combustion
air introduced into the firebox to the mass of dry fuel consumed (grams
of dry air per gram of dry wood burned).

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Test Facility. Insulated Solid Pack Chimney, Platform Scale and
Monitor, Test Facility Temperature Monitor, Balance, Moisture Meter,
Anemometer, Barometer, Draft Gauge, Humidity Gauge, Wood Heater Flue,
and Test Facility. Same as Method 28, sections 6.1, 6.2, and 6.4 to
6.12, respectively.
6.2 Sampling System. Probe, Condenser, Valve, Pump, Rate Meter,
Flexible Bag, Pressure Gauge, and Vacuum Gauge. Same as Method 3,
sections 6.2.1 to 6.2.8, respectively. Alternatively, the sampling
system described in Method 5H, section 6.1 may be used.
6.3 Exhaust Gas Analysis. Use one or both of the following:
6.3.1 Orsat Analyzer. Same as Method 3, section 6.1.3
6.3.2 Instrumental Analyzers. Same as Method 5H, sections 6.1.3.4
and 6.1.3.5, for CO2 and CO analyzers, except use a CO
analyzer with a range of 0 to 5 percent and use a CO2
analyzer with a range of 0 to 5 percent. Use an O2 analyzer
capable of providing a measure of O2 in the range of 0 to 25
percent by volume at least once every 10 minutes.

7.0 Reagents and Standards

7.1 Test Fuel and Test Fuel Spacers. Same as Method 28, sections 7.1
and 7.2, respectively.
7.2 Cylinder Gases. For each of the three analyzers, use the same
concentration as specified in sections 7.2.1, 7.2.2, and 7.2.3 of Method
6C.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Wood Heater Air Supply Adjustments.
8.1.1 This section describes how dampers are to be set or adjusted
and air inlet ports closed or sealed during Method 28A tests. The
specifications in this section are intended to ensure that affected
facility determinations are made on the facility configurations that
could reasonably be expected to be employed by the user. They are also
intended to prevent circumvention of the standard through the addition
of an air port that would often be blocked off in actual use. These
specifications are based on the assumption that consumers will remove
such items as dampers or other closure mechanism stops if this can be
done readily with household tools; that consumers will block air inlet
passages not visible during normal operation of the appliance using
aluminum tape or parts generally available at retail stores; and that
consumers will cap off any threaded or flanged air inlets. They also
assume that air leakage around glass doors, sheet metal joints or
through inlet grilles visible during normal operation of the appliance
would not be further blocked or taped off by a consumer.
8.1.2 It is not the intention of this section to cause an appliance
that is clearly designed, intended, and, in most normal installations,
used as a fireplace to be converted into a wood heater for purposes of
applicability testing. Such a fireplace would be identifiable by such
features as large or multiple glass doors or panels that are not
gasketed, relatively unrestricted air inlets intended, in large part, to
limit smoking and fogging of glass surfaces, and other aesthetic
features not normally included in wood heaters.
8.1.3 Adjustable Air Supply Mechanisms. Any commercially available
flue damper, other adjustment mechanism or other air

[[Page 583]]

inlet port that is designed, intended or otherwise reasonably expected
to be adjusted or closed by consumers, installers, or dealers and which
could restrict air into the firebox shall be set so as to achieve
minimum air into the firebox (i.e., closed off or set in the most closed
position).
8.1.3.1 Flue dampers, mechanisms and air inlet ports which could
reasonably be expected to be adjusted or closed would include:
8.1.3.1.1 All internal or externally adjustable mechanisms
(including adjustments that affect the tightness of door fittings) that
are accessible either before and/or after installation.
8.1.3.1.2 All mechanisms, other inlet ports, or inlet port stops
that are identified in the owner's manual or in any dealer literature as
being adjustable or alterable. For example, an inlet port that could be
used to provide access to an outside air duct but which is identified as
being closable through use of additional materials whether or not they
are supplied with the facility.
8.1.3.1.3 Any combustion air inlet port or commercially available
flue damper or mechanism stop, which would readily lend itself to
closure by consumers who are handy with household tools by the removal
of parts or the addition of parts generally available at retail stores
(e.g., addition of a pipe cap or plug, addition of a small metal plate
to an inlet hole on a nondecorative sheet metal surface, or removal of
riveted or screwed damper stops).
8.1.3.1.4 Any flue damper, other adjustment mechanisms or other air
inlet ports that are found and documented in several (e.g., a number
sufficient to reasonably conclude that the practice is not unique or
uncommon) actual installations as having been adjusted to a more closed
position, or closed by consumers, installers, or dealers.
8.1.4 Air Supply Adjustments During Test. The test shall be
performed with all air inlets identified under this section in the
closed or most closed position or in the configuration which otherwise
achieves the lowest air inlet (i.e., greatest blockage).

Note: For the purposes of this section, air flow shall not be
minimized beyond the point necessary to maintain combustion or beyond
the point that forces smoke into the room.

8.1.5 Notwithstanding section 8.1.1, any flue damper, adjustment
mechanism, or air inlet port (whether or not equipped with flue dampers
or adjusting mechanisms) that is visible during normal operation of the
appliance and which could not reasonably be closed further or blocked
except through means that would significantly degrade the aesthetics of
the facility (e.g., through use of duct tape) will not be closed further
or blocked.
8.2 Sampling System.
8.2.1 Sampling Location. Same as Method 5H, section 8.1.2.
8.2.2 Sampling System Set Up. Set up the sampling equipment as
described in Method 3, section 8.1.
8.3 Wood Heater Installation, Test Facility Conditions, Wood Heater
Firebox Volume, and Test Fuel Charge. Same as Method 28, sections 8.4
and 8.6 to 8.8, respectively.
8.4 Pretest Ignition. Same as Method 28, section 8.11. Set the wood
heater air supply settings to achieve a burn rate in Category 1 or the
lowest achievable burn rate (see section 8.1).
8.5 Test Run. Same as Method 28, section 8.12. Begin sample
collection at the start of the test run as defined in Method 28, section
8.12.1.
8.5.1 Gas Analysis.
8.5.1.1 If Method 3 is used, collect a minimum of two bag samples
simultaneously at a constant sampling rate for the duration of the test
run. A minimum sample volume of 30 liters (1.1 ft\3\) per bag is
recommended.
8.5.1.2 If instrumental gas concentration measurement procedures are
used, conduct the gas measurement system performance tests, analyzer
calibration, and analyzer calibration error check outlined in Method 6C,
sections 8.2.3, 8.2.4, 8.5, and 10.0, respectively. Sample at a constant
rate for the duration of the test run.
8.5.2 Data Recording. Record wood heater operational data, test
facility temperature, sample train flow rate, and fuel weight data at
intervals of no greater than 10 minutes.
8.5.3 Test Run Completion. Same as Method 28, section 8.13.

9.0 Quality Control

9.1 Data Validation. The following quality control procedure is
suggested to provide a check on the quality of the data.
9.1.1 Calculate a fuel factor, Fo, using Equation 28A-1
in section 12.2.
9.1.2 If CO is present in quantities measurable by this method,
adjust the O2 and CO2 values before performing the
calculation for Fo as shown in section 12.3 and 12.4.
9.1.3 Compare the calculated Fo factor with the expected
Fo range for wood (1.000-1.120). Calculated Fo
values beyond this acceptable range should be investigated before
accepting the test results. For example, the strength of the solutions
in the gas analyzer and the analyzing technique should be checked by
sampling and analyzing a known concentration, such as air. If no
detectable or correctable measurement error can be identified, the test
should be repeated. Alternatively, determine a range of air-to-fuel
ratio results that could include the correct value by using an
Fo value of 1.05 and calculating a potential range of
CO2 and O2 values. Acceptance of such results will
be based on whether the calculated range includes the

[[Page 584]]

exemption limit and the judgment of the Administrator.
9.2 Method 3 Analyses. Compare the results of the analyses of the
two bag samples. If all the gas components (O2, CO, and
CO2) values for the two analyses agree within 0.5 percent
(e.g., 6.0 percent O2 for bag 1 and 6.5 percent O2
for bag 2, agree within 0.5 percent), the results of the bag analyses
may be averaged for the calculations in section 12. If the analysis
results do not agree within 0.5 percent for each component, calculate
the air-to-fuel ratio using both sets of analyses and report the
results.

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedures

11.1 Method 3 Integrated Bag Samples. Within 4 hours after the
sample collection, analyze each bag sample for percent CO2,
O2, and CO using an Orsat analyzer as described in Method 3,
section 11.0.
11.2 Instrumental Analyzers. Average the percent CO2, CO,
and O2 values for the test run.

12.0 Data Analyses and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figure after the
final calculation. Other forms of the equations may be used as long as
they give equivalent results.
12.1 Nomenclature.

Md = Dry molecular weight, g/g-mole (lb/lb-mole).
NT = Total gram-moles of dry exhaust gas per kg of wood
burned (lb-moles/lb).
%CO2 = Percent CO2 by volume (dry basis).
%CO = Percent CO by volume (dry basis).
%N2 = Percent N2 by volume (dry basis).
%O2 = Percent O2 by volume (dry basis).
YHC = Assumed mole fraction of HC (dry as CH4) =
0.0088 for catalytic wood heaters; = 0.0132 for noncatalytic
wood heaters. = 0.0080 for pellet-fired wood heaters.
YCO = Measured mole fraction of CO (e.g., 1 percent CO = .01
mole fraction), g/g-mole (lb/lb-mole).
YCO2 = Measured mole fraction of COCO2 (e.g., 10
percent CO2 = .10 mole fraction), g/g-mole (lb/lb-
mole).
0.280 = Molecular weight of N2 or CO, divided by 100.
0.320 = Molecular weight of O2 divided by 100.
0.440 = Molecular weight of CO2 divided by 100.
20.9 = Percent O2 by volume in ambient air.
42.5 = Gram-moles of carbon in 1 kg of dry wood assuming 51 percent
carbon by weight dry basis (.0425 lb/lb-mole).
510 = Grams of carbon in exhaust gas per kg of wood burned.
1,000 = Grams in 1 kg.

12.2 Fuel Factor. Use Equation 28A-1 to calculate the fuel factor.
[GRAPHIC] [TIFF OMITTED] TR17OC00.433

12. 3 Adjusted %CO2. Use Equation 28A-2 to adjust
CO2 values if measurable CO is present.
[GRAPHIC] [TIFF OMITTED] TR17OC00.434

12.4 Adjusted %O2. Use Equation 28A-3 to adjust
O2 value if measurable CO is present.
[GRAPHIC] [TIFF OMITTED] TR17OC00.435

12.5 Dry Molecular Weight. Use Equation 28A-4 to calculate the dry
molecular weight of the stack gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.436

Note: The above equation does not consider argon in air (about 0.9
percent, molecular weight of 39.9). A negative error of about 0.4
percent is introduced. Argon may

[[Page 585]]

be included in the analysis using procedures subject to approval of the
Administrator.

12.6 Dry Moles of Exhaust Gas. Use Equation 28A-5 to calculate the
total moles of dry exhaust gas produced per kilogram of dry wood burned.
[GRAPHIC] [TIFF OMITTED] TR17OC00.437

12.7 Air-to-Fuel Ratio. Use Equation 28A-6 to calculate the air-to-
fuel ratio on a dry mass basis.
[GRAPHIC] [TIFF OMITTED] TR17OC00.438

12.8 Burn Rate. Calculate the fuel burn rate as in Method 28,
section 12.4.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as section 16.0 of Method 3 and section 17 of Method 5G.

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Test Method 28R for Certification and Auditing of Wood Heaters

1.0 Scope and Application

1.1 This test method applies to certification and auditing of wood-
fired room heaters and fireplace inserts.
1.2 The test method covers the fueling and operating protocol for
measuring particulate emissions, as well as determining burn rates, heat
output and efficiency.
1.3 Particulate emissions are measured by the dilution tunnel method
as specified in ASTM E2515-11 Standard Test Method for Determination of
Particulate Matter Emissions Collected in a Dilution Tunnel (IBR, see
Sec. 60.17). Upon request, four-inch filters may be used. Upon request,
Teflon membrane filters or Teflon-coated glass fiber filters may be
used.

2.0 Procedures

2.1 This method incorporates the provisions of ASTM E2780-10 (IBR,
see Sec. 60.17) except as follows:
2.1.1 The burn rate categories, low burn rate requirement, and
weightings in Method 28 shall be used.
2.1.2 The startup procedures shall be the same as in Method 28.
2.1.3 Manufacturers shall not specify a smaller volume of the
firebox for testing than the full usable firebox.
2.1.4 Prior to testing, the heater must be operated for a minimum of
50 hours using a medium burn rate. The conditioning may be at the
manufacturer's facility prior to the certification test. If the
conditioning is at the certification test laboratory, the pre-burn for
the first test can be included as part of the conditioning requirement.
2.2 Manufacturers may use ASTM E871-82 (reapproved 2013) (IBR, see
Sec. 60.17) as an alternative to the procedures in Method 5H or Method
28 for determining total weight basis moisture in the analysis sample of
particulate wood fuel.

Test Method 28WHH for Measurement of Particulate Emissions and Heating
Efficiency of Wood-Fired Hydronic Heating Appliances

1.0 Scope and Application

1.1 This test method applies to wood-fired hydronic heating
appliances. The units typically transfer heat through circulation of a
liquid heat exchange media such as water or a water-antifreeze mixture.
1.2 The test method measures particulate emissions and delivered
heating efficiency at specified heat output rates based on the
appliance's rated heating capacity.
1.3 Particulate emissions are measured by the dilution tunnel method
as specified in ASTM E2515-11 Standard Test Method for Determination of
Particulate Matter Emissions Collected in a Dilution Tunnel (IBR, see
Sec. 60.17). Upon request, four-inch filters may be used. Upon request,
Teflon membrane filters or Teflon-coated glass fiber filters may be
used. Delivered efficiency is measured by determining the heat output
through measurement of the flow rate and temperature change of water
circulated through a heat exchanger external to the appliance and
determining the input from the mass of dry wood fuel and its higher
heating value. Delivered efficiency does not attempt to account for
pipeline loss.
1.4 Products covered by this test method include both pressurized
and non-pressurized heating appliances intended to be fired with wood.
These products are wood-fired hydronic heating appliances that the
manufacturer specifies for indoor or outdoor installation. They are
often connected to a heat exchanger by insulated pipes and normally
include a pump to circulate heated liquid. They are used to heat
structures such as homes, barns and greenhouses and can heat domestic
hot water, spas or swimming pools.
1.5 Distinguishing features of products covered by this standard
include:
1.5.1 Manufacturer specifies for indoor or outdoor installation.

[[Page 586]]

1.5.2 A firebox with an access door for hand loading of fuel.
1.5.3 Typically, an aquastat that controls combustion air supply to
maintain the liquid in the appliance within a predetermined temperature
range provided sufficient fuel is available in the firebox.
1.5.4 A chimney or vent that exhausts combustion products from the
appliance.
1.6 The values stated are to be regarded as the standard whether in
I-P or SI units. The values given in parentheses are for information
only.

2.0 Summary of Method and References

2.1 Particulate matter emissions are measured from a wood-fired
hydronic heating appliance burning a prepared test fuel crib in a test
facility maintained at a set of prescribed conditions. Procedures for
determining burn rates, and particulate emissions rates and for reducing
data are provided.
2.2 Referenced Documents
2.2.1 EPA Standards
2.2.1.1 Method 28 Certification and Auditing of Wood Heaters
2.2.2 Other Standards
2.2.2.1 ASTM E2515-11--Standard Test Method for Determination of
Particulate Matter Emissions Collected in a Dilution Tunnel (IBR, see
Sec. 60.17).
2.2.2.2 CSA-B415.1-10 Performance Testing of Solid-Fuel-Burning
Heating Appliances (IBR, see Sec. 60.17).

3.0 Terminology

3.1 Definitions.
3.1.1 Hydronic Heating--A heating system in which a heat source
supplies energy to a liquid heat exchange media such as water that is
circulated to a heating load and returned to the heat source through
pipes.
3.1.2 Aquastat--A control device that opens or closes a circuit to
control the rate of fuel consumption in response to the temperature of
the heating media in the heating appliance.
3.1.3 Delivered Efficiency--The percentage of heat available in a
test fuel charge that is delivered to a simulated heating load as
specified in this test method.
3.1.4 Manufacturer's Rated Heat Output Capacity--The value in Btu/hr
(MJ/hr) that the manufacturer specifies that a particular model of
hydronic heating appliance is capable of supplying at its design
capacity as verified by testing, in accordance with Section 13.
3.1.5 Burn Rate--The rate at which test fuel is consumed in an
appliance. Measured in pounds (lbs) or kilograms of wood (dry basis) per
hour (lb/hr or kg/hr).
3.1.6 Firebox--The chamber in the appliance in which the test fuel
charge is placed and combusted.
3.1.7 Test Fuel Charge--The collection of test fuel layers placed in
the appliance at the start of the emission test run.
3.1.8 Test Fuel Layer--Horizontal arrangement of test fuel units.
3.1.9 Test Fuel Unit--One or more test fuel pieces with \3/4\ inch
(19 mm) spacers attached to the bottom and to one side. If composed of
multiple test fuel pieces, the bottom spacer may be one continuous
piece.
3.1.10 Test Fuel Piece--A single 4 x 4 (4 0.25 inches by 4 0.25
inches) [100 6 mm by 100 6 mm] white or red oak wood piece cut to
the length required.
3.1.11 Test Run--An individual emission test that encompasses the
time required to consume the mass of the test fuel charge.
3.1.12 Overall Efficiency (SLM)--The efficiency for each test run as
determined using the CSA B415.1-10 (IBR, see Sec. 60.17) stack loss
method.
3.1.13 Thermopile--A device consisting of a number of thermocouples
connected in series, used for measuring differential temperature.

4.0 Summary of Test Method

4.1 Dilution Tunnel. Emissions are determined using the ``dilution
tunnel'' method specified in ASTM E2515-11 Standard Test Method for
Determination of Particulate Matter Emissions Collected in a Dilution
Tunnel (IBR, see Sec. 60.17). The flow rate in the dilution tunnel is
maintained at a constant level throughout the test cycle and accurately
measured. Samples of the dilution tunnel flow stream are extracted at a
constant flow rate and drawn through high efficiency filters. The
filters are dried and weighed before and after the test to determine the
emissions catch and this value is multiplied by the ratio of tunnel flow
to filter flow to determine the total particulate emissions produced in
the test cycle.
4.2 Efficiency. The efficiency test procedure takes advantage of the
fact that this type of appliance delivers heat through circulation of
the heated liquid (water) from the appliance to a remote heat exchanger
and back to the appliance. Measurements of the water temperature
difference as it enters and exits the heat exchanger along with the
measured flow rate allow for an accurate determination of the useful
heat output of the appliance. The input is determined by weight of the
test fuel charge, adjusted for moisture content, multiplied by the
higher heating value. Additional measurements of the appliance weight
and temperature at the beginning and end of a test cycle are used to
correct for heat stored in the appliance. Overall efficiency (SLM) is
determined using the CSA B415.1-10 (IBR, see Sec. 60.17) stack loss
method for data quality assurance purposes.
4.3 Operation. Appliance operation is conducted on a hot-to-hot test
cycle meaning that the appliance is brought to operating

[[Page 587]]

temperature and a coal bed is established prior to the addition of the
test fuel charge and measurements are made for each test fuel charge
cycle. The measurements are made under constant heat draw conditions
within predetermined ranges. No attempt is made to modulate the heat
demand to simulate an indoor thermostat cycling on and off in response
to changes in the indoor environment. Four test categories are used.
These are:
4.3.1 Category I: A heat output of 15 percent or less of
manufacturer's rated heat output capacity.
4.3.2 Category II: A heat output of 16 percent to 24 percent of
manufacturer's rated heat output capacity.
4.3.3 Category III: A heat output of 25 percent to 50 percent of
manufacturer's rated heat output capacity.
4.3.4 Category IV: Manufacturer's rated heat output capacity.

5.0 Significance and Use

5.1 The measurement of particulate matter emission rates is an
important test method widely used in the practice of air pollution
control.
5.1.1 These measurements, when approved by state or federal
agencies, are often required for the purpose of determining compliance
with regulations and statutes.
5.1.2 The measurements made before and after design modifications
are necessary to demonstrate the effectiveness of design changes in
reducing emissions and make this standard an important tool in
manufacturers' research and development programs.
5.2 Measurement of heating efficiency provides a uniform basis for
comparison of product performance that is useful to the consumer. It is
also required to relate emissions produced to the useful heat
production.
5.3 This is a laboratory method and is not intended to be fully
representative of all actual field use. It is recognized that users of
hand-fired, wood-burning equipment have a great deal of influence over
the performance of any wood-burning appliance. Some compromises in
realism have been made in the interest of providing a reliable and
repeatable test method.

6.0 Test Equipment

6.1 Scale. A platform scale capable of weighing the appliance under
test and associated parts and accessories when completely filled with
water to an accuracy of 1.0 pound (0.5 kg).
6.2 Heat Exchanger. A water-to-water heat exchanger capable of
dissipating the expected heat output from the system under test.
6.3 Water Temperature Difference Measurement. A Type--T 'special
limits' thermopile with a minimum of 5 pairs of junctions shall be used
to measure the temperature difference in water entering and leaving the
heat exchanger. The temperature difference measurement uncertainty of
this type of thermopile is equal to or less than 0.50 [deg]F (0.25
[deg]C). Other temperature measurement methods may be used if the
temperature difference measurement uncertainty is equal to or less than
0.50 [deg]F (0.25 [deg]C).
6.4 Water Flow Meter. A water flow meter shall be installed in the
inlet to the load side of the heat exchanger. The flow meter shall have
an accuracy of 1 percent of measured flow.
6.4.1 Optional--Appliance Side Water Flow Meter. A water flow meter
with an accuracy of 1 percent of the flow rate is recommended to
monitor supply side water flow rate.
6.5 Optional Recirculation Pump. Circulating pump used during test
to prevent stratification of liquid being heated.
6.6 Water Temperature Measurement--Thermocouples or other
temperature sensors to measure the water temperature at the inlet and
outlet of the load side of the heat exchanger. Must meet the calibration
requirements specified in section 10.1.
6.7 Wood Moisture Meter--Calibrated electrical resistance meter
capable of measuring test fuel moisture to within 1 percent moisture
content. Must meet the calibration requirements specified in section
10.4.
6.8 Flue Gas Temperature Measurement--Must meet the requirements of
CSA B415.1-10 (IBR, see Sec. 60.17), clause 6.2.2.
6.9 Test Room Temperature Measurement--Must meet the requirements of
CSA B415.1-10 (IBR, see Sec. 60.17), clause 6.2.1.
6.10 Flue Gas Composition Measurement--Must meet the requirements of
CSA B415.1-10 (IBR, see Sec. 60.17), clauses 6.3.1 through 6.3.3.

7.0 Safety

7.1 These tests involve combustion of wood fuel and substantial
release of heat and products of combustion. The heating system also
produces large quantities of very hot water and the potential for steam
production and system pressurization. Appropriate precautions must be
taken to protect personnel from burn hazards and respiration of products
of combustion.

8.0 Sampling, Test Specimens and Test Appliances

8.1 Test specimens shall be supplied as complete appliances
including all controls and accessories necessary for installation in the
test facility. A full set of specifications and design and assembly
drawings shall be provided when the product is to be placed under
certification of a third-party agency. The manufacturer's written
installation and operating instructions are to be used as a

[[Page 588]]

guide in the set-up and testing of the appliance.

9.0 Preparation of Test Equipment

9.1 The appliance is to be placed on a scale capable of weighing the
appliance fully loaded with a resolution of 1.0 lb (0.5 kg).
9.2 The appliance shall be fitted with the type of chimney
recommended or provided by the manufacturer and extending to 15 0.5
feet (4.6 0.15 m) from the upper surface of the scale. If no flue or
chimney system is recommended or provided by the manufacturer, connect
the appliance to a flue of a diameter equal to the flue outlet of the
appliance. The flue section from the appliance flue collar to 8 0.5
feet above the scale shall be single wall stove pipe and the remainder
of the flue shall be double wall insulated class A chimney.
9.3 Optional Equipment Use
9.3.1 A recirculation pump may be installed between connections at
the top and bottom of the appliance to minimize thermal stratification
if specified by the manufacturer. The pump shall not be installed in
such a way as to change or affect the flow rate between the appliance
and the heat exchanger.
9.3.2 If the manufacturer specifies that a thermal control valve or
other device be installed and set to control the return water
temperature to a specific set point, the valve or other device shall be
installed and set per the manufacturer's written instructions.
9.4 Prior to filling the tank, weigh and record the appliance mass.
9.5 Heat Exchanger
9.5.1 Plumb the unit to a water-to-water heat exchanger with
sufficient capacity to draw off heat at the maximum rate anticipated.
Route hoses, electrical cables, and instrument wires in a manner that
does not influence the weighing accuracy of the scale as indicated by
placing dead weights on the platform and verifying the scale's accuracy.
9.5.2 Locate thermocouples to measure the water temperature at the
inlet and outlet of the load side of the heat exchanger.
9.5.3 Install a thermopile meeting the requirements of section 6.3
to measure the water temperature difference between the inlet and outlet
of the load side of the heat exchanger.
9.5.4 Install a calibrated water flow meter in the heat exchanger
load side supply line. The water flow meter is to be installed on the
cooling water inlet side of the heat exchanger so that it will operate
at the temperature at which it is calibrated.
9.5.5 Place the heat exchanger in a box with 2 in. (50 mm) of
expanded polystyrene (EPS) foam insulation surrounding it to minimize
heat losses from the heat exchanger.
9.5.6 The reported efficiency and heat output rate shall be based on
measurements made on the load side of the heat exchanger.
9.5.7 Temperature instrumentation per section 6.6 shall be installed
in the appliance outlet and return lines. The average of the outlet and
return water temperature on the supply side of the system shall be
considered the average appliance temperature for calculation of heat
storage in the appliance (TFavg and TIavg).
Installation of a water flow meter in the supply side of the system is
optional.
9.6 Fill the system with water. Determine the total weight of the
water in the appliance when the water is circulating. Verify that the
scale indicates a stable weight under operating conditions. Make sure
air is purged properly.

10.0 Calibration and Standardization

10.1 Water Temperature Sensors. Temperature measuring equipment
shall be calibrated before initial use and at least semi-annually
thereafter. Calibrations shall be in compliance with National Institute
of Standards and Technology (NIST) Monograph 175, Standard Limits of
Error.
10.2 Heat Exchanger Load Side Water Flow Meter.
10.2.1 The heat exchanger load side water flow meter shall be
calibrated within the flow range used for the test run using NIST
traceable methods. Verify the calibration of the water flow meter before
and after each test run and at least once during each test run by
comparing the water flow rate indicated by the flow meter to the mass of
water collected from the outlet of the heat exchanger over a timed
interval. Volume of the collected water shall be determined based on the
water density calculated from section 13, Eq. 8, using the water
temperature measured at the flow meter. The uncertainty in the
verification procedure used shall be 1 percent or less. The water flow
rate determined by the collection and weighing method shall be within 1
percent of the flow rate indicated by the water flow meter.
10.3 Scales. The scales used to weigh the appliance and test fuel
charge shall be calibrated using NIST traceable methods at least once
every 6 months.
10.4 Moisture Meter. The moisture meter shall be calibrated per the
manufacturer's instructions and checked before each use.
10.5 Flue Gas Analyzers--In accordance with CSA B415.1-10 (IBR, see
Sec. 60.17), clause 6.8.

11.0 Conditioning

11.1 Prior to testing, the appliance is to be operated for a minimum
of 50 hours using a medium heat draw rate. The conditioning may be at
the manufacturer's facility prior to the certification test. If the
conditioning is at the certification test laboratory, the pre-burn for
the first test can be included as

[[Page 589]]

part of the conditioning requirement. If conditioning is included in
pre-burn, then the appliance shall be aged with fuel meeting the
specifications outlined in sections 12.2 with a moisture content between
19 and 25 percent on a dry basis. Operate the appliance at a medium burn
rate (Category II or III) for at least 10 hours for noncatalytic
appliances and 50 hours for catalytic appliances. Record and report
hourly flue gas exit temperature data and the hours of operation. The
aging procedure shall be conducted and documented by a testing
laboratory.

12.0 Procedure

12.1 Appliance Installation. Assemble the appliance and parts in
conformance with the manufacturer's written installation instructions.
Clean the flue with an appropriately sized, wire chimney brush before
each certification test series.
12.2 Fuel. Test fuel charge fuel shall be red (Quercus ruba L.) or
white (Quercus alba) oak 19 to 25 percent moisture content on a dry
basis. Piece length shall be 80 percent of the firebox depth rounded
down to the nearest 1 inch (25mm) increment. For example, if the firebox
depth is 46 inches (1168mm) the 4 x 4 piece length would be 36 inches
(46 inches x 0.8 = 36.8 inches rounded down to 36 inches). Pieces are to
be placed in the firebox parallel to the longest firebox dimension. For
fireboxes with sloped surfaces that create a non-uniform firebox length,
the piece length shall be adjusted for each layer based on 80 percent of
the length at the level where the layer is placed. Pieces are to be
spaced \3/4\ inches (19 mm) apart on all faces. The first fuel layer may
be assembled using fuel units consisting of multiple 4 x 4s consisting
of single pieces with bottom and side spacers of 3 or more pieces if
needed for a stable layer. The second layer may consist of fuel units
consisting of no more than two pieces with spacers attached on the
bottom and side. The top two layers of the fuel charge must consist of
single pieces unless the fuel charge is only three layers. In that
instance only the top layer must consist of single units. Three-quarter
inch (19 mm) by 1.5 inch (38 mm) spacers shall be attached to the bottom
of piece to maintain a \3/4\ inch (19 mm) separation. When a layer
consists of two or more units of 4 x 4s an additional \3/4\ inch (19 mm)
thick by 1.5 inch (38 mm) wide spacer shall be attached to the vertical
face of each end of one 4 x 4, such that the \3/4\ inch (19 mm) space
will be maintained when two 4 x 4 units or pieces are loaded side by
side. In cases where a layer contains an odd number of 4 x 4s one piece
shall not be attached, but shall have spacers attached in a manner that
will provide for the \3/4\ inch (19 mm) space to be maintained (See
Figure 1). Spacers shall be attached perpendicular to the length of the
4 x 4s such that the edge of the spacer is 1 0.25 inch from the end of
the 4 x 4s in the previous layers. Spacers shall be red or white oak and
will be attached with either nails (non-galvanized), brads or oak
dowels. The use of kiln-dried wood is not allowed.
12.2.1 Using a fuel moisture meter as specified in section 6.7 of
the test method, determine the fuel moisture for each test fuel piece
used for the test fuel load by averaging at least five fuel moisture
meter readings measured parallel to the wood grain. Penetration of the
moisture meter insulated electrodes for all readings shall be \1/4\ the
thickness of the fuel piece or 19 mm (\3/4\ in.), whichever is lesser.
One measurement from each of three sides shall be made at approximately
3 inches from each end and the center. Two additional measurements shall
be made centered between the other three locations. Each individual
moisture content reading shall be in the range of 18 to 28 percent on a
dry basis. The average moisture content of each piece of test fuel shall
be in the range of 19 to 25 percent. It is not required to measure the
moisture content of the spacers. Moisture shall not be added to
previously dried fuel pieces except by storage under high humidity
conditions and temperature up to 100 [deg]F. Fuel moisture shall be
measured within 4 hours of using the fuel for a test.
12.2.2 Firebox Volume. Determine the firebox volume in cubic feet.
Firebox volume shall include all areas accessible through the fuel
loading door where firewood could reasonably be placed up to the
horizontal plane defined by the top of the loading door. A drawing of
the firebox showing front, side and plan views or an isometric view with
interior dimensions shall be provided by the manufacturer and verified
by the laboratory. Calculations for firebox volume from computer aided
design (CAD) software programs are acceptable and shall be included in
the test report if used. If the firebox volume is calculated by the
laboratory the firebox drawings and calculations shall be included in
the test report.
12.2.3 Test Fuel Charge. Test fuel charges shall be determined by
multiplying the firebox volume by 10 pounds (4.54 kg) per ft\3\ (28L),
or a higher load density as recommended by the manufacturer's printed
operating instructions, of wood (as used wet weight). Select the number
of pieces of standard fuel that most nearly match this target weight.
This is the standard fuel charge for all tests. For example, if the
firebox loading area volume is 10 ft\3\ (280L) and the firebox depth is
46 inches (1168 mm), test fuel charge target is 100 lbs (45 kg) minimum
and the piece length is 36 inches (914 mm). If eight 4 x 4s, 36 inches
long weigh 105 lbs (48 kg), use 8 pieces for each test fuel charge. All
test fuel charges will be of the same configuration.

[[Page 590]]

12.3 Sampling Equipment. Prepare the particulate emission sampling
equipment as defined by ASTM E2515-11 Standard Test Method for
Determination of Particulate Matter Emissions Collected in a Dilution
Tunnel (IBR, see Sec. 60.17). Upon request, four-inch filters may be
used. Upon request, Teflon membrane filters or Teflon-coated glass fiber
filters may be used.
12.4 Appliance Startup. The appliance shall be fired with wood fuel
of any species, size and moisture content at the laboratories'
discretion to bring it up to operating temperature. Operate the
appliance until the water is heated to the upper operating control limit
and has cycled at least two times. Then remove all unburned fuel, zero
the scale and verify the scales accuracy using dead weights.
12.4.1 Pretest Burn Cycle. Reload appliance with oak wood and allow
it to burn down to the specified coal bed weight. The pretest burn cycle
fuel charge weight shall be within 10 percent of the test fuel charge
weight. Piece size and length shall be selected such that
charcoalization is achieved by the time the fuel charge has burned down
to the required coal bed weight. Pieces with a maximum thickness of
approximately 2 inches have been found to be suitable. Charcoalization
is a general condition of the test fuel bed evidenced by an absence of
large pieces of burning wood in the coal bed and the remaining fuel
pieces being brittle enough to be broken into smaller charcoal pieces
with a metal poker. Manipulations to the fuel bed prior to the start of
the test run are to be done to achieve charcoalization while maintaining
the desired heat output rate. During the pre-test burn cycle and at
least one hour prior to starting the test run, adjust water flow to the
heat exchanger to establish the target heat draw for the test. For the
first test run the heat draw rate shall be equal to the manufacturer's
rated heat output capacity.
12.4.1.1 Allowable Adjustments. Fuel addition or subtractions, and
coal bed raking shall be kept to a minimum but are allowed up to 15
minutes prior to the start of the test run. For the purposes of this
method, coal bed raking is the use of a metal tool (poker) to stir
coals, break burning fuel into smaller pieces, dislodge fuel pieces from
positions of poor combustion, and check for the condition of
charcoalization. Record all adjustments to and additions or subtractions
of fuel, and any other changes to the appliance operations that occur
during pretest ignition period. During the 15-minute period prior to the
start of the test run, the wood heater loading door shall not be open
more than a total of 1 minute. Coal bed raking is the only adjustment
allowed during this period.
12.4.2 Coal Bed Weight. The appliance is to be loaded with the test
fuel charge when the coal bed weight is between 10 percent and 20
percent of the test fuel charge weight. Coals may be raked as necessary
to level the coal bed but may only be raked and stirred once between 15
to 20 minutes prior to the addition of the test fuel charge.
12.5 Test Runs. For all test runs, the return water temperature to
the hydronic heater must be equal to or greater than 120 [deg]F.
Aquastat or other heater output control device settings that are
adjustable shall be set using manufacturer specifications, either as
factory set or in accordance with the owner's manual, and shall remain
the same for all burn categories.
Complete a test run in each heat output rate category, as follows:
12.5.1 Test Run Start. Once the appliance is operating normally and
the pretest coal bed weight has reached the target value per section
12.4.2, tare the scale and load the full test charge into the appliance.
Time for loading shall not exceed 5 minutes. The actual weight of the
test fuel charge shall be measured and recorded within 30 minutes prior
to loading. Start all sampling systems.
12.5.1.1 Record all water temperatures, differential water
temperatures and water flow rates at time intervals of one minute or
less.
12.5.1.2 Record particulate emissions data per the requirements of
ASTM E2515 (IBR, see Sec. 60.17).
12.5.1.3 Record data needed to determine overall efficiency (SLM)
per the requirements of CSA B415.1-10 (IBR, see Sec. 60.17), clauses
6.2.1, 6.2.2, 6.3, 8.5.7, 10.4.3 (a), 10.4.3(f), and 13.7.9.3
12.5.1.3.1 Measure and record the test room air temperature in
accordance with the requirements of CSA B415.1-10 (IBR, see Sec.
60.17), clauses 6.2.1, 8.5.7 and 10.4.3 (g).
12.5.1.3.2 Measure and record the flue gas temperature in accordance
with the requirements of CSA B415.1-10 (IBR, see Sec. 60.17), clauses
6.2.2, 8.5.7 and 10.4.3 (f).
12.5.1.3.3 Determine and record the carbon monoxide (CO) and carbon
dioxide (CO2) concentrations in the flue gas in accordance
with CSA B415.1-10 (IBR, see Sec. 60.17), clauses 6.3, 8.5.7 and 10.4.3
(i) and (j).
12.5.1.3.4 Measure and record the test fuel weight per the
requirements of CSA B415.1-10 (IBR, see Sec. 60.17), clauses 8.5.7 and
10.4.3 (h).
12.5.1.3.5 Record the test run time per the requirements of CSA
B415.1-10 (IBR, see Sec. 60.17), clauses 10.4.3 (a).
12.5.1.4 Monitor the average heat output rate on the load side of
the heat exchanger. If the heat output rate gets close to the upper or
lower limit of the target range (5 percent) adjust the water flow
through the heat exchanger to compensate. Make changes as infrequently
as possible while maintaining the target heat output rate. The first
test run shall be conducted at the Category IV heat output rate to
validate that

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the appliance is capable of producing the manufacturer's rated heat
output capacity.
12.5.2 Test Fuel Charge Adjustment. It is acceptable to adjust the
test fuel charge (i.e., reposition) once during a test run if more than
60 percent of the initial test fuel charge weight has been consumed and
more than 10 minutes have elapsed without a measurable (1 lb or 0. 5 kg)
weight change while the operating control is in the demand mode. The
time used to make this adjustment shall be less than 60 seconds.
12.5.3 Test Run Completion. The test run is completed when the
remaining weight of the test fuel charge is 0.0 lb (0.0 kg). End the
test run when the scale has indicated a test fuel charge weight of 0.0
lb (0.0 kg) or less for 30 seconds.
12.5.3.1 At the end of the test run, stop the particulate sampling
train and overall efficiency (SLM) measurements, and record the run
time, and all final measurement values.
12.5.4 Heat Output Capacity Validation. The first test run must
produce a heat output rate that is within 10 percent of the
manufacturer's rated heat output capacity (Category IV) throughout the
test run and an average heat output rate within 5 percent of the
manufacturer's rated heat output capacity. If the appliance is not
capable of producing a heat output within these limits, the
manufacturer's rated heat output capacity is considered not validated
and testing is to be terminated. In such cases, the tests may be
restarted using a lower heat output capacity if requested by the
manufacturer.
12.5.5 Additional Test Runs. Using the manufacturer's rated heat
output capacity as a basis, conduct a test for additional heat output
categories as specified in section 4.3. It is not required to run these
tests in any particular order.
12.5.6 Alternative Heat Output Rate for Category I. If an appliance
cannot be operated in the Category I heat output range due to stopped
combustion, two test runs shall be conducted at heat output rates within
Category II, provided that the completed test run burn rate is no
greater than the burn rate expected in home use. If this rate cannot be
achieved, the test is not valid.
When the alternative heat output rate is used, the weightings for
the weighted averages indicated in Table 2 shall be the average of the
Category I and II weightings and shall be applied to both Category II
results. The two completed runs in Category II will be deemed to meet
the requirement for runs completed in both Category I and Category II.
Appliances that are not capable of operation within Category II (<25
percent of maximum) cannot be evaluated by this test method. The test
report must include full documentation and discussion of the attempted
runs, completed rums and calculations.
12.5.6.1 Stopped Fuel Combustion. Evidence that an appliance cannot
be operated at a Category I heat output rate due to stopped fuel
combustion shall include documentation of two or more attempts to
operate the appliance in burn rate Category I and fuel combustion has
stopped prior to complete consumption of the test fuel charge. Stopped
fuel combustion is evidenced when an elapsed time of 60 minutes or more
has occurred without a measurable (1 lb or 0.5 kg) weight change in the
test fuel charge while the appliance operating control is in the demand
mode. Report the evidence and the reasoning used to determine that a
test in burn rate Category I cannot be achieved. For example, two
unsuccessful attempts to operate at an output rate of 10 percent of the
rated output capacity are not sufficient evidence that burn rate
Category I cannot be achieved. Note that section 12.5.6 requires that
the completed test run burn rate can be no greater than the burn rate
expected in home use. If this rate cannot be achieved, the test is not
valid.
12.5.7 Appliance Overheating. Appliances shall be capable of
operating in all heat output categories without overheating to be rated
by this test method. Appliance overheating occurs when the rate of heat
withdrawal from the appliance is lower than the rate of heat production
when the unit control is in the idle mode. This condition results in the
water in the appliance continuing to increase in temperature well above
the upper limit setting of the operating control. Evidence of
overheating includes: 1 hour or more of appliance water temperature
increase above the upper temperature set-point of the operating control,
exceeding the temperature limit of a safety control device (independent
from the operating control), boiling water in a non-pressurized system
or activation of a pressure or temperature relief valve in a pressurized
system.
12.6 Additional Test Runs. The testing laboratory may conduct more
than one test run in each of the heat output categories specified in
section 4.3.1. If more than one test run is conducted at a specified
heat output rate, the results from at least two-thirds of the test runs
in that heat output rate category shall be used in calculating the
weighted average emission rate (See section 14.1.14). The measurement
data and results of all test runs shall be reported regardless of which
values are used in calculating the weighted average emission rate.

13.0 Calculation of Results

13.1 Nomenclature

ET--Total particulate emissions for the full test run as
determined per ASTM E2515-11 (IBR, see Sec. 60.17) in grams

[[Page 592]]

Eg/MJ--Emissions rate in grams per megajoule of heat output
Elb/mmBtu output--Emissions rate in pounds per million Btu of
heat output
Eg/kg--Emissions factor in grams per kilogram of dry fuel
burned
Eg/hr--Emissions factor in grams per hour
HHV--Higher heating value of fuel = 8600 Btu/lb (19.990 MJ/kg)
LHV--Lower heating value of fuel = 7988 Btu/lb (18.567 MJ/kg)
FT--Temperature difference between water entering and exiting the heat
exchanger
Qout--Total heat output in BTU's (megajoules)
Qin--Total heat input available in test fuel charge in BTU
(megajoules)
M--Mass flow rate of water in lb/min (kg/min)
Vi--Volume of water indicated by a totalizing flow meter at
the ith reading in gallons (liters)
Vf--Volumetric flow rate of water in heat exchange system in
gallons per minute (liters/min)
K--Total length of test run in hours
ti--Data sampling interval in minutes
jdel--Delivered heating efficiency in percent
Fi--Weighting factor for heat output category i (See Table 2)
T1--Temperature of water at the inlet on the supply side of the heat
exchanger
T2--Temperature of the water at the outlet on the supply side of the
heat exchanger
T3--Temperature of water at the inlet to the load side of the heat
exchanger
TIavg--Average temperature of the appliance and water at start of the
test
[GRAPHIC] [TIFF OMITTED] TR16MR15.022

TFavg--Average temperature of the applicance and water at the
end of the test
[GRAPHIC] [TIFF OMITTED] TR16MR15.023

MC--Fuel moisture content in percent dry basis
MCi--Average moisture content of individual 4 x 4 fuel pieces
in percent dry basis
MCsp--Moisture content of spacers assumed to be 10 percent
dry basis
m--Density of water in pounds per gallon
Cp--Specific heat of water in Btu/lb, [deg]F
Csteel--Specific heat of steel (0.1 Btu/lb, [ordm]F)
Wfuel--Fuel charge weight in pounds (kg)
Wi--Weight of individual fuel 4 x 4 pieces in pounds (kg)
Wsp--Weight of all spacers used in a fuel load in pounds (kg)
Wapp--Weight of empty appliance in pounds
Wwa--Weight of water in supply side of the system in pounds

13.2 After the test is completed, determine the particulate
emissions ET in accordance with ASTM E2515-11 (IBR, see Sec.
60.17).

13.3 Determine Average Fuel Load Moisture Content
[GRAPHIC] [TIFF OMITTED] TR16MR15.024

13.4 Determine heat input
[GRAPHIC] [TIFF OMITTED] TR16MR15.025

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13.5 Determine Heat Output and Efficiency

13.5.1 Determine heat output as:

Qout = M [Heat output determined for each sampling time
interval] + Change in heat stored in the appliance.
[GRAPHIC] [TIFF OMITTED] TR16MR15.026

Note: The subscript (i) indicates the parameter value for sampling
time interval ti.
Mi = Mass flow rate = gal/min x density of water (lb/gal) =
lb/min
[GRAPHIC] [TIFF OMITTED] TR16MR15.027

Csteel = 0.1 Btu/lb, [deg] F
[GRAPHIC] [TIFF OMITTED] TR16MR15.028

Note: Vi is the total water volume at the end of interval i and Vi-1
is the total water volume at the beginning of the time interval. This
calculation is necessary when a totalizing type water meter is used.

13.5.2 Determine heat output rate as:

[GRAPHIC] [TIFF OMITTED] TR16MR15.029

13.5.3 Determine emission rates and emission factors as:
[GRAPHIC] [TIFF OMITTED] TR16MR15.030

13.5.4 Determine delivered efficiency as:

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[GRAPHIC] [TIFF OMITTED] TR16MR15.031

13.5.5 Determine jSLM--Overall Efficiency (SLM) using Stack
Loss

For determination of the average overall thermal efficiency
(jSLM) for the test run, use the data collected over the full
test run and the calculations in accordance with CSA B415.1-10 (IBR, see
Sec. 60.17), clause 13.7 except for 13.7.2 (e), (f), (g), and (h), use
the following average fuel properties for oak: percent C = 50.0, percent
H = 6.6, percent O = 43.2, percent ash = 0.2 percent. The averaging
period for determination of efficiency by the stack loss method allows
averaging over 10 minute time periods for flue gas temperature, flue gas
CO2, and flue gas CO for the determination of the efficiency.
However, under some cycling conditions the ``on'' period may be short
relative to this 10 minute period. For this reason, during cycling
operation the averaging period for these parameters may not be longer
than the burner on period divided by 10. The averaging period need not
be shorter than one minute. During the off period, under cycling
operation, the averaging periods specified may be used. Where short
averaging times are used, however, the averaging period for fuel
consumption may still be at 10 minutes. This average wood consumption
rate shall be applied to all of the smaller time intervals included.
13.5.5.1 Whenever the CSA B415.1-10 (IBR, see Sec. 60.17) overall
efficiency is found to be lower than the overall efficiency based on
load side measurements, as determined by Eq. 16 of this method, section
14.1.7 of the test report must include a discussion of the reasons for
this result.

13.6 Weighted Average Emissions and Efficiency

13.6.1 Determine the weighted average emission rate and delivered
efficiency from the individual tests in the specified heat output
categories. The weighting factors (Fi) are derived from an analysis of
ASHRAE bin data which provides details of normal building heating
requirements in terms of percent of design capacity and time in a
particular capacity range--or ``bin''--over the course of a heating
season. The values used in this method represent an average of data from
several cities located in the northern United States.
[GRAPHIC] [TIFF OMITTED] TR16MR15.003

13.7 Average Heat Output (Qout-8hr) and Efficiency
((javg-8hr) for 8 hour burn time.
13.7.1 Units tested under this standard typically require infrequent
fuelling, 8 to 12 hours intervals being typical. Rating unit's based on
an average output sustainable over an 8 hour duration will assist
consumers in appropriately sizing units to match the theoretical heat
demand of their application.
13.7.2 Calculations:
[GRAPHIC] [TIFF OMITTED] TR16MR15.004

Where:

Y1 = Test duration just above 8 hrs
Y2 = Test duration just below 8 hrs
X1 = Actual load for duration Y1
X2 = Actual load for duration Y2
jdel1 = Average delivered efficiency for duration Y1
jdel2 = Average delivered efficiency for duration Y2

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13.7.2.1 Determine the test durations and actual load for each
category as recorded in Table 1A.
13.7.2.2 Determine the data point that has the nearest duration
greater than 8 hrs.

X1 = Actual load,
Y1 = Test duration, and
jdel1 = Average delivered efficiency for this data point

13.7.2.3 Determine the data point that has the nearest duration less
than 8 hours.
X2 = Actual load,
Y2 = Test duration, and
jdel2 = Average delivered efficiency for this data point

13.7.2.4 Example:

Category Actual Load Duration
[Category Actual Load Duration jdel]
------------------------------------------------------------------------
(Btu/Hr) (Hr) (%)
------------------------------------------------------------------------
1 15,000............................................ 10.2 70.0
2 26,000............................................ 8.4 75.5
3 50,000............................................ 6.4 80.1
4 100,000........................................... 4.7 80.9
------------------------------------------------------------------------

Category 2 duration is just above 8 hours, therefore: X1 = 26,000
Btu/hr, jdel1 = 75.5% and Y1 = 8.4 hrs
Category 3 duration is just below 8 hours, therefore: X2 = 50,000
Btu/hr, jdel2 = 80.1% and Y2 = 6.4 hrs

Qout-8hr = 26,000 + {(8--8.4) x [(50,000--26,000)/(6.4--
8.4)]} = 30,800 BTU/hr
javg-8hr = 75.5 + {(8--8.4) x [(80.1--75.5)/(6.4--8.4)]} =
76.4%

13.8 Carbon Monoxide Emissions

For each minute of the test period, the carbon monoxide emission
rate shall be calculated as:
[GRAPHIC] [TIFF OMITTED] TR16MR15.005

Total CO emissions for each of the three test periods
(CO--1, CO--2, CO--3) shall be
calculated as the sum of the emission rates for each of the 1 minute
intervals.
Total CO emission for the test run, COT, shall be
calculated as the sum of CO--1, CO--2, and
CO--3.

14.0 Report

14.1.1 The report shall include the following.
14.1.2 Name and location of the laboratory conducting the test.
14.1.3 A description of the appliance tested and its condition, date
of receipt and dates of tests.
14.1.4 A statement that the test results apply only to the specific
appliance tested.
14.1.5 A statement that the test report shall not be reproduced
except in full, without the written approval of the laboratory.
14.1.6 A description of the test procedures and test equipment
including a schematic or other drawing showing the location of all
required test equipment. Also, a description of test fuel sourcing,
handling and storage practices shall be included.
14.1.7 Details of deviations from, additions to or exclusions from
the test method, and their data quality implications on the test results
(if any), as well as information on specific test conditions, such as
environmental conditions.
14.1.8 A list of participants and observers present for the tests.
14.1.9 Data and drawings indicating the fire box size and location
of the fuel charge.
14.1.10 Drawings and calculations used to determine firebox volume.
14.1.11 Information for each test run fuel charge including piece
size, moisture content, and weight.
14.1.12 All required data for each test run shall be provided in
spreadsheet format. Formulae used for all calculations shall be
accessible for review.
14.1.13 Test run duration for each test.
14.1.14 Calculated results for delivered efficiency at each burn
rate and the weighted average emissions reported as total emissions in
grams, pounds per mm Btu of delivered heat, grams per MJ of delivered
heat, grams per kilogram of dry fuel and grams per hour. Results shall
be reported for each heat output category and the weighted average.
14.1.15 Tables 1A, 1B, 1C and Table 2 must be used for presentation
of results in test reports.
14.1.16 A statement of the estimated uncertainty of measurement of
the emissions and efficiency test results.
14.1.17 Raw data, calibration records, and other relevant
documentation shall be retained by the laboratory for a minimum of 7
years.

15.0 Precision and Bias

15.1 Precision--It is not possible to specify the precision of the
procedure in Method 28WHH because the appliance operation and

[[Page 596]]

fueling protocols and the appliances themselves produce variable amounts
of emissions and cannot be used to determine reproducibility or
repeatability of this measurement method.
15.2 Bias--No definitive information can be presented on the bias of
the procedure in Method 28WHH for measuring solid fuel burning hydronic
heater emissions because no material having an accepted reference value
is available.

16.0 Keywords

16.1 Solid fuel, hydronic heating appliances, wood-burning hydronic
heaters.
[GRAPHIC] [TIFF OMITTED] TR16MR15.006

[[Page 597]]

[GRAPHIC] [TIFF OMITTED] TR16MR15.007

[[Page 598]]

[GRAPHIC] [TIFF OMITTED] TR16MR15.008

[[Page 599]]

Test Method 28WHH for Certification of Cord Wood-Fired Hydronic Heating
Appliances With Partial Thermal Storage: Measurement of Particulate
Matter (PM) and Carbon Monoxide (CO) Emissions and Heating Efficiency of
Wood-Fired Hydronic Heating Appliances With Partial Thermal Storage

1.0 Scope and Application

1.1 This test method applies to wood-fired hydronic heating
appliances with heat storage external to the appliance. The units
typically transfer heat through circulation of a liquid heat exchange
media such as water or a water-antifreeze mixture. Throughout this
document, the term ``water'' will be used to denote any of the heat
transfer liquids approved for use by the manufacturer.
1.2 The test method measures PM and CO emissions and delivered
heating efficiency at specified heat output rates referenced against the
appliance's rated heating capacity as specified by the manufacturer and
verified under this test method.
1.3 PM emissions are measured by the dilution tunnel method as
specified in the EPA Method 28WHH and the standards referenced therein
with the exceptions noted in section 12.5.9. Delivered efficiency is
measured by determining the fuel energy input and appliance output. Heat
output is determined through measurement of the flow rate and
temperature change of water circulated through a heat exchanger external
to the appliance and the increase in energy of the external storage.
Heat input is determined from the mass of dry wood fuel and its higher
heating value (HHV). Delivered efficiency does not attempt to account
for pipeline loss.
1.4 Products covered by this test method include both pressurized
and non-pressurized hydronic heating appliances intended to be fired
with wood and for which the manufacturer specifies for indoor or outdoor
installation. The system, which includes the heating appliance and
external storage, is commonly connected to a heat exchanger by insulated
pipes and normally includes a pump to circulate heated liquid. These
systems are used to heat structures such as homes, barns and
greenhouses. They also provide heat for domestic hot water, spas and
swimming pools.
1.5 Distinguishing features of products covered by this standard
include:
1.5.1 The manufacturer specifies the application for either indoor
or outdoor installation.
1.5.2 A firebox with an access door for hand loading of fuel.
1.5.3 Typically an aquastat mounted as part of the appliance that
controls combustion air supply to maintain the liquid in the appliance
within a predetermined temperature range provided sufficient fuel is
available in the firebox. The appliance may be equipped with other
devices to control combustion.
1.5.4 A chimney or vent that exhausts combustion products from the
appliance.
1.5.5 A liquid storage system, typically water, which is not large
enough to accept all of the heat produced when a full load of wood is
burned and the storage system starts a burn cycle at 125 [deg]F.
1.5.6 The heating appliances require external thermal storage and
these units will only be installed as part of a system which includes
thermal storage. The manufacturer specifies the minimum amount of
thermal storage required. However, the storage system shall be large
enough to ensure that the boiler (heater) does not cycle, slumber, or go
into an off-mode when operated in a Category III load condition (See
section 4.3).
1.6 The values stated are to be regarded as the standard whether in
I-P or SI units. The values given in parentheses are for information
only.

2.0 Summary of Method and References

2.1 PM and CO emissions are measured from a wood-fired hydronic
heating appliance burning a prepared test fuel charge in a test facility
maintained at a set of prescribed conditions. Procedures for determining
heat output rates, PM and CO emissions, and efficiency and for reducing
data are provided.

2.2 Referenced Documents

2.2.1 EPA Standards
2.2.1.1 Method 28 Certification and Auditing of Wood Heaters
2.2.1.2 Method 28WHH Measurement of Particulate Emissions and
Heating Efficiency of Wood-Fired Hydronic Heating Appliances and the
Standards Referenced therein.
2.2.2 Other Standards
2.2.2.1 CSA-B415.1-10 Performance Testing of Solid-Fuel-Burning
Heating Appliances

3.0 Terminology

3.1 Definitions

3.1.1 Hydronic Heating--A heating system in which a heat source
supplies energy to a liquid heat exchange media such as water that is
circulated to a heating load and returned to the heat source through
pipes.
3.1.2 Aquastat--A control device that opens or closes a circuit to
control the rate of fuel consumption in response to the temperature of
the heating media in the heating appliance.
3.1.3 Delivered Efficiency--The percentage of heat available in a
test fuel charge that is delivered to a simulated heating load or the
storage system as specified in this test method.

[[Page 600]]

3.1.4 Emission Factor--The emission of a pollutant expressed in mass
per unit of energy (typically) output from the boiler/heater.
3.1.5 Emission Index--The emission of a pollutant expressed in mass
per unit mass of fuel used.
3.1.6 Emission Rate--The emission of a pollutant expressed in mass
per unit time
3.1.7 Manufacturer's Rated Heat Output Capacity--The value in Btu/hr
(MJ/hr) that the manufacturer specifies that a particular model of
hydronic heating appliance is capable of supplying at its design
capacity as verified by testing, in accordance with section 12.5.4.
3.1.8 Heat Output Rate--The average rate of energy output from the
appliance during a specific test period in Btu/hr (MJ/hr).
3.1.9 Firebox--The chamber in the appliance in which the test fuel
charge is placed and combusted.
3.1.10 NIST--National Institute of Standards and Technology.
3.1.11 Test Fuel Charge--The collection of test fuel placed in the
appliance at the start of the emission test run.
3.1.12 Test Run--An individual emission test which encompasses the
time required to consume the mass of the test fuel charge. The time of
the test run also considers the time for the energy to be drawn from the
thermal storage.
3.1.13 Test Run Under ``Cold-to-Cold'' Condition--Under this test
condition the test fuel is added into an empty chamber along with
kindling and ignition materials (paper). The boiler/heater at the start
of this test is typically 125[deg] to 130 [deg]F.
3.1.14 Test Run Under ``Hot-to-Hot'' Condition--Under this test
condition the test fuel is added onto a still-burning bed of charcoals
produced in a pre-burn period. The boiler/heater water is near its
operating control limit at the start of the test.
3.1.15 Overall Efficiency, also known as Stack Loss Efficiency--The
efficiency for each test run as determined using the CSA B415.1-10 (IBR,
see Sec. 60.17) stack loss method (SLM).
3.1.16 Phases of a Burn Cycle--The ``startup phase'' is defined as
the period from the start of the test until 15 percent of the test fuel
charge is consumed. The ``steady-state phase'' is defined as the period
from the end of the startup phase to a point at which 80 percent of the
test fuel charge is consumed. The ``end phase'' is defined as the time
from the end of the steady-state period to the end of the test.
3.1.17 Thermopile--A device consisting of a number of thermocouples
connected in series, used for measuring differential temperature.
3.1.18 Slumber Mode--This is a mode in which the temperature of the
water in the boiler/heater has exceeded the operating control limit and
the control has changed the boiler/heater fan speed, dampers, and/or
other operating parameters to minimize the heat output of the boiler/
heater.

4.0 Summary of Test Method

4.1 Dilution Tunnel. Emissions are determined using the ``dilution
tunnel'' method specified in EPA Method 28WHH and the standards
referenced therein. The flow rate in the dilution tunnel is maintained
at a constant level throughout the test cycle and accurately measured.
Samples of the dilution tunnel flow stream are extracted at a constant
flow rate and drawn through high efficiency filters. The filters are
dried and weighed before and after the test to determine the emissions
collected and this value is multiplied by the ratio of tunnel flow to
filter flow to determine the total particulate emissions produced in the
test cycle.
4.2 Efficiency. The efficiency test procedure takes advantage of the
fact that this type of system delivers heat through circulation of the
heated liquid (water) from the system to a remote heat exchanger (e.g.
baseboard radiators in a room) and back to the system. Measurements of
the cooling water temperature difference as it enters and exits the test
system heat exchanger along with the measured flow rate allow for an
accurate determination of the useful heat output of the appliance. Also
included in the heat output is the change in the energy content in the
storage system during a test run. Energy input to the appliance during
the test run is determined by weight of the test fuel charge, adjusted
for moisture content, multiplied by the higher heating value. Additional
measurements of the appliance weight and temperature at the beginning
and end of a test cycle are used to correct for heat stored in the
appliance. Overall efficiency (SLM) is determined using the CSA B415.1-
10 (IBR, see Sec. 60.17) stack loss method for data quality assurance
purposes.
4.3 Operation. Four test categories are defined for use in this
method. These are:
4.3.1 Category I: A heat output of 15 percent or less of
manufacturer's rated heat output capacity.
4.3.2 Category II: A heat output of 16 percent to 24 percent of
manufacturer's rated heat output capacity.
4.3.3 Category III: A heat output of 25 percent to 50 percent of
manufacturer's rated heat output capacity.
4.3.4 Category IV: Manufacturer's Rated Heat Output Capacity. These
heat output categories refer to the output from the system by way of the
load heat exchanger installed for the test. The output from just the
boiler/heater part of the system may be higher for all or part of a
test, as part of this boiler/heater output goes to storage.
For the Category III and IV runs, appliance operation is conducted
on a hot-to-hot test

[[Page 601]]

cycle meaning that the appliance is brought to operating temperature and
a coal bed is established prior to the addition of the test fuel charge
and measurements are made for each test fuel charge cycle. The
measurements are made under constant heat draw conditions within pre-
determined ranges. No attempt is made to modulate the heat demand to
simulate an indoor thermostat cycling on and off in response to changes
in the indoor environment.
For the Category I and II runs, the unit is tested with a ``cold
start.'' At the manufacturer's option, the Category II and III runs may
be waived and it may be assumed that the particulate emission values and
efficiency values determined in the startup, steady-state, and end
phases of Category I are applicable in Categories II and III for the
purpose of determining the annual averages in lb/mmBtu and g/MJ (See
section 13). For the annual average in g/hr, the length of time for
stored heat to be drawn from thermal storage shall be determined for the
test load requirements of the respective category.
All test operations and measurements shall be conducted by personnel
of the laboratory responsible for the submission of the test report.

5.0 Significance and Use

5.1 The measurement of particulate matter emission and CO rates is
an important test method widely used in the practice of air pollution
control.
5.1.1 These measurements, when approved by state or federal
agencies, are often required for the purpose of determining compliance
with regulations and statutes.
5.1.2 The measurements made before and after design modifications
are necessary to demonstrate the effectiveness of design changes in
reducing emissions and make this standard an important tool in
manufacturers' research and development programs.
5.2 Measurement of heating efficiency provides a uniform basis for
comparison of product performance that is useful to the consumer. It is
also required to relate emissions produced to the useful heat
production.
5.3 This is a laboratory method and is not intended to be fully
representative of all actual field use. It is recognized that users of
hand-fired, wood-burning equipment have a great deal of influence over
the performance of any wood-burning appliance. Some compromises in
realism have been made in the interest of providing a reliable and
repeatable test method.

6.0 Test Equipment

6.1 Scale. A platform scale capable of weighing the boiler/heater
under test and associated parts and accessories when completely filled
with water to an accuracy of 1.0 pound (0.5 kg) and a readout
resolution of 0.2 pound (0.1 kg).
6.2 Heat Exchanger. A water-to-water heat exchanger capable of
dissipating the expected heat output from the system under test.
6.3 Water Temperature Difference Measurement. A Type--T 'special
limits' thermopile with a minimum of 5 pairs of junctions shall be used
to measure the temperature difference in water entering and leaving the
heat exchanger. The temperature difference measurement uncertainty of
this type of thermopile is equal to or less than 0.50 [deg]F (0.25
[deg]C). Other temperature measurement methods may be used if the
temperature difference measurement uncertainty is equal to or less than
0.50 [deg]F (0.25 [deg]C). This measurement uncertainty shall include
the temperature sensor, sensor well arrangement, piping arrangements,
lead wire, and measurement/recording system. The response time of the
temperature measurement system shall be less than half of the time
interval at which temperature measurements are recorded.
6.4 Water Flow Meter. A water flow meter shall be installed in the
inlet to the load side of the heat exchanger. The flow meter shall have
an accuracy of 1 percent of measured flow.
6.4.1 Optional--Appliance Side Water Flow Meter. A water flow meter
with an accuracy of 1 percent of the flow rate is recommended to
monitor supply side water flow rate.
6.5 Optional Recirculation Pump. Circulating pump used during test
to prevent stratification, in the boiler/heater, of liquid being heated.
6.6 Water Temperature Measurement. Thermocouples or other
temperature sensors to measure the water temperature at the inlet and
outlet of the load side of the heat exchanger must meet the calibration
requirements specified in 10.1 of this method.
6.7 Lab Scale. For measuring the moisture content of wood slices as
part of the overall wood moisture determination. Accuracy of 0.01
pounds.
6.8 Flue Gas Temperature Measurement. Must meet the requirements of
CSA B415.1-10 (IBR, see Sec. 60.17), clause 6.2.2.
6.9 Test Room Temperature Measurement. Must meet the requirements of
CSA B415.1-10 (IBR, see Sec. 60.17), clause 6.2.1.
6.10 Flue Gas Composition Measurement. Must meet the requirements of
CSA B415.1-10 (IBR, see Sec. 60.17), clauses 6.3.1 through 6.3.3.
6.11 Dilution Tunnel CO Measurement. In parallel with the flue gas
composition measurements, the CO concentration in the dilution tunnel
shall also be measured and reported at time intervals not to exceed one
minute. This analyzer shall meet the zero and span drift requirements of
CSA B415.1-10 (IBR, see Sec. 60.17). In addition the measurement
repeatability shall be better than 15

[[Page 602]]

ppm over the range of CO levels observed in the dilution tunnel.

7.0 Safety

8.0 Sampling, Test Specimens and Test Appliances

8.1 Test specimens shall be supplied as complete appliances, as
described in marketing materials, including all controls and accessories
necessary for installation in the test facility. A full set of
specifications, installation and operating instructions, and design and
assembly drawings shall be provided when the product is to be placed
under certification of a third-party agency. The manufacturer's written
installation and operating instructions are to be used as a guide in the
set-up and testing of the appliance and shall be part of the test
record.
8.2 The size, connection arrangement, and control arrangement for
the thermal storage shall be as specified in the manufacturer's
documentation. It is not necessary to use the specific storage system
that the boiler/heater will be marketed with. However, the capacity of
the system used in the test cannot be greater than that specified as the
minimum allowable for the boiler/heater.
8.3 All system control settings shall be the as-shipped, default
settings. These default settings shall be the same as those communicated
in a document to the installer or end user. These control settings and
the documentation of the control settings as to be provided to the
installer or end user shall be part of the test record.
8.4 Where the manufacturer defines several alternatives for the
connection and loading arrangement, one shall be defined in the
appliance documentation as the default or standard installation. It is
expected that this will be the configuration for use with a simple
baseboard heating system. This is the configuration to be followed for
these tests. The manufacturer's documentation shall define the other
arrangements as optional or alternative arrangements.

9.0 Preparation of Test Equipment

9.1 The appliance is to be placed on a scale capable of weighing the
appliance fully loaded with a resolution of 0.2 lb (0.1 kg).
9.2 The appliance shall be fitted with the type of chimney
recommended or provided by the manufacturer and extending to 15 0.5
feet (4.6 0.15 m) from the upper surface of the scale. If no flue or
chimney system is recommended or provided by the manufacturer, connect
the appliance to a flue of a diameter equal to the flue outlet of the
appliance. The flue section from the appliance flue collar to 8 0.5
feet above the scale shall be single wall stove pipe and the remainder
of the flue shall be double wall insulated class A chimney.
9.3 Optional Equipment Use
9.3.1 A recirculation pump may be installed between connections at
the top and bottom of the appliance to minimize thermal stratification
if specified by the manufacturer. The pump shall not be installed in
such a way as to change or affect the flow rate between the appliance
and the heat exchanger.
9.3.2 If the manufacturer specifies that a thermal control valve or
other device be installed and set to control the return water
temperature to a specific set point, the valve or other device shall be
installed and set per the manufacturer's written instructions.
9.4 Prior to filling the boiler/heater with water, weigh and record
the appliance mass.
9.5 Heat Exchanger
9.5.1 Plumb the unit to a water-to-water heat exchanger with
sufficient capacity to draw off heat at the maximum rate anticipated.
Route hoses and electrical cables and instrument wires in a manner that
does not influence the weighing accuracy of the scale as indicated by
placing dead weights on the platform and verifying the scale's accuracy.
9.5.2 Locate thermocouples to measure the water temperature at the
inlet and outlet of the load side of the heat exchanger.
9.5.3 Install a thermopile (or equivalent instrumentation) meeting
the requirements of section 6.3 to measure the water temperature
difference between the inlet and outlet of the load side of the heat
exchanger
9.5.4 Install a calibrated water flow meter in the heat exchanger
load side supply line. The water flow meter is to be installed on the
cooling water inlet side of the heat exchanger so that it will operate
at the temperature at which it is calibrated.
9.5.5 Place the heat exchanger in a box with 2 in. (50 mm) of
expanded polystyrene (EPS) foam insulation surrounding it to minimize
heat losses from the heat exchanger.
9.5.6 The reported efficiency and heat output rate shall be based on
measurements made on the load side of the heat exchanger.
9.5.7 Temperature instrumentation per section 6.6 shall be installed
in the appliance outlet and return lines. The average of the outlet and
return water temperature on the supply side of the system shall be
considered the average appliance temperature for calculation of heat
storage in the appliance (TFavg and TIavg). Installation of a water flow
meter in the supply side of the system is optional.

[[Page 603]]

9.6 Storage Tank. The storage tank shall include a destratification
pump as illustrated in Figure 1. The pump will draw from the bottom of
the tank and return to the top as illustrated. Temperature sensors (TS1
and TS2 in Figure 1) shall be included to measure the temperature in the
recirculation loop. The valve plan in Figure 1 allows the tank
recirculation loop to operate and the boiler/heater-to-heat exchanger
loop to operate at the same time but in isolation. This would typically
be done before the start of a test or following completion of a test to
determine the end of test average tank temperature. The nominal flow
rate in the storage tank recirculation loop can be estimated based on
pump manufacturers' performance curves and any significant restriction
in the recirculation loop.
9.7 Fill the system with water. Determine the total weight of the
water in the appliance when the water is circulating. Verify that the
scale indicates a stable weight under operating conditions. Make sure
air is purged properly.

10.0 Calibration and Standardization

10.1 Water Temperature Sensors. Temperature measuring equipment
shall be calibrated before initial use and at least semi-annually
thereafter. Calibrations shall be in compliance with National Institute
of Standards and Technology (NIST) Monograph 175, Standard Limits of
Error.
10.2 Heat Exchanger Load Side Water Flow Meter.
10.2.1 The heat exchanger load side water flow meter shall be
calibrated within the flow range used for the test run using NIST-
traceable methods. Verify the calibration of the water flow meter before
and after each test run and at least once during each test run by
comparing the water flow rate indicated by the flow meter to the mass of
water collected from the outlet of the heat exchanger over a timed
interval. Volume of the collected water shall be determined based on the
water density calculated from section 13, Eq. 12, using the water
temperature measured at the flow meter. The uncertainty in the
verification procedure used shall be 1 percent or less. The water flow
rate determined by the collection and weighing method shall be within 1
percent of the flow rate indicated by the water flow meter.
10.3 Scales. The scales used to weigh the appliance and test fuel
charge shall be calibrated using NIST-traceable methods at least once
every 6 months.
10.4 Flue Gas Analyzers--In accordance with CSA B415.1-10 (IBR, see
Sec. 60.17), clause 6.8.

11.0 Conditioning

11.1 Prior to testing, an appliance is to be operated for a minimum
of 50 hours using a medium heat draw rate. The conditioning may be at
the manufacturer's facility prior to the certification test. If the
conditioning is at the certification test laboratory, the pre-burn for
the first test can be included as part of the conditioning requirement.
If conditioning is included in pre-burn, then the appliance shall be
aged with fuel meeting the specifications outlined in section 12.2 with
a moisture content between 19 and 25 percent on a dry basis. Operate the
appliance at a medium heat output rate (Category II or III) for at least
10 hours for non-catalytic appliances and 50 hours for catalytic
appliances. Record and report hourly flue gas exit temperature data and
the hours of operation. The aging procedure shall be conducted and
documented by a testing laboratory.

12.0 Procedure

[[Page 604]]

[GRAPHIC] [TIFF OMITTED] TR16MR15.009

Where:

WSliceWet = weight of the slice before drying in pounds
WSliceDry = weight of the slice after drying in pounds
MCSlice = moisture content of the slice in % dry basis

The average moisture content of the entire test load (MC) shall be
determined using Eq. 6. Each individual slice shall have a moisture
content in the range of 18 percent to 28 percent on a dry basis. The
average moisture content for the test fuel load shall be in the range of
19 percent to 25 percent. Moisture shall not be added to previously
dried fuel pieces except by storage under high humidity conditions and
temperature up to 100 [deg]F. Fuel moisture measurement shall begin
within 4 hours of using the fuel batch for a test. Use of a pin-type
meter to estimate the moisture content prior to a test is recommended.
12.2.2 Firebox Volume. Determine the firebox volume in cubic feet.
Firebox volume shall include all areas accessible through the fuel
loading door where firewood could reasonably be placed up to the
horizontal plane defined by the top of the loading door. A drawing of
the firebox showing front, side and plan views or an isometric view with
interior dimensions shall be provided by the manufacturer and verified
by the laboratory. Calculations for firebox volume from computer aided
design (CAD) software programs are acceptable and shall be included in
the test report if used. If the firebox volume is calculated by the
laboratory the firebox drawings and calculations shall be included in
the test report.
12.2.3 Test Fuel charge. Test fuel charges shall be determined by
multiplying the firebox volume by 10 pounds (4.54 kg) per ft\3\ (28L),
or a higher load density as recommended by the manufacturer's printed
operating instructions, of wood (as used wet weight). Select the number
of pieces of cord wood that most nearly match this target weight.
However, the test fuel charge cannot be less than the target of 10
pounds (4.54 kg) per ft\3\ (28L).
12.3 Sampling Equipment. Prepare the particulate emission sampling
equipment as defined by EPA Method 28WHH and the standards referenced
therein.
12.4 Appliance Startup. The appliance shall be fired with wood fuel
of any species, size and moisture content, at the laboratory's
discretion, to bring it up to operating temperature. Operate the
appliance until the water is heated to the upper operating control limit
and has cycled at least two times. Then remove all unburned fuel, zero
the scale and verify the scales accuracy using dead weights.
12.4.1 Startup Procedure for Category III and IV Test Runs, ``Hot-
to-Hot.''
12.4.1.1 Pretest t Burn Cycle. Following appliance startup (section
12.4), reload appliance with oak cord wood and allow it to burn down to
the specified coal bed weight. The pre-test burn cycle fuel charge
weight shall be within 10 percent of the test fuel charge weight. Piece
size and length shall be selected such that charcoalization is achieved
by the time the fuel charge has burned down to the required coal bed
weight. Pieces with a maximum thickness of approximately 2 inches have
been found to be suitable. Charcoalization is a general condition of the
test fuel bed evidenced by an absence of large pieces of burning wood in
the coal bed and the remaining fuel pieces being brittle enough to be
broken into smaller charcoal pieces with a metal poker. Manipulations to
the fuel bed prior to the start of the test run are to be done to
achieve charcoalization while maintaining the desired heat output rate.
During the pre-test burn cycle and at least one hour prior to starting
the test run, adjust water flow to the heat exchanger to establish the
target heat draw for the test. For the first test run the heat draw rate
shall be equal to the manufacturer's rated heat output capacity.
12.4.1.2 Allowable Adjustments. Fuel addition or subtractions, and
coal bed raking shall be kept to a minimum but are allowed up to 15
minutes prior to the start of the test run. For the purposes of this
method, coal bed raking is the use of a metal tool (poker) to stir
coals, break burning fuel into smaller pieces, dislodge fuel pieces from
positions of poor combustion, and check for the condition of
charcoalization. Record all adjustments to and additions or subtractions
of fuel, and any other changes to the appliance operations that occur
during pretest ignition period. During the 15-minute period prior to the
start of the test run, the wood heater loading door shall not be open
more than a total of 1 minute. Coal bed raking is the only adjustment
allowed during this period.
12.4.1.3 Coal Bed Weight. The appliance is to be loaded with the
test fuel charge when the coal bed weight is between 10 percent and 20
percent of the test fuel charge weight. Coals may be raked as necessary
to level the coal bed but may only be raked and stirred

[[Page 605]]

once between 15 to 20 minutes prior to the addition of the test fuel
charge.
12.4.1.4 Storage. The Category III and IV test runs may be done
either with or without the thermal storage. If thermal storage is used,
the initial temperature of the storage must be 125 [deg]F or greater at
the start of the test. The storage may be heated during the pre-test
burn cycle or it may be heated by external means. If thermal storage is
used, prior to the start of the test run, the storage tank
destratification pump, shown in Figure 1, shall be operated until the
total volume pumped exceeds 1.5 times the tank volume and the difference
between the temperature at the top and bottom of the storage tank
(TS1 and TS2) is less than 1 [deg]F. These two
temperatures shall then be recorded to determine the starting average
tank temperature. The total volume pumped may be based on the nominal
flow rate of the destratification pump (See section 9.6). If the
Category III and IV runs are done with storage, it is recognized that
during the last hour of the pre-burn cycle the storage tank must be
mixed to achieve a uniform starting temperature and cannot receive heat
from the boiler/heater during this time. During this time period, the
boiler/heater might cycle or go into a steady reduced output mode.
(Note--this would happen, for example, in a Category IV run if the
actual maximum output of the boiler/heater exceed the manufacturer's
rated output.) A second storage tank may be used temporarily to enable
the boiler/heater to operate during this last hour of the pre-burn
period as it will during the test period. The temperature of this second
storage tank is not used in the calculations but the return water to the
boiler/heater (after mixing device if used) must be 125 [deg]F or
greater.
12.4.2 Startup Procedure for Category I and II Test Runs, ``Cold-to-
Cold.''
12.4.2.1 Initial Temperatures. This test shall be started with both
the boiler/heater and the storage at a minimum temperature of 125
[deg]F. The boiler/heater maximum temperature at the start of this test
shall be 135 [deg]F. The boiler/heater and storage may be heated through
a pre-burn or it may be heated by external means.
12.4.2.2 Firebox Condition at Test Start. Prior to the start of this
test remove all ash and charcoal from the combustion chamber(s). The
loading of the test fuel and kindling should follow the manufacturer's
recommendations, subject to the following constraints: Up to 10 percent
kindling and paper may be used which is in addition to the fuel load.
Further, up to 10 percent of the fuel load (i.e., included in the 10 lb/
ft\3\) may be smaller than the main fuel. This startup fuel shall still
be larger than 2 inches.
12.4.2.3 Storage. The Category I and II test runs shall be done with
thermal storage. The initial temperature of the storage must be 125
[deg]F or greater at the start of the test. The storage may be heated
during the pre-test burn cycle or it may be heated by external means.
Prior to the start of the test run, the storage tank destratification
pump, shown in Figure 1, shall be operated until the total volume pumped
exceeds 1.5 times the tank volume and the difference between the
temperature at the top and bottom of the storage tank (TS1
and TS2) is less than 1 [deg]F. These two temperatures shall
then be recorded to determine the starting average tank temperature. The
total volume pumped may be based on the nominal flow rate of the
destratification pump (See section 9.6).
12.5 Test Runs. For all test runs, the return water temperature to
the hydronic heater must be equal to or greater than 120 [deg]F (this is
lower than the initial tank temperature to allow for any pipeline
losses). Where the storage system is used, flow of water from the
boiler/heater shall be divided between the storage tank and the heat
exchanger such that the temperature change of the circulating water
across the heat exchanger shall be 30 5 [deg]F, averaged over the
entire test run. This is typically adjusted using the system valves.
Complete a test run in each heat output rate category, as follows:
12.5.1 Test Run Start. For Category III and IV runs: Once the
appliance is operating normally and the pretest coal bed weight has
reached the target value per section 12.4.1, tare the scale and load the
full test charge into the appliance. Time for loading shall not exceed 5
minutes. The actual weight of the test fuel charge shall be measured and
recorded within 30 minutes prior to loading. Start all sampling systems.
For Category I and II runs: Once the appliance has reached the
starting temperature, tare the scale and load the full test charge,
including kindling into the appliance. The actual weight of the test
fuel charge shall be measured and recorded within 30 minutes prior to
loading. Light the fire following the manufacturer's written normal
startup procedure. Start all sampling systems.
12.5.1.1 Record all water temperatures, differential water
temperatures and water flow rates at time intervals of one minute or
less.
12.5.1.2 Record particulate emissions data per the requirements of
EPA Method 28WHH and the standards referenced therein.
12.5.1.3 Record data needed to determine overall efficiency (SLM)
per the requirements of CSA B415.1-10 (IBR, see Sec. 60.17) clauses
6.2.1, 6.2.2, 6.3, 8.5.7, 10.4.3(a), 10.4.3(f), and 13.7.9.3
12.5.1.3.1 Measure and record the test room air temperature in
accordance with the requirements of CSA B415.1-10 (IBR, see Sec.
60.17), clauses 6.2.1, 8.5.7 and 10.4.3(g).

[[Page 606]]

12.5.1.3.2 Measure and record the flue gas temperature in accordance
with the requirements of CSA B415.1-10 (IBR, see Sec. 60.17), clauses
6.2.2, 8.5.7 and 10.4.3(f).
12.5.1.3.3 Determine and record the carbon monoxide (CO) and carbon
dioxide (CO2) concentrations in the flue gas in accordance
with CSA B415.1-10 (IBR, see Sec. 60.17), clauses 6.3, 8.5.7 and
10.4.3(i) and (j).
12.5.1.3.4 Measure and record the test fuel weight per the
requirements of CSA B415.1-10 (IBR, see Sec. 60.17), clauses 8.5.7 and
10.4.3(h).
12.5.1.3.5 Record the test run time per the requirements of CSA
B415.1-10 (IBR, see Sec. 60.17), clause 10.4.3(a).
12.5.1.3.6 Record and document all settings and adjustments, if any,
made to the boiler/heater as recommended/required by manufacturer's
instruction manual for different combustion conditions or heat loads.
These may include temperature setpoints, under and over-fire air
adjustment, or other adjustments that could be made by an operator to
optimize or alter combustion. All such settings shall be included in the
report for each test run.
12.5.1.4 Monitor the average heat output rate on the load side of
the heat exchanger based on water temperatures and flow. If the heat
output rate over a 10 minute averaging period gets close to the upper or
lower limit of the target range (5 percent), adjust the water flow
through the heat exchanger to compensate. Make changes as infrequently
as possible while maintaining the target heat output rate. The first
test run shall be conducted at the Category IV heat output rate to
validate that the appliance is capable of producing the manufacturer's
rated heat output capacity.
12.5.2 Test Fuel Charge Adjustment. It is acceptable to adjust the
test fuel charge (i.e., reposition) once during a test run if more than
60 percent of the initial test fuel charge weight has been consumed and
more than 10 minutes have elapsed without a measurable (1 lb or 0.5 kg)
weight change while the operating control is in the demand mode. The
time used to make this adjustment shall be less than 60 seconds.
12.5.3 Test Run Completion. For the Category III and IV, ``hot-to-
hot'' test runs, the test run is completed when the remaining weight of
the test fuel charge is 0.0 lb (0.0 kg). (WFuelBurned = Wfuel) End the
test run when the scale has indicated a test fuel charge weight of 0.0
lb (0.0 kg) or less for 30 seconds.
For the Category I and II ``cold-to-cold'' test runs, the test run
is completed; and the end of a test is defined at the first occurrence
of any one of the following:
(a) The remaining weight of the test fuel charge is less than 1
percent of the total test fuel weight (WFuelBurned > 0.99 Wfuel);
(b) The automatic control system on the boiler/heater switches to an
off mode. In this case, the boiler/heater fan (if used) is typically
stopped and all air flow dampers are closed by the control system. Note
that this off mode cannot be an ``overheat'' or emergency shutdown which
typically requires a manual reset; or
(c) If the boiler/heater does not have an automatic off mode: After
90 percent of the fuel load has been consumed and the scale has
indicated a rate of change of the test fuel charge of less than 1.0 lb/
hr for a period of 10 minutes or longer. Note--this is not considered
``stopped fuel combustion,'' See section 12.5.6.1.
12.5.3.1 At the end of the test run, stop the particulate sampling
train and overall efficiency (SLM) measurements, and record the run
time, and all final measurement values.
12.5.3.2 At the end of the test run, continue to operate the storage
tank destratification pump until the total volume pumped exceeds 1.5
times the tank volume. The maximum average of the top and bottom
temperatures measured after this time may be taken as the average tank
temperature at the end of the tests (TFSavg, See section 13.1). The
total volume pumped may be based on the nominal flow rate of the
destratification pump (See section 9.6).
12.5.3.3 For the Category I and II test runs, there is a need to
determine the energy content of the unburned fuel remaining in the
chamber if the remaining mass in the chamber is greater than 1 percent
of the test fuel weight. Following the completion of the test, as soon
as safely practical, this remaining fuel is removed from the chamber,
separated from the remaining ash and weighed. This separation could be
implemented with a slotted ``scoop'' or similar tool. A \1/4\ inch
opening size in the separation tool shall be used to separate the ash
and charcoal. This separated char is assigned a heating value of 12,500
Btu/lb.
12.5.4 Heat Output Capacity Validation. The first test run must
produce a heat output rate that is within 10 percent of the
manufacturer's rated heat output capacity (Category IV) throughout the
test run and an average heat output rate within 5 percent of the
manufacturer's rated heat output capacity. If the appliance is not
capable of producing a heat output within these limits, the
manufacturer's rated heat output capacity is considered not validated
and testing is to be terminated. In such cases, the tests may be
restarted using a lower heat output capacity if requested by the
manufacturer. Alternatively, during the Category IV run, if the rated
output cannot be maintained for a 15 minute interval, the manufacturer
may elect to reduce the rated output to match the test and complete the
Category IV run on this basis. The target outputs for Categories I, II,
and III shall then be recalculated based on this change in rated output
capacity.
12.5.5 Additional Test Runs. Using the manufacturer's rated heat
output capacity

[[Page 607]]

as a basis, conduct a test for additional heat output categories as
specified in section 4.3. It is not required to run these tests in any
particular order.
12.5.6 Alternative Heat Output Rate for Category I. If an appliance
cannot be operated in the Category I heat output range due to stopped
combustion, two test runs shall be conducted at heat output rates within
Category II. When this is the case, the weightings for the weighted
averages indicated in section 14.1.15 shall be the average of the
Category I and II weighting's and shall be applied to both Category II
results. Appliances that are not capable of operation within Category II
(<25 percent of maximum) cannot be evaluated by this test method.
12.5.6.1 Stopped Fuel Combustion. Evidence that an appliance cannot
be operated at a Category I heat output rate due to stopped fuel
combustion shall include documentation of two or more attempts to
operate the appliance in heat output rate Category I and fuel combustion
has stopped prior to complete consumption of the test fuel charge.
Stopped fuel combustion is evidenced when an elapsed time of 60 minutes
or more has occurred without a measurable (1 lb or 0.5 kg) weight change
in the test fuel charge while the appliance operating control is in the
demand mode. Report the evidence and the reasoning used to determine
that a test in heat output rate Category I cannot be achieved. For
example, two unsuccessful attempts to operate at an output rate of 10
percent of the rated output capacity are not sufficient evidence that
heat output rate Category I cannot be achieved.
12.5.7 Appliance Overheating. Appliances with their associated
thermal storage shall be capable of operating in all heat output
categories without overheating to be rated by this test method.
Appliance overheating occurs when the rate of heat withdrawal from the
appliance is lower than the rate of heat production when the unit
control is in the idle mode. This condition results in the water in the
appliance continuing to increase in temperature well above the upper
limit setting of the operating control. Evidence of overheating
includes: 1 hour or more of appliance water temperature increase above
the upper temperature set-point of the operating control, exceeding the
temperature limit of a safety control device (independent from the
operating control--typically requires manual reset), boiling water in a
non-pressurized system or activation of a pressure or temperature relief
valve in a pressurized system.
12.5.8 Option to Eliminate Tests in Category II and III. Following
successful completion of a test run in Category I, the manufacturer may
eliminate the Category II and III tests. For the purpose of calculating
the annual averages for particulates and efficiency, the values obtained
in the Category I run shall be assumed to apply also to Category II and
Category III. It is envisioned that this option would be applicable to
systems which have sufficient thermal storage such that the fuel load in
the Category I test can be completely consumed without the system
reaching its upper operating temperature limit. In this case, the
boiler/heater would likely be operating at maximum thermal output during
the entire test and this output rate may be higher than the
manufacturer's rated heat output capacity. The Category II and III runs
would then be the same as the Category I run. It may be assumed that the
particulate emission values and efficiency values determined in the
startup, steady-state, and end phases of Category I are applicable in
Categories II and III, for the purpose of determining the annual
averages in lb/mmBtu and g/MJ (See section 13). For the annual average
in g/hr, the length of time for stored heat to be drawn from thermal
storage shall be determined for the test load requirements of the
respective category.
12.5.9 Modification to Measurement Procedure in EPA Method 28WHH to
Determine Emissions Separately During the Startup, Steady-State and End
Phases. With one of the two particulate sampling trains used, filter
changes shall be made at the end of the startup phase and the steady-
state phase (See section 3.0). This shall be done to determine the
particulate emission rate and particulate emission index for the
startup, steady-state, and end phases individually. For this one train,
the particulates measured during each of these three phases shall be
added together to also determine the particulate emissions for the whole
run.
12.5.10 Modification to Measurement Procedure in EPA Method 28WHH
and the Standards Referenced therein on Averaging Period for
Determination of Efficiency by the Stack Loss Method. The methods
currently defined in Method 28WHH allow averaging over 10-minute time
periods for flue gas temperature, flue gas CO2, and flue gas
CO for the determination of the efficiency with the stack loss method.
However, under some cycling conditions the ``on'' period may be short
relative to this 10-minute period. For this reason, during cycling
operation the averaging period for these parameters may not be longer
than the burner on period divided by 10. The averaging period need not
be shorter than one minute. During the off period, under cycling
operation, averaging periods as specified in EPA Method 28WHH and the
standards referenced therein, may be used. Where short averaging times
are used, however, the averaging period for fuel consumption may still
be at 10 minutes. This average wood consumption rate shall be applied to
all of the smaller time intervals included.

[[Page 608]]

12.6 Additional Test Runs. The testing laboratory may conduct more
than one test run in each of the heat output categories specified in
section 4.3. If more than one test run is conducted at a specified heat
output rate, the results from at least two-thirds of the test runs in
that heat output rate category shall be used in calculating the weighted
average emission rate. The measurement data and results of all test runs
shall be reported regardless of which values are used in calculating the
weighted average emission rate.

13.0 Calculation of Results

13.1 Nomenclature

COs--Carbon monoxide measured in the dilution tunnel at
arbitrary time in ppm dry basis.
COg/min--Carbon monoxide emission rate in g/min.
COT--Total carbon monoxide emission for the full test run in
grams.
CO--1--Startup period carbon monoxide emissions in grams.
CO--2--Steady-state period carbon monoxide emission in grams.
CO--3--End period carbon monoxide emission in grams.
ET--Total particulate emissions for the full test run as
determined per EPA Method 28WHH and the standards referenced
therein in grams.
E1--Startup period particulate emissions in grams.
E2--Steady-state period particulate emissions in grams.
E3--End period particulate emissions in grams.
E1--g/kg--Startup period particulate emission index in grams
per kg fuel.
E2--g/kg--Steady-state period particulate emission index in
grams per kg fuel.
E3--g/kg--End period particulate emission index in grams per
kg fuel.
E1--g/hr--Startup period particulate emission rate in grams
per hour.
E2--g/hr--Steady-state period particulate emission rate in
grams per hour.
E3--g/hr--End period particulate emission rate in grams per
hour.
Eg/MJ--Emission rate in grams per MJ of heat output.
Elb/mmBtu output--Emissions rate in pounds per million Btu of
heat output.
Eg/kg--Emissions factor in grams per kilogram of dry fuel
burned.
Eg/hr--Emission factor in grams per hour.
HHV--Higher heating value of fuel = 8600 Btu/lb (19.990 MJ/kg).
LHV--Lower heating value of fuel = 7988 Btu/lb (18.567 MJ/kg).
FT--Temperature difference between cooling water entering and exiting
the heat exchanger.
Qout--Total heat output in Btu (MJ).
Qin--Total heat input available in test fuel charge in Btu's
(MJ).
Qstd--Volumetric flow rate in dilution tunnel in dscfm.
M--Mass flow rate of water in lb/min (kg/min).
Vi--Volume of water indicated by a totalizing flow meter at
the ith reading in gallons (liters).
Vf--Volumetric flow rate of water in heat exchange system in
gallons per minute (liters/min).
K--Total length of burn period in hours (K1 + K2 +
K3).
K1--Length of time of the startup period in hours.
K2--Length of time of the steady-state period in hours.
K3--Length of time of the end period in hours.
K4--Length of time for stored heat to be used following a
burn period in hours.
ti--Data sampling interval in minutes.
jdel--Delivered heating efficiency in percent.
Fi--Weighting factor for heat output category i. (See Table
2.)
T1--Temperature of water at the inlet on the supply side of the heat
exchanger, [deg]F.
T2--Temperature of the water at the outlet on the supply side of the
heat exchanger, [deg]F.
T3--Temperature of cooling water at the inlet to the load side of the
heat exchanger, [deg]F.
T4--Temperature of cooling water at the outlet of the load side of the
heat exchanger, [deg]F.
T5--Temperature of the hot water supply as it leaves the boiler/heater,
[deg]F.
T6--Temperature of return water as it enters the boiler/heater, [deg]F.
T7--Temperature in the boiler/heater optional destratification loop at
the top of the boiler/heater, [deg]F.
T8--Temperature in the boiler/heater optional destratification loop at
the bottom of the boiler/heater, [deg]F.
TIavg--Average temperature of the appliance and water at
start of the test.
[GRAPHIC] [TIFF OMITTED] TR16MR15.032

TFavg--Average temperature of the appliance and water at the
end of the test.

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[GRAPHIC] [TIFF OMITTED] TR16MR15.033

TIS1--Temperature at the inlet to the storage system at the
start of the test.
TIS2--Temperature at the outlet from the storage system at
the start of the test.
TFS1--Temperature at the inlet to the storage system at the
end of the test.
TFS2--Temperature at the outlet from the storage system at
the end of the test.
TISavg--Average temperature of the storage system at the
start of the test.
[GRAPHIC] [TIFF OMITTED] TR16MR15.034

TFSavg--Average temperature of the storage system at the end
of the test.
[GRAPHIC] [TIFF OMITTED] TR16MR15.035

MC--Fuel moisture content in percent dry basis.
m--Density of water in pounds per gallon.
mInitial--Density of water in the boiler/heater system at the
start of the test in pounds per gallons.
mboiler/heater--Density of water in the boiler/heater system
at an arbitrary time during the test in pounds per gallon.
Cp--Specific heat of water in Btu/lb, [deg]F.
Csteel--Specific heat of steel (0.1 Btu/lb, [deg]F).
Vboiler/heater--total volume of water in the boiler/heater
system on the weight scale in gallons.
Wfuel--Fuel charge weight, as-fired or ``wet'', in pounds
(kg).
Wfuel--1--Fuel consumed during the startup period in pounds
(kg).
Wfuel--2--Fuel consumed during the steady state period in
pounds (kg).
Wfuel--3--Fuel consumed during the end period in pounds (kg).
WFuelBurned--Weight of fuel that has been burned from the
start of the test to an arbitrary time, including the needed
correction for the change in density and weight of the water
in the boiler/heater system on the scale in pounds (kg).
WRemainingFuel--Weight of unburned fuel separated from the
ash at the end of a test. Useful only for Category I and
Category II tests.
Wapp--Weight of empty appliance in pounds (kg).
Wwat--Weight of water in supply side of the system in pounds
(kg).
WScaleInitial--Weight reading on the scale at the start of
the test, just after the test load has been added in pounds
(kg).
WScale--Reading of the weight scale at an arbitrary time
during the test run in pounds (kg).
WStorageTank--Weight of the storage tank empty in pounds
(kg).
WWaterStorage--Weight of the water in the storage tank at
TISavg in pounds (kg).

13.2 After the test is completed, determine the particulate
emissions ET in accordance with EPA Method 28WHH and the
standards referenced therein.
13.3 Determination of the weight of fuel that has been burned at an
arbitrary time.
For the purpose of tracking the consumption of the test fuel load
during a test run the following may be used to calculate the weight of
fuel that burned since the start of the test:
[GRAPHIC] [TIFF OMITTED] TR16MR15.036

Water density, m, is calculated using Equation 12.

13.4 Determine Average Fuel Load Moisture Content.

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[GRAPHIC] [TIFF OMITTED] TR16MR15.037

13.5 Determine Heat Input.
[GRAPHIC] [TIFF OMITTED] TR16MR15.038

13.5.1 Correction to Qin for the Category I and II tests,
where there is greater than 1 percent of the test fuel charge in the
chamber at the end of the test period.
[GRAPHIC] [TIFF OMITTED] TR16MR15.044

13.6 Determine Heat Output, Efficiency, and Emissions.
13.6.1 Determine heat output as:
Qout = M [Heat output determined for each sampling time
interval] + Change in heat stored in the appliance + Change in heat in
storage tank.
[GRAPHIC] [TIFF OMITTED] TR16MR15.039

Note: The subscript (i) indicates the parameter value for sampling
time interval ti.Mi = Mass flow rate = gal/min x
density of water (lb/gal) = lb/min.
[GRAPHIC] [TIFF OMITTED] TR16MR15.040

Csteel = 0.1 Btu/lb, -[deg] F.
[GRAPHIC] [TIFF OMITTED] TR16MR15.041

Note: Vi is the total water volume at the end of interval
i and Vi-1 is the total water volume at the beginning of the
time interval. This calculation is necessary when a totalizing type
water meter is used.
13.6.2 Determine Heat Output Rate Over Burn Period (K1 +
K2 + K3) as:

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[GRAPHIC] [TIFF OMITTED] TR16MR15.042

13.6.3 Determine Emission Rates and Emission Factors as:
[GRAPHIC] [TIFF OMITTED] TR16MR15.043

If thermal storage is not used in a Category III or IV run, then
K4 = 0.

E1--g/kg = E1/(Wfuel--1/(1 + MC/
100)), g/dry kg.
E2--g/kg = E2/(Wfuel--2/(1 + MC/
100)), g/dry kg.
E3--g/kg = E3/(Wfuel--3/(1 + MC/
100)), g/dry kg.
E1--g/hr = E1/K1, g/hr.
E2--g/hr = E2/K2, g/hr.
E3--g/hr = E3/K3, g/hr.
13.6.4 Determine delivered efficiency as:
[GRAPHIC] [TIFF OMITTED] TR16MR15.014

13.6.5 Determine jSLM--Overall Efficiency, also known as
Stack Loss Efficiency, using stack loss method (SLM).
For determination of the average overall thermal efficiency
(jSLM) for the test run, use the data collected over the full
test run and the calculations in accordance with CSA B415.1-10 (IBR, see
Sec. 60.17), clause 13.7 except for 13.7.2(e), (f), (g), and (h), use
the following average fuel properties for oak: %C = 50.0, %H = 6.6, %O =
43.2, %Ash = 0.2.
13.6.5.1 Whenever the CSA B415.1-10 (IBR, see Sec. 60.17) overall
efficiency is found to be lower than the overall efficiency based on
load side measurements, as determined by Eq. 22 of this method, section
14.1.7 of the test report must include a discussion of the reasons for
this result. For a test where the CSA B415.1-10 overall efficiency SLM
is less than 2 percentage points lower than the overall efficiency based
on load side measurements, the efficiency based on load side
measurements shall be considered invalid. [Note on the rationale for the
2 percentage points limit. The SLM method does not include boiler/heater
jacket losses and, for this reason, should provide an efficiency which
is actually higher than the efficiency based on the energy input and
output measurements or ``delivered efficiency.'' A delivered efficiency
that is higher than the efficiency based on the SLM could be considered
suspect. A delivered efficiency greater than 2 percentage points higher
than the efficiency based on the SLM, then, clearly indicates a
measurement error.]
13.6.6 Carbon Monoxide Emissions
For each minute of the test period, the carbon monoxide emission
rate shall be calculated as:
[GRAPHIC] [TIFF OMITTED] TR16MR15.015

Total CO emissions for each of the three test periods
(CO--1, CO--2, CO--3) shall be
calculated as the sum of the emission rates for each of the 1-minute
intervals. Total CO emission for the test run, COT, shall be
calculated as the sum of CO--1, CO--2, and
CO--3.

[[Page 612]]

13.7 Weighted Average Emissions and Efficiency.
13.7.1 Determine the weighted average emission rate and delivered
efficiency from the individual tests in the specified heat output
categories. The weighting factors (Fi) are derived from an
analysis of ASHRAE bin data which provides details of normal building
heating requirements in terms of percent of design capacity and time in
a particular capacity range--or ``bin''--over the course of a heating
season. The values used in this method represent an average of data from
several cities located in the northern United States.
[GRAPHIC] [TIFF OMITTED] TR16MR15.016

If, as discussed in section 12.5.8, the option to eliminate tests in
Category II and III is elected, the values of efficiency and particulate
emission rate as measured in Category I, shall be assigned also to
Category II and III for the purpose of determining the annual averages.

14.0 Report

14.1.1 The report shall include the following:
14.1.2 Name and location of the laboratory conducting the test.
14.1.3 A description of the appliance tested and its condition, date
of receipt and dates of tests.
14.1.4 A description of the minimum amount of external thermal
storage that is required for use with this system. This shall be
specified both in terms of volume in gallons and stored energy content
in Btu with a storage temperature ranging from 125 [deg]F to the
manufacturer's specified setpoint temperature.
14.1.5 A statement that the test results apply only to the specific
appliance tested.
14.1.6 A statement that the test report shall not be reproduced
except in full, without the written approval of the laboratory.
14.1.7 A description of the test procedures and test equipment
including a schematic or other drawing showing the location of all
required test equipment. Also, a description of test fuel sourcing,
handling and storage practices shall be included.
14.1.8 Details of deviations from, additions to or exclusions from
the test method, and their data quality implications on the test results
(if any), as well as information on specific test conditions, such as
environmental conditions.
14.1.9 A list of participants and their roles and observers present
for the tests.
14.1.10 Data and drawings indicating the fire box size and location
of the fuel charge.
14.1.11 Drawings and calculations used to determine firebox volume.
14.1.12 Information for each test run fuel charge including piece
size, moisture content and weight.
14.1.13 All required data and applicable blanks for each test run
shall be provided in spreadsheet format both in the printed report and
in a computer file such that the data can be easily analyzed and
calculations easily verified. Formulas used for all calculations shall
be accessible for review.
14.1.14 For each test run, K1,K2,
K3, the total CO and particulate emission for each of these
three periods, and K4.
14.1.15 Calculated results for delivered efficiency at each heat
output rate and the weighted average emissions reported as total
emissions in grams, pounds per mm Btu of delivered heat, grams per MJ of
delivered heat, grams per kilogram of dry fuel and grams per hour.
Results shall be reported for each heat output category and the weighted
average.
14.1.16 Tables 1A, 1B, 1C, 1D, 1E and Table 2 must be used for
presentation of results in test reports.
14.1.17 A statement of the estimated uncertainty of measurement of
the emissions and efficiency test results.
14.1.18 A plot of CO emission rate in grams/minute vs. time, based
on 1 minute averages, for the entire test period, for each run.
14.1.19 A plot of estimated boiler/heater energy release rate in
Btu/hr based on 10 minute averages, for the entire test period, for each
run. This will be calculated from the fuel used, the wood heating value
and moisture content, and the SLM efficiency during each 10 minute
period.
14.1.20 Raw data, calibration records, and other relevant
documentation shall be retained by the laboratory for a minimum of 7
years.

15.0 Precision and Bias

15.1 Precision--It is not possible to specify the precision of the
procedure in this test method because the appliance operation and

[[Page 613]]

fueling protocols and the appliances themselves produce variable amounts
of emissions and cannot be used to determine reproducibility or
repeatability of this test method.
15.2 Bias--No definitive information can be presented on the bias of
the procedure in this test method for measuring solid fuel burning
hydronic heater emissions because no material having an accepted
reference value is available.

16.0 Keywords

16.1 Solid fuel, hydronic heating appliances, wood-burning hydronic
heaters, partial thermal storage.

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[GRAPHIC] [TIFF OMITTED] TR16MR15.018

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[GRAPHIC] [TIFF OMITTED] TR16MR15.020

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[GRAPHIC] [TIFF OMITTED] TR16MR15.021

Method 29--Determination of Metals Emissions From Stationary Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 5 and Method 12.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Antimony (Sb)........................................... 7440-36-0
Arsenic (As)............................................ 7440-38-2
Barium (Ba)............................................. 7440-39-3
Beryllium (Be).......................................... 7440-41-7
Cadmium (Cd)............................................ 7440-43-9
Chromium (Cr)........................................... 7440-47-3
Cobalt (Co)............................................. 7440-48-4
Copper (Cu)............................................. 7440-50-8
Lead (Pb)............................................... 7439-92-1
Manganese (Mn).......................................... 7439-96-5
Mercury (Hg)............................................ 7439-97-6
Nickel (Ni)............................................. 7440-02-0
Phosphorus (P).......................................... 7723-14-0
Selenium (Se)........................................... 7782-49-2
Silver (Ag)............................................. 7440-22-4
Thallium (Tl)........................................... 7440-28-0
Zinc (Zn)............................................... 7440-66-6
------------------------------------------------------------------------

1.2 Applicability. This method is applicable to the determination of
metals emissions from stationary sources. This method may be used to
determine particulate emissions in addition to the metals emissions if
the prescribed procedures and precautions are followed.
1.2.1 Hg emissions can be measured, alternatively, using EPA Method
101A of Appendix B, 40 CFR Part 61. Method 101-A measures only Hg but it
can be of special interest to sources which need to measure both Hg and
Mn emissions.

2.0 Summary of Method

2.1 Principle. A stack sample is withdrawn isokinetically from the
source, particulate emissions are collected in the probe and on a heated
filter, and gaseous emissions are then collected in an aqueous acidic
solution of hydrogen peroxide (analyzed for all metals including Hg) and
an aqueous acidic solution of potassium permanganate (analyzed only for
Hg). The recovered samples are digested, and appropriate fractions are
analyzed for Hg by cold vapor atomic absorption spectroscopy (CVAAS) and
for Sb, As, Ba, Be, Cd, Cr, Co,

[[Page 619]]

Cu, Pb, Mn, Ni, P, Se, Ag, Tl, and Zn by inductively coupled argon
plasma emission spectroscopy (ICAP) or atomic absorption spectroscopy
(AAS). Graphite furnace atomic absorption spectroscopy (GFAAS) is used
for analysis of Sb, As, Cd, Co, Pb, Se, and Tl if these elements require
greater analytical sensitivity than can be obtained by ICAP. If one so
chooses, AAS may be used for analysis of all listed metals if the
resulting in-stack method detection limits meet the goal of the testing
program. Similarly, inductively coupled plasma-mass spectroscopy (ICP-
MS) may be used for analysis of Sb, As, Ba, Be, Cd, Cr, Co, Cu, Pb, Mn,
Ni, Ag, Tl and Zn.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Iron (Fe) can be a spectral interference during the analysis of
As, Cr, and Cd by ICAP. Aluminum (Al) can be a spectral interference
during the analysis of As and Pb by ICAP. Generally, these interferences
can be reduced by diluting the analytical sample, but such dilution
raises the in-stack detection limits. Background and overlap corrections
may be used to adjust for spectral interferences. Refer to Method 6010
of Reference 2 in section 16.0 or the other analytical methods used for
details on potential interferences to this method. For all GFAAS
analyses, use matrix modifiers to limit interferences, and matrix match
all standards.

5.0 Safety

5.1 Disclaimer. This method may involve hazardous materials,
operations, and equipment. This test method may not address all of the
safety problems associated with its use. It is the responsibility of the
user of this test method to establish appropriate safety and health
practices and to determine the applicability of regulatory limitations
prior to performing this test method.
5.2 Corrosive Reagents. The following reagents are hazardous.
Personal protective equipment and safe procedures are useful in
preventing chemical splashes. If contact occurs, immediately flush with
copious amounts of water at least 15 minutes. Remove clothing under
shower and decontaminate. Treat residual chemical burn as thermal burn.
5.2.1 Nitric Acid (HNO3). Highly corrosive to eyes, skin,
nose, and lungs. Vapors cause bronchitis, pneumonia, or edema of lungs.
Reaction to inhalation may be delayed as long as 30 hours and still be
fatal. Provide ventilation to limit exposure. Strong oxidizer. Hazardous
reaction may occur with organic materials such as solvents.
5.2.2 Sulfuric Acid (H2SO4). Rapidly
destructive to body tissue. Will cause third degree burns. Eye damage
may result in blindness. Inhalation may be fatal from spasm of the
larynx, usually within 30 minutes. May cause lung tissue damage with
edema. 1 mg/m\3\ for 8 hours will cause lung damage or, in higher
concentrations, death. Provide ventilation to limit inhalation. Reacts
violently with metals and organics.
5.2.3 Hydrochloric Acid (HC1). Highly corrosive liquid with toxic
vapors. Vapors are highly irritating to eyes, skin, nose, and lungs,
causing severe damage. May cause bronchitis, pneumonia, or edema of
lungs. Exposure to concentrations of 0.13 to 0.2 percent can be lethal
to humans in a few minutes. Provide ventilation to limit exposure.
Reacts with metals, producing hydrogen gas.
5.2.4 Hydrofluoric Acid (HF). Highly corrosive to eyes, skin, nose,
throat, and lungs. Reaction to exposure may be delayed by 24 hours or
more. Provide ventilation to limit exposure.
5.2.5 Hydrogen Peroxide (H2O2). Irritating to
eyes, skin, nose, and lungs. 30% H2O2 is a strong
oxidizing agent. Avoid contact with skin, eyes, and combustible
material. Wear gloves when handling.
5.2.6 Potassium Permanganate (KMnO4). Caustic, strong
oxidizer. Avoid bodily contact with.
5.2.7 Potassium Persulfate. Strong oxidizer. Avoid bodily contact
with. Keep containers well closed and in a cool place.
5.3 Reaction Pressure. Due to the potential reaction of the
potassium permanganate with the acid, there could be pressure buildup in
the acidic KMnO4 absorbing solution storage bottle. Therefore
these bottles shall not be fully filled and shall be vented to relieve
excess pressure and prevent explosion potentials. Venting is required,
but not in a manner that will allow contamination of the solution. A No.
70-72 hole drilled in the container cap and Teflon liner has been used.

6.0 Equipment and Supplies

6.1 Sampling. A schematic of the sampling train is shown in Figure
29-1. It has general similarities to the Method 5 train.
6.1.1 Probe Nozzle (Probe Tip) and Borosilicate or Quartz Glass
Probe Liner. Same as Method 5, sections 6.1.1.1 and 6.1.1.2, except that
glass nozzles are required unless alternate tips are constructed of
materials that are free from contamination and will not interfere with
the sample. If a probe tip other than glass is used, no correction to
the sample test results to compensate for the nozzle's effect on the
sample is allowed. Probe fittings of plastic such as Teflon,
polypropylene, etc. are recommended instead of metal fittings to prevent
contamination. If one chooses to do so, a single glass piece consisting
of a combined probe tip and probe liner may be used.
6.1.2 Pitot Tube and Differential Pressure Gauge. Same as Method 2,
sections 6.1 and 6.2, respectively.

[[Page 620]]

6.1.3 Filter Holder. Glass, same as Method 5, section 6.1.1.5,
except use a Teflon filter support or other non-metallic, non-
contaminating support in place of the glass frit.
6.1.4 Filter Heating System. Same as Method 5, section 6.1.1.6.
6.1.5 Condenser. Use the following system for condensing and
collecting gaseous metals and determining the moisture content of the
stack gas. The condensing system shall consist of four to seven
impingers connected in series with leak-free ground glass fittings or
other leak-free, non-contaminating fittings. Use the first impinger as a
moisture trap. The second impinger (which is the first HNO3/
H2O2 impinger) shall be identical to the first
impinger in Method 5. The third impinger (which is the second
HNO3/H2O2 impinger) shall be a
Greenburg Smith impinger with the standard tip as described for the
second impinger in Method 5, section 6.1.1.8. The fourth (empty)
impinger and the fifth and sixth (both acidified KMnO4)
impingers are the same as the first impinger in Method 5. Place a
temperature sensor capable of measuring to within 1 [deg]C (2 [deg]F) at
the outlet of the last impinger. If no Hg analysis is planned, then the
fourth, fifth, and sixth impingers are not used.
6.1.6 Metering System, Barometer, and Gas Density Determination
Equipment. Same as Method 5, sections 6.1.1.9, 6.1.2, and 6.1.3,
respectively.
6.1.7 Teflon Tape. For capping openings and sealing connections, if
necessary, on the sampling train.
6.2 Sample Recovery. Same as Method 5, sections 6.2.1 through 6.2.8
(Probe-Liner and Probe-Nozzle Brushes or Swabs, Wash Bottles, Sample
Storage Containers, Petri Dishes, Glass Graduated Cylinder, Plastic
Storage Containers, Funnel and Rubber Policeman, and Glass Funnel),
respectively, with the following exceptions and additions:
6.2.1 Non-metallic Probe-Liner and Probe-Nozzle Brushes or Swabs.
Use non-metallic probe-liner and probe-nozzle brushes or swabs for
quantitative recovery of materials collected in the front-half of the
sampling train.
6.2.2 Sample Storage Containers. Use glass bottles (see section 8.1
of this Method) with Teflon-lined caps that are non-reactive to the
oxidizing solutions, with capacities of 1000- and 500-ml, for storage of
acidified KMnO4--containing samples and blanks. Glass or
polyethylene bottles may be used for other sample types.
6.2.3 Graduated Cylinder. Glass or equivalent.
6.2.4 Funnel. Glass or equivalent.
6.2.5 Labels. For identifying samples.
6.2.6 Polypropylene Tweezers and/or Plastic Gloves. For recovery of
the filter from the sampling train filter holder.
6.3 Sample Preparation and Analysis.
6.3.1 Volumetric Flasks, 100-ml, 250-ml, and 1000-ml. For
preparation of standards and sample dilutions.
6.3.2 Graduated Cylinders. For preparation of reagents.
6.3.3 Parr Bombs or Microwave Pressure Relief Vessels with Capping
Station (CEM Corporation model or equivalent). For sample digestion.
6.3.4 Beakers and Watch Glasses. 250-ml beakers, with watch glass
covers, for sample digestion.
6.3.5 Ring Stands and Clamps. For securing equipment such as
filtration apparatus.
6.3.6 Filter Funnels. For holding filter paper.
6.3.7 Disposable Pasteur Pipets and Bulbs.
6.3.8 Volumetric Pipets.
6.3.9 Analytical Balance. Accurate to within 0.1 mg.
6.3.10 Microwave or Conventional Oven. For heating samples at fixed
power levels or temperatures, respectively.
6.3.11 Hot Plates.
6.3.12 Atomic Absorption Spectrometer (AAS). Equipped with a
background corrector.
6.3.12.1 Graphite Furnace Attachment. With Sb, As, Cd, Co, Pb, Se,
and Tl hollow cathode lamps (HCLs) or electrodeless discharge lamps
(EDLs). Same as Reference 2 in section 16.0. Methods 7041 (Sb), 7060
(As), 7131 (Cd), 7201 (Co), 7421 (Pb), 7740 (Se), and 7841 (Tl).
6.3.12.2 Cold Vapor Mercury Attachment. With a mercury HCL or EDL,
an air recirculation pump, a quartz cell, an aerator apparatus, and a
heat lamp or desiccator tube. The heat lamp shall be capable of raising
the temperature at the quartz cell by 10 [deg]C above ambient, so that
no condensation forms on the wall of the quartz cell. Same as Method
7470 in Reference 2 in section 16.0. See note 2: section 11.1.3 for
other acceptable approaches for analysis of Hg in which analytical
detection limits of 0.002 ng/ml were obtained.
6.3.13 Inductively Coupled Argon Plasma Spectrometer. With either a
direct or sequential reader and an alumina torch. Same as EPA Method
6010 in Reference 2 in section 16.0.
6.3.14 Inductively Coupled Plasma-Mass Spectrometer.
Same as EPA Method 6020 in Reference 2 in section 16.0.

7.0 Reagents and Standards

7.1 Unless otherwise indicated, it is intended that all reagents
conform to the specifications established by the Committee on Analytical
Reagents of the American Chemical Society, where such specifications are
available. Otherwise, use the best available grade.
7.2 Sampling Reagents.
7.2.1 Sample Filters. Without organic binders. The filters shall
contain less than 1.3 g/

[[Page 621]]

in.\2\ of each of the metals to be measured. Analytical results provided
by filter manufacturers stating metals content of the filters are
acceptable. However, if no such results are available, analyze filter
blanks for each target metal prior to emission testing. Quartz fiber
filters meeting these requirements are recommended. However, if glass
fiber filters become available which meet these requirements, they may
be used. Filter efficiencies and unreactiveness to sulfur dioxide
(SO2) or sulfur trioxide (SO3) shall be as
described in section 7.1.1 of Method 5.
7.2.2 Water. To conform to ASTM Specification D1193-77 or 91, Type
II (incorporated by reference--see Sec. 60.17). If necessary, analyze
the water for all target metals prior to field use. All target metals
should be less than 1 ng/ml.
7.2.3 HNO3, Concentrated. Baker Instra-analyzed or
equivalent.
7.2.4 HCl, Concentrated. Baker Instra-analyzed or equivalent.
7.2.5 H2O2, 30 Percent (V/V).
7.2.6 KMnO4.
7.2.7 H2SO4, Concentrated.
7.2.8 Silica Gel and Crushed Ice. Same as Method 5, sections 7.1.2
and 7.1.4, respectively.
7.3 Pretest Preparation of Sampling Reagents.
7.3.1 HNO3/H2O2 Absorbing Solution,
5 Percent HNO3/10 Percent H2O2. Add
carefully with stirring 50 ml of concentrated HNO3 to a 1000-
ml volumetric flask containing approximately 500 ml of water, and then
add carefully with stirring 333 ml of 30 percent
H2O2. Dilute to volume with water. Mix well. This
reagent shall contain less than 2 ng/ml of each target metal.
7.3.2 Acidic KMnO4 Absorbing Solution, 4 Percent
KMnO4 (W/V), 10 Percent H2SO4 (V/V).
Prepare fresh daily. Mix carefully, with stirring, 100 ml of
concentrated H2SO4 into approximately 800 ml of
water, and add water with stirring to make a volume of 1 liter: this
solution is 10 percent H2SO4 (V/V). Dissolve, with
stirring, 40 g of KMnO4 into 10 percent
H2SO4 (V/V) and add 10 percent
H2SO4 (V/V) with stirring to make a volume of 1
liter. Prepare and store in glass bottles to prevent degradation. This
reagent shall contain less than 2 ng/ml of Hg.
Precaution: To prevent autocatalytic decomposition of the
permanganate solution, filter the solution through Whatman 541 filter
paper.
7.3.3 HNO3, 0.1 N. Add with stirring 6.3 ml of
concentrated HNO3 (70 percent) to a flask containing
approximately 900 ml of water. Dilute to 1000 ml with water. Mix well.
This reagent shall contain less than 2 ng/ml of each target metal.
7.3.4 HCl, 8 N. Carefully add with stirring 690 ml of concentrated
HCl to a flask containing 250 ml of water. Dilute to 1000 ml with water.
Mix well. This reagent shall contain less than 2 ng/ml of Hg.
7.4 Glassware Cleaning Reagents.
7.4.1 HNO3, Concentrated. Fisher ACS grade or equivalent.
7.4.2 Water. To conform to ASTM Specifications D1193, Type II.
7.4.3 HNO3, 10 Percent (V/V). Add with stirring 500 ml of
concentrated HNO3 to a flask containing approximately 4000 ml
of water. Dilute to 5000 ml with water. Mix well. This reagent shall
contain less than 2 ng/ml of each target metal.
7.5 Sample Digestion and Analysis Reagents. The metals standards,
except Hg, may also be made from solid chemicals as described in
Reference 3 in section 16.0. Refer to References 1, 2, or 5 in section
16.0 for additional information on Hg standards. The 1000 g/ml
Hg stock solution standard may be made according to section 7.2.7 of
Method 101A.
7.5.1 HCl, Concentrated.
7.5.2 HF, Concentrated.
7.5.3 HNO3, Concentrated. Baker Instra-analyzed or
equivalent.
7.5.4 HNO3, 50 Percent (V/V). Add with stirring 125 ml of
concentrated HNO3 to 100 ml of water. Dilute to 250 ml with
water. Mix well. This reagent shall contain less than 2 ng/ml of each
target metal.
7.5.5 HNO3, 5 Percent (V/V). Add with stirring 50 ml of
concentrated HNO3 to 800 ml of water. Dilute to 1000 ml with
water. Mix well. This reagent shall contain less than 2 ng/ml of each
target metal.
7.5.6 Water. To conform to ASTM Specifications D1193, Type II.
7.5.7 Hydroxylamine Hydrochloride and Sodium Chloride Solution. See
Reference 2 In section 16.0 for preparation.
7.5.8 Stannous Chloride. See Reference 2 in section 16.0 for
preparation.
7.5.9 KMnO4, 5 Percent (W/V). See Reference 2 in section
16.0 for preparation.
7.5.10 H2SO4, Concentrated.
7.5.11 Potassium Persulfate, 5 Percent (W/V). See Reference 2 in
section 16.0 for preparation.
7.5.12 Nickel Nitrate, Ni(N03) 2
6H20.
7.5.13 Lanthanum Oxide, La203.
7.5.14 Hg Standard (AAS Grade), 1000 g/ml.
7.5.15 Pb Standard (AAS Grade), 1000 g/ml.
7.5.16 As Standard (AAS Grade), 1000 g/ml.
7.5.17 Cd Standard (AAS Grade), 1000 g/ml.
7.5.18 Cr Standard (AAS Grade), 1000 g/ml.
7.5.19 Sb Standard (AAS Grade), 1000 g/ml.
7.5.20 Ba Standard (AAS Grade), 1000 g/ml.
7.5.21 Be Standard (AAS Grade), 1000 g/ml.
7.5.22 Co Standard (AAS Grade), 1000 g/ml.
7.5.23 Cu Standard (AAS Grade), 1000 g/ml.
7.5.24 Mn Standard (AAS Grade), 1000 g/ml.
7.5.25 Ni Standard (AAS Grade), 1000 g/ml.
7.5.26 P Standard (AAS Grade), 1000 g/ml.
7.5.27 Se Standard (AAS Grade), 1000 g/ml.
7.5.28 Ag Standard (AAS Grade), 1000 g/ml.

[[Page 622]]

7.5.29 Tl Standard (AAS Grade), 1000 g/ml.
7.5.30 Zn Standard (AAS Grade), 1000 g/ml.
7.5.31 Al Standard (AAS Grade), 1000 g/ml.
7.5.32 Fe Standard (AAS Grade), 1000 g/ml.
7.5.33 Hg Standards and Quality Control Samples. Prepare fresh
weekly a 10 g/ml intermediate Hg standard by adding 5 ml of
1000 g/ml Hg stock solution prepared according to Method 101A
to a 500-ml volumetric flask; dilute with stirring to 500 ml by first
carefully adding 20 ml of 15 percent HNO3 and then adding
water to the 500-ml volume. Mix well. Prepare a 200 ng/ml working Hg
standard solution fresh daily: add 5 ml of the 10 g/ml
intermediate standard to a 250-ml volumetric flask, and dilute to 250 ml
with 5 ml of 4 percent KMnO4, 5 ml of 15 percent
HNO3, and then water. Mix well. Use at least five separate
aliquots of the working Hg standard solution and a blank to prepare the
standard curve. These aliquots and blank shall contain 0.0, 1.0, 2.0,
3.0, 4.0, and 5.0 ml of the working standard solution containing 0, 200,
400, 600, 800, and 1000 ng Hg, respectively. Prepare quality control
samples by making a separate 10 g/ml standard and diluting
until in the calibration range.
7.5.34 ICAP Standards and Quality Control Samples. Calibration
standards for ICAP analysis can be combined into four different mixed
standard solutions as follows:

Mixed Standard Solutions for ICAP Analysis
------------------------------------------------------------------------
Solution Elements
------------------------------------------------------------------------
I................................. As, Be, Cd, Mn, Pb, Se, Zn.
II................................ Ba, Co, Cu, Fe.
III............................... Al, Cr, Ni.
IV................................ Ag, P, Sb, Tl.
------------------------------------------------------------------------

Prepare these standards by combining and diluting the appropriate
volumes of the 1000 g/ml solutions with 5 percent
HNO3. A minimum of one standard and a blank can be used to
form each calibration curve. However, prepare a separate quality control
sample spiked with known amounts of the target metals in quantities in
the mid-range of the calibration curve. Suggested standard levels are 25
g/ml for Al, Cr and Pb, 15 g/ml for Fe, and 10
g/ml for the remaining elements. Prepare any standards
containing less than 1 g/ml of metal on a daily basis.
Standards containing greater than 1 g/ml of metal should be
stable for a minimum of 1 to 2 weeks. For ICP-MS, follow Method 6020 in
EPA Publication SW-846 Third Edition (November 1986) including updates
I, II, IIA, IIB and III, as incorporated by reference in Sec. 60.17(i).
7.5.35 GFAAS Standards. Sb, As, Cd, Co, Pb, Se, and Tl. Prepare a 10
g/ml standard by adding 1 ml of 1000 g/ml standard to
a 100-ml volumetric flask. Dilute with stirring to 100 ml with 10
percent HNO3. For GFAAS, matrix match the standards. Prepare
a 100 ng/ml standard by adding 1 ml of the 10 g/ml standard to
a 100-ml volumetric flask, and dilute to 100 ml with the appropriate
matrix solution. Prepare other standards by diluting the 100 ng/ml
standards. Use at least five standards to make up the standard curve.
Suggested levels are 0, 10, 50, 75, and 100 ng/ml. Prepare quality
control samples by making a separate 10 g/ml standard and
diluting until it is in the range of the samples. Prepare any standards
containing less than 1 g/ml of metal on a daily basis.
Standards containing greater than 1 g/ml of metal should be
stable for a minimum of 1 to 2 weeks.
7.5.36 Matrix Modifiers.
7.5.36.1 Nickel Nitrate, 1 Percent (V/V). Dissolve 4.956 g of
Ni(N03)26H20 or other nickel compound
suitable for preparation of this matrix modifier in approximately 50 ml
of water in a 100-ml volumetric flask. Dilute to 100 ml with water.
7.5.36.2 Nickel Nitrate, 0.1 Percent (V/V). Dilute 10 ml of 1
percent nickel nitrate solution to 100 ml with water. Inject an equal
amount of sample and this modifier into the graphite furnace during
GFAAS analysis for As.
7.5.36.3 Lanthanum. Carefully dissolve 0.5864 g of
La203 in 10 ml of concentrated HN03,
and dilute the solution by adding it with stirring to approximately 50
ml of water. Dilute to 100 ml with water, and mix well. Inject an equal
amount of sample and this modifier into the graphite furnace during
GFAAS analysis for Pb.
7.5.37 Whatman 40 and 541 Filter Papers (or equivalent). For
filtration of digested samples.

8.0 Sample Collection, Preservation, Transport, and Storage

8.1 Sampling. The complexity of this method is such that, to obtain
reliable results, both testers and analysts must be trained and
experienced with the test procedures, including source sampling; reagent
preparation and handling; sample handling; safety equipment and
procedures; analytical calculations; reporting; and the specific
procedural descriptions throughout this method.
8.1.1 Pretest Preparation. Follow the same general procedure given
in Method 5, section 8.1, except that, unless particulate emissions are
to be determined, the filter need not be desiccated or weighed. First,
rinse all sampling train glassware with hot tap water and then wash in
hot soapy water. Next, rinse glassware three times with tap water,
followed by three additional rinses with water. Then soak all glassware
in a 10 percent (V/V) nitric acid solution for a minimum of 4 hours,
rinse three times with water, rinse a final time with acetone, and allow
to air dry. Cover all glassware openings where contamination can occur
until the sampling train is assembled for sampling.

[[Page 623]]

8.1.2 Preliminary Determinations. Same as Method 5, section 8.1.2.
8.1.3 Preparation of Sampling Train.
8.1.3.1 Set up the sampling train as shown in Figure 29-1. Follow
the same general procedures given in Method 5, section 8.3, except place
100 ml of the HNO3/H2O2 solution
(Section 7.3.1 of this method) in each of the second and third impingers
as shown in Figure 29-1. Place 100 ml of the acidic KMnO4
absorbing solution (Section 7.3.2 of this method) in each of the fifth
and sixth impingers as shown in Figure 29-1, and transfer approximately
200 to 300 g of pre-weighed silica gel from its container to the last
impinger. Alternatively, the silica gel may be weighed directly in the
impinger just prior to final train assembly.
8.1.3.2 Based on the specific source sampling conditions, the use of
an empty first impinger can be eliminated if the moisture to be
collected in the impingers will be less than approximately 100 ml.
8.1.3.3 If Hg analysis will not be performed, the fourth, fifth, and
sixth impingers as shown in Figure 29-1 are not required.
8.1.3.4 To insure leak-free sampling train connections and to
prevent possible sample contamination problems, use Teflon tape or other
non-contaminating material instead of silicone grease.
Precaution: Exercise extreme care to prevent contamination within
the train. Prevent the acidic KMnO4 from contacting any
glassware that contains sample material to be analyzed for Mn. Prevent
acidic H2O2 from mixing with the acidic
KMnO4.
8.1.4 Leak-Check Procedures. Follow the leak-check procedures given
in Method 5, section 8.4.2 (Pretest Leak-Check), section 8.4.3 (Leak-
Checks During the Sample Run), and section 8.4.4 (Post-Test Leak-
Checks).
8.1.5 Sampling Train Operation. Follow the procedures given in
Method 5, section 8.5. When sampling for Hg, use a procedure analogous
to that described in section 8.1 of Method 101A, 40 CFR Part 61,
Appendix B, if necessary to maintain the desired color in the last
acidified permanganate impinger. For each run, record the data required
on a data sheet such as the one shown in Figure 5-3 of Method 5.
8.1.6 Calculation of Percent Isokinetic. Same as Method 5, section
12.11.
8.2 Sample Recovery.
8.2.1 Begin cleanup procedures as soon as the probe is removed from
the stack at the end of a sampling period. The probe should be allowed
to cool prior to sample recovery. When it can be safely handled, wipe
off all external particulate matter near the tip of the probe nozzle and
place a rinsed, non-contaminating cap over the probe nozzle to prevent
losing or gaining particulate matter. Do not cap the probe tip tightly
while the sampling train is cooling; a vacuum can form in the filter
holder with the undesired result of drawing liquid from the impingers
onto the filter.
8.2.2 Before moving the sampling train to the cleanup site, remove
the probe from the sampling train and cap the open outlet. Be careful
not to lose any condensate that might be present. Cap the filter inlet
where the probe was fastened. Remove the umbilical cord from the last
impinger and cap the impinger. Cap the filter holder outlet and impinger
inlet. Use non-contaminating caps, whether ground-glass stoppers,
plastic caps, serum caps, or Teflon tape to close these openings.
8.2.3 Alternatively, the following procedure may be used to
disassemble the train before the probe and filter holder/oven are
completely cooled: Initially disconnect the filter holder outlet/
impinger inlet and loosely cap the open ends. Then disconnect the probe
from the filter holder or cyclone inlet and loosely cap the open ends.
Cap the probe tip and remove the umbilical cord as previously described.
8.2.4 Transfer the probe and filter-impinger assembly to a cleanup
area that is clean and protected from the wind and other potential
causes of contamination or loss of sample. Inspect the train before and
during disassembly and note any abnormal conditions. Take special
precautions to assure that all the items necessary for recovery do not
contaminate the samples. The sample is recovered and treated as follows
(see schematic in Figures 29-2a and 29-2b):
8.2.5 Container No. 1 (Sample Filter). Carefully remove the filter
from the filter holder and place it in its labeled petri dish container.
To handle the filter, use either acid-washed polypropylene or Teflon
coated tweezers or clean, disposable surgical gloves rinsed with water
and dried. If it is necessary to fold the filter, make certain the
particulate cake is inside the fold. Carefully transfer the filter and
any particulate matter or filter fibers that adhere to the filter holder
gasket to the petri dish by using a dry (acid-cleaned) nylon bristle
brush. Do not use any metal-containing materials when recovering this
train. Seal the labeled petri dish.
8.2.6 Container No. 2 (Acetone Rinse). Perform this procedure only
if a determination of particulate emissions is to be made.
Quantitatively recover particulate matter and any condensate from the
probe nozzle, probe fitting, probe liner, and front half of the filter
holder by washing these components with a total of 100 ml of acetone,
while simultaneously taking great care to see that no dust on the
outside of the probe or other surfaces gets in the sample. The use of
exactly 100 ml is necessary for the subsequent blank correction
procedures. Distilled water may be used instead of acetone when approved
by the Administrator and shall be used when specified by the
Administrator; in these cases, save a

[[Page 624]]

water blank and follow the Administrator's directions on analysis.
8.2.6.1 Carefully remove the probe nozzle, and clean the inside
surface by rinsing with acetone from a wash bottle while brushing with a
non-metallic brush. Brush until the acetone rinse shows no visible
particles, then make a final rinse of the inside surface with acetone.
8.2.6.2 Brush and rinse the sample exposed inside parts of the probe
fitting with acetone in a similar way until no visible particles remain.
Rinse the probe liner with acetone by tilting and rotating the probe
while squirting acetone into its upper end so that all inside surfaces
will be wetted with acetone. Allow the acetone to drain from the lower
end into the sample container. A funnel may be used to aid in
transferring liquid washings to the container. Follow the acetone rinse
with a non-metallic probe brush. Hold the probe in an inclined position,
squirt acetone into the upper end as the probe brush is being pushed
with a twisting action three times through the probe. Hold a sample
container underneath the lower end of the probe, and catch any acetone
and particulate matter which is brushed through the probe until no
visible particulate matter is carried out with the acetone or until none
remains in the probe liner on visual inspection. Rinse the brush with
acetone, and quantitatively collect these washings in the sample
container. After the brushing, make a final acetone rinse of the probe
as described above.
8.2.6.3 It is recommended that two people clean the probe to
minimize sample losses. Between sampling runs, keep brushes clean and
protected from contamination. Clean the inside of the front-half of the
filter holder by rubbing the surfaces with a non-metallic brush and
rinsing with acetone. Rinse each surface three times or more if needed
to remove visible particulate. Make a final rinse of the brush and
filter holder. After all acetone washings and particulate matter have
been collected in the sample container, tighten the lid so that acetone
will not leak out when shipped to the laboratory. Mark the height of the
fluid level to determine whether or not leakage occurred during
transport. Clearly label the container to identify its contents.
8.2.7 Container No. 3 (Probe Rinse). Keep the probe assembly clean
and free from contamination during the probe rinse. Rinse the probe
nozzle and fitting, probe liner, and front-half of the filter holder
thoroughly with a total of 100 ml of 0.1 N HNO3, and place
the wash into a sample storage container. Perform the rinses as
applicable and generally as described in Method 12, section 8.7.1.
Record the volume of the rinses. Mark the height of the fluid level on
the outside of the storage container and use this mark to determine if
leakage occurs during transport. Seal the container, and clearly label
the contents. Finally, rinse the nozzle, probe liner, and front-half of
the filter holder with water followed by acetone, and discard these
rinses.

Note: The use of a total of exactly 100 ml is necessary for the
subsequent blank correction procedures.

8.2.8 Container No. 4 (Impingers 1 through 3, Moisture Knockout
Impinger, when used, HNO3/H2O2
Impingers Contents and Rinses). Due to the potentially large quantity of
liquid involved, the tester may place the impinger solutions from
impingers 1 through 3 in more than one container, if necessary. Measure
the liquid in the first three impingers to within 0.5 ml using a
graduated cylinder. Record the volume. This information is required to
calculate the moisture content of the sampled flue gas. Clean each of
the first three impingers, the filter support, the back half of the
filter housing, and connecting glassware by thoroughly rinsing with 100
ml of 0.1 N HNO3 using the procedure as applicable in Method
12, section 8.7.3.

Note: The use of exactly 100 ml of 0.1 N HNO3 rinse is
necessary for the subsequent blank correction procedures. Combine the
rinses and impinger solutions, measure and record the final total
volume. Mark the height of the fluid level, seal the container, and
clearly label the contents.

8.2.9 Container Nos. 5A (0.1 N HNO3), 5B
(KMnO4/H2SO4 absorbing solution), and
5C (8 N HCl rinse and dilution).
8.2.9.1 When sampling for Hg, pour all the liquid from the impinger
(normally impinger No. 4) that immediately preceded the two permanganate
impingers into a graduated cylinder and measure the volume to within 0.5
ml. This information is required to calculate the moisture content of
the sampled flue gas. Place the liquid in Container No. 5A. Rinse the
impinger with exactly 100 ml of 0.1 N HNO3 and place this
rinse in Container No. 5A.
8.2.9.2 Pour all the liquid from the two permanganate impingers into
a graduated cylinder and measure the volume to within 0.5 ml. This
information is required to calculate the moisture content of the sampled
flue gas. Place this acidic KMnO4 solution into Container No.
5B. Using a total of exactly 100 ml of fresh acidified KMnO4
solution for all rinses (approximately 33 ml per rinse), rinse the two
permanganate impingers and connecting glassware a minimum of three
times. Pour the rinses into Container No. 5B, carefully assuring
transfer of all loose precipitated materials from the two impingers.
Similarly, using 100 ml total of water, rinse the permanganate impingers
and connecting glass a minimum of three times, and pour the rinses into
Container 5B, carefully assuring transfer of any loose precipitated
material. Mark the height of the fluid level, and

[[Page 625]]

clearly label the contents. Read the Precaution: in section 7.3.2.

Note: Due to the potential reaction of KMnO4 with acid,
pressure buildup can occur in the sample storage bottles. Do not fill
these bottles completely and take precautions to relieve excess
pressure. A No. 70-72 hole drilled in the container cap and Teflon liner
has been used successfully.

8.2.9.3 If no visible deposits remain after the water rinse, no
further rinse is necessary. However, if deposits remain on the impinger
surfaces, wash them with 25 ml of 8 N HCl, and place the wash in a
separate sample container labeled No. 5C containing 200 ml of water.
First, place 200 ml of water in the container. Then wash the impinger
walls and stem with the HCl by turning the impinger on its side and
rotating it so that the HCl contacts all inside surfaces. Use a total of
only 25 ml of 8 N HCl for rinsing both permanganate impingers combined.
Rinse the first impinger, then pour the actual rinse used for the first
impinger into the second impinger for its rinse. Finally, pour the 25 ml
of 8 N HCl rinse carefully into the container. Mark the height of the
fluid level on the outside of the container to determine if leakage
occurs during transport.
8.2.10 Container No. 6 (Silica Gel). Note the color of the
indicating silica gel to determine whether it has been completely spent
and make a notation of its condition. Transfer the silica gel from its
impinger to its original container and seal it. The tester may use a
funnel to pour the silica gel and a rubber policeman to remove the
silica gel from the impinger. The small amount of particles that might
adhere to the impinger wall need not be removed. Do not use water or
other liquids to transfer the silica gel since weight gained in the
silica gel impinger is used for moisture calculations. Alternatively, if
a balance is available in the field, record the weight of the spent
silica gel (or silica gel plus impinger) to the nearest 0.5 g.
8.2.11 Container No. 7 (Acetone Blank). If particulate emissions are
to be determined, at least once during each field test, place a 100-ml
portion of the acetone used in the sample recovery process into a
container labeled No. 7. Seal the container.
8.2.12 Container No. 8A (0.1 N HNO3 Blank). At least once
during each field test, place 300 ml of the 0.1 N HNO3
solution used in the sample recovery process into a container labeled
No. 8A. Seal the container.
8.2.13 Container No. 8B (Water Blank). At least once during each
field test, place 100 ml of the water used in the sample recovery
process into a container labeled No. 8B. Seal the container.
8.2.14 Container No. 9 (5 Percent HNO3/10 Percent
H2O2 Blank). At least once during each field test,
place 200 ml of the 5 Percent HNO3/10 Percent
H2O2 solution used as the nitric acid impinger
reagent into a container labeled No. 9. Seal the container.
8.2.15 Container No. 10 (Acidified KMnO4 Blank). At least
once during each field test, place 100 ml of the acidified
KMnO4 solution used as the impinger solution and in the
sample recovery process into a container labeled No. 10. Prepare the
container as described in section 8.2.9.2. Read the Precaution: in
section 7.3.2 and read the note in section 8.2.9.2.
8.2.16 Container No. 11 (8 N HCl Blank). At least once during each
field test, place 200 ml of water into a sample container labeled No.
11. Then carefully add with stirring 25 ml of 8 N HCl. Mix well and seal
the container.
8.2.17 Container No. 12 (Sample Filter Blank). Once during each
field test, place into a petri dish labeled No. 12 three unused blank
filters from the same lot as the sampling filters. Seal the petri dish.
8.3 Sample Preparation. Note the level of the liquid in each of the
containers and determine if any sample was lost during shipment. If a
noticeable amount of leakage has occurred, either void the sample or use
methods, subject to the approval of the Administrator, to correct the
final results. A diagram illustrating sample preparation and analysis
procedures for each of the sample train components is shown in Figure
29-3.
8.3.1 Container No. 1 (Sample Filter).
8.3.1.1 If particulate emissions are being determined, first
desiccate the filter and filter catch without added heat (do not heat
the filters to speed the drying) and weigh to a constant weight as
described in section 11.2.1 of Method 5.
8.3.1.2 Following this procedure, or initially, if particulate
emissions are not being determined in addition to metals analysis,
divide the filter with its filter catch into portions containing
approximately 0.5 g each. Place the pieces in the analyst's choice of
either individual microwave pressure relief vessels or Parr Bombs. Add 6
ml of concentrated HNO3 and 4 ml of concentrated HF to each
vessel. For microwave heating, microwave the samples for approximately
12 to 15 minutes total heating time as follows: heat for 2 to 3 minutes,
then turn off the microwave for 2 to 3 minutes, then heat for 2 to 3
minutes, etc., continue this alternation until the 12 to 15 minutes
total heating time are completed (this procedure should comprise
approximately 24 to 30 minutes at 600 watts). Microwave heating times
are approximate and are dependent upon the number of samples being
digested simultaneously. Sufficient heating is evidenced by sorbent
reflux within the vessel. For conventional heating, heat the Parr Bombs
at 140 [deg]C (285 [deg]F) for 6 hours. Then cool the samples to room
temperature, and combine with the acid digested probe rinse as required
in section 8.3.3.

[[Page 626]]

8.3.1.3 If the sampling train includes an optional glass cyclone in
front of the filter, prepare and digest the cyclone catch by the
procedures described in section 8.3.1.2 and then combine the digestate
with the digested filter sample.
8.3.2 Container No. 2 (Acetone Rinse). Note the level of liquid in
the container and confirm on the analysis sheet whether or not leakage
occurred during transport. If a noticeable amount of leakage has
occurred, either void the sample or use methods, subject to the approval
of the Administrator, to correct the final results. Measure the liquid
in this container either volumetrically within 1 ml or gravimetrically
within 0.5 g. Transfer the contents to an acid-cleaned, tared 250-ml
beaker and evaporate to dryness at ambient temperature and pressure. If
particulate emissions are being determined, desiccate for 24 hours
without added heat, weigh to a constant weight according to the
procedures described in section 11.2.1 of Method 5, and report the
results to the nearest 0.1 mg. Redissolve the residue with 10 ml of
concentrated HNO3. Quantitatively combine the resultant
sample, including all liquid and any particulate matter, with Container
No. 3 before beginning section 8.3.3.
8.3.3 Container No. 3 (Probe Rinse). Verify that the pH of this
sample is 2 or lower. If it is not, acidify the sample by careful
addition with stirring of concentrated HNO3 to pH 2. Use
water to rinse the sample into a beaker, and cover the beaker with a
ribbed watch glass. Reduce the sample volume to approximately 20 ml by
heating on a hot plate at a temperature just below boiling. Digest the
sample in microwave vessels or Parr Bombs by quantitatively transferring
the sample to the vessel or bomb, carefully adding the 6 ml of
concentrated HNO3, 4 ml of concentrated HF, and then
continuing to follow the procedures described in section 8.3.1.2. Then
combine the resultant sample directly with the acid digested portions of
the filter prepared previously in section 8.3.1.2. The resultant
combined sample is referred to as ``Sample Fraction 1''. Filter the
combined sample using Whatman 541 filter paper. Dilute to 300 ml (or the
appropriate volume for the expected metals concentration) with water.
This diluted sample is ``Analytical Fraction 1''. Measure and record the
volume of Analytical Fraction 1 to within 0.1 ml. Quantitatively remove
a 50-ml aliquot and label as ``Analytical Fraction 1B''. Label the
remaining 250-ml portion as ``Analytical Fraction 1A''. Analytical
Fraction 1A is used for ICAP or AAS analysis for all desired metals
except Hg. Analytical Fraction 1B is used for the determination of
front-half Hg.
8.3.4 Container No. 4 (Impingers 1-3). Measure and record the total
volume of this sample to within 0.5 ml and label it ``Sample Fraction
2''. Remove a 75- to 100-ml aliquot for Hg analysis and label the
aliquot ``Analytical Fraction 2B''. Label the remaining portion of
Container No. 4 as ``Sample Fraction 2A''. Sample Fraction 2A defines
the volume of Analytical Fraction 2A prior to digestion. All of Sample
Fraction 2A is digested to produce ``Analytical Fraction 2A''.
Analytical Fraction 2A defines the volume of Sample Fraction 2A after
its digestion and the volume of Analytical Fraction 2A is normally 150
ml. Analytical Fraction 2A is analyzed for all metals except Hg. Verify
that the pH of Sample Fraction 2A is 2 or lower. If necessary, use
concentrated HNO3 by careful addition and stirring to lower
Sample Fraction 2A to pH 2. Use water to rinse Sample Fraction 2A into a
beaker and then cover the beaker with a ribbed watchglass. Reduce Sample
Fraction 2A to approximately 20 ml by heating on a hot plate at a
temperature just below boiling. Then follow either of the digestion
procedures described in sections 8.3.4.1 or 8.3.4.2.
8.3.4.1 Conventional Digestion Procedure. Add 30 ml of 50 percent
HNO3, and heat for 30 minutes on a hot plate to just below
boiling. Add 10 ml of 3 percent H2O2 and heat for
10 more minutes. Add 50 ml of hot water, and heat the sample for an
additional 20 minutes. Cool, filter the sample, and dilute to 150 ml (or
the appropriate volume for the expected metals concentrations) with
water. This dilution produces Analytical Fraction 2A. Measure and record
the volume to within 0.1 ml.
8.3.4.2 Microwave Digestion Procedure. Add 10 ml of 50 percent
HNO3 and heat for 6 minutes total heating time in
alternations of 1 to 2 minutes at 600 Watts followed by 1 to 2 minutes
with no power, etc., similar to the procedure described in section
8.3.1. Allow the sample to cool. Add 10 ml of 3 percent
H2O2 and heat for 2 more minutes. Add 50 ml of hot
water, and heat for an additional 5 minutes. Cool, filter the sample,
and dilute to 150 ml (or the appropriate volume for the expected metals
concentrations) with water. This dilution produces Analytical Fraction
2A. Measure and record the volume to within 0.1 ml.

Note: All microwave heating times given are approximate and are
dependent upon the number of samples being digested at a time. Heating
times as given above have been found acceptable for simultaneous
digestion of up to 12 individual samples. Sufficient heating is
evidenced by solvent reflux within the vessel.

8.3.5 Container No. 5A (Impinger 4), Container Nos. 5B and 5C
(Impingers 5 and 6). Keep the samples in Containers Nos. 5A, 5B, and 5C
separate from each other. Measure and record the volume of 5A to within
0.5 ml. Label the contents of Container No. 5A to be Analytical Fraction
3A. To remove any brown MnO2 precipitate from the contents of
Container No. 5B, filter its contents through

[[Page 627]]

Whatman 40 filter paper into a 500 ml volumetric flask and dilute to
volume with water. Save the filter for digestion of the brown
MnO2 precipitate. Label the 500 ml filtrate from Container
No. 5B to be Analytical Fraction 3B. Analyze Analytical Fraction 3B for
Hg within 48 hours of the filtration step. Place the saved filter, which
was used to remove the brown MnO2 precipitate, into an
appropriately sized vented container, which will allow release of any
gases including chlorine formed when the filter is digested. In a
laboratory hood which will remove any gas produced by the digestion of
the MnO2, add 25 ml of 8 N HCl to the filter and allow to
digest for a minimum of 24 hours at room temperature. Filter the
contents of Container No. 5C through a Whatman 40 filter into a 500-ml
volumetric flask. Then filter the result of the digestion of the brown
MnO2 from Container No. 5B through a Whatman 40 filter into
the same 500-ml volumetric flask, and dilute and mix well to volume with
water. Discard the Whatman 40 filter. Mark this combined 500-ml dilute
HCl solution as Analytical Fraction 3C.
8.3.6 Container No. 6 (Silica Gel). Weigh the spent silica gel (or
silica gel plus impinger) to the nearest 0.5 g using a balance.

9.0 Quality Control

9.1 Field Reagent Blanks, if analyzed. Perform the digestion and
analysis of the blanks in Container Nos. 7 through 12 that were produced
in sections 8.2.11 through 8.2.17, respectively. For Hg field reagent
blanks, use a 10 ml aliquot for digestion and analysis.
9.1.1 Digest and analyze one of the filters from Container No. 12
per section 8.3.1, 100 ml from Container No. 7 per section 8.3.2, and
100 ml from Container No. 8A per section 8.3.3. This step produces
blanks for Analytical Fractions 1A and 1B.
9.1.2 Combine 100 ml of Container No. 8A with 200 ml from Container
No. 9, and digest and analyze the resultant volume per section 8.3.4.
This step produces blanks for Analytical Fractions 2A and 2B.
9.1.3 Digest and analyze a 100-ml portion of Container No. 8A to
produce a blank for Analytical Fraction 3A.
9.1.4 Combine 100 ml from Container No. 10 with 33 ml from Container
No. 8B to produce a blank for Analytical Fraction 3B. Filter the
resultant 133 ml as described for Container No. 5B in section 8.3.5,
except do not dilute the 133 ml. Analyze this blank for Hg within 48 hr
of the filtration step, and use 400 ml as the blank volume when
calculating the blank mass value. Use the actual volumes of the other
analytical blanks when calculating their mass values.
9.1.5 Digest the filter that was used to remove any brown
MnO2 precipitate from the blank for Analytical Fraction 3B by
the same procedure as described in section 8.3.5 for the similar sample
filter. Filter the digestate and the contents of Container No. 11
through Whatman 40 paper into a 500-ml volumetric flask, and dilute to
volume with water. These steps produce a blank for Analytical Fraction
3C.
9.1.6 Analyze the blanks for Analytical Fraction Blanks 1A and 2A
per section 11.1.1 and/or section 11.1.2. Analyze the blanks for
Analytical Fractions 1B, 2B, 3A, 3B, and 3C per section 11.1.3. Analysis
of the blank for Analytical Fraction 1A produces the front-half reagent
blank correction values for the desired metals except for Hg; Analysis
of the blank for Analytical Fraction 1B produces the front-half reagent
blank correction value for Hg. Analysis of the blank for Analytical
Fraction 2A produces the back-half reagent blank correction values for
all of the desired metals except for Hg, while separate analyses of the
blanks for Analytical Fractions 2B, 3A, 3B, and 3C produce the back-half
reagent blank correction value for Hg.
9.2 Quality Control Samples. Analyze the following quality control
samples.
9.2.1 ICAP and ICP-MS Analysis. Follow the respective quality
control descriptions in section 8 of Methods 6010 and 6020 in EPA
Publication SW-846 Third Edition (November 1986) including updates I,
II, IIA, IIB and III, as incorporated by reference in Sec. 60.17(i).
For the purposes of a source test that consists of three sample runs,
modify those requirements to include the following: two instrument check
standard runs, two calibration blank runs, one interference check sample
at the beginning of the analysis (analyze by Method of Standard
Additions unless within 25 percent), one quality control sample to check
the accuracy of the calibration standards (required to be within 25
percent of calibration), and one duplicate analysis (required to be
within 20 percent of average or repeat all analyses).
9.2.2 Direct Aspiration AAS and/or GFAAS Analysis for Sb, As, Ba,
Be, Cd, Cu, Cr, Co, Pb, Ni, Mn, Hg, P, Se, Ag, Tl, and Zn. Analyze all
samples in duplicate. Perform a matrix spike on at least one front-half
sample and one back-half sample, or one combined sample. If recoveries
of less than 75 percent or greater than 125 percent are obtained for the
matrix spike, analyze each sample by the Method of Standard Additions.
Analyze a quality control sample to check the accuracy of the
calibration standards. If the results are not within 20 percent, repeat
the calibration.
9.2.3 CVAAS Analysis for Hg. Analyze all samples in duplicate.
Analyze a quality control sample to check the accuracy of the
calibration standards (if not within 15 percent, repeat calibration).
Perform a matrix spike on one sample (if not within 25 percent, analyze
all samples by the Method of Standard Additions). Additional information
on quality control can be obtained from Method

[[Page 628]]

7470 in EPA Publication SW-846 Third Edition (November 1986) including
updates I, II, IIA, IIB and III, as incorporated by reference in Sec.
60.17(i), or in Standard Methods for Water and Wastewater Method 303F.

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.

10.1 Sampling Train Calibration. Calibrate the sampling train
components according to the indicated sections of Method 5: Probe Nozzle
(Section 10.1); Pitot Tube (Section 10.2); Metering System (Section
10.3); Probe Heater (Section 10.4); Temperature Sensors (Section 10.5);
Leak-Check of the Metering System (Section 8.4.1); and Barometer
(Section 10.6).
10.2 Inductively Coupled Argon Plasma Spectrometer Calibration.
Prepare standards as outlined in section 7.5. Profile and calibrate the
instrument according to the manufacturer's recommended procedures using
those standards. Check the calibration once per hour. If the instrument
does not reproduce the standard concentrations within 10 percent,
perform the complete calibration procedures. Perform ICP-MS analysis by
following Method 6020 in EPA Publication SW-846 Third Edition (November
1986) including updates I, II, IIA, IIB and III, as incorporated by
reference in Sec. 60.17(i).
10.3 Atomic Absorption Spectrometer--Direct Aspiration AAS, GFAAS,
and CVAAS analyses. Prepare the standards as outlined in section 7.5 and
use them to calibrate the spectrometer. Calibration procedures are also
outlined in the EPA methods referred to in Table 29-2 and in Method 7470
in EPA Publication SW-846 Third Edition (November 1986) including
updates I, II, IIA, IIB and III, as incorporated by reference in Sec.
60.17(i), or in Standard Methods for Water and Wastewater Method 303F
(for Hg). Run each standard curve in duplicate and use the mean values
to calculate the calibration line. Recalibrate the instrument
approximately once every 10 to 12 samples.

11.0 Analytical Procedure

11.1 Sample Analysis. For each sampling train sample run, seven
individual analytical samples are generated; two for all desired metals
except Hg, and five for Hg. A schematic identifying each sample
container and the prescribed analytical preparation and analysis scheme
is shown in Figure 29-3. The first two analytical samples, labeled
Analytical Fractions 1A and 1B, consist of the digested samples from the
front-half of the train. Analytical Fraction 1A is for ICAP, ICP-MS or
AAS analysis as described in sections 11.1.1 and 11.1.2, respectively.
Analytical Fraction 1B is for front-half Hg analysis as described in
section 11.1.3. The contents of the back-half of the train are used to
prepare the third through seventh analytical samples. The third and
fourth analytical samples, labeled Analytical Fractions 2A and 2B,
contain the samples from the moisture removal impinger No. 1, if used,
and HNO3/H2O2 impingers Nos. 2 and 3.
Analytical Fraction 2A is for ICAP, ICP-MS or AAS analysis for target
metals, except Hg. Analytical Fraction 2B is for analysis for Hg. The
fifth through seventh analytical samples, labeled Analytical Fractions
3A, 3B, and 3C, consist of the impinger contents and rinses from the
empty impinger No. 4 and the H2SO4/
KMnO4 Impingers Nos. 5 and 6. These analytical samples are
for analysis for Hg as described in section 11.1.3. The total back-half
Hg catch is determined from the sum of Analytical Fractions 2B, 3A, 3B,
and 3C. Analytical Fractions 1A and 2A can be combined proportionally
prior to analysis.
11.1.1 ICAP and ICP-MS Analysis. Analyze Analytical Fractions 1A and
2A by ICAP using Method 6010 or Method 200.7 (40 CFR 136, Appendix C).
Calibrate the ICAP, and set up an analysis program as described in
Method 6010 or Method 200.7. Follow the quality control procedures
described in section 9.2.1. Recommended wavelengths for analysis are as
shown in Table 29-2. These wavelengths represent the best combination of
specificity and potential detection limit. Other wavelengths may be
substituted if they can provide the needed specificity and detection
limit, and are treated with the same corrective techniques for spectral
interference. Initially, analyze all samples for the target metals
(except Hg) plus Fe and Al. If Fe and Al are present, the sample might
have to be diluted so that each of these elements is at a concentration
of less than 50 ppm so as to reduce their spectral interferences on As,
Cd, Cr, and Pb. Perform ICP-MS analysis by following Method 6020 in EPA
Publication SW-846 Third Edition (November 1986) including updates I,
II, IIA, IIB and III, as incorporated by reference in Sec. 60.17(i).

Note: When analyzing samples in a HF matrix, an alumina torch should
be used; since all front-half samples will contain HF, use an alumina
torch.

11.1.2 AAS by Direct Aspiration and/or GFAAS. If analysis of metals
in Analytical Fractions 1A and 2A by using GFAAS or direct aspiration
AAS is needed, use Table 29-3 to determine which techniques and
procedures to apply for each target metal. Use Table 29-3, if necessary,
to determine techniques for minimization of interferences. Calibrate the
instrument according to section 10.3 and follow the quality control
procedures specified in section 9.2.2.
11.1.3 CVAAS Hg analysis. Analyze Analytical Fractions 1B, 2B, 3A,
3B, and 3C separately for Hg using CVAAS following the method outlined
in Method 7470 in EPA Publication SW-846 Third Edition (November

[[Page 629]]

1986) including updates I, II, IIA, IIB and III, as incorporated by
reference in Sec. 60.17(i), or in Standard Methods for Water and
Wastewater Analysis, 15th Edition, Method 303F, or, optionally using
note no. 2 at the end of this section. Set up the calibration curve
(zero to 1000 ng) as described in Method 7470 or similar to Method 303F
using 300-ml BOD bottles instead of Erlenmeyers. Perform the following
for each Hg analysis. From each original sample, select and record an
aliquot in the size range from 1 ml to 10 ml. If no prior knowledge of
the expected amount of Hg in the sample exists, a 5 ml aliquot is
suggested for the first dilution to 100 ml (see note no. 1 at end of
this section). The total amount of Hg in the aliquot shall be less than
1 g and within the range (zero to 1000 ng) of the calibration
curve. Place the sample aliquot into a separate 300-ml BOD bottle, and
add enough water to make a total volume of 100 ml. Next add to it
sequentially the sample digestion solutions and perform the sample
preparation described in the procedures of Method 7470 or Method 303F.
(See note no. 2 at the end of this section). If the maximum readings are
off-scale (because Hg in the aliquot exceeded the calibration range;
including the situation where only a 1-ml aliquot of the original sample
was digested), then dilute the original sample (or a portion of it) with
0.15 percent HNO3 (1.5 ml concentrated HNO3 per
liter aqueous solution) so that when a 1- to 10-ml aliquot of the ``0.15
HNO3 percent dilution of the original sample'' is digested
and analyzed by the procedures described above, it will yield an
analysis within the range of the calibration curve.

Note No. 1: When Hg levels in the sample fractions are below the in-
stack detection limit given in Table 29-1, select a 10 ml aliquot for
digestion and analysis as described.
Note No. 2: Optionally, Hg can be analyzed by using the CVAAS
analytical procedures given by some instrument manufacturer's
directions. These include calibration and quality control procedures for
the Leeman Model PS200, the Perkin Elmer FIAS systems, and similar
models, if available, of other instrument manufacturers. For digestion
and analyses by these instruments, perform the following two steps: (1),
Digest the sample aliquot through the addition of the aqueous
hydroxylamine hydrochloride/sodium chloride solution the same as
described in this section: (The Leeman, Perkin Elmer, and similar
instruments described in this note add automatically the necessary
stannous chloride solution during the automated analysis of Hg.); (2),
Upon completion of the digestion described in (1), analyze the sample
according to the instrument manufacturer's directions. This approach
allows multiple (including duplicate) automated analyses of a digested
sample aliquot.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

A = Analytical detection limit, g/ml.
B = Liquid volume of digested sample prior to aliquotting for analysis,
ml.
C = Stack sample gas volume, dsm\3\.
Ca1 = Concentration of metal in Analytical Fraction 1A as
read from the standard curve, g/ml.
Ca2 = Concentration of metal in Analytical Fraction 2A as
read from the standard curve, (g/ml).
Cs = Concentration of a metal in the stack gas, mg/dscm.
D = In-stack detection limit, g/m\3\.
Fa = Aliquot factor, volume of Sample Fraction 2 divided by
volume of Sample Fraction 2A (see section 8.3.4.)
Fd = Dilution factor (Fd = the inverse of the
fractional portion of the concentrated sample in the solution
actually used in the instrument to produce the reading
Ca1. For example, if a 2 ml aliquot of Analytical
Fraction 1A is diluted to 10 ml to place it in the calibration
range, Fd = 5).
Hgbh = Total mass of Hg collected in the back-half of the
sampling train, g.
Hgbh2 = Total mass of Hg collected in Sample Fraction 2,
g.
Hgbh3(A,B,C) = Total mass of Hg collected separately in
Fraction 3A, 3B, or 3C, g.
Hgbhb = Blank correction value for mass of Hg detected in
back-half field reagent blanks, g.
Hgfh = Total mass of Hg collected in the front-half of the
sampling train (Sample Fraction 1), g.
Hgfhb = Blank correction value for mass of Hg detected in
front-half field reagent blank, g.
Hgt = Total mass of Hg collected in the sampling train,
g.
Mbh = Total mass of each metal (except Hg) collected in the
back-half of the sampling train (Sample Fraction 2),
g.
Mbhb = Blank correction value for mass of metal detected in
back-half field reagent blank, g.
Mfh = Total mass of each metal (except Hg) collected in the
front half of the sampling train (Sample Fraction 1),
g.
Mfhb = Blank correction value for mass of metal detected in
front-half field reagent blank, g.
Mt = Total mass of each metal (separately stated for each
metal) collected in the sampling train, g.
Mt = Total mass of that metal collected in the sampling
train, g; (substitute Hgt for
Mt for the Hg calculation).
Qbh2 = Quantity of Hg, g, TOTAL in the ALIQUOT of
Analytical Fraction 2B selected for digestion and analysis .

Note: For example, if a 10 ml aliquot of Analytical Fraction 2B is
taken and digested and analyzed (according to section 11.1.3 and

[[Page 630]]

its notes nos. 1 and 2), then calculate and use the total amount of Hg
in the 10 ml aliquot for Qbh2.

Qbh3(A,B,C) = Quantity of Hg, g, TOTAL, separately,
in the ALIQUOT of Analytical Fraction 3A, 3B, or 3C selected
for digestion and analysis (see notes in sections 12.7.1 and
12.7.2 describing the quantity ``Q'' and calculate similarly).
Qfh = Quantity of Hg, g, TOTAL in the ALIQUOT of
Analytical Fraction 1B selected for digestion and analysis.

Note: For example, if a 10 ml aliquot of Analytical Fraction 1B is
taken and digested and analyzed (according to section 11.1.3 and its
notes nos. 1 and 2), then calculate and use the total amount of Hg in
the 10 ml aliquot for Qfh.

Va = Total volume of digested sample solution (Analytical
Fraction 2A), ml (see section 8.3.4.1 or 8.3.4.2, as
applicable).
Vf1B = Volume of aliquot of Analytical Fraction 1B analyzed,
ml.

Note: For example, if a 1 ml aliquot of Analytical Fraction 1B was
diluted to 50 ml with 0.15 percent HNO3 as described in
section 11.1.3 to bring it into the proper analytical range, and then 1
ml of that 50-ml was digested according to section 11.1.3 and analyzed,
Vf1B would be 0.02 ml.

Vf2B = Volume of Analytical Fraction 2B analyzed, ml.

Note: For example, if 1 ml of Analytical Fraction 2B was diluted to
10 ml with 0.15 percent HNO3 as described in section 11.1.3
to bring it into the proper analytical range, and then 5 ml of that 10
ml was analyzed, Vf2B would be 0.5 ml.

Vf3(A,B,C) = Volume, separately, of Analytical Fraction 3A,
3B, or 3C analyzed, ml (see previous notes in sections 12.7.1
and 12.7.2, describing the quantity ``V'' and calculate
similarly).
Vm(std) = Volume of gas sample as measured by the dry gas
meter, corrected to dry standard conditions, dscm.
Vsoln,1 = Total volume of digested sample solution
(Analytical Fraction 1), ml.
Vsoln,1 = Total volume of Analytical Fraction 1, ml.
Vsoln,2 = Total volume of Sample Fraction 2, ml.
Vsoln,3(A,B,C) = Total volume, separately, of Analytical
Fraction 3A, 3B, or 3C, ml.
K4 = 10^-3 mg/g.

12.2 Dry Gas Volume. Using the data from this test, calculate
Vm(std), the dry gas sample volume at standard conditions as
outlined in section 12.3 of Method 5.
12.3 Volume of Water Vapor and Moisture Content. Using the total
volume of condensate collected during the source sampling, calculate the
volume of water vapor Vw(std) and the moisture content
Bws of the stack gas. Use Equations 5-2 and 5-3 of Method 5.
12.4 Stack Gas Velocity. Using the data from this test and Equation
2-9 of Method 2, calculate the average stack gas velocity.
12.5 In-Stack Detection Limits. Calculate the in-stack method
detection limits shown in Table 29-4 using the conditions described in
section 13.3.1 as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.439

12.6 Metals (Except Hg) in Source Sample.
12.6.1 Analytical Fraction 1A, Front-Half, Metals (except Hg).
Calculate separately the amount of each metal collected in Sample
Fraction 1 of the sampling train using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.440

Note: If Analytical Fractions 1A and 2A are combined, use
proportional aliquots. Then make appropriate changes in Equations 29-2
through 29-4 to reflect this approach.

12.6.2 Analytical Fraction 2A, Back-Half, Metals (except Hg).
Calculate separately the amount of each metal collected in Fraction 2 of
the sampling train using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.441

12.6.3 Total Train, Metals (except Hg). Calculate the total amount
of each of the quantified metals collected in the sampling train as
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.442

Note: If the measured blank value for the front half
(Mfhb) is in the range 0.0 to ``A'' g (where ``A''
g equals the value determined by multiplying 1.4 g/
in.2 times the actual area in in.2 of the sample filter), use
Mfhb to correct the emission sample value (Mfh);
if Mfhb exceeds ``A'' g, use the greater of I or II:
I. ``A'' g.
II. The lesser of (a) Mfhb, or (b) 5 percent of
Mfh. If the measured blank value for the back-half
(Mbhb) is in the range 0.0 to 1 g, use
Mbhb to correct the emission sample value (Mbh);
if Mbhb exceeds 1 g, use the greater of I or II:
I. 1 g.

[[Page 631]]

II. The lesser of (a) Mbhb, or (b) 5 percent of
Mbh.

12.7 Hg in Source Sample.
12.7.1 Analytical Fraction 1B; Front-Half Hg. Calculate the amount
ofHg collected in the front-half, Sample Fraction 1, of the sampling
train by using Equation 29-5:
[GRAPHIC] [TIFF OMITTED] TR17OC00.443

12.7.2 Analytical Fractions 2B, 3A, 3B, and 3C; Back Half Hg.
12.7.2.1 Calculate the amount of Hg collected in Sample Fraction 2
by using Equation 29-6:
[GRAPHIC] [TIFF OMITTED] TR17OC00.444

12.7.2.2 Calculate each of the back-half Hg values for Analytical
Fractions 3A, 3B, and 3C by using Equation 29-7:
[GRAPHIC] [TIFF OMITTED] TR17OC00.445

12.7.2.3 Calculate the total amount of Hg collected in the back-half
of the sampling train by using Equation 29-8:
[GRAPHIC] [TIFF OMITTED] TR17OC00.446

12.7.3 Total Train Hg Catch. Calculate the total amount of Hg
collected in the sampling train by using Equation 29-9:
[GRAPHIC] [TIFF OMITTED] TR17OC00.447

Note: If the total of the measured blank values (Hgfhb +
Hgbhb) is in the range of 0.0 to 0.6 g, then use the
total to correct the sample value (Hgfh + Hgbh);
if it exceeds 0.6 g, use the greater of I. or II:
I. 0.6 g.
II. The lesser of (a) (Hgfhb + Hgbhb), or (b)
5 percent of the sample value (Hgfh + Hgbh).

12.8 Individual Metal Concentrations in Stack Gas. Calculate the
concentration of each metal in the stack gas (dry basis, adjusted to
standard conditions) by using Equation 29-10:
[GRAPHIC] [TIFF OMITTED] TR17OC00.448

12.9 Isokinetic Variation and Acceptable Results. Same as Method 5,
sections 12.11 and 12.12, respectively.

13.0 Method Performance

13.1 Range. For the analysis described and for similar analyses, the
ICAP response is linear over several orders of magnitude. Samples
containing metal concentrations in the nanograms per ml (ng/ml) to
micrograms per ml (g/ml) range in the final analytical solution
can be analyzed using this method. Samples containing greater than
approximately 50 g/ml As, Cr, or Pb should be diluted to that
level or lower for final analysis. Samples containing greater than
approximately 20 g/ml of Cd should be diluted to that level
before analysis.
13.2 Analytical Detection Limits.

Note: See section 13.3 for the description of in-stack detection
limits.

13.2.1 ICAP analytical detection limits for the sample solutions
(based on SW-846, Method 6010) are approximately as follows: Sb (32 ng/
ml), As (53 ng/ml), Ba (2 ng/ml), Be (0.3 ng/ml), Cd (4 ng/ml), Cr (7
ng/ml), Co (7 ng/ml), Cu (6 ng/ml), Pb (42 ng/ml), Mn (2 ng/ml), Ni (15
ng/ml), P (75 ng/ml), Se (75 ng/ml), Ag (7 ng/ml), Tl (40 ng/ml), and Zn
(2 ng/ml). ICP-MS analytical detection limits (based on SW-846, Method
6020) are lower generally by

[[Page 632]]

a factor of ten or more. Be is lower by a factor of three. The actual
sample analytical detection limits are sample dependent and may vary due
to the sample matrix.
13.2.2 The analytical detection limits for analysis by direct
aspiration AAS (based on SW-846, Method 7000 series) are approximately
as follows: Sb (200 ng/ml), As (2 ng/ml), Ba (100 ng/ml), Be (5 ng/ml),
Cd (5 ng/ml), Cr (50 ng/ml), Co (50 ng/ml), Cu (20 ng/ml), Pb (100 ng/
ml), Mn (10 ng/ml), Ni (40 ng/ml), Se (2 ng/ml), Ag (10 ng/ml), Tl (100
ng/ml), and Zn (5 ng/ml).
13.2.3 The detection limit for Hg by CVAAS (on the resultant volume
of the digestion of the aliquots taken for Hg analyses) can be
approximately 0.02 to 0.2 ng/ml, depending upon the type of CVAAS
analytical instrument used. 13.2.4 The use of GFAAS can enhance the
detection limits compared to direct aspiration AAS as follows: Sb (3 ng/
ml), As (1 ng/ml), Be (0.2 ng/ml), Cd (0.1 ng/ml), Cr (1 ng/ml), Co (1
ng/ml), Pb (1 ng/ml), Se (2 ng/ml), and Tl (1 ng/ml).
13.3 In-stack Detection Limits.
13.3.1 For test planning purposes in-stack detection limits can be
developed by using the following information: (1) The procedures
described in this method, (2) the analytical detection limits described
in section 13.2 and in SW-846,(3) the normal volumes of 300 ml
(Analytical Fraction 1) for the front-half and 150 ml (Analytical
Fraction 2A) for the back-half samples, and (4) a stack gas sample
volume of 1.25 m\3\. The resultant in-stack method detection limits for
the above set of conditions are presented in Table 29-1 and were
calculated by using Eq. 29-1 shown in section 12.5.
13.3.2 To ensure optimum precision/resolution in the analyses, the
target concentrations of metals in the analytical solutions should be at
least ten times their respective analytical detection limits. Under
certain conditions, and with greater care in the analytical procedure,
these concentrations can be as low as approximately three times the
respective analytical detection limits without seriously impairing the
precision of the analyses. On at least one sample run in the source
test, and for each metal analyzed, perform either repetitive analyses,
Method of Standard Additions, serial dilution, or matrix spike addition,
etc., to document the quality of the data.
13.3.3 Actual in-stack method detection limits are based on actual
source sampling parameters and analytical results as described above. If
required, the method in-stack detection limits can be improved over
those shown in Table 29-1 for a specific test by either increasing the
sampled stack gas volume, reducing the total volume of the digested
samples, improving the analytical detection limits, or any combination
of the three. For extremely low levels of Hg only, the aliquot size
selected for digestion and analysis can be increased to as much as 10
ml, thus improving the in-stack detection limit by a factor of ten
compared to a 1 ml aliquot size.
13.3.3.1 A nominal one hour sampling run will collect a stack gas
sampling volume of about 1.25 m\3\. If the sampling time is increased to
four hours and 5 m\3\ are collected, the in-stack method detection
limits would be improved by a factor of four compared to the values
shown in Table 29-1.
13.3.3.2 The in-stack detection limits assume that all of the sample
is digested and the final liquid volumes for analysis are the normal
values of 300 ml for Analytical Fraction 1, and 150 ml for Analytical
Fraction 2A. If the volume of Analytical Fraction 1 is reduced from 300
to 30 ml, the in-stack detection limits for that fraction of the sample
would be improved by a factor of ten. If the volume of Analytical
Fraction 2A is reduced from 150 to 25 ml, the in-stack detection limits
for that fraction of the sample would be improved by a factor of six.
Matrix effect checks are necessary on sample analyses and typically are
of much greater significance for samples that have been concentrated to
less than the normal original sample volume. Reduction of Analytical
Fractions 1 and 2A to volumes of less than 30 and 25 ml, respectively,
could interfere with the redissolving of the residue and could increase
interference by other compounds to an intolerable level.
13.3.3.3 When both of the modifications described in sections
13.3.3.1 and 13.3.3.2 are used simultaneously on one sample, the
resultant improvements are multiplicative. For example, an increase in
stack gas volume by a factor of four and a reduction in the total liquid
sample digested volume of both Analytical Fractions 1 and 2A by a factor
of six would result in an improvement by a factor of twenty-four of the
in-stack method detection limit.
13.4 Precision. The precision (relative standard deviation) for each
metal detected in a method development test performed at a sewage sludge
incinerator were found to be as follows:

Sb (12.7 percent), As (13.5 percent), Ba (20.6 percent), Cd (11.5
percent), Cr (11.2 percent), Cu (11.5 percent), Pb (11.6 percent), P
(14.6 percent), Se (15.3 percent), Tl (12.3 percent), and Zn (11.8
percent). The precision for Ni was 7.7 percent for another test
conducted at a source simulator. Be, Mn, and Ag were not detected in the
tests. However, based on the analytical detection limits of the ICAP for
these metals, their precisions could be similar to those for the other
metals when detected at similar levels.

[[Page 633]]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 Alternative Analyzer. Samples may also be analyzed by cold
vapor atomic fluorescence spectrometry.
16.2 [Reserved]

17.0 References

1. Method 303F in Standard Methods for the Examination of Water
Wastewater, 15th Edition, 1980. Available from the American Public
Health Association, 1015 18th Street N.W., Washington, D.C. 20036.
2. EPA Methods 6010, 6020, 7000, 7041, 7060, 7131, 7421, 7470, 7740,
and 7841, Test Methods for Evaluating Solid Waste: Physical/Chemical
Methods. SW-846, Third Edition, November 1986, with updates I, II, IIA,
IIB and III. Office of Solid Waste and Emergency Response, U. S.
Environmental Protection Agency, Washington, DC 20460.
3. EPA Method 200.7, Code of Federal Regulations, Title 40, Part
136, Appendix C. July 1, 1987.
4. EPA Methods 1 through 5, Code of Federal Regulations, Title 40,
Part 60, Appendix A, July 1, 1991.
5. EPA Method 101A, Code of Federal Regulations, Title 40, Part 61,
Appendix B, July 1, 1991.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

Table 29-1--In Stack Method Detection Limits (ug/m\3\) for the Front-Half, the Back Half, and the Total Sampling
Train Using ICAP, GFAAS, and CVAAS
----------------------------------------------------------------------------------------------------------------
Front-half: Back-half:
Metal probe and Back-half: impringers 4-6 Total train
filter impinters 1-3 \a\
----------------------------------------------------------------------------------------------------------------
Antimony........................................ \1\ 7.7 (0.7) \1\ 3.8 (0.4) .............. \1\ 11.5 (1.1)
Arsenic......................................... \1\ 12.7 (0.3) \1\ 6.4 (0.1) .............. \1\ 19.1 (0.4)
Barium.......................................... 0.5 0.3 .............. 0.8
Beryllium....................................... \1\ 0.07 \1\ 0.04 .............. \1\ 0.11
(0.05) (0.03) (0.08)
Cadmium......................................... \1\ 1.0 (0.02) \1\ 0.5 (0.01) .............. \1\ 1.5 (0.03)
Chromium........................................ \1\ 1.7 (0.2) \1\ 0.8 (0.1) .............. \1\ 2.5 (0.3)
Cobalt.......................................... \1\ 1.7 (0.2) \1\ 0.8 (0.1) .............. \1\ 2.5 (0.3)
Copper.......................................... 1.4 0.7 .............. 2.1
Lead............................................ \1\ 10.1 (0.2) \1\ 5.0 (0.1) .............. \1\ 15.1 (0.3)
Manganese....................................... \1\ 0.5 (0.2) \1\ 0.2 (0.1) .............. \1\ 0.7 (0.3)
Mercury......................................... \2\ 0.06 \2\ 0.3 \2\ 0.2 \2\ 0.56
Nickel.......................................... 3.6 1.8 .............. 5.4
Phosphorus...................................... 18 9 .............. 27
Selenium........................................ \1\ 18 (0.5) \1\ 9 (0.3) .............. \1\ 27 (0.8)
Silver.......................................... 1.7 0.9 (0.7) .............. 2.6
Thallium........................................ \1\ 9.6 (0.2) \1\ 4.8 (0.1) .............. \1\ 14.4 (0.3)
Zinc............................................ 0.5 0.3 .............. 0.8
----------------------------------------------------------------------------------------------------------------
\a\ Mercury analysis only.
\1\ Detection limit when analyzed by ICAP or GFAAS as shown in parentheses (see section 11.1.2).
\2\ Detection limit when anaylzed by CVAAS, estimated for Back-half and Total Train. See sections 13.2 and
11.1.3. Note: Actual method in-stack detection limits may vary from these values, as described in section
13.3.3.

Table 29-2--Recommended Wavelengths for ICAP Analysis
------------------------------------------------------------------------
Wavelength
Analyte (nm)
------------------------------------------------------------------------
Aluminum (Al)........................................... 308.215
Antimony (Sb)........................................... 206.833
Arsenic (As)............................................ 193.696
Barium (Ba)............................................. 455.403
Beryllium (Be).......................................... 313.042
Cadmium (Cd)............................................ 226.502
Chromium (Cr)........................................... 267.716
Cobalt (Co)............................................. 228.616
Copper (Cu)............................................. 328.754
Iron (Fe)............................................... 259.940
Lead (Pb)............................................... 220.353
Manganese (Mn).......................................... 257.610
Nickel (Ni)............................................. 231.604
Phosphorus (P).......................................... 214.914
Selenium (Se)........................................... 196.026
Silver (Ag)............................................. 328.068
Thallium (T1)........................................... 190,864
Zinc (Zn)............................................... 213,856
------------------------------------------------------------------------

Table 29-3--Applicable Techniques, Methods and Minimization of Interferences for AAS Analysis
----------------------------------------------------------------------------------------------------------------
Interferences
Metal Technique SW-846 \1\ Wavelength --------------------------------------
Methods No. (nm) Cause Minimization
----------------------------------------------------------------------------------------------------------------
Fe........................... Aspiration...... 7380 248.3 Contamination.. Great care taken to
avoid
contamination.

[[Page 634]]

Pb........................... Aspiration...... 7420 283.3 217.0 nm Background
alternate. correction
required.
Pb........................... Furnace......... 7421 283.3 Poor recoveries Matrix modifier, add
10 l of
phosphorus acid to
1 ml of prepared
sample in sampler
cup.
Mn........................... Aspiration...... 7460 279.5 403.1 nm Background
alternate. correction
required.
Ni........................... Aspiration...... 7520 232.0 352.4 nm Background
alternate Fe, correction
Co, and Cr. required. Matrix
Nonlinear matching or nitrous-
response. oxide/acetylene
flame
Sample dilution or
use 352.3 nm line
Se........................... Furnace......... 7740 196.0 Volatility..... Spike samples and
reference materials
and add nickel
nitrate to minimize
volatilization.
Adsorption & Background
scatter. correction is
required and Zeeman
background
correction can be
useful.
Ag........................... Aspiration...... 7760 328.1 Adsorption & Background
scatter AgCl correction is
insoluble. required. Avoid
hydrochloric acid
unless silver is in
solution as a
chloride complex.
Sample and
standards monitored
for aspiration
rate.
Tl........................... Aspiration...... 7840 276.8 Background
correction is
required.
Hydrochloric acid
should not be used.
Tl........................... Furnace......... 7841 276.8 Hydrochloric Background
acid or correction is
chloride. required. Verify
that losses are not
occurring for
volatilization by
spiked samples or
standard addition;
Palladium is a
suitable matrix
modifier.
Zn........................... Aspiration...... 7950 213.9 High Si, Cu, & Strontium removes Cu
P and phosphate.
Contamination. Great care taken to
avoid
contamination.
Sb........................... Aspiration...... 7040 217.6 1000 mg/ml Pb, Use secondary
Ni, Cu, or wavelength of 231.1
acid. nm; match sample &
standards acid
concentration or
use nitrous oxide/
acetylene flame.
Sb........................... Furnace......... 7041 217.6 High Pb........ Secondary wavelength
or Zeeman
correction.
As........................... Furnace......... 7060 193.7 Arsenic Spike samples and
Volatilization add nickel nitrate
Aluminum. solution to
digestates prior to
analysis. Use
Zeeman background
correction.
Ba........................... Aspiration...... 7080 553.6
Calcium........
Barium High hollow cathode
Ionization. current and narrow
band set.
2 ml of KCl per 100
m1 of sample.
Be........................... Aspiration...... 7090 234.9 500 ppm Al. Add 0.1% fluoride.
High Mg and Si.
Be........................... Furnace......... 7091 234.9 Be in optical Optimize parameters
path. to minimize
effects.
Cd........................... Aspiration...... 7130 228.8 Absorption and Background
light correction is
scattering. required.
Cd........................... Furnace......... 7131 228.8 As above....... As above.
Excess Chloride Ammonium phosphate
............... used as a matrix
Pipet Tips..... modifier.
Use cadmium-free
tips.
Cr........................... Aspiration...... 7190 357.9 Alkali metal... KCl ionization
suppressant in
samples and
standards--Consult
mfgs' literature.
Co........................... Furnace......... 7201 240.7 Excess chloride Use Method of
Standard Additions.
Cr........................... Furnace......... 7191 357.9 200 mg/L Ca and All calcium nitrate
P. for a know constant
effect and to
eliminate effect of
phosphate.
Cu........................... Aspiration...... 7210 324.7 Absorption and Consult
Scatter. manufacturer's
manual.
----------------------------------------------------------------------------------------------------------------
\1\ Refer to EPA publication SW-846 (Reference 2 in section 16.0).

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Method 30A--Determination of Total Vapor Phase Mercury Emissions From
Stationary Sources (Instrumental Analyzer Procedure)

1.0 Scope and Application

What Is Method 30A?

Method 30A is a procedure for measuring total vapor phase mercury
(Hg) emissions from stationary sources using an instrumental analyzer.
This method is particularly appropriate for performing emissions testing
and for conducting relative accuracy test audits (RATAs) of mercury
continuous emissions monitoring systems (Hg CEMS) and sorbent trap
monitoring systems at coal-fired combustion sources. Quality assurance
and quality control requirements are included to assure that you, the
tester, collect

[[Page 639]]

data of known and acceptable quality for each testing site. This method
does not completely describe all equipment, supplies, and sampling
procedures and analytical procedures you will need but refers to other
test methods for some of the details. Therefore, to obtain reliable
results, you should also have a thorough knowledge of these additional
methods which are also found in appendices A-1 and A-3 to this part:
(a) Method 1--Sample and Velocity Traverses for Stationary Sources.
(b) Method 4--Determination of Moisture Content in Stack Gases.
1.1 Analytes. What does this method determine? This method is
designed to measure the mass concentration of total vapor phase Hg in
flue gas, which represents the sum of elemental Hg (Hg\0\) and oxidized
forms of Hg (Hg⁺²), in mass concentration units of micrograms
per cubic meter (g/m\3\).

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Elemental Hg (Hg\0\).............. 7439-97-6 Typically <2% of
Calibration Span.
Oxidized Hg (Hg+2)................ .............. (Same).
------------------------------------------------------------------------

1.2 Applicability. When is this method required? Method 30A is
offered as a reference method for emission testing and for RATAs of Hg
CEMS and sorbent trap monitoring systems at coal-fired boilers. Method
30A may also be specified for other source categories in the future,
either by New Source Performance Standards (NSPS), National Emission
Standards for Hazardous Air Pollutants (NESHAP), emissions trading
programs, State Implementation Plans (SIP), or operating permits that
require measurement of Hg concentrations in stationary source emissions
to determine compliance with an applicable emission standard or limit,
or to conduct RATAs of Hg CEMS and sorbent trap monitoring systems.
1.3 Data Quality Objectives (DQO). How good must my collected data
be? Method 30A has been designed to provide data of high and known
quality for Hg emission testing and for relative accuracy testing of Hg
monitoring systems including Hg CEMS and sorbent trap monitoring
systems. In these and other applications, the principle objective is to
ensure the accuracy of the data at the actual emission levels
encountered. To meet this objective, calibration standards prepared
according to an EPA traceability protocol must be used and measurement
system performance tests are required.

2.0 Summary of Method

In this method, a sample of the effluent gas is continuously
extracted and conveyed to an analyzer capable of measuring the total
vapor phase Hg concentration. Elemental and oxidized mercury (i.e.,
Hg\0\ and Hg⁺²) may be measured separately or simultaneously
but, for purposes of this method, total vapor phase Hg is the sum of
Hg\0\ and Hg⁺². You must meet the performance requirements of
this method (i.e., system calibration, interference testing, dynamic
spiking, and system integrity/drift checks) to validate your data. The
dynamic spiking requirement is deferred until January 1, 2009.

3.0 Definitions

3.1 Calibration Curve means the relationship between an analyzer's
response to the injection of a series of calibration gases and the
actual concentrations of those gases.
3.2 Calibration Gas means a gas standard containing Hg\0\ or
HgCl2 at a known concentration that is produced and certified
in accordance with an EPA traceability protocol for certification of Hg
calibration standards.
3.2.1 Zero Gas means a calibration gas with a concentration that is
below the level detectable by the measurement system.
3.2.2 Low-Level Gas means a calibration gas with a concentration
that is 10 to 30 percent of the calibration span.
3.2.3 Mid-Level Gas means a calibration gas with a concentration
that is 40 to 60 percent of the calibration span.
3.2.4 High-Level Gas means a calibration gas whose concentration is
equal to the calibration span.
3.3 Converter means a device that reduces oxidized mercury
(Hg⁺²) to elemental mercury (Hg\0\).
3.4 Calibration Span means the upper limit of valid instrument
response during sampling. To the extent practicable the measured
emissions are to be between 10 and 100 percent of the selected
calibration span (i.e., the measured emissions should be within the
calibrated range determined by the Low- and High-Level gas standards).
It is recommended that the calibration span be at least twice the native
concentration to accommodate the dynamic spiking procedure.
3.5 Centroidal Area means the central area that has the same shape
as the stack or duct cross section and is no greater than one percent of
the stack or duct total cross-sectional area.
3.6 Data Recorder means the equipment that permanently records the
concentrations reported by the analyzer.
3.7 Drift Check means the test to determine the difference between
the measurement system readings obtained in a post-run system integrity
check and the prior pre-run system integrity check at a specific
calibration gas concentration level (i.e., zero, mid-level, or high-
level).
3.8 Dynamic Spiking means a procedure in which a known mass or
concentration of vapor phase HgCl2 is injected into the probe
sample gas stream at a known flow rate, in

[[Page 640]]

order to assess the effects of the flue gas matrix on the accuracy of
the measurement system.
3.9 Gas Analyzer means the equipment that detects the total vapor
phase Hg being measured and generates an output proportional to its
concentration.
3.10 Interference Test means the test to detect analyzer responses
to compounds other than Hg, usually gases present in the measured gas
stream, that are not adequately accounted for in the calibration
procedure and may cause measurement bias.
3.11 Measurement System means all of the equipment used to determine
the Hg concentration. The measurement system may generally include the
following major subsystems: sample acquisition, Hg⁺² to
Hg⁰ converter, sample transport, sample conditioning, flow
control/gas manifold, gas analyzer, and data recorder.
3.12 Native Concentration means the total vapor phase Hg
concentration in the effluent gas stream.
3.13 NIST means the National Institute of Standards and Technology,
located in Gaithersburg, Maryland.
3.14 Response Time means the time it takes for the measurement
system, while operating normally at its target sample flow rate or
dilution ratio, to respond to a known step change in gas concentration
(from a low-level to a high-level gas) and to read within 5 percent of
the stable high-level gas response.
3.15 Run means a series of gas samples taken successively from the
stack or duct. A test normally consists of a specific number of runs.
3.16 System Calibration Error means the difference between the
measured concentration of a low-, mid-, or high-level Hg\0\ calibration
gas and the certified concentration of the gas when it is introduced in
system calibration mode.
3.17 System Calibration Mode means introducing the calibration gases
into the measurement system at the probe, upstream of all sample
conditioning components.
3.18 Test refers to the series of runs required by the applicable
regulation.

4.0 Interferences

Interferences will vary among instruments and potential instrument-
specific spectral and matrix interferences must be evaluated through the
interference test and the dynamic spiking tests.

5.0 Safety

What safety measures should I consider when using this method?

This method may require you to work with hazardous materials and in
hazardous conditions. You are encouraged to establish safety procedures
before using the method. Among other precautions, you should become
familiar with the safety recommendations in the gas analyzer user's
manual. Occupational Safety and Health Administration (OSHA) regulations
concerning use of compressed gas cylinders and noxious gases may apply.

6.0 Equipment and Supplies

6.1 What do I need for the measurement system? This method is
intended to be applicable to multiple instrumental technologies. You may
use any equipment and supplies that meet the following specifications.
6.1.1 All wetted sampling system components, including probe
components prior to the point at which the calibration gas is
introduced, must be chemically inert to all Hg species. Materials such
as perfluoroalkoxy (PFA) Teflon \TM\, quartz, treated stainless steel
(SS) are examples of such materials. [Note: These materials of
construction are required because components prior to the calibration
gas injection point are not included in the system calibration error,
system integrity, and interference tests.]
6.1.2 The interference, system calibration error, system integrity,
drift and dynamic spiking test criteria must all be met by the system
used.
6.1.3 The system must be capable of measuring and controlling sample
flow rate.
6.1.4 All system components prior to the Hg⁺² to Hg\0\
converter must be maintained at a sample temperature above the acid gas
dew point.
6.2 Measurement System Components. Figure 30A-1 in section 17.0 is
an example schematic of a Method 30A measurement system.
6.2.1 Sample Probe. The probe must be made of the appropriate
materials as noted in section 6.1.1, heated when necessary (see section
6.1.4), configured with ports for introduction of calibration and
spiking gases, and of sufficient length to traverse all of the sample
points.
6.2.2 Filter or Other Particulate Removal Device. The filter or
other particulate removal device is considered to be a part of the
measurement system, must be made of appropriate materials as noted in
section 6.1.1, and must be included in all system tests.
6.2.3 Sample Line. The sample line that connects the probe to the
converter, conditioning system and analyzer must be made of appropriate
materials as noted in section 6.1.1.
6.2.4 Conditioning Equipment. For dry basis measurements, a
condenser, dryer or other suitable device is required to remove moisture
continuously from the sample gas. Any equipment needed to heat the
probe, or sample line to avoid condensation prior to the moisture
removal component is also required. For wet basis systems, you must keep
the sample above its dew point either by: (1) Heating the sample line
and all sample transport components up to the inlet of

[[Page 641]]

the analyzer (and, for hot-wet extractive systems, also heating the
analyzer) or (2) by diluting the sample prior to analysis using a
dilution probe system. The components required to do either of the above
are considered to be conditioning equipment.
6.2.5 Sampling Pump. A pump is needed to push or pull the sample gas
through the system at a flow rate sufficient to minimize the response
time of the measurement system. If a mechanical sample pump is used and
its surfaces are in contact with the sample gas prior to detection, the
pump must be leak free and must be constructed of a material that is
non-reactive to the gas being sampled (see section 6.1.1). For dilution-
type measurement systems, an ejector pump (eductor) may be used to
create a sufficient vacuum that sample gas will be drawn through a
critical orifice at a constant rate. The ejector pump may be constructed
of any material that is non-reactive to the gas being sampled.
6.2.6 Calibration Gas System(s). One or more systems may be needed
to introduce calibration gases into the measurement system. A system
should be able to flood the sampling probe sufficiently to prevent entry
of gas from the effluent stream.
6.2.7 Dynamic Spiking Port. For the purposes of the dynamic spiking
procedure described in section 8.2.7, the measurement system must be
equipped with a port to allow introduction of the dynamic spike gas
stream with the sample gas stream, at a point as close as possible to
the inlet of the probe so as to ensure adequate mixing. The same port
used for system calibrations and calibration error checks may be used
for dynamic spiking purposes.
6.2.8 Sample Gas Delivery. The sample line may feed directly to a
converter, to a by-pass valve (for speciating systems), or to a sample
manifold. All valve and/or manifold components must be made of material
that is non-reactive to the gas sampled and the calibration gas, and
must be configured to safely discharge any excess gas.
6.2.9 Hg Analyzer. An instrument is required that continuously
measures the total vapor phase Hg in the gas stream and meets the
applicable specifications in section 13.0.
6.2.10 Data Recorder. A recorder, such as a computerized data
acquisition and handling system (DAHS), digital recorder, strip chart,
or data logger, is required for recording measurement data.
6.3 Moisture Measurement System. If correction of the measured Hg
emissions for moisture is required (see section 8.5), either Method 4 in
appendix A-3 to this part or other moisture measurement methods approved
by the Administrator will be needed to measure stack gas moisture
content.

7.0 Reagents and Standards

7.1 Calibration Gases. What calibration gases do I need? You will
need calibration gases of known concentrations of Hg\0\ and
HgCl2. Special reagents and equipment may be required to
prepare the HgCl\2\ gas standards (e.g., a NIST-traceable solution of
HgCl2 and a gas generator equipped with mass flow
controllers).
The following calibration gas concentrations are required:
7.1.1 High-Level Gas. Equal to the selected calibration span.
7.1.2 Mid-Level Gas. 40 to 60 percent of the calibration span.
7.1.3 Low-Level Gas. 10 to 30 percent of the calibration span.
7.1.4 Zero Gas. No detectable Hg.
7.1.5 Dynamic Spike Gas. The exact concentration of the
HgCl2 calibration gas used to perform the pre-test dynamic
spiking procedure described in section 8.2.7 depends on the native Hg
concentration in the stack The spike gas must produce a spiked sample
concentration above the native concentration, as specified in section
8.2.7.2.2.
7.2 Interference Test. What reagents do I need for the interference
test? Use the appropriate test gases listed in Table 30A-3 in section
17.0 (i.e., the potential interferents for the source to be tested, as
identified by the instrument manufacturer) to conduct the interference
check. These gases need not be of protocol gas quality.

8.0 Sample Collection

Emission Test Procedure

Figure 30A-2 in section 17.0 presents an overview of the test
procedures required by this method. Since you may choose different
options to comply with certain performance criteria, you must identify
the specific options and associated frequencies you select and document
your results in regard to the performance criteria.
8.1 Sample Point Selection. What sampling site and sampling points
do I select?
8.1.1 When this method is used solely for Hg emission testing (e.g.,
to determine compliance with an emission standard or limit), use twelve
sampling points located according to Table 1-1 or Table 1-2 of Method 1
in appendix A-1 to this part. Alternatively, you may conduct a
stratification test as described in section 8.1.3 to determine the
number and location of the sampling points.
8.1.2 When this method is used for relative accuracy testing of a Hg
CEMS or sorbent trap monitoring system, follow the sampling

[[Page 642]]

site selection and sampling point layout procedures for gas monitor RATA
testing described in the appropriate performance specification or
applicable regulation (e.g., Performance Specification 2, section 8.1.3
of appendix B to this part or section 6.5.6 of appendix A to part 75 of
this chapter), with one exception. If you elect to perform
stratification testing as part of the sampling point selection process,
perform the testing in accordance with section 8.1.3 of this method (see
also ``Summary Table of QA/QC Requirements'' in section 9.0).
8.1.3 Determination of Stratification. If you elect to perform
stratification testing as part of the sampling point selection process
and the test results show your effluent gas stream to be unstratified or
minimally stratified, you may be allowed to sample at fewer points or at
different points than would otherwise be required.
8.1.3.1 Test Procedure. To test for stratification, use a probe of
appropriate length to measure the total vapor phase Hg concentration at
twelve traverse points located according to Table 1-1 or Table 1-2 of
Method 1 in appendix A-1 to this part. Alternatively, for a sampling
location where stratification is expected (e.g., after a wet scrubber or
at a point where dissimilar gas streams are combined together), if a 12-
point Hg stratification test has been previously performed at that
location and the results of the test showed the location to be minimally
stratified or unstratified according to the criteria in section 8.1.3.2,
you may perform an abbreviated 3-point or 6-point Hg stratification test
at the points specified in section 6.5.6.2(a) of appendix A to part 75
of this chapter in lieu of performing the 12-point test. Sample for a
minimum of twice the system response time (see section 8.2.6) at each
traverse point. Calculate the individual point and mean Hg
concentrations.
8.1.3.2 Acceptance Criteria and Sampling Point Location.
8.1.3.2.1 If the Hg concentration at each traverse point differs
from the mean concentration for all traverse points by no more than: (a)
5 percent of the mean concentration; or (b) 0.2 g/m\3\
(whichever is less restrictive), the gas stream is considered to be
unstratified and you may collect samples from a single point that most
closely matches the mean.
8.1.3.2.2 If the 5 percent or 0.2 g/m\3\ criterion in
section 8.1.3.2.1 is not met, but the Hg concentration at each traverse
point differs from the mean concentration for all traverse points by no
more than: (a)10 percent of the mean; or (b)0.5 g/m\3\
(whichever is less restrictive), the gas stream is considered to be
minimally stratified, and you may take samples from three points,
provided the points are located on the measurement line exhibiting the
highest average Hg concentration during the stratification test. If the
stack diameter (or equivalent diameter, for a rectangular stack or duct)
is greater than 2.4 meters (7.8 ft), locate the three sampling points at
0.4, 1.0, and 2.0 meters from the stack or duct wall. Alternatively, if
a RATA required by part 75 of this chapter is being conducted, you may
locate the three points at 4.4, 14.6, and 29.6 percent of the duct
diameter, in accordance with Method 1 in appendix A-1 to this part. For
stack or duct diameters of 2.4 meters (7.8 ft) or less, locate the three
sampling points at 16.7, 50.0, and 83.3 percent of the measurement line.
8.1.3.2.3 If the gas stream is found to be stratified because the 10
percent or 0.5 g/m\3\ criterion in section 8.1.3.2.2 is not
met, then either locate three sampling points at 16.7, 50.0, and 83.3
percent of the measurement line that exhibited the highest average Hg
concentration during the stratification test, or locate twelve traverse
points for the test in accordance with Table 1-1 or Table 1-2 of Method
1 in appendix A-1 to this part; or, if a RATA required by part 75 of
this chapter is being conducted, locate six Method 1 points along the
measurement line that exhibited the highest average Hg concentration.
8.1.3.3 Temporal Variations. Temporal variations in the source Hg
concentration during a stratification test may complicate the
determination of stratification. If temporal variations are a concern,
you may use the following procedure to normalize the stratification test
data. A second Hg measurement system, i.e., either an installed Hg CEMS
or another Method 30A system, is required to perform this procedure.
Position the sampling probe of the second Hg measurement system at a
fixed point in the stack or duct, at least one meter from the stack or
duct wall. Then, each time that the Hg concentration is measured at one
of the stratification test points, make a concurrent measurement of Hg
concentration at the fixed point. Normalize the Hg concentration
measured at each traverse point, by multiplying it by the ratio of
CF,avg to CF, where CF is the
corresponding fixed-point Hg concentration measurement, and
CF,avg is the average of all of the fixed-point measurements
over the duration of the stratification test. Evaluate the results of
the stratification test according to section 8.1.3.2, using the
normalized Hg concentrations.
8.1.3.4 Stratification Testing Exemption. Stratification testing
need not be performed at a test location where it would otherwise be
required to justify using fewer sample points or different sample
points, if the owner or operator documents that the Hg concentration in
the stack gas is expected to be 3 g/m\3\ or less at the time of
a Hg monitoring system RATA or an Hg emissions test. To demonstrate that
a particular test location qualifies for the stratification testing
exemption, representative Hg emissions data must be collected just prior
to the RATA or

[[Page 643]]

emissions test. At least one hour of Hg concentration data is required
for the demonstration. The data used for the demonstration shall be
recorded at process operating conditions that closely approximate the
operating conditions that will exist during the RATA or emissions test.
It is recommended that collection of the demonstration data be
integrated with the on-site pretest procedures required by the reference
method being used for the RATA or emissions test (whether this method or
another approved Hg reference method is used). Quality-assured data from
an installed Hg monitoring system may also be used for the
demonstration. If a particular test location qualifies for the
stratification testing exemption, sampling shall be performed at three
points, as described in section 8.1.3.2.2 of this method. The owner or
operator shall fully document the method used to collect the
demonstration data and shall keep this documentation on file with the
data from the associated RATA or Hg emissions test.
8.1.3.5 Interim Alternative Stratification Test Procedures. In the
time period between the effective date of this method and January 1,
2009, you may follow one of the following two procedures. Substitute a
stratification test for sulfur dioxide (SO2) for the Hg
stratification test described in section 8.1.3.1. If this option is
chosen, follow the test procedures in section 6.5.6.1 of appendix A to
part 75 of this chapter. Evaluate the test results and determine the
sampling point locations according to section 6.5.6.3 of appendix A to
part 75 of this chapter. If the sampling location is found to be
minimally stratified or unstratified for SO2, it shall be
considered minimally stratified or unstratified for Hg. Alternatively,
you may forgo stratification testing, assume the gas stream is minimally
stratified, and sample at three points as described in section 8.1.3.2.2
of this method.
8.2 Initial Measurement System Performance Tests. What initial
performance criteria must my system meet before I begin sampling? Before
measuring emissions, perform the following procedures:
(a) Interference Test;
(b) Calibration Gas Verification;
(c) Measurement System Preparation;
(d) 3-Point System Calibration Error Test;
(e) System Integrity Check;
(f) Measurement System Response Time Test; and
(g) Dynamic Spiking Test.
8.2.1 Interference Test (Optional). Your measurement system should
be free of known interferences. It is recommended that you conduct this
interference test of your measurement system prior to its initial use in
the field to verify that the candidate test instrument is free from
inherent biases or interferences resulting from common combustion
emission constituents. If you have multiple measurement systems with
components of the same make and model numbers, you need only perform
this interference check on one system and you may also rely on an
interference test conducted by the manufacturer on a system having
components of the same make and model(s) of the system that you use. The
interference test procedure is found in section 8.6 of this method.
8.2.2 Calibration Gas Verification. How must I verify the
concentrations of my calibration gases?
8.2.2.1 Cylinder Gas Standards. When cylinder gas standards are used
for Hg⁰, obtain a certificate from the gas manufacturer and
confirm that the documentation includes all information required by an
EPA traceability protocol (see section 16). Confirm that the
manufacturer certification is complete and current. Ensure that the
calibration gas certifications have not expired.
8.2.2.2 Other Calibration Standards. All other calibration standards
for HgCl2 and Hg⁰, such as gas generators, must
meet the requirements of an EPA traceability protocol (see section 16),
and the certification procedures must be fully documented in the test
report.
8.2.2.3 Calibration Span. Select the calibration span (i.e., high-
level gas concentration) so that the measured source emissions are 10 to
100 percent of the calibration span. This requirement is waived for
applications in which the Hg concentrations are consistently below 1
g/m\3\; however, the calibration span for these low-
concentration applications shall not exceed 5 g/m\3\.
8.2.3 Measurement System Preparation. How do I prepare my
measurement system for use? Assemble, prepare, and precondition the
measurement system according to your standard operating procedure.
Adjust the system to achieve the correct sampling rate or dilution ratio
(as applicable). Then, conduct a 3-point system calibration error test
using Hg⁰ as described in section 8.2.4, an initial system
integrity check using HgCl2 and a zero gas as described in
section 8.2.5, and a pre-test dynamic spiking test as described in
section 8.2.7.
8.2.4 System Calibration Error Test. Conduct a 3-point system
calibration error test before the first test run. Use Hg\0\ standards
for this test. Introduce the low-, mid-, and high-level calibration
gases in any order, in system calibration mode, unless you desire to
determine the system response time during this test, in which case,
inject the gases such that the high-level injection directly follows the
low-level injection. For non-dilution systems, you may adjust the system
to maintain the correct flow rate at the analyzer during the test, but
you may not make adjustments for any other purpose. For dilution
systems, you must operate the measurement system at the appropriate
dilution

[[Page 644]]

ratio during all system calibration error checks, and you may make only
the adjustments necessary to maintain the proper ratio. After each gas
injection, wait until a stable response has been obtained. Record the
analyzer's final, stable response to each calibration gas on a form
similar to Table 30A-1 in section 17.0. For each calibration gas,
calculate the system calibration error using Equation 30A-1 in section
12.2. The calibration error specification in section 13.1 must be met
for the low-, mid-, and high-level gases. If the calibration error
specification is not met for all three gases, take corrective action and
repeat the test until an acceptable 3-point calibration is achieved.
8.2.5 System Integrity Check. Perform a two-point system integrity
check before the first test run. Use the zero gas and either the mid- or
high-level HgCl2 calibration gas for the check, whichever one
best represents the total vapor phase Hg concentration levels in the
stack. Record the data on a form similar to Table 30A-2 in section 17.0.
The system integrity check specification in section 13.2 must be met for
both the zero gas and the mid- or high-level gas. If the system
integrity specification is not met for both gases, take corrective
action and repeat the test until an acceptable system integrity check is
achieved.
8.2.6 Measurement System Response Time. The measurement system
response time is used to determine the minimum sampling time for each
sampling point and is equal to the time that is required for the
measured Hg concentration to increase from the stable low-level
calibration gas response to a value within 5 percent of the stable high-
level calibration gas response during the system calibration error test
in section 8.2.4. Round off the measured system response time to the
nearest minute.
8.2.7 Dynamic Spiking Test. You must perform dynamic spiking prior
to the first test run to validate your test data. The purpose of this
procedure is to demonstrate that the site-specific flue gas matrix does
not adversely affect the accuracy of the measurement system. The
specifications in section 13.5 must be met to validate your data. If
these specifications are not met for the pre-test dynamic spiking, you
may not proceed with the test until satisfactory results are obtained.
For the time period between the effective date of this method and
January 1, 2009, the dynamic spiking requirement is waived.
8.2.7.1 How do I perform dynamic spiking? Dynamic spiking is a gas
phase application of the method of standard additions, which involves
injecting a known quantity of Hg into the measurement system upstream of
all sample conditioning components, similar to system calibration mode,
except the probe is not flooded and the resulting sample stream includes
both effluent gas and the spike gas. You must follow a written procedure
that details how the spike is added to the system, how the spike
dilution factor (DF) is measured, and how the Hg concentration data are
collected and processed.
8.2.7.2 Spiking Procedure Requirements.
8.2.7.2.1 Spiking Gas Requirements. The spike gas must also be a
HgCl2 calibration gas certified by an EPA traceability
protocol. You must choose concentrations that can produce the target
levels while being injected at a volumetric flow rate that is
20 percent of the total volumetric flow rate through the
measurement system (i.e., sample flow rate plus spike gas flow rate).
8.2.7.2.2 Target Spiking Level. The target level for spiking must be
150 to 200 percent of the native Hg concentration; however, if the
native Hg concentration is <1 g/m\3\, set the target level to
add between 1 and 4 g/m\3\ Hg⁺² to the native
concentration. Use Equation 30A-5 in section 12.5 to calculate the
acceptable range of spike gas concentrations at the target level. Then
select a spike gas concentration in that range.
8.2.7.2.3 Spike Injections. You must inject spikes in such a manner
that the spiking does not alter the total volumetric sample system flow
rate and dilution ratio (if applicable). You must collect at least 3
data points, and the relative standard deviation (RSD) specification in
section 13.5 must be met. Each data point represents a single spike
injection, and pre- and post-injection measurements of the native Hg
concentration (or diluted native concentration, as applicable) are
required for each spike injection.
8.2.7.2.4 Spike Dilution Factor (DF). For each spike injection, DF,
the dilution factor must be determined. DF is the ratio of the total
volumetric flow rate of gas through the measurement system to the spike
gas flow rate. This factor must be 5. The spiking mass
balance calculation is directly dependent on the accuracy of the DF
determination. As a result, high accuracy total volumetric flow rate and
spike gas flowrate measurements are required. These flow rates may be
determined by direct or indirect measurement. Calibrated flow meters,
venturies, orifices or tracer gas measurements are examples of potential
flow measurement techniques.
8.2.7.2.5 Concentrations. The measurement system must record total
vapor phase Hg concentrations continuously during the dynamic spiking
procedure. It is possible that dynamic spiking at a level close to 200
percent of the native Hg concentration may cause the measured Hg
concentration to exceed the calibration span value. Avoid this by
choosing a lower spiking level or by recalibration at a higher span. The
measurements shall not exceed 120 percent of the calibration span. The
``baseline'' measurements made between spikes may represent

[[Page 645]]

the native Hg concentration (if spike gas flow is stopped between
injections) or the native Hg concentration diluted by blank or carrier
gas flowing at the same rate as the spike gas (if gas flow cannot be
stopped between injections). Each baseline measurement must include at
least 4 readings or 1 minute (whichever is greater) of stable responses.
Use Equation 30A-10 or 30A-11 in section 12.10 (as applicable) to
convert baseline measurements to native concentration.
8.2.7.2.6 Recovery. Calculate spike recoveries using Equation 30A-7
in section 12.7. Mass recoveries may be calculated from stable responses
based on injected mass flows or from integrated response peaks based on
total mass injected. Calculate the mean and RSD for the three (or more)
spike injections and compare to the specifications in section 13.5.
8.2.7.2.7 Error Adjustment Option. You may adjust the measurement
data collected during dynamic spiking for the system calibration error
using Equation 30A-3 in section 12. To do this, perform the initial
system integrity check prior to the dynamic spiking test, and perform
another system integrity check following the dynamic spiking test and
before the first test run. If you choose this option, you must apply
Equation 30A-3 to both the spiked sample concentration measurement
(Css) and the baseline or native concentration measurement
(Cnative), each substituted in place of Cavg in
the equation.
8.2.7.3 Example Spiking Procedure Using a Hot Vapor Calibration
Source Generator.
(a) Introduce the spike gas into the probe using a hot vapor
calibration source generator and a solution of HgCl2 in
dilute HC1 and HNO3. The calibrator uses a mass flow
controller (accurate within 2 percent) to measure the gas flow, and the
solution feed is measured using a top-loading balance accurate to 0.01g.
The challenges of injecting oxidized Hg may make it impractical to stop
the flow of gas between spike injections. In this case, operate the hot
vapor calibration source generator continuously during the spiking
procedure, swapping blank solutions for HgCl2 solutions when
switching between spiking and baseline measurements.
(b) If applicable, monitor the measurement system to make sure the
total sampling system flow rate and the sample dilution ratio do not
change during this procedure. Record all data on a data sheet similar to
Table 30A-5 in section 17.0. If the Hg measurement system design makes
it impractical to measure the total volumetric flow rate through the
system, use a spike gas that includes a tracer for measuring the
dilution factor, DF (see Equation 30A-9 in section 12.9). Allow the
measurements to stabilize between each spike injection, average the pre-
and post-injection baseline measurements, and calculate the native
concentration. If this measurement shifts by more than 5 percent during
any injection, it may be necessary to discard that data point and repeat
the injection to achieve the required RSD among the injections. If the
spikes persistently show poor repeatability, or if the recoveries are
not within the range specified in section 13.5, take corrective action.
8.2.8 Run Validation. How do I confirm that each run I conduct is
valid?
8.2.8.1 System Integrity Checks.
(a) Before and after each test run, perform a two-point system
integrity check using the same procedure as the initial system integrity
check described in section 8.2.5. You may use data from that initial
system integrity check as the pre-run data for the first test run,
provided it is the most recent system integrity check done before the
first run. You may also use the results of a successful post-run system
integrity check as the pre-run data for the next test run. Do not make
any adjustments to the measurement system during these checks, other
than to maintain the target calibration gas flow rate and the proper
dilution ratio.
(b) As a time-saving alternative, you may, at the risk of
invalidating multiple test runs, skip one or more integrity checks
during a test day. Provided there have been no auto-calibrations or
other instrument alterations, a single integrity check may suffice as a
post-run check to validate (or invalidate) as many consecutive test runs
as can be completed during a single test day. All subsequent test days
must begin with a pre-run system integrity check subject to the same
performance criteria and corrective action requirements as a post-run
system integrity check.
(c) Each system integrity check must meet the criteria for system
integrity checks in section 13.2. If a post-run system integrity check
is failed, all test runs since the last passed system integrity check
are invalid. If a post-run or a pre-run system integrity check is
failed, you must take corrective action and pass another 3-point Hg\0\
system calibration error test (Section 8.2.4) followed by another system
integrity check before conducting any additional test runs. Record the
results of the pre- and post-run system integrity checks on a form
similar to Table 30A-2 in section 17.0.
8.2.8.2 Drift Check. Using the data from the successful pre- and
post-run system integrity checks, calculate the zero and upscale drift,
using Equation 30A-2 in section 12.3. Exceeding the section 13.3
specification does not invalidate the run, but corrective action must be
taken and a new 3-point Hg\0\ system calibration error test and a system
integrity check must be passed before any more runs are made.
8.3 Dilution-Type Systems--Special Considerations. When a dilution-
type measurement system is used, there are three important
considerations that must be taken into

[[Page 646]]

account to ensure the quality of the emissions data. First, the critical
orifice size and dilution ratio must be selected properly so that the
sample dew point will be below the sample line and analyzer
temperatures. Second, a high-quality, accurate dilution controller must
be used to maintain the correct dilution ratio during sampling. The
dilution controller should be capable of monitoring the dilution air
pressure, orifice upstream pressure, eductor vacuum, and sample flow
rates. Third, differences between the molecular weight of calibration
gas mixtures, dilution air, and the stack gas molecular weight must be
considered because these can affect the dilution ratio and introduce
measurement bias.
8.4 Sampling.
(a) Position the probe at the first sampling point. Allow the system
to flush and equilibrate for at least two times the measurement system
response time before recording any data. Then, traverse and record
measurements at all required sampling points. Sample at each traverse
point for an equal length of time, maintaining the appropriate sample
flow rate or dilution ratio (as applicable). For all Hg instrumental
method systems, the minimum sampling time at each sampling point must be
at least two times the system response time, but not less than 10
minutes. For concentrating systems, the minimum sampling time must also
include at least 4 concentration measurement cycles.
(b) After recording data for the appropriate period of time at the
first traverse point, you may move the sample probe to the next point
and continue recording, omitting the requirement to allow the system to
equilibrate for two times the system response time before recording data
at the subsequent traverse points. You must, however, sample at this and
all subsequent traverse points for the required minimum amount of time
specified in this section. If you must remove the probe from the stack
for any reason, you must again allow the sampling system to equilibrate
for at least two times the system response time prior to resuming data
recording.
(c) If at any point the measured Hg concentration exceeds the
calibration span value, you must at a minimum identify and report this
as a deviation from the method. Depending on the data quality objectives
of the test, this event may require corrective action before proceeding.
If the average Hg concentration for any run exceeds the calibration span
value, the run is invalidated.
8.5 Moisture Correction. If the moisture basis (wet or dry) of the
measurements made with this method is different from the moisture basis
of either: (1) The applicable emission limit; or (2) a Hg CEMS or
sorbent trap monitoring system being evaluated for relative accuracy,
you must determine the moisture content of the flue gas and correct the
measured gas concentrations to a dry basis using Method 4 in appendix A-
3 of this part or other appropriate methods, subject to the approval of
the Administrator.
8.6 Optional Interference Test Procedure.
(a) Select an appropriate calibration span that reflects the
source(s) to be tested and perform the interference check at 40 percent
of the lowest calibration span value anticipated, e.g., 10 g/
m\3\. Alternatively, successfully conducting the interference test at an
absolute Hg concentration of 2 g/m\3\ will demonstrate
performance for an equivalent calibration span of 5 g/m\3\, the
lowest calibration span allowed for Method 30A testing. Therefore,
performing the interference test at the 2 /m\3\ level will
serve to demonstrate acceptable performance for all calibration spans
greater than or equal to 5 g/m\3\.
(b) Introduce the interference test gases listed in Table 30A-3 in
section 17.0 into the measurement system separately or as a mixture. The
interference test gases HCl and NO must be introduced as a mixture. The
interference test gases must be introduced into the sampling system at
the probe such that the interference gas mixtures pass through all
filters, scrubbers, conditioners, and other components as would be
configured for normal sampling.
(c) The interference test must be performed using HgCl2,
and each interference test gas (or gas mixture) must be evaluated in
triplicate. This is accomplished by measuring the Hg response first with
only the HgCl2 gas present and then when adding the
interference test gas(es) while maintaining the HgCl2
concentration of the test stream constant. It is important that the
equipment used to conduct the interference test be of sufficient quality
so as to be capable of blending the HgCl2 and interference
gases while maintaining the Hg concentration constant. Gas blending
system or manifolds may be used.
(d) The duration of each test should be for a sufficient period of
time to ensure the Hg measurement system surfaces are conditioned and a
stable output is obtained. Measure the Hg response of the analyzer to
these gases in g/m3. Record the responses and determine the
overall interference response using Table 30A-4 in section 17.0 and the
equations presented in section 12.11. The specification in section 13.4
must be met.
(e) A copy of these data, including the date completed and a signed
certification, must be included with each test report. The intent of
this test is that the interference test results are intended to be valid
for the life of the system. As a result, the Hg measurement system
should be operated and tested in a configuration consistent with the
configuration that will be used for field applications. However, if the
system used for field testing is not consistent with the system that was
interference-tested, the interference test

[[Page 647]]

must be repeated before it is used for any field applications. Examples
of such conditions include, but are not limited to: major changes in
dilution ratio (for dilution based systems), changes in catalyst
materials, changes in filtering device design or materials, changes in
probe design or configuration, and changes in gas conditioning materials
or approaches.

9.0 Quality Control

What quality control measures must I take?

The table which follows is a summary of the mandatory, suggested,
and alternative quality assurance and quality control measures and the
associated frequency and acceptance criteria. All of the QC data, along
with the run data, must be documented and included in the test report.

Summary Table of QA/QC Requirements
----------------------------------------------------------------------------------------------------------------
Status \1\ Process or element QA/QC specification Acceptance criteria Checking frequency
----------------------------------------------------------------------------------------------------------------
S.................. Identify Data User.. Regulatory Agency or Before designing test....
other primary end
user of data.
M.................. Analyzer Design..... Analyzer range...... Sufficiently >high-level
gas to allow
determination of system
calibration error.
S.................. Analyzer resolution <2.0 % of full-scale Manufacturer design......
or sensitivity. range.
S.................. Interference Overall response 3% of
calibration span.
Alternatively,
overall response
0.3
g/m\3\.
M.................. Calibration Gases... Traceability Validation of
protocol. concentration required.
M.................. High-level Hg\0\ gas Equal to the Each calibration error
calibration span. test..
M.................. Mid-level Hg\0\ gas. 40 to 60% of Each calibration error
calibration span. test..
M.................. Low-level Hg\0\ gas. 10 to 30% of Each calibration error
calibration span. test..
M.................. High-level HgCl2 gas Equal to the Each system integrity
calibration span. check (if it better
represents Cnative than
the mid level gas)..
M.................. Mid-level HgCl2..... 40 to 60% of Each system gas integrity
calibration span. check (if it better
represents Cnative than
the high level gas)..
M.................. Zero gas............ Each system
integrity check..
M.................. Dynamic spike gas A high-concentration Pre-test; dynamic spiking
(Cnative 1 g/ produce a spiked 09..
m\3\). sample
concentration that
is 150 to 200% of
the native
concentration.
M.................. Dynamic spike gas A high-concentration Pre-test; dynamic spiking
(Cnative <1 g/m\3\). produce a spiked 09..
sample
concentration that
is 1 to 2 g/m\3\ above the
native
concentration.
S.................. Data Recorder Design Data resolution..... 0.5% of full- Manufacturer design.
scale.
M.................. Sample Extraction... Probe material...... Inert to sample Each run.
constituents (e.g., PFA
Teflon, or quartz if
stack >500 [deg]F).
M.................. Sample Extraction... Probe, filter and For dry-basis analyzers, Each run.
sample line keep sample above the
temperature. dew point, by heating
prior to moisture
removal.
For wet-basis analyzers,
keep sample above dew
point at all times, by
heating or dilution.
M.................. Sample Extraction... Calibration valve Inert to sample Each test.
material. constituents (e.g., PFA
Teflon or PFA Teflon
coated).
S.................. Sample Extraction... Sample pump material Inert to sample Each test.
constituents.
M.................. Sample Extraction... Manifold material... Inert to sample Each test.
constituents.

[[Page 648]]

M.................. Particulate Removal. Filter inertness.... Pass calibration error Each calibration
check. error check.
M.................. System Calibration System calibration CE 5.0 % of Before initial run
Performance. error (CE) test. the calibration span for and after a failed
the low-, mid-or high- system integrity
level Hg\0\ calibration check or drift
gas. test.
Alternative
specification: 0.5 g/m\3\
absolute difference
between system response
and reference value.
M.................. System Calibration System integrity Error 5.0% of Before initial run,
Performance. check. the calibration span for after each run, at
the zero and mid- or the beginning of
high-level HgCl2 subsequent test
calibration gas. days, and after a
Alternative failed system
specification: 0.5 g/m\3\ drift test.
absolute difference
between system response
and reference value.
M.................. System Performance.. System response time Used to determine minimum During initial 3-
sampling time per point. point system
calibration error
test.
M.................. System Performance.. Drift............... 3.0% of At least once per
calibration span for the test day.
zero and mid- or high-
level gas.
Alternative
specification: 0.3 g/m\3\
absolute difference
between pre- and post-
run system calibration
error percentages..
M.................. System Performance.. Minimum sampling The greater of two times Each sampling point.
time. the system response time
or 10 minutes.
Concentrating systems
must also include at
least 4 cycles.
M.................. System Performance.. Percentage spike Percentage spike Before initial run;
recovery and recovery, at the target dynamic spiking not
relative standard level: 100 10%. required until 1/1/
deviation. Relative standard 09.
deviation: 5
percent.
Alternative
specification: absolute
difference between
calculated and measured
spike values 0.5 g/m\3\.
M.................. Sample Point Number and Location For emission testing Prior to first run.
Selection. of Sample Points. applications, use 12
points, located
according to Method 1 in
appendix A-1 to this
part, unless the results
of a stratification test
allow fewer points to be
used.
For Part 60 RATAs,
follow the
procedures in
Performance
Specification 2,
section 8.1.3, and
for Part 75 RATAs,
follow the
procedures in
section 6.5.6 of
appendix A to Part
75. That is:
At any test
location, you may
use 3 sample points
located at 16.7,
50.0, and 83.3% of
a ``long''
measurement line
passing through the
centroidal area; or
At any test
location, you may
use 6 sample points
along a diameter,
located according
to Method 1 (Part
75 RATAs, only); or

[[Page 649]]

At a
location where
stratification is
not expected and
the measurement
line is >2.4 m (7.8
ft), you may use 3
sample points
located along a
``short''
measurement line at
0.4, 1.0, and 2.0 m
from the stack or
duct wall or, for
Part 75 only,
sample points may
be located at 4.4,
14.6, and 29.6% of
the measurement
line; or
After a wet
scrubber or at a
point where
dissimilar gas
streams are
combined, either
locate 3 sample
points along the
``long''
measurement line or
locate 6 Method 1
points along a
diameter (Part 75,
only), unless the
results of a
stratification test
allow you to use a
``short'' 3-point
measurement line or
to sample at a
single point.
If it can
be demonstrated
that stack gas
concentration is
3 g/m\3\, then the
test site is
exempted from
stratification
testing. Use the 3-
point ``short''
measurement line if
the stack diameter
is >2.4 m (7.8 ft)
and the 3-point
``long'' line for
stack diameters 2.4 m (7.8
ft).

[[Page 650]]

A.................. Sample Point Stratification Test If the Hg Prior to first run.
Selection (See section concentration\2\ at each Prior to 1/1/09, you
8.1.3).. traverse point during may (1) forgo
the stratification test stratification
is: testing and use 3
Within 5% of sampling points (as
mean, use 1-point per section
sampling (at the point 8.1.3.2.2) or (2)
closest to the mean); or. perform a SO2
Not within 5% stratification test
of mean, but is within (see sections
10% of mean, use 3- 6.5.6.1 and 6.5.6.3
point sampling. Locate of appendix A to
points according to part 75), in lieu
section 8.1.3.2.2 of of a Hg
this method.. stratification
Alternatively, if the Hg test. If the test
concentration at each location is
point is:. unstratified or
Within 0.2 minimally
g/m\3\ of mean, stratified for SO2,
use 1-point sampling (at it can be
the point closest to the considered
mean); or. unstratified or
Not within 0.2 minimally
g/m\3\ of mean, stratified for Hg
but is within 0.5 also.
g/m\3\ of mean,
use 3-point sampling.
Locate points according
to section 8.1.3.2.2 of
this method..
M.................. Data Recording...... Frequency........... Once per cycle........... During run.
S.................. Data Parameters..... Sample concentration All analyzer readings Each run.
and calibration during each run within
span. calibration span.
M.................. Data Parameters..... Sample concentration All analyzer readings Each spike
and calibration during dynamic spiking injection.
span. tests within 120% of
calibration span.
M.................. Data Parameters..... Sample concentration Average Hg concentration Each run.
and calibration for the run calibration span.
----------------------------------------------------------------------------------------------------------------
\1\ M = Mandatory; S = Suggested; A = Alternative.
\2\ These may either be the unadjusted Hg concentrations or concentrations normalized to account for temporal
variations.

10.0 Calibration and Standardization

What measurement system calibrations are required?

Your analyzer must be calibrated with Hg[deg] standards. The initial
3-point system calibration error test described in section 8.2.4 is
required before you start the test. Also, prior to and following test
runs, the two-point system integrity checks described in sections 8.2.5
and 8.2.8 are required. On and after January 1, 2009, the pre-test
dynamic spiking procedure described in section 8.2.7 is also required to
verify that the accuracy of the measurement system is suitable and not
adversely affected by the flue gas matrix.

11.0 Analytical Procedures

Because sample collection and analysis are performed together (see
section 8), additional discussion of the analytical procedure is not
necessary.

12.0 Calculations and Data Analysis

You must follow the procedures for calculations and data analysis
listed in this section.

12.1 Nomenclature. The terms used in the equations are defined as
follows:
Bws = Moisture content of sample gas as measured by Method 4
in Appendix A-3 to this part, percent/100.
Cavg = Average unadjusted Hg concentration for the test run,
as indicated by the data recorder g/m\3\.
Cbaseline = Average Hg concentration measured before and
after dynamic spiking injections, g/m\3\.
Cd = Hg concentration, dry basis, g/m\3\.
Cdif = Absolute value of the difference between the measured
Hg concentrations of the reference HgCl2
calibration gas, with and without the individual or combined
interference gases, g/m\3\.
Cdif avg = Average of the 3 absolute values of the difference
between the measured Hg concentrations of the reference
HgCl2 calibration gas, with and without the
individual or combined interference gases, g/m\3\.
Cgas = Average Hg concentration in the effluent gas for the
test run, adjusted for system calibration error, g/
m\3\.

[[Page 651]]

Cint = Measured Hg concentration of the reference
HgCl2 calibration gas plus the individual or
combined interference gases, g/m\3\.
Cm = Average of pre- and post-run system integrity check
responses for the upscale (i.e., mid- or high-level)
calibration gas, g/m\3\.
Cma = Actual concentration of the upscale (i.e., mid- or
high-level) calibration gas used for the system integrity
checks, g/m\3\.
C0 = Average of pre- and post-run system integrity check
responses from the zero gas, g/m\3\.
Cnative = Vapor phase Hg concentration in the source
effluent, g/m\3\.
Cref = Measured Hg concentration of the reference
HgCl2 calibration gas alone, in the interference
test, g/m\3\.
Cs = Measured concentration of a calibration gas (zero-, low-
, mid-, or high-level), when introduced in system calibration
mode, g/m\3\.
Cspike = Actual Hg concentration of the spike gas,
g/m\3\.
C*spike = Hg concentration of the spike gas required to
achieve a certain target value for the spiked sample Hg
concentration, g/m\3\.
Css = Measured Hg concentration of the spiked sample at the
target level, g/m\3\.
C*ss = Expected Hg concentration of the spiked sample at the
target level, g/m\3\.
Ctarget = Target Hg concentration of the spiked sample,
g/m\3\.
CTnative = Measured tracer gas concentration present in
native effluent gas, ppm.
CTdir = Tracer gas concentration injected with spike gas,
ppm.
CTv = Diluted tracer gas concentration measured in a spiked
sample, ppm.
Cv = Certified Hg[deg] or HgCl2 concentration of a
calibration gas (zero, low, mid, or high), g/m\3\.
Cw = Hg concentration measured under moist sample conditions,
wet basis, g/m\3\.
CS = Calibration span, g/m\3\.
D = Zero or upscale drift, percent of calibration span.
DF = Dilution factor of the spike gas, dimensionless.
I = Interference response, percent of calibration span.
Qprobe = Total flow rate of the stack gas sample plus the
spike gas, liters/min.
Qspike = Flow rate of the spike gas, liters/min.
Ri = Individual injection spike recovery, %.
R = Mean value of spike recoveries at a particular target level, %.
RSD = Relative standard deviation, %;.
SCE = System calibration error, percent of calibration span.
SCEi = Pre-run system calibration error during the two-point
system integrity check, percent of calibration span.
SCEf = Post-run system calibration error during the two-point
system integrity check, percent of calibration span.

12.2 System Calibration Error. Use Equation 30A-1 to calculate the
system calibration error. Equation 30A-1 applies to: 3-point system
calibration error tests performed with Hg[deg] standards; and pre- and
post-run two-point system integrity checks performed with
HgCl2.
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12.3 Drift Assessment. Use Equation 30A-2 to separately calculate
the zero and upscale drift for each test run.
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12.3 Effluent Hg Concentration. For each test run, calculate
Cavg, the arithmetic average of all valid Hg concentration
values recorded during the run. Then, adjust the value of
Cavg for system calibration error, using Equation 30A-3.
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12.4 Moisture Correction. Use Equation 30A-4a if your measurements
need to be corrected to a dry basis.
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Use Equation 30A-4b if your measurements need to be corrected to a
wet basis.
[GRAPHIC] [TIFF OMITTED] TR07SE07.009

12.5 Dynamic Spike Gas Concentrations. Use Equation 30A-5 to
determine the spike gas concentration needed to produce a spiked sample
with a certain ``target'' Hg concentration.

[[Page 652]]

[GRAPHIC] [TIFF OMITTED] TR07SE07.010

12.6 Spiked Sample Concentration. Use Equation 30A-6 to determine
the expected or theoretical Hg concentration of a spiked sample.
[GRAPHIC] [TIFF OMITTED] TR07SE07.011

12.7 Spike Recovery. Use Equation 30A-7 to calculate the percentage
recovery of each spike.
[GRAPHIC] [TIFF OMITTED] TR07SE07.012

12.8 Relative Standard Deviation. Use Equation 30A-8 to calculate
the relative standard deviation of the individual percentage spike
recovery values from the mean.
[GRAPHIC] [TIFF OMITTED] TR07SE07.013

12.9 Spike Dilution Factor. Use Equation 30A-9 to calculate the
spike dilution factor, using either direct flow measurements or tracer
gas measurements.
[GRAPHIC] [TIFF OMITTED] TR07SE07.014

12.10 Native Concentration. For spiking procedures that inject blank
or carrier gases (at the spiking flow rate, Qspike) between
spikes, use Equation 30A-10 to calculate the native concentration.
[GRAPHIC] [TIFF OMITTED] TR07SE07.015

For spiking procedures that halt all injections between spikes, the
native concentration equals the average baseline concentration (see
Equation 30A-11).
[GRAPHIC] [TIFF OMITTED] TR07SE07.016

12.11 Overall Interference Response. Use equation 30A-12 to
calculate the overall interference response.
[GRAPHIC] [TIFF OMITTED] TR07SE07.017

Where, for each interference gas (or mixture):

[[Page 653]]

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[GRAPHIC] [TIFF OMITTED] TR07SE07.019

13.0 Method Performance

13.1 System Calibration Error Test. This specification applies to
the 3-point system calibration error tests using Hg⁰. At each
calibration gas level tested (low-, mid-, or high-level), the
calibration error must be within 5.0 percent of the calibration span.
Alternatively, the results are acceptable if | Cs -
Cv | 0.5 g/m\3\.
13.2 System Integrity Checks. This specification applies to all pre-
and post-run 2-point system integrity checks using HgCl2 and
zero gas. At each calibration gas level tested (zero and mid- or high-
level), the error must be within 5.0 percent of the calibration span.
Alternatively, the results are acceptable if | Cs -
Cv | 0.5 g/m\3\.
13.3 Drift. For each run, the low-level and upscale drift must be
less than or equal to 3.0 percent of the calibration span. The drift is
also acceptable if the pre- and post-run system integrity check
responses do not differ by more than 0.3 g/m\3\ (i.e., |
Cs post-run - Cs pre-run | 0.3
g/m\3\).
13.4 Interference Test. Summarize the results following the format
contained in Table 30A-4. For each interference gas (or mixture),
calculate the mean difference between the measurement system responses
with and without the interference test gas(es). The overall interference
response for the analyzer that was used for the test (calculated
according to Equation 30A-12), must not be greater than 3.0 percent of
the calibration span used for the test (see section 8.6). The results of
the interference test are also acceptable if the sum of the absolute
average differences for all interference gases (i.e., M
Cdif avg) does not exceed 0.3 g/m\3\.
13.5 Dynamic Spiking Test. For the pre-test dynamic spiking, the
mean value of the percentage spike recovery must be 100 10 percent. In
addition, the relative standard deviation (RSD) of the individual
percentage spike recovery values from the mean must be 5.0
percent. Alternatively, if the mean percentage recovery is not met, the
results are acceptable if the absolute difference between the
theoretical spiked sample concentration (see section 12.6) and the
actual average value of the spiked sample concentration is
0.5 g/m\3\.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. EPA Traceability Protocol for Qualification and Certification of
Elemental Mercury Gas Generators, expected publication date December
2008, see www.epa.gov/ttn/emc.
2. EPA Traceability Protocol for Qualification and Certification of
Oxidized Mercury Gas Generators, expected publication date December
2008, see www.epa.gov/ttn/emc.
3. EPA Traceability Protocol for Assay and Certification of Gaseous
Calibration Standards, expected revision publication date December 2008,
see www.epa.gov/ttn/emc.

17.0 Figures and Tables

[[Page 654]]

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[[Page 655]]

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[[Page 656]]

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[[Page 657]]

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Table 30A-3--Interference Check Gas Concentrations
------------------------------------------------------------------------
Concentration, tentative--(balance
Potential interferent gas \1\ N2)
------------------------------------------------------------------------
CO2............................... 15% 1% CO2
CO................................ 100 20 ppm
HCl \2\........................... 100 20 ppm
NO \2\............................ 250 50 ppm
SO2............................... 200 20 ppm
O2................................ 3% 1% O2
H2O............................... 10% 1% H2O
Nitrogen.......................... Balance
Other.............................
------------------------------------------------------------------------
\1\ Any of these specific gases can be tested at a lower level if the
manufacturer has provided reliable means for limiting or scrubbing
that gas to a specified level.
\2\ HCl and NO must be tested as a mixture.

[[Page 658]]

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[[Page 659]]

[GRAPHIC] [TIFF OMITTED] TR07SE07.025

[[Page 660]]

Method 30B--Determination of Total Vapor Phase Mercury Emissions From
Coal-Fired Combustion Sources Using Carbon Sorbent Traps

1.0 Scope and Application

What is Method 30B?

Method 30B is a procedure for measuring total vapor phase mercury
(Hg) emissions from coal-fired combustion sources using sorbent trap
sampling and an extractive or thermal analytical technique. This method
is only intended for use only under relatively low particulate
conditions (e.g., sampling after all pollution control devices). Quality
assurance and quality control requirements are included to assure that
you, the tester, collect data of known and acceptable quality for each
testing program. This method does not completely describe all equipment,
supplies, and sampling and analytical procedures you will need, but
instead refers to other test methods for some of the details. Therefore,
to obtain reliable results, you should also have a thorough knowledge of
these additional methods which are found in Appendices A-1 and A-3 to
this part:
(a) Method 1--Sample and Velocity Traverses for Stationary Sources.
(b) Method 4--Determination of Moisture Content in Stack Gases.
(c) Method 5--Determination of Particulate Matter Emissions from
Stationary Sources
1.1 Analytes. What does this method determine? This method is
designed to measure the mass concentration of total vapor phase Hg in
flue gas, including elemental Hg (Hg\0\) and oxidized forms of Hg
(Hg⁺²), in micrograms per dry standard cubic meter
(g/dscm).

------------------------------------------------------------------------
Analytical range and
Analyte CAS No. sensitivity
------------------------------------------------------------------------
Elemental Hg (Hg \0\ )............. 7439-97-6 Typically 0.1 g/dscm to >50
g/dscm.
Oxidized Hg (Hg+2)................. ........... (Same)
------------------------------------------------------------------------

1.2 Applicability. When is this method required? Method 30B is a
reference method for relative accuracy test audits (RATAs) of vapor
phase Hg CEMS and sorbent trap monitoring systems installed at coal-
fired boilers and is also appropriate for Hg emissions testing at such
boilers. It is intended for use only under relatively low particulate
conditions (i.e., sampling after all pollution control devices); in
cases where significant amounts of particle-bound Hg may be present, an
isokinetic sampling method for Hg should be used. Method 30B may also be
specified by New Source Performance Standards (NSPS), National Emission
Standards for Hazardous Air Pollutants (NESHAP), emissions trading
programs, State Implementation Plans (SIPs), and operating permits that
require measurement of Hg concentrations in stationary source emissions,
either to determine compliance with an applicable emission standard or
limit, or to conduct RATAs of Hg CEMS and sorbent trap monitoring
systems.
1.3 Data Quality Objectives (DQO). How good must my collected data
be? Method 30B has been designed to provide data of high and known
quality for Hg emissions testing and for RATA testing of Hg monitoring
systems, including CEMS and sorbent trap monitors. In these and other
applications, the principal objective is to ensure the accuracy of the
data at the actual emissions levels and in the actual emissions matrix
encountered. To meet this objective, NIST-traceable calibration
standards must be used and method performance tests are required.

2.0 Summary of Method

Known volumes of flue gas are extracted from a stack or duct through
paired, in-stack sorbent media traps at an appropriate flow rate.
Collection of mercury on the sorbent media in the stack mitigates
potential loss of mercury during transport through a probe/sample line.
For each test run, paired train sampling is required to determine
measurement precision and verify acceptability of the measured emissions
data. A field recovery test which assesses recovery of an elemental Hg
spike to determine measurement bias is also used to verify data
acceptability. The sorbent traps are recovered from the sampling system,
prepared for analysis as needed, and analyzed by any suitable
determinative technique that can meet the performance criteria.

3.0 Definitions

3.1 Analytical System is the combined equipment and apparatus used
to perform sample analyses. This includes any associated sample
preparation apparatus e.g., digestion equipment, spiking systems,
reduction devices, etc., as well as analytical instrumentation such as
UV AA and UV AF cold vapor analyzers.
3.2 Calibration Standards are the Hg containing solutions prepared
from NIST traceable standards and are used to directly calibrate
analytical systems.
3.3 Independent Calibration Standard is a NIST traceable standard
obtained from a source or supplier independent of that for the
calibration standards and is used to confirm the integrity of the
calibration standards used.
3.4 Method Detection Limit (MDL) is the lowest mass of Hg greater
than zero that can be estimated and reported by your candidate
analytical technique. The MDL is statistically derived from replicate
low level measurements near your analytical instrument's detection
level.

[[Page 661]]

3.5 NIST means the National Institute of Standards and Technology,
located in Gaithersburg, Maryland.
3.6 Run means a series of gas samples taken successively from the
stack or duct. A test normally consists of a specific number of runs.
3.7 Sorbent Trap means a cartridge or sleeve containing a sorbent
media (typically activated carbon treated with iodine or some other
halogen) with multiple sections separated by an inert material such as
glass wool. These sorbent traps are optimized for the quantitative
capture of elemental and oxidized forms of Hg and can be analyzed by
multiple techniques.
3.8 Test refers to the series of runs required by the applicable
regulation.
3.9 Thermal Analysis means an analytical technique where the
contents of the sorbent traps are analyzed using a thermal technique
(desorption or combustion) to release the captured Hg in a detectable
form for quantification.
3.10 Wet Analysis means an analytical technique where the contents
of the sorbent tube are first leached or digested to quantitatively
transfer the captured Hg to liquid solution for subsequent analysis.

4.0 Interferences

Interferences may result from the sorbent trap material used as well
as from the measurement environment itself. The iodine present on some
sorbent traps may impart a negative measurement bias. High levels of
sulfur trioxide (SO3) are also suspected to compromise the
performance of sorbent trap Hg capture. These, and other, potential
interferences are assessed by performing the analytical matrix
interference, Hg\0\ and HgCl2 analytical bias and field
recovery tests.

5.0 Safety

What safety measures should I consider when using this method? This
method may require you to work with hazardous materials and in hazardous
conditions. You are encouraged to establish safety procedures before
using the method. Among other precautions, you should become familiar
with the safety recommendations in the gas analyzer user's manual.
Occupational Safety and Health Administration (OSHA) regulations
concerning use of compressed gas cylinders and noxious gases may apply.
5.1 Site Hazards. Prior to applying these procedures/specifications
in the field, the potential hazards at the test site should be
considered; advance coordination with the site is critical to understand
the conditions and applicable safety policies. At a minimum, portions of
the sampling system will be hot, requiring appropriate gloves, long
sleeves, and caution in handling this equipment.
5.2 Laboratory Safety. Policies should be in place to minimize risk
of chemical exposure and to properly handle waste disposal in the
laboratory. Personnel shall wear appropriate laboratory attire according
to a Chemical Hygiene Plan established by the laboratory.
5.3 Reagent Toxicity/Carcinogenicity. The toxicity and
carcinogenicity of any reagents used must be considered. Depending upon
the sampling and analytical technologies selected, this measurement may
involve hazardous materials, operations, and equipment and this method
does not address all of the safety problems associated with implementing
this approach. It is the responsibility of the user to establish
appropriate safety and health practices and determine the applicable
regulatory limitations prior to performance. Any chemical should be
regarded as a potential health hazard and exposure to these compounds
should be minimized. Chemists should refer to the Material Safety Data
Sheet (MSDS) for each chemical used.
5.4 Waste Disposal. Any waste generated by this procedure must be
disposed of according to a hazardous materials management plan that
details and tracks various waste streams and disposal procedures.

6.0 Equipment and Supplies

The following list is presented as an example of key equipment and
supplies likely required to measure vapor-phase Hg using a sorbent trap
sampling system. It is recognized that additional equipment and supplies
may be needed. Collection of paired samples is required.
6.1 Sorbent Trap Sampling System. A typical sorbent trap sampling
system is shown in Figure 30B-1 in section 17.0. The sorbent trap
sampling system shall include the following components:
6.1.1 Sorbent Traps. The sorbent media used to collect Hg must be
configured in a trap with at least two distinct segments or sections,
connected in series, that are amenable to separate analyses. section 1
is designated for primary capture of gaseous Hg. section 2 is designated
as a backup section for determination of vapor phase Hg breakthrough.
Each sorbent trap must be inscribed or otherwise permanently marked with
a unique identification number, for tracking purposes. The sorbent media
may be any collection material (e.g., carbon, chemically-treated filter,
etc.) capable of quantitatively capturing and recovering for subsequent
analysis, all gaseous forms of Hg in the emissions from the intended
application. Selection of the sorbent media shall be based on the
material's ability to achieve the performance criteria contained in this
method as well as the sorbent's vapor phase

[[Page 662]]

Hg capture efficiency for the emissions matrix and the expected sampling
duration at the test site. The sorbent media must be obtained from a
source that can demonstrate their quality assurance and quality control
(see section 7.2). The paired sorbent traps are supported on a probe (or
probes) and inserted directly into the flue gas stream.
6.1.2 Sampling Probe Assembly. Each probe assembly shall have a
leak-free attachment to the sorbent trap(s). Each sorbent trap must be
mounted at the entrance of or within the probe such that the gas sampled
enters the trap directly. Each probe/sorbent trap assembly must be
heated to a temperature sufficient to prevent liquid condensation in the
sorbent trap(s). Auxiliary heating is required only where the stack
temperature is too low to prevent condensation. Use a calibrated
thermocouple to monitor the stack temperature. A single probe capable of
operating the paired sorbent traps may be used. Alternatively,
individual probe/sorbent trap assemblies may be used, provided that the
individual sorbent traps are co-located to ensure representative Hg
monitoring.
6.1.3 Moisture Removal Device. A moisture removal device or system
shall be used to remove water vapor from the gas stream prior to
entering dry gas flow metering devices.
6.1.4 Vacuum Pump. Use a leak-tight, vacuum pump capable of
operating within the system's flow range.
6.1.5 Gas Flow Meter. A gas flow meter (such as a dry gas meter,
thermal mass flow meter, or other suitable measurement device) shall be
used to determine the total sample volume on a dry basis, in units of
standard cubic meters. The meter must be sufficiently accurate to
measure the total sample volume to within 2 percent and must be
calibrated at selected flow rates across the range of sample flow rates
at which the sampling train will be operated. The gas flow meter shall
be equipped with any necessary auxiliary measurement devices (e.g.,
temperature sensors, pressure measurement devices) needed to correct the
sample volume to standard conditions.
6.1.6 Sample Flow Rate Meter and Controller. Use a flow rate
indicator and controller for maintaining necessary sampling flow rates.
6.1.7 Temperature Sensor. Same as section 6.1.1.7 of Method 5 in
Appendix A-3 to this part.
6.1.8 Barometer. Same as section 6.1.2 of Method 5 in Appendix A-3
to this part.
6.1.9 Data Logger (optional). Device for recording associated and
necessary ancillary information (e.g., temperatures, pressures, flow,
time, etc.).
6.2 Gaseous Hg\0\ Sorbent Trap Spiking System. A known mass of
gaseous Hg\0\ must be either present on or spiked onto the first section
of sorbent traps in order to perform the Hg\0\ and HgCl2
analytical bias test and the field recovery study. Any approach capable
of quantitatively delivering known masses of Hg\0\ onto sorbent traps is
acceptable. Several spiking technologies or devices are available to
meet this objective. Their practicality is a function of Hg mass spike
levels. For low levels, NIST-certified or NIST-traceable gas generators
or tanks may be suitable. An alternative system, capable of delivering
almost any mass required, makes use of NIST-certified or NIST-traceable
Hg salt solutions (e.g., HgCl2,
Hg(NO3)2). With this system, an aliquot of known
volume and concentration is added to a reaction vessel containing a
reducing agent (e.g., stannous chloride); the Hg salt solution is
reduced to Hg\0\ and purged onto the sorbent trap using an impinger
sparging system. When available, information on example spiking systems
will be posted at http://www.epa.gov/ttn/emc.
6.3 Sample Analysis Equipment. Any analytical system capable of
quantitatively recovering and quantifying total Hg from the sorbent
media selected is acceptable provided that the analysis can meet the
performance criteria described in this method. Example recovery
techniques include acid leaching, digestion, and thermal desorption/
direct combustion. Example analytical techniques include, but are not
limited to, ultraviolet atomic fluorescence (UV AF), ultraviolet atomic
absorption (UV AA) with and without gold trapping, and X-ray
fluorescence (XRF) analysis.
6.3 Moisture Measurement System. If correction of the measured Hg
emissions for moisture is required (see section 8.3.3.7), either Method
4 in Appendix A-3 to this part or other moisture measurement methods
approved by the Administrator will be needed to measure stack gas
moisture content.

7.0 Reagents and Standards

7.1 Reagents and Standards. Only NIST-certified or NIST-traceable
calibration standards, standard reference materials, and reagents shall
be used for the tests and procedures required by this method.
7.2 Sorbent Trap Media. The sorbent trap media shall be prepared
such that the material used for testing is of known and acceptable
quality. Sorbent supplier quality assurance/quality control measures to
ensure appropriate and consistent performance such as sorptive capacity,
uniformity of preparation treatments, and background levels shall be
considered.

8.0 Sample Collection and Handling

This section presents the sample collection and handling procedures
along with the pretest and on-site performance tests required by this
method. Since you may choose different options to comply with certain
performance criteria, each test report must identify the specific
options selected and

[[Page 663]]

document the results with respect to the performance criteria of this
method.
8.1 Sample Point Selection. What sampling site and sampling points
do I select? Same as section 8.1 of Method 30A of this appendix.
8.2 Measurement System Performance Tests. What performance criteria
must my measurement system meet? The following laboratory and field
procedures and associated criteria of this section are designed to
ensure (1) selection of a sorbent and analytical technique combination
capable of quantitative collection and analysis of gaseous Hg, (2)
collection of an adequate amount of Hg on each sorbent trap during field
tests, and (3) adequate performance of the method for each test program:
The primary objectives of these performance tests are to characterize
and verify the performance of your intended analytical system and
associated sampling and analytical procedures, and to define the minimum
amount of Hg (as the sample collection target) that can be quantified
reliably.
(a) Analytical Matrix Interference Test;
(b) Determination of Minimum Sample Mass;
(c) Hg\0\ and HgCl2 Analytical Bias Test;
(d) Determination of Nominal Sample Volume;
(e) Field Recovery Test.
8.2.1 Analytical Matrix Interference Test and Minimum Sample
Dilution.
(a) The analytical matrix interference test is a laboratory
procedure. It is required only if you elect to use a liquid digestion
analytical approach and needs to be performed only once for each sorbent
material used. The purpose of the test is to verify the presence or
absence of known and potential analytical matrix interferences,
including the potential negative bias associated with iodine common to
many sorbent trap materials. The analytical matrix interference test
determines the minimum dilution (if any) necessary to mitigate matrix
effects on the sample digestate solutions.
(b) The result of the analytical matrix interference test, i.e., the
minimum sample dilution required (if any) for all sample analyses, is
used to establish the minimum sample mass needed for the Hg\0\ and
HgCl2 analytical bias test and to determine the nominal
sample volume for a test run. The analytical matrix interference test is
sorbent material-specific and shall be performed for each sorbent
material you intend to use for field sampling and analysis. The test
shall be performed using a mass of sorbent material comparable to the
sorbent mass typically used in the first section of the trap for
sampling. Similar sorbent materials from different sources of supply are
considered to be different materials and must be tested individually.
You must conduct the analytical matrix interference test for each
sorbent material prior to the analysis of field samples.
8.2.1.1 Analytical Matrix Interference Test Procedures. Digest and
prepare for analysis a representative mass of sorbent material
(unsampled) according to your intended laboratory techniques for field
samples. Analyze the digestate according to your intended analytical
conditions at the least diluted level you intend to use for sample
analysis (e.g., undiluted, 1 in 10 dilution, etc.). Determine the Hg
concentration of the undiluted digestate solution. Prepare a series of
solutions with a fixed final volume containing graduated aliquots of the
sample digestate and, a fixed aliquot of a calibration standard (with
the balance being Hg-free reagent or H20) to establish
solutions of varied digestate dilution ratio (e.g., 1:2, 1:5, 1:10,
1:100, etc.--see example in section 8.2.1.3, below). One of these
solutions should contain only the aliquot of the calibration standard in
Hg-free reagent or H2O. This will result in a series of
solutions where the amount of Hg is held relatively constant and only
the volume of digestate diluted is varied. Analyze each of these
solutions following intended sample analytical procedures and
conditions, determining the concentration for each solution.
8.2.1.2 Analytical Matrix Interference Test Acceptance Criteria.
Compare the measured concentration of each solution containing digestate
to the measured concentration of the digestate-free solution. The lowest
dilution ratio of any solution having a Hg concentration within 5
percent of the digestate-free solution is the minimum dilution ratio
required for analysis of all samples. If you desire to measure the
digestate without dilution, the 5 percent criterion must be met at a
dilution ratio of at least 9:10 (i.e., 90% digestate).
8.2.1.3 Example Analytical Matrix Interference Test. An example
analytical matrix interference test is presented below. Additional
information on the conduct of the analytical matrix interference test
will be posted at http://www.epa.gov/ttn/emc. Determine the most
sensitive working range for the analyzer to be used. This will be a
narrow range of concentrations. Digest and prepare for analysis a
representative mass of sorbent material (unsampled) according to your
intended laboratory techniques for sample preparation and analysis.
Prepare a calibration curve for the most sensitive analytical region,
e.g., 0.0, 0.5, 1.0, 3.0, 5.0, 10 ppb. Using the highest calibration
standard, e.g., 10.0 ppb, prepare a series of solutions by adding
successively smaller increments of the digestate to a fixed volume of
the calibration standard and bringing each solution to a final fixed
volume with mercury-free deionized water (diH2O). To 2.0 ml
of the calibration standard add 18.0, 10.0, 4.0, 2.0, 1.0, 0.2, and 0.0
ml of the digestate. Bring the final volume of each solution to a total
volume of

[[Page 664]]

20 ml by adding 0.0, 8.0, 14.0, 16.0, 17.0, 17.8, and 18.0 ml of
diH2O. This will yield solutions with dilution ratios of
9:10, 1:2, 1:5, 1:10, 1:20, 1:100, and 0:10, respectively. Determine the
Hg concentration of each solution. The dilution ratio of any solution
having a concentration that is within 5 percent of the concentration of
the solution containing 0.0 ml of digestate is an acceptable dilution
ratio for analyzing field samples. If more than one solution meets this
criterion, the one with the lowest dilution ratio is the minimum
dilution required for analysis of field samples. If the 9:10 dilution
meets this criterion, then no sample dilution is required.
8.2.2 Determination of Minimum Sample Mass. The minimum mass of Hg
that must be collected per sample must be determined. This information
is necessary in order to effectively perform the Hg\0\ and
HgCl2 Analytical Bias Test, to estimate target sample
volumes/sample times for test runs, and to ensure the quality of the
measurements. The determination of minimum sample mass is a direct
function of analytical technique, measurement sensitivity, dilutions,
etc. This determination is required for all analytical techniques. Based
on the analytical approach you employ, you should determine the most
sensitive calibration range. Based on a calibration point within that
range, you must consider all sample treatments (e.g., dilutions) to
determine the mass of sample that needs to be collected to ensure that
all sample analyses fall within your calibration curve.
8.2.2.1 Determination of Minimum Calibration Concentration or Mass.
Based on your instrument's sensitivity and linearity, determine the
calibration concentrations or masses that make up a representative low
level calibration range. Verify that you are able to meet the multipoint
calibration performance criteria in section 11.0 of this method. Select
a calibration concentration or mass that is no less than 2 times the
lowest concentration or mass in your calibration curve. The lowest point
in your calibration curve must be at least 5, and preferably 10, times
the Method Detection Limit (MDL), which is the minimum amount of the
analyte that can be detected and reported. The MDL must be determined at
least once for the analytical system using an MDL study such as that
found in section 15.0 to Method 301 of appendix A to part 63 of this
chapter.

Note to section 8.2.2.1: While it might be desirable to base the
minimum calibration concentration or mass on the lowest point in the
calibration curve, selecting a higher concentration or mass is necessary
to ensure that all analyses of the field samples will fall within the
calibration curve. Therefore, it is strongly recommended that you select
a minimum calibration concentration or mass that is sufficiently above
the lowest point of the calibration curve (see examples in sections
8.2.2.2.1 and 8.2.2.2.2 below).

8.2.2.2 Determination of Minimum Sample Mass. Based on your minimum
calibration concentration or mass and other sample treatments including,
but not limited to, final digestate volume and minimum sample dilution,
determine the minimum sample mass. Consideration should also be given to
the Hg levels expected to be measured in section 2 of the sorbent traps
and to the breakthrough criteria presented in Table 9-1.
8.2.2.2.1 Example Determination of Minimum Sample Mass for Thermal
Desorption Analysis. A thermal analysis system has been calibrated at
five Hg mass levels: 10 ng, 20 ng, 50 ng, 100 ng, 200 ng, and shown to
meet the calibration performance criteria in this method. Based on 2
times the lowest point in the calibration curve, 20 ng is selected as
the minimum calibration mass. Because the entire sample is analyzed and
there are no dilutions involved, the minimum sample mass is also 20 ng.

Note: In this example, if the typical background (blank) Hg levels
in section 2 were relatively high (e.g., 3 to 5 ng), a sample mass of 20
ng might not have been sufficient to ensure that the breakthrough
criteria in Table 9-1 would be met, thereby necessitating the use of a
higher point on the calibration curve (e.g., 50 ng) as the minimum
calibration and sample mass.

8.2.2.2.2 Example Determination of Minimum Sample Mass for Acid
Leachate/Digestate Analysis. A cold vapor analysis system has been
calibrated at four Hg concentration levels: 2 ng/L, 5 ng, 10 ng/L, 20
ng/L, and shown to meet the calibration performance criteria in this
method. Based on 2 times the lowest point in the calibration curve, 4
ng/L was selected as the minimum calibration concentration. The final
sample volume of a digestate is nominally 50 ml (0.05 L) and the minimum
dilution necessary was determined to be 1:100 by the Analytical Matrix
Interference Test of section 8.2.1. The following calculation would be
used to determine the minimum sample mass.

Minimum sample mass = (4 ng/L) x (0.05 L) x (100) = 20 ng

Note: In this example, if the typical background (blank) Hg levels
in section 2 were relatively high (e.g., 3 to 5 ng), a sample mass of 20
ng might not have been sufficient to ensure that the breakthrough
criterion in Table 9-1 would be met, thereby necessitating the use of a
higher point on the calibration curve (e.g., 10 ng/L) as the minimum
calibration concentration.

8.2.3 Hg\0\ and HgCl2 Analytical Bias Test. Before
analyzing any field samples, the laboratory must demonstrate the ability
to recover and accurately quantify Hg\0\ and HgCl2

[[Page 665]]

from the chosen sorbent media by performing the following analytical
bias test for sorbent traps spiked with Hg\0\ and HgCl2. The
analytical bias test is performed at a minimum of two distinct sorbent
trap Hg loadings that will: (1) Represent the lower and upper bound of
sample Hg loadings for application of the analytical technique to the
field samples, and (2) be used for data validation.
8.2.3.1 Hg\0\ and HgCl2 Analytical Bias Test Procedures.
Determine the lower and upper bound mass loadings. The minimum sample
mass established in section 8.2.2.2 can be used for the lower bound Hg
mass loading although lower Hg loading levels are acceptable. The upper
bound Hg loading level should be an estimate of the greatest mass
loading that may result as a function of stack concentration and volume
sampled. As previously noted, this test defines the bounds that actual
field samples must be within in order to be valid.
8.2.3.1.1 Hg\0\ Analytical Bias Test. Analyze the front section of
three sorbent traps containing Hg\0\ at the lower bound mass loading
level and the front section of three sorbent traps containing Hg\0\ at
the upper bound mass loading level. In other words, analyze each mass
loading level in triplicate. You may refer to section 6.2 for spiking
guidance. Prepare and analyze each spiked trap, using the same
techniques that will be used to prepare and analyze the field samples.
The average recovery for the three traps at each mass loading level must
be between 90 and 110 percent. If multiple types of sorbent media are to
be analyzed, a separate analytical bias test is required for each
sorbent material.
8.2.3.1.2 HgCl2 Analytical Bias Test. Analyze the front
section of three sorbent traps containing HgCl2 at the lower
bound mass loading level and the front section of three traps containing
HgCl2 at the upper bound mass loading level. HgCl2
can be spiked as a gas, or as a liquid solution containing
HgCl2. However the liquid volume spiked must be <100
L. Prepare and analyze each spiked trap, using the techniques
that will be used to prepare and analyze the field samples. The average
recovery for three traps at each spike concentration must be between 90
and 110 percent. Again, if multiple types of sorbent media are to be
analyzed, a separate analytical bias test is required for each sorbent
material.
8.2.4 Determination of Target Sample Volume. The target sample
volume is an estimate of the sample volume needed to ensure that valid
emissions data are collected (i.e., that sample mass Hg loadings fall
within the analytical calibration curve and are within the upper and
lower bounds set by the analytical bias tests). The target sample volume
and minimum sample mass can also be determined by performing a
diagnostic test run prior to initiation of formal testing.
Example: If the minimum sample mass is 50 ng and the concentration
of mercury in the stack gas is estimated to be 2 g/m\3\ (ng/L)
then the following calculation would be used to determine the target
sample volume:

Target Sample Volume = (50 ng) / (2 ng/L) = 25 L

Note to Section 8.2.4: For the purposes of relative accuracy testing
of Hg monitoring systems under subpart UUUUU of part 63 of this chapter
and Performance Specifications 12A and 12B in appendix B to this part,
when the stack gas Hg concentration is expected to be very low (<0.5
g/dscm), you may estimate the Hg concentration at 0.5
g/dscm.

8.2.5 Determination of Sample Run Time. Sample run time will be a
function of minimum sample mass (see section 8.2.2), target sample
volume and nominal equipment sample flow rate. The minimum sample run
time for conducting relative accuracy test audits of Hg monitoring
systems is 30 minutes and for emissions testing to characterize an
emission source is 1 hour. The target sample run time can be calculated
using the following example.

Example: If the target sample volume has been determined to be 25 L,
then the following formula would be used to determine the sampling time
necessary to acquire 25 L of gas when sampling at a rate of 0.4 L/min.

Sampling time (min) = 25 L / 0.4 L/min = 63 minutes

8.2.6 Field Recovery Test. The field recovery test provides a test
program-specific verification of the performance of the combined
sampling and analytical approach. Three sets of paired samples, one of
each pair which is spiked with a known level of Hg, are collected and
analyzed and the average recovery of the spiked samples is used to
verify performance of the measurement system under field conditions
during that test program. The conduct of this test requires an estimate
or confirmation of the stack Hg concentrations at the time of testing.
8.2.6.1 Calculation of Pre-sampling Spiking Level. Determine the
sorbent trap spiking level for the field recovery test using estimates
of the stack Hg concentration, the target sample flow rate, and the
planned sample duration. First, determine the Hg mass expected to be
collected in section 1 of the sorbent trap. The pre-sampling spike must
be within 50 to 150 percent of this expected mass.

Example calculation: For an expected stack Hg concentration of 5 ug/
m\3\ (ng/L) a target sample rate of 0.40 liters/min, and a sample
duration of 1 hour:

(0.40 L/min) * (60 min) * (5ng/L) = 120 ng

A Hg spike of 60 to 180 ng (50-150% of 120 ng) would be appropriate.
8.2.6.2 Procedures. Set up two identical sampling trains. One of the
sampling trains

[[Page 666]]

shall be designated the spiked train and the other the unspiked train.
Spike Hg\0\ onto the front section of the sorbent trap in the spiked
train before sampling. The mass of Hg spiked shall be 50 to 150 percent
of the mass expected to be collected with the unspiked train. Sample the
stack gas with the two trains simultaneously using the same procedures
as for the field samples (see section 8.3). The total sample volume must
be within 20 percent of the target sample volume for the field sample
test runs. Analyze the sorbent traps from the two trains utilizing the
same analytical procedures and instrumentation as for the field samples
(see section 11.0). Determine the fraction of spiked Hg recovered (R)
using the equations in section 12.7. Repeat this procedure for a total
of three runs. Report the individual R values in the test report; the
average of the three R values must be between 85 and 115 percent.

Note to section 8.2.6.2: It is acceptable to perform the field
recovery test concurrent with actual test runs (e.g., through the use of
a quad probe). It is also acceptable to use the field recovery test runs
as test runs for emissions testing or for the RATA of a Hg monitoring
system under subpart UUUUU of part 63 of this chapter and Performance
Specifications 12A and 12B in appendix B to this part, if certain
conditions are met. To determine whether a particular field recovery
test run may be used as a RATA run, subtract the mass of the Hg\0\ spike
from the total Hg mass collected in sections 1 and 2 of the spiked trap.
The difference represents the mass of Hg in the stack gas sample. Divide
this mass by the sample volume to obtain the Hg concentration in the
effluent gas stream, as measured with the spiked trap. Compare this
concentration to the corresponding Hg concentration measured with the
unspiked trap. If the paired trains meet the relative deviation and
other applicable data validation criteria in Table 9-1, then the average
of the two Hg concentrations may be used as an emissions test run value
or as the reference method value for a RATA run.

8.3 Sampling. This section describes the procedures and criteria for
collecting the field samples for analysis. As noted in section 8.2.6,
the field recovery test samples are also collected using these
procedures.
8.3.1 Pre-test leak check. Perform a leak check of the sampling
system with the sorbent traps in place. For each of the paired sampling
trains, draw a vacuum in the train, and adjust the vacuum to H15'' Hg;
and, using the gas flow meter, determine leak rate. The leak rate for an
individual train must not exceed 4 percent of the target sampling rate.
Once the leak check passes this criterion, carefully release the vacuum
in the sample train, then seal the sorbent trap inlet until the probe is
ready for insertion into the stack or duct.
8.3.2 Determination of Flue Gas Characteristics. Determine or
measure the flue gas measurement environment characteristics (gas
temperature, static pressure, gas velocity, stack moisture, etc.) in
order to determine ancillary requirements such as probe heating
requirements (if any), initial sampling rate, moisture management, etc.
8.3.3 Sample Collection
8.3.3.1 Remove the plug from the end of each sorbent trap and store
each plug in a clean sorbent trap storage container. Remove the stack or
duct port cap and insert the probe(s). Secure the probe(s) and ensure
that no leakage occurs between the duct and environment.
8.3.3.2 Record initial data including the sorbent trap ID, date, and
the run start time.
8.3.3.3 Record the initial gas flow meter reading, stack
temperature, meter temperatures (if needed), and any other appropriate
information, before beginning sampling. Begin sampling and target a
sampling flow rate similar to that for the field recovery test. Then, at
regular intervals (5 minutes) during the sampling period,
record the date and time, the sample flow rate, the gas meter reading,
the stack temperature, the flow meter temperatures (if using a dry gas
meter), temperatures of heated equipment such as the vacuum lines and
the probes (if heated), and the sampling system vacuum readings. Adjust
the sampling flow rate as necessary to maintain the initial sample flow
rate. Ensure that the total volume sampled for each run is within 20
percent of the total volume sampled for the field recovery test.
8.3.3.4 Data Recording. Obtain and record any essential operating
data for the facility during the test period, e.g., the barometric
pressure must be obtained for correcting sample volume to standard
conditions when using a dry gas meter. At the end of the data collection
period, record the final gas flow meter reading and the final values of
all other essential parameters.
8.3.3.5 Post-Test Leak Check. When sampling is completed, turn off
the sample pump, remove the probe(s) with sorbent traps from the port,
and carefully seal the end of each sorbent trap. Perform another leak
check of each sampling train with the sorbent trap in place, at the
maximum vacuum reached during the sampling period. Record the leakage
rates and vacuums. The leakage rate for each train must not exceed 4
percent of the average sampling rate for the data collection period.
Following each leak check, carefully release the vacuum in the sample
train.
8.3.3.6 Sample Recovery. Recover each sampled sorbent trap by
removing it from the probe and sealing both ends. Wipe any deposited
material from the outside of the sorbent

[[Page 667]]

trap. Place the sorbent trap into an appropriate sample storage
container and store/preserve in appropriate manner (see section
8.3.3.8).
8.3.3.7 Stack Gas Moisture Determination. If the moisture basis of
the measurements made with this method (dry) is different from the
moisture basis of either: (1) the applicable emission limit; or (2) a Hg
CEMS being evaluated for relative accuracy, you must determine the
moisture content of the flue gas and correct for moisture using Method 4
in appendix A-3 to this part. If correction of the measured Hg
concentrations for moisture is required, at least one Method 4 moisture
determination shall be made during each test run.
8.3.3.8 Sample Handling, Preservation, Storage, and Transport. While
the performance criteria of this approach provide for verification of
appropriate sample handling, it is still important that the user
consider, determine, and plan for suitable sample preservation, storage,
transport, and holding times for these measurements. Therefore,
procedures in ASTM WK223 ``Guide for Packaging and Shipping
Environmental Samples for Laboratory Analysis'' shall be followed for
all samples, where appropriate. To avoid Hg contamination of the
samples, special attention should be paid to cleanliness during
transport, field handling, sampling, recovery, and laboratory analysis,
as well as during preparation of the sorbent cartridges. Collection and
analysis of blank samples (e.g., reagent, sorbent, field, etc.,) is
useful in verifying the absence or source of contaminant Hg.
8.3.3.9 Sample Custody. Proper procedures and documentation for
sample chain of custody are critical to ensuring data integrity. The
chain of custody procedures in ASTM D4840-99 ``Standard Guide for
Sampling Chain-of-Custody Procedures'' shall be followed for all samples
(including field samples and blanks).

9.0 Quality Assurance and Quality Control

Table 9-1 summarizes the QA/QC performance criteria that are used to
validate the Hg emissions data from Method 30B sorbent trap measurement
systems.

Table 9-1--Quality Assurance/Quality Control Criteria for Method 30B
----------------------------------------------------------------------------------------------------------------
QA/QC test or specification Acceptance criteria Frequency Consequences if not met
----------------------------------------------------------------------------------------------------------------
Gas flow meter calibration (At 3 Calibration factor (Yi) Prior to initial use Recalibrate at 3 points
settings or points). at each flow rate must and when post-test until the acceptance
be within 2% of the check is not within criteria are met.
average value (Y). 5% of Y.
Gas flow meter post-test calibration Calibration factor (Yi) After each field test. Recalibrate gas flow
check (Single-point). must be within 5% of For mass flow meters, meter at 3 points to
the Y value from the must be done on-site, determine a new value
most recent 3-point using stack gas. of Y. For mass flow
calibration. meters, must be done
on-site, using stack
gas. Apply the new Y
value to the field
test data.
Temperature sensor calibration....... Absolute temperature Prior to initial use Recalibrate; sensor may
measures by sensor and before each test not be used until
within 1.5% of a thereafter. specification is met.
reference sensor.
Barometer calibration................ Absolute pressure Prior to initial use Recalibrate; instrument
measured by instrument and before each test may not be used until
within 10 mm Hg of thereafter. specification is met.
reading with a mercury
barometer or NIST
traceable barometer.
Pre-test leak check.................. 4% of target Prior to sampling...... Sampling shall not
sampling rate. commence until the
leak check is passed.
Post-test leak check................. 4% of After sampling......... Sample invalidated.*
average sampling rate.
Analytical matrix interference test Establish minimum Prior to analyzing any Field sample results
(wet chemical analysis, only). dilution (if any) field samples; repeat not validated.
needed to eliminate for each type of
sorbent matrix sorbent used.
interferences.
Analytical bias test................. Average recovery Prior to analyzing Field samples shall not
between 90% and 110% field samples and be analyzed until the
for Hg\0\ and HgCl2 at prior to use of new percent recovery
each of the 2 spike sorbent media. criteria has been met.
concentration levels.
Multipoint analyzer calibration...... Each analyzer reading On the day of analysis, Recalibrate until
within 10% of true before analyzing any successful.
value and r\2\0.99.
Analysis of independent calibration Within 10% of true Following daily Recalibrate and repeat
standard. value. calibration, prior to independent standard
analyzing field analysis until
samples. successful.

[[Page 668]]

Analysis of continuing calibration Within 10% of true Following daily Recalibrate and repeat
verification standard (CCVS). value. calibration, after independent standard
analyzing 10 field samples, samples until
and at end of each set successful, if
of analyses. possible; for
destructive
techniques, samples
invalidated.
Test run total sample volume......... Within 20% of total Each individual sample. Sample invalidated.
volume sampled during
field recovery test.
Sorbent trap section 2 breakthrough.. For compliance/ Every sample........... Sample invalidated.*
emissions testing:
10% of
section 1 Hg mass
for Hg
concentrations >1
g/dscm;.
20% of
section 1 Hg mass
for Hg
concentrations 1 g/
dscm.
50% of
section 1 Hg mass
if the stack Hg
concentration is
30% of
the Hg
concentration that
is equivalent to
the applicable
emission limit.
For relative accuracy
testing:
10% of
section 1 Hg mass
for Hg
concentrations >1
g/dscm;.
20% of
section 1 Hg mass
for Hg
concentrations 1 g/
dscm and >0.5
g/dscm;.
50% of
section 1 Hg mass
for Hg
concentrations 0.5 g/dscm >0.1
g/dscm;.
no criterion for Hg
concentrations 0.1 g/dscm (must meet
all other QA/QC
specifications).
Paired sorbent trap agreement........ 10% Relative Every run.............. Run invalidated.*
Deviation (RD) mass
for Hg concentrations
>1 g/dscm;
20% RD or
0.2 g/dscm absolute
difference for Hg
concentrations 1 g/dscm.
Sample analysis...................... Within valid All Section 1 samples Reanalyze at more
calibration range where stack Hg concentrated level if
(within calibration concentration is 0.02 g/ invalidated if not
dscm except in case within calibrated
where stack Hg range.
concentration is 30% of the
applicable emission
limit.
Sample analysis...................... Within bounds of Hg\0\ All Section 1 samples Expand bounds of Hg\0\
and HgCl2 Analytical where stack Hg and HgCl2 Analytical
Bias Test. concentration is 0.5 g/ successful, samples
dscm. invalidated.
Field recovery test.................. Average recovery Once per field test.... Field sample runs not
between 85% and 115% validated without
for Hg\0\. successful field
recovery test.
----------------------------------------------------------------------------------------------------------------
* And data from the pair of sorbent traps are also invalidated.

10.0 Calibration and Standardization

10.1 Only NIST-certified and NIST-traceable calibration standards
(i.e., calibration gases, solutions, etc.) shall be used for the spiking
and analytical procedures in this method.
10.2 Gas Flow Meter Calibration.
10.2.1 Preliminaries. The manufacturer or equipment supplier of the
gas flow meter should perform all necessary set-up, testing,
programming, etc., and should provide the end user with any necessary
instructions, to

[[Page 669]]

ensure that the meter will give an accurate readout of dry gas volume in
standard cubic meters for this method.
10.2.2 Initial Calibration. Prior to its initial use, a calibration
of the gas flow meter shall be performed. The initial calibration may be
done by the manufacturer, by the equipment supplier, or by the end user.
If the flow meter is volumetric in nature (e.g., a dry gas meter), the
manufacturer or end user may perform a direct volumetric calibration
using any gas. For a mass flow meter, the manufacturer, equipment
supplier, or end user may calibrate the meter using either: (1) A
bottled gas mixture containing 12 0.5% CO2, 7 0.5%
O2, and balance N2 (when this method is applied to
coal-fired boilers); (2) a bottled gas mixture containing
CO2, O2, and N2 in proportions
representative of the expected stack gas composition; or (3) the actual
stack gas.
10.2.2.1 Initial Calibration Procedures. Determine an average
calibration factor (Y) for the gas flow meter by calibrating it at three
sample flow rate settings covering the range of sample flow rates at
which the sampling system will be operated. You may either follow the
procedures in section 10.3.1 of Method 5 in appendix A-3 to this part or
in section 16 of Method 5 in appendix A-3 to this part. If a dry gas
meter is being calibrated, use at least five revolutions of the meter at
each flow rate.
10.2.2.2 Alternative Initial Calibration Procedures. Alternatively,
you may perform the initial calibration of the gas flow meter using a
reference gas flow meter (RGFM). The RGFM may be: (1) A wet test meter
calibrated according to section 10.3.1 of Method 5 in appendix A-3 to
this part; (2) a gas flow metering device calibrated at multiple flow
rates using the procedures in section 16 of Method 5 in appendix A-3 to
this part; or (3) a NIST-traceable calibration device capable of
measuring volumetric flow to an accuracy of 1 percent. To calibrate the
gas flow meter using the RGFM, proceed as follows: While the Method 30B
sampling system is sampling the actual stack gas or a compressed gas
mixture that simulates the stack gas composition (as applicable),
connect the RGFM to the discharge of the system. Care should be taken to
minimize the dead volume between the gas flow meter being tested and the
RGFM. Concurrently measure dry stack gas volume with the RGFM and the
flow meter being calibrated for at least 10 minutes at each of three
flow rates covering the typical range of operation of the sampling
system. For each set of concurrent measurements, record the total sample
volume, in units of dry standard cubic meters (dscm), measured by the
RGFM and the gas flow meter being tested.
10.2.2.3 Initial Calibration Factor. Calculate an individual
calibration factor Yi at each tested flow rate from section
10.2.2.1 or 10.2.2.2 of this method (as applicable) by taking the ratio
of the reference sample volume to the sample volume recorded by the gas
flow meter. Average the three Yi values, to determine Y, the
calibration factor for the flow meter. Each of the three individual
values of Yi must be within 0.02 of Y. Except as otherwise
provided in sections 10.2.2.4 and 10.2.2.5 of this method, use the
average Y value from the initial 3-point calibration to adjust
subsequent gas volume measurements made with the gas flow meter.
10.2.2.4 Pretest On-Site Calibration Check (Optional). For a mass
flow meter, if the most recent 3-point calibration of the flow meter was
performed using a compressed gas mixture, you may want to conduct the
following on-site calibration check prior to testing, to ensure that the
flow meter will accurately measure the volume of the stack gas: While
sampling stack gas, check the calibration of the flow meter at one
intermediate flow rate setting representative of normal operation of the
sampling system. If the pretest calibration check shows that the value
of Yi, the calibration factor at the tested flow rate,
differs from the current value of Y by more than 5 percent, perform a
full 3-point recalibration of the meter using stack gas to determine a
new value of Y, and (except as otherwise provided in section 10.2.2.5 of
this method) apply the new Y value to the data recorded during the field
test.
10.2.2.5 Post-Test Calibration Check. Check the calibration of the
gas flow meter following each field test at one intermediate flow rate
setting, either at, or in close proximity to, the average sample flow
rate during the field test. For dry gas meters, ensure at least three
revolutions of the meter during the calibration check. For mass flow
meters, this check must be performed before leaving the test site, while
sampling stack gas. If a one-point calibration check shows that the
value of Yi at the tested flow rate differs by more than 5
percent from the current value of Y, repeat the full 3-point calibration
procedure to determine a new value of Y, and apply the new Y value to
the gas volume measurements made with the gas flow meter during the
field test that was just completed. For mass flow meters, perform the 3-
point recalibration while sampling stack gas.
10.3 Thermocouples and Other Temperature Sensors. Use the procedures
and criteria in Section 10.3 of Method 2 in appendix A-1 to this part to
calibrate in-stack temperature sensors and thermocouples. Dial
thermometers shall be calibrated against mercury-in-glass thermometers
or equivalent. Calibrations must be performed prior to initial use and
before each field test thereafter. At each calibration point, the
absolute temperature measured by the temperature sensor must agree to
within 1.5 percent of the temperature measured with the reference

[[Page 670]]

sensor, otherwise the sensor may not continue to be used.
10.4 Barometer. Calibrate against a mercury barometer or other NIST-
traceable barometer as per Section 10.6 of Method 5 in appendix A-3 to
this part. Calibration must be performed prior to initial use and before
each test program, and the absolute pressure measured by the barometer
must agree to within 10 mm Hg of the pressure measured by the mercury
or other NIST-traceable barometer, otherwise the barometer may not
continue to be used.
10.5 Other Sensors and Gauges. Calibrate all other sensors and
gauges according to the procedures specified by the instrument
manufacturer(s).
10.6 Analytical System Calibration. See section 11.1 of this method.

11.0 Analytical Procedures

The analysis of Hg in the field and quality control samples may be
conducted using any instrument or technology capable of quantifying
total Hg from the sorbent media and meeting the performance criteria in
this method. Because multiple analytical approaches, equipment and
techniques are appropriate for the analysis of sorbent traps, it is not
possible to provide detailed, technique-specific analytical procedures.
As they become available, detailed procedures for a variety of candidate
analytical approaches will be posted at http://www.epa.gov/ttn/emc.
11.1 Analytical System Calibration. Perform a multipoint calibration
of the analyzer at three or more upscale points over the desired
quantitative range (multiple calibration ranges shall be calibrated, if
necessary). The field samples analyzed must fall within a calibrated,
quantitative range and meet the performance criteria specified below.
For samples suitable for aliquotting, a series of dilutions may be
needed to ensure that the samples fall within a calibrated range.
However, for sorbent media samples consumed during analysis (e.g., when
using thermal desorption techniques), extra care must be taken to ensure
that the analytical system is appropriately calibrated prior to sample
analysis. The calibration curve range(s) should be determined such that
the levels of Hg mass expected to be collected and measured will fall
within the calibrated range. The calibration curve may be generated by
directly introducing standard solutions into the analyzer or by spiking
the standards onto the sorbent media and then introducing into the
analyzer after preparing the sorbent/standard according to the
particular analytical technique. For each calibration curve, the value
of the square of the linear correlation coefficient, i.e., r\2\, must be
[gteqt]0.99, and the analyzer response must be within 10 percent of the
reference value at each upscale calibration point. Calibrations must be
performed on the day of the analysis, before analyzing any of the
samples. Following calibration, an independent standard shall be
analyzed. The measured value of the independently prepared standard must
be within 10 percent of the expected value.
11.2 Sample Preparation. Carefully separate the sections of each
sorbent trap. Combine for analysis all materials associated with each
section; any supporting substrate that the sample gas passes through
prior to entering a media section (e.g., glass wool separators, acid gas
traps, etc.) must be analyzed with that segment.
11.3 Field Sample Analyses. Analyze the sorbent trap samples
following the same procedures that were used for conducting the Hg\0\
and HgCl2 analytical bias tests. The individual sections of
the sorbent trap and their respective components must be analyzed
separately (i.e., section 1 and its components, then section 2 and its
components). All sorbent trap section 1 sample analyses must be within
the calibrated range of the analytical system as specified in Table 9-1.
For wet analyses, the sample can simply be diluted to fall within the
calibrated range. However, for the destructive thermal analyses, samples
that are not within the calibrated range cannot be re-analyzed. As a
result, the sample cannot be validated, and another sample must be
collected. It is strongly suggested that the analytical system be
calibrated over multiple ranges so that thermally analyzed samples fall
within the calibrated range. The total mass of Hg measured in each
sorbent trap section 1 must also fall within the lower and upper mass
limits established during the initial Hg\0\ and HgCl2
analytical bias test. If a sample is analyzed and found to fall outside
of these limits, it is acceptable for an additional Hg\0\ and
HgCl2 analytical bias test to be performed that now includes
this level. However, some samples (e.g., the mass collected in trap
section 2), may have Hg levels so low that it may not be possible to
quantify them in the analytical system's calibrated range. Because a
reliable estimate of these low-level Hg measurements is necessary to
fully validate the emissions data, the MDL (see section 8.2.2.1 of this
method) is used to establish the minimum amount that can be detected and
reported. If the measured mass or concentration is below the lowest
point in the calibration curve and above the MDL, the analyst must
estimate the mass or concentration of the sample based on the analytical
instrument response relative to an additional calibration standard at a
concentration or mass between the MDL and the lowest point in the
calibration curve. This is accomplished by establishing a response
factor (e.g., area counts per Hg mass or concentration) and estimating
the amount of Hg present in the sample based on the analytical response
and this response factor.

[[Page 671]]

Example: The analysis of a particular sample results in a measured
mass above the MDL, but below the lowest point in the calibration curve
which is 10 ng. An MDL of 1.3 ng Hg has been established by the MDL
study. A calibration standard containing 5 ng of Hg is analyzed and
gives an analytical response of 6,170 area counts, which equates to a
response factor of 1,234 area counts/ng Hg. The analytical response for
the sample is 4,840 area counts. Dividing the analytical response for
the sample (4,840 area counts) by the response factor gives 3.9 ng Hg,
which is the estimated mass of Hg in the sample.

11.4 Analysis of Continuing Calibration Verification Standard
(CCVS). After no more than 10 samples and at the end of each set of
analyses, a continuing calibration verification standard must be
analyzed. The measured value of the continuing calibration standard must
be within 10 percent of the expected value.
11.5 Blanks. The analysis of blanks is optional. The analysis of
blanks is useful to verify the absence of, or an acceptable level of, Hg
contamination. Blank levels should be considered when quantifying low Hg
levels and their potential contribution to meeting the sorbent trap
section 2 breakthrough requirements; however, correcting sorbent trap
results for blank levels is prohibited.

12.0 Calculations and Data Analysis

You must follow the procedures for calculation and data analysis
listed in this section.
12.1 Nomenclature. The terms used in the equations are defined as
follows:

B = Breakthrough (%).
Bws = Moisture content of sample gas as measured by Method 4,
percent/100.
Ca = Concentration of Hg for the sample collection period,
for sorbent trap ``a'' (g/dscm).
Cb = Concentration of Hg for the sample collection period,
for sorbent trap ``b'' (g/dscm).
Cd = Hg concentration, dry basis (g/dscm).
Crec = Concentration of spiked compound measured (g/
m\3\).
Cw = Hg concentration, wet basis (g/m\3\).
m1 = Mass of Hg measured on sorbent trap section 1
(g).
m2 = Mass of Hg measured on sorbent trap section 2
(g).
mrecovered = Mass of spiked Hg recovered in Analytical Bias
or Field Recovery Test (g).
ms = Total mass of Hg measured on spiked trap in Field
Recovery Test (g).
mspiked = Mass of Hg spiked in Analytical Bias or Field
Recovery Test (g).
mu = Total mass of Hg measured on unspiked trap in Field
Recovery Test (g).
R = Percentage of spiked mass recovered (%).
RD = Relative deviation between the Hg concentrations from traps ``a''
and ``b'' (%).
vs = Volume of gas sampled, spiked trap in Field Recovery
Test (dscm).
Vt = Total volume of dry gas metered during the collection
period (dscm); for the purposes of this method, standard
temperature and pressure are defined as 20 [deg]C and 760 mm
Hg, respectively.
vu = Volume of gas sampled, unspiked trap in Field Recovery
Test (dscm).

12.2 Calculation of Spike Recovery (Analytical Bias Test). Calculate
the percent recovery of Hg\0\ and HgCl2 using Equation 30B-1.
[GRAPHIC] [TIFF OMITTED] TR07SE07.028

12.3 Calculation of Breakthrough. Use Equation 30B-2 to calculate
the percent breakthrough to the second section of the sorbent trap.
[GRAPHIC] [TIFF OMITTED] TR07SE07.029

12.4 Calculation of Hg Concentration. Calculate the Hg concentration
measured with sorbent trap ``a'', using Equation 30B-3.
[GRAPHIC] [TIFF OMITTED] TR07SE07.030

For sorbent trap ``b'', replace ``Ca '' with
``Cb '' in Equation 30B-3. Report the average concentration,
i.e., \1/2\ (Ca + Cb).
12.5 Moisture Correction. Use Equation 30B-4 if your measurements
need to be corrected to a wet basis.
[GRAPHIC] [TIFF OMITTED] TR07SE07.031

12.6 Calculation of Paired Trap Agreement. Calculate the relative
deviation (RD) between the Hg concentrations measured with the paired
sorbent traps using Equation 30B-5.
[GRAPHIC] [TIFF OMITTED] TR07SE07.032

12.7 Calculation of Measured Spike Hg Concentration (Field Recovery
Test). Calculate the measured spike concentration using Equation 30B-6.
[GRAPHIC] [TIFF OMITTED] TR07SE07.033

Then calculate the spiked Hg recovery, R, using Equation 30B-7.

[[Page 672]]

[GRAPHIC] [TIFF OMITTED] TR07SE07.034

13.0 Method Performance

How do I validate my data? Measurement data are validated using
initial, one-time laboratory tests coupled with test program-specific
tests and procedures. The analytical matrix interference test and the
Hg\0\ and HgCl2 analytical bias test described in section 8.2
are used to verify the appropriateness of the selected analytical
approach(es) as well as define the valid working ranges for sample
analysis. The field recovery test serves to verify the performance of
the combined sampling and analysis as applied for each test program.
Field test samples are validated by meeting the above requirements as
well as meeting specific sampling requirements (i.e., leak checks,
paired train agreement, total sample volume agreement with field
recovery test samples) and analytical requirements (i.e., valid
calibration curve, continuing calibration performance, sample results
within calibration curve and bounds of Hg\0\ and HgCl2
analytical bias test). Complete data validation requirements are
summarized in Table 9-1.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

17.0 Figures and Tables

[[Page 673]]

[GRAPHIC] [TIFF OMITTED] TR07SE07.026

[36 FR 24877, Dec. 23, 1971]

Editorial Note: For Federal Register citations affecting appendix A-
8 to part 60, see the List of CFR sections Affected, which appears in
the Finding Aids section of the printed volume and at www.fdsys.gov.

[[Page 674]]

Sec. Appendix B to Part 60--Performance Specifications

Performance Specification 1--Specifications and test procedures for
continuous opacity monitoring systems in stationary sources
Performance Specification 2--Specifications and Test Procedures for
SO2 and NOX Continuous Emission
Monitoring Systems in Stationary Sources
Performance Specification 3--Specifications and Test Procedures for
O2 and CO2 Continuous Emission
Monitoring Systems in Stationary Sources
Performance Specification 4--Specifications and Test Procedures for
Carbon Monoxide Continuous Emission Monitoring Systems in
Stationary Sources
Performance Specification 4A--Specifications and Test Procedures for
Carbon Monoxide Continuous Emission Monitoring Systems in
Stationary Sources
Performance Specification 4B--Specifications and Test Procedures for
Carbon Monoxide and Oxygen Continuous Monitoring Systems in
Stationary Sources
Performance Specification 5--Specifications and Test Procedures for TRS
Continuous Emission Monitoring Systems in Stationary Sources
Performance Specification 6--Specifications and Test Procedures for
Continuous Emission Rate Monitoring Systems in Stationary
Sources
Performance Specification 7--Specifications and Test Procedures for
Hydrogen Sulfide Continuous Emission Monitoring Systems in
Stationary Sources
Performance Specification 8--Performance Specifications for Volatile
Organic Compound Continuous Emission Monitoring Systems in
Stationary Sources
Performance Specification 8A--Specifications and Test Procedures for
Total Hydrocarbon Continuous Monitoring Systems in Stationary
Sources
Performance Specification 9--Specifications and Test Procedures for Gas
Chromatographic Continuous Emission Monitoring Systems in
Stationary Sources
Performance Specification 11--Specifications and Test Procedures for
Particulate Matter Continuous Emission Monitoring Systems at
Stationary Sources
Performance Specification 12A--Specifications and Text Procedures for
Total Vapor Phase Mercury Continuous Emission Monitoring
Systems in Stationary Sources
Performance Specification 15--Performance Specification for Extractive
FTIR Continuous Emissions Monitor Systems in Stationary
Sources

Performance Specification 1--Specifications and Test Procedures for
Continuous Opacity Monitoring Systems in Stationary Sources

1.0 What Is the Purpose and Applicability of Performance Specification
1?

Performance Specification 1 (PS-1) provides (1) requirements for the
design, performance, and installation of a continuous opacity monitoring
system (COMS) and (2) data computation procedures for evaluating the
acceptability of a COMS. It specifies activities for two groups (1) the
owner or operator and (2) the opacity monitor manufacturer.
1.1 Measurement Parameter. PS-1 covers the instrumental measurement
of opacity caused by attenuation of projected light due to absorption
and scatter of the light by particulate matter in the effluent gas
stream.
1.2 What COMS must comply with PS-1? If you are an owner or operator
of a facility with a COMS as a result of this Part, then PS-1 applies to
your COMS if one of the following is true:
(1) Your facility has a new COMS installed after February 6, 2001;
or
(2) Your COMS is replaced, relocated, or substantially refurbished
(in the opinion of the regulatory authority) after February 6, 2001; or
(3) Your COMS was installed before February 6, 2001 and is
specifically required by regulatory action other than the promulgation
of PS-1 to be recertified.
If you are an opacity monitor manufacturer, then paragraph 8.2
applies to you.
1.3 Does PS-1 apply to a facility with an applicable opacity limit
less than 10 percent? If you are an owner or operator of a facility with
a COMS as a result of this Part and the applicable opacity limit is less
than 10 percent, then PS-1 applies to your COMS as described in section
1.2; taking into account (through statistical procedures or otherwise)
the uncertainties associated with opacity measurements, and following
the conditions for attenuators selection for low opacity applications as
outlined in section 8.1(3)(ii). At your option, you, the source owner or
operator, may select to establish a reduced full scale range of no less
than 50 percent opacity instead of the 80 percent as prescribed in
section 3.5, if the applicable opacity limit for your facility is less
than 10 percent. The EPA recognizes that reducing the range of the
analyzer to 50 percent does not necessarily result in any measurable
improvement in measurement accuracy at opacity levels less than 10
percent; however, it may allow improved chart recorder interpretation.
1.4 What data uncertainty issues apply to COMS data? The measurement
uncertainties

[[Page 675]]

associated with COMS data result from several design and performance
factors including limitations on the availability of calibration
attenuators for opacities less than about 6 percent (3 percent for
single-pass instruments), calibration error tolerances, zero and upscale
drift tolerances, and allowance for dust compensation that are
significant relative to low opacity levels. The full scale requirements
of this PS may also contribute to measurement uncertainty for opacity
measurements where the applicable limits are below 10 percent opacity.

2.0 What Are the Basic Requirements of PS-1?

PS-1 requires (1) opacity monitor manufacturers comply with a
comprehensive series of design and performance specifications and test
procedures to certify opacity monitoring equipment before shipment to
the end user, (2) the owner or operator to follow installation
guidelines, and (3) the owner or operator to conduct a set of field
performance tests that confirm the acceptability of the COMS after it is
installed.
2.1 ASTM D 6216-98 is the reference for design specifications,
manufacturer's performance specifications, and test procedures. The
opacity monitor manufacturer must periodically select and test an
opacity monitor, that is representative of a group of monitors produced
during a specified period or lot, for conformance with the design
specifications in ASTM D 6216-98. The opacity monitor manufacturer must
test each opacity monitor for conformance with the manufacturer's
performance specifications in ASTM D 6216-98.
2.2 section 8.1(2) provides guidance for locating an opacity monitor
in vertical and horizontal ducts. You are encouraged to seek approval
for the opacity monitor location from the appropriate regulatory
authority prior to installation.
2.3 After the COMS is installed and calibrated, the owner or
operator must test the COMS for conformance with the field performance
specifications in PS-1.

3.0 What Special Definitions Apply to PS-1?

3.1 All definitions and discussions from section 3 of ASTM D 6216-98
are applicable to PS-1.
3.2 Centroid Area. A concentric area that is geometrically similar
to the stack or duct cross-section and is no greater than 1 percent of
the stack or duct cross-sectional area.
3.3 Data Recorder. That portion of the installed COMS that provides
a permanent record of the opacity monitor output in terms of opacity.
The data recorder may include automatic data reduction capabilities.
3.4 External Audit Device. The inherent design, equipment, or
accommodation of the opacity monitor allowing the independent assessment
of the COMS's calibration and operation.
3.5 Full Scale. The maximum data display output of the COMS. For
purposes of recordkeeping and reporting, full scale will be greater than
80 percent opacity.
3.6 Operational Test Period. A period of time (168 hours) during
which the COMS is expected to operate within the established performance
specifications without any unscheduled maintenance, repair, or
adjustment.
3.7 Primary Attenuators. Those devices (glass or grid filter that
reduce the transmission of light) calibrated according to procedures in
section 7.1.
3.8 Secondary Attenuators. Those devices (glass or grid filter that
reduce the transmission of light) calibrated against primary attenuators
according to procedures in section 7.2.
3.9 System Response Time. The amount of time the COMS takes to
display 95 percent of a step change in opacity on the COMS data
recorder.

4.0 Interferences. Water Droplets

5.0 What Do I Need To Know To Ensure the Safety of Persons Using PS-1?

The procedures required under PS-1 may involve hazardous materials,
operations, and equipment. PS-1 does not purport to address all of the
safety problems associated with these procedures. Before performing
these procedures, you must establish appropriate safety and health
practices, and you must determine the applicable regulatory limitations.
You should consult the COMS user's manual for specific precautions to
take.

6.0 What Equipment and Supplies Do I Need?

6.1 Continuous Opacity Monitoring System. You, as owner or operator,
are responsible for purchasing an opacity monitor that meets the
specifications of ASTM D 6216-98, including a suitable data recorder or
automated data acquisition handling system. Example data recorders
include an analog strip chart recorder or more appropriately an
electronic data acquisition and reporting system with an input signal
range compatible with the analyzer output.
6.2 Calibration Attenuators. You, as owner or operator, are
responsible for purchasing a minimum of three calibration attenuators
that meet the requirements of PS-1. Calibration attenuators are optical
filters with neutral spectral characteristics. Calibration attenuators
must meet the requirements in section 7 and must be of sufficient size
to attenuate the entire light beam received by the detector of the COMS.
For transmissometers operating over a narrow bandwidth (e.g., laser), a
calibration attenuator's value is determined for the actual operating
wavelengths of the transmissometer.

[[Page 676]]

Some filters may not be uniform across the face. If errors result in the
daily calibration drift or calibration error test, you may want to
examine the across-face uniformity of the filter.
6.3 Calibration Spectrophotometer. Whoever calibrates the
attenuators must have a spectrophotometer that meets the following
minimum design specifications:

------------------------------------------------------------------------
Parameter Specification
------------------------------------------------------------------------
Wavelength range.......................... 300-800 nm.
Detector angle of view.................... <10[deg].
Accuracy.................................. <0.5% transmittance, NIST
traceable calibration.
------------------------------------------------------------------------

7.0 What Reagents and Standards Do I Need?

You will need to use attenuators (i.e., neutral density filters) to
check the daily calibration drift and calibration error of a COMS.
Attenuators are designated as either primary or secondary based on how
they are calibrated.
7.1 Attenuators are designated primary in one of two ways:
(1) They are calibrated by NIST; or
(2) They are calibrated on a 6-month frequency through the
assignment of a luminous transmittance value in the following manner:
(i) Use a spectrophotometer meeting the specifications of section
6.3 to calibrate the required filters. Verify the spectrophotometer
calibration through use of a NIST 930D Standard Reference Material
(SRM). A SRM 930D consists of three neutral density glass filters and a
blank, each mounted in a cuvette. The wavelengths and temperature to be
used in the calibration are listed on the NIST certificate that
accompanies the reported values. Determine and record a transmittance of
the SRM values at the NIST wavelengths (three filters at five
wavelengths each for a total of 15 determinations). Calculate a percent
difference between the NIST certified values and the spectrophotometer
response. At least 12 of the 15 differences (in percent) must be within
0.5 percent of the NIST SRM values. No difference can be greater than
1.0 percent. Recalibrate the SRM or service the spectrophotometer if
the calibration results fail the criteria.
(ii) Scan the filter to be tested and the NIST blank from wavelength
380 to 780 nm, and record the spectrophotometer percent transmittance
responses at 10 nm intervals. Test in this sequence: blank filter,
tested filter, tested filter rotated 90 degrees in the plane of the
filter, blank filter. Calculate the average transmittance at each 10 nm
interval. If any pair of the tested filter transmittance values (for the
same filter and wavelength) differ by more than 0.25 percent, rescan
the tested filter. If the filter fails to achieve this tolerance, do not
use the filter in the calibration tests of the COMS.
(iii) Correct the tested filter transmittance values by dividing the
average tested filter transmittance by the average blank filter
transmittance at each 10 nm interval.
(iv) Calculate the weighted (to the response of the human eye),
tested filter transmittance by multiplying the transmittance value by
the corresponding response factor shown in table 1-1, to obtain the
Source C Human Eye Response.
(v) Recalibrate the primary attenuators semi-annually if they are
used for the required calibration error test. Recalibrate the primary
attenuators annually if they are used only for calibration of secondary
attenuators.
7.2 Attenuators are designated secondary if the filter calibration
is done using a laboratory-based transmissometer. Conduct the secondary
attenuator calibration using a laboratory-based transmissometer
calibrated as follows:
(i) Use at least three primary filters of nominal luminous
transmittance 50, 70 and 90 percent, calibrated as specified in section
7.1(2)(i), to calibrate the laboratory-based transmissometer. Determine
and record the slope of the calibration line using linear regression
through zero opacity. The slope of the calibration line must be between
0.99 and 1.01, and the laboratory-based transmissometer reading for each
primary filter must not deviate by more than 2 percent from the linear
regression line. If the calibration of the laboratory-based
transmissometer yields a slope or individual readings outside the
specified ranges, secondary filter calibrations cannot be performed.
Determine the source of the variations (either transmissometer
performance or changes in the primary filters) and repeat the
transmissometer calibration before proceeding with the attenuator
calibration.
(ii) Immediately following the laboratory-based transmissometer
calibration, insert the secondary attenuators and determine and record
the percent effective opacity value per secondary attenuator from the
calibration curve (linear regression line).
(iii) Recalibrate the secondary attenuators semi-annually if they
are used for the required calibration error test.

8.0 What Performance Procedures Are Required To Comply With PS-1?

Procedures to verify the performance of the COMS are divided into
those completed by the owner or operator and those completed by the
opacity monitor manufacturer.
8.1 What procedures must I follow as the Owner or Operator?
(1) You must purchase an opacity monitor that complies with ASTM D
6216-98 and obtain a certificate of conformance from the opacity monitor
manufacturer.

[[Page 677]]

(2) You must install the opacity monitor at a location where the
opacity measurements are representative of the total emissions from the
affected facility. You must meet this requirement by choosing a
measurement location and a light beam path as follows:
(i) Measurement Location. Select a measurement location that is (1)
at least 4 duct diameters downstream from all particulate control
equipment or flow disturbance, (2) at least 2 duct diameters upstream of
a flow disturbance, (3) where condensed water vapor is not present, and
(4) accessible in order to permit maintenance.
(ii) Light Beam Path. Select a light beam path that passes through
the centroidal area of the stack or duct. Also, you must follow these
additional requirements or modifications for these measurement
locations:

------------------------------------------------------------------------
If your measurement location Then use a light
is in a: And is: beam path that is:
------------------------------------------------------------------------
1. Straight vertical section Less than 4 In the plane defined
of stack or duct. equivalent by the upstream
diameters bend (see figure 1-
downstream from a 1).
bend.
2. Straight vertical section Less than 4 In the plane defined
of stack or duct. equivalent by the downstream
diameters upstream bend (see figure 1-
from a bend. 2).
3. Straight vertical section Less than 4 In the plane defined
of stack or duct. equivalent by the upstream
diameters bend (see figure 1-
downstream and is 3).
also less than 1
diameter upstream
from a bend.
4. Horizontal section of At least 4 In the horizontal
stack or duct. equivalent plane that is
diameters between \1/3\ and
downstream from a \1/2\ the distance
vertical bend. up the vertical
axis from the
bottom of the duct
(see figure 1-4).
5. Horizontal section of Less than 4 In the horizontal
duct. equivalent plane that is
diameters between \1/2\ and
downstream from a \2/3\ the distance
vertical bend. up the vertical
axis from the
bottom of the duct
for upward flow in
the vertical
section, and is
between \1/3\ and
\1/2\ the distance
up the vertical
axis from the
bottom of the duct
for downward flow
(figure 1-5).
------------------------------------------------------------------------

(iii) Alternative Locations and Light Beam Paths. You may select
locations and light beam paths, other than those cited above, if you
demonstrate, to the satisfaction of the Administrator or delegated
agent, that the average opacity measured at the alternative location or
path is equivalent to the opacity as measured at a location meeting the
criteria of sections 8.1(2)(i) and 8.1(2)(ii). The opacity at the
alternative location is considered equivalent if (1) the average opacity
value measured at the alternative location is within 10 percent of the
average opacity value measured at the location meeting the installation
criteria, and (2) the difference between any two average opacity values
is less than 2 percent opacity (absolute). You use the following
procedure to conduct this demonstration: simultaneously measure the
opacities at the two locations or paths for a minimum period of time
(e.g., 180-minutes) covering the range of normal operating conditions
and compare the results. The opacities of the two locations or paths may
be measured at different times, but must represent the same process
operating conditions. You may use alternative procedures for determining
acceptable locations if those procedures are approved by the
Administrator.
(3) Field Audit Performance Tests. After you install the COMS, you
must perform the following procedures and tests on the COMS.
(i) Optical Alignment Assessment. Verify and record that all
alignment indicator devices show proper alignment. A clear indication of
alignment is one that is objectively apparent relative to reference
marks or conditions.
(ii) Calibration Error Check. Conduct a three-point calibration
error test using three calibration attenuators that produce outlet
pathlength corrected, single-pass opacity values shown in ASTM D 6216-
98, section 7.5. If your applicable limit is less than 10 percent
opacity, use attenuators as described in ASTM D 6216-98, section 7.5 for
applicable standards of 10 to 19 percent opacity. Confirm the external
audit device produces the proper zero value on the COMS data recorder.
Separately, insert each calibration attenuators (low, mid, and high-
level) into the external audit device. While inserting each attenuator,
(1) ensure that the entire light beam passes through the attenuator, (2)
minimize interference from reflected light, and (3) leave the attenuator
in place for at least two times the shortest recording interval on the
COMS data recorder. Make a total of five nonconsecutive readings for
each attenuator. At the end of the test, correlate each attenuator
insertion to the corresponding value from the data recorder. Subtract
the single-pass calibration attenuator values corrected to the stack
exit conditions from the COMS responses. Calculate the arithmetic mean
difference, standard deviation, and confidence coefficient of the five
measurements value using equations 1-3, 1-4, and 1-5. Calculate the
calibration error as the sum of the absolute value of the mean

[[Page 678]]

difference and the 95 percent confidence coefficient for each of the
three test attenuators using equation 1-6. Report the calibration error
test results for each of the three attenuators.
(iii) System Response Time Check. Using a high-level calibration
attenuator, alternately insert the filter five times and remove it from
the external audit device. For each filter insertion and removal,
measure the amount of time required for the COMS to display 95 percent
of the step change in opacity on the COMS data recorder. For the upscale
response time, measure the time from insertion to display of 95 percent
of the final, steady upscale reading. For the downscale response time,
measure the time from removal to display 5 percent of the initial
upscale reading. Calculate the mean of the five upscale response time
measurements and the mean of the five downscale response time
measurements. Report both the upscale and downscale response times.
(iv) Averaging Period Calculation and Recording Check. After the
calibration error check, conduct a check of the averaging period
calculation (e.g., 6-minute integrated average). Consecutively insert
each of the calibration error check attenuators (low, mid, and high-
level) into the external audit device for a period of two times the
averaging period plus 1 minute (e.g., 13 minutes for a 6-minute
averaging period). Compare the path length corrected opacity value of
each attenuator to the valid average value calculated by the COMS data
recording device for that attenuator.
(4) Operational Test Period. Before conducting the operational
testing, you must have successfully completed the field audit tests
described in sections 8.1(3)(i) through 8.1(3)(iv). Then, you operate
the COMS for an initial 168-hour test period while the source is
operating under normal operating conditions. If normal operations
contain routine source shutdowns, include the source's down periods in
the 168-hour operational test period. However, you must ensure that the
following minimum source operating time is included in the operational
test period: (1) For a batch operation, the operational test period must
include at least one full cycle of batch operation during the 168-hour
period unless the batch operation is longer than 168 hours or (2) for
continuous operating processes, the unit must be operating for at least
50 percent of the 168-hour period. Except during times of instrument
zero and upscale calibration drift checks, you must analyze the effluent
gas for opacity and produce a permanent record of the COMS output.
During this period, you may not perform unscheduled maintenance, repair,
or adjustment to the COMS. Automatic zero and calibration adjustments
(i.e., intrinsic adjustments), made by the COMS without operator
intervention or initiation, are allowable at any time. At the end of the
operational test period, verify and record that the COMS optical
alignment is still correct. If the test period is interrupted because of
COMS failure, record the time when the failure occurred. After the
failure is corrected, you restart the 168-hour period and tests from the
beginning (0-hour). During the operational test period, perform the
following test procedures:
(i) Zero Calibration Drift Test. At the outset of the 168-hour
operational test period and at each 24-hour interval, the automatic
calibration check system must initiate the simulated zero device to
allow the zero drift to be determined. Record the COMS response to the
simulated zero device. After each 24-hour period, subtract the COMS zero
reading from the nominal value of the simulated zero device to calculate
the 24-hour zero drift (ZD). At the end of the 168-hour period,
calculate the arithmetic mean, standard deviation, and confidence
coefficient of the 24-hour ZDs using equations 1-3, 1-4, and 1-5.
Calculate the sum of the absolute value of the mean and the absolute
value of the confidence coefficient using equation 1-6, and report this
value as the 24-hour ZD error.
(ii) Upscale Calibration Drift Test. At each 24-hour interval after
the simulated zero device value has been checked, check and record the
COMS response to the upscale calibration device. After each 24-hour
period, subtract the COMS upscale reading from the nominal value of the
upscale calibration device to calculate the 24-hour calibration drift
(CD). At the end of the 168-hour period, calculate the arithmetic mean,
standard deviation, and confidence coefficient of the 24-hour CD using
equations 1-3, 1-4, and 1-5. Calculate the sum of the absolute value of
the mean and the absolute value of the confidence coefficient using
equation 1-6, and report this value as the 24-hour CD error.
(5) Retesting. If the COMS fails to meet the specifications for the
tests conducted under the operational test period, make the necessary
corrections and restart the operational test period. Depending on the
opinion of the enforcing agency, you may have to repeat some or all of
the field audit tests.
8.2 What are the responsibilities of the Opacity Monitor
Manufacturer?
You, the manufacturer, must carry out the following activities:
(1) Conduct the verification procedures for design specifications in
section 6 of ASTM D 6216-98.
(2) Conduct the verification procedures for performance
specifications in section 7 of ASTM D 6216-98.
(3) Provide to the owner or operator, a report of the opacity
monitor's conformance to the design and performance specifications
required in sections 6 and 7 of ASTM D 6216-98 in accordance with the
reporting requirements of section 9 in ASTM D 6216-98.

[[Page 679]]

9.0 What quality control measures are required by PS-1?

Opacity monitor manufacturers must initiate a quality program
following the requirements of ASTM D 6216-98, section 8. The quality
program must include (1) a quality system and (2) a corrective action
program.

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure [Reserved]

12.0 What Calculations Are Needed for PS-1?

12.1 Desired Attenuator Values. Calculate the desired attenuator
value corrected to the emission outlet pathlength as follows:
[GRAPHIC] [TIFF OMITTED] TR10AU00.008

Where:

OP1 = Nominal opacity value of required low-, mid-, or high-
range calibration attenuators.
OP2 = Desired attenuator opacity value from ASTM D 6216-98,
section 7.5 at the opacity limit required by the applicable
subpart.
L1 = Monitoring pathlength.
L2 = Emission outlet pathlength.
12.2 Luminous Transmittance Value of a Filter. Calculate the
luminous transmittance of a filter as follows:
[GRAPHIC] [TIFF OMITTED] TR10AU00.009

Where:

LT = Luminous transmittance
Ti = Weighted tested filter transmittance.
12.3 Arithmetic Mean. Calculate the arithmetic mean of a data set as
follows:
[GRAPHIC] [TIFF OMITTED] TR10AU00.010

Where:
[GRAPHIC] [TIFF OMITTED] TR10AU00.011

12.4 Standard Deviation. Calculate the standard deviation as
follows:
[GRAPHIC] [TIFF OMITTED] TR10AU00.012

Where:

Sd = Standard deviation of a data set.

12.5 Confidence Coefficient. Calculate the 2.5 percent error
confidence coefficient (one-tailed) as follows:
[GRAPHIC] [TIFF OMITTED] TR10AU00.013

Where:

CC = Confidence coefficient
t0.975 = t - value (see table 1-2).

12.6 Calibration Error. Calculate the error (calibration error, zero
drift error, and calibration drift error) as follows:
[GRAPHIC] [TIFF OMITTED] TR10AU00.014

Where:

Er = Error.

12.7 Conversion of Opacity Values for Monitor Pathlength to Emission
Outlet Pathlength. When the monitor pathlength is different from the
emission outlet pathlength, use either of the following equations to
convert from one basis to the other (this conversion may be
automatically calculated by the monitoring system):
[GRAPHIC] [TIFF OMITTED] TR10AU00.015

[GRAPHIC] [TIFF OMITTED] TR10AU00.016

[[Page 680]]

Where:

Op1 = Opacity of the effluent based upon L1.
Op2 = Opacity of the effluent based upon L2.
L1 = Monitor pathlength.
L2 = Emission outlet pathlength.
OD1 = Optical density of the effluent based upon
L1.
OD2 = Optical density of the effluent based upon
L2.

12.8 Mean Response Wavelength. Calculate the mean of the effective
spectral response curve from the individual responses at the specified
wavelength values as follows:
[GRAPHIC] [TIFF OMITTED] TR10AU00.017

Where:

L = mean of the effective spectral response curve
Li = The specified wavelength at which the response
gi is calculated at 20 nm intervals.
gi = The individual response value at Li.

13.0 What Specifications Does a COMS Have To Meet for Certification?

A COMS must meet the following design, manufacturer's performance,
and field audit performance specifications:
13.1 Design Specifications. The opacity monitoring equipment must
comply with the design specifications of ASTM D 6216-98.
13.2 Manufacturer's Performance Specifications. The opacity monitor
must comply with the manufacturer's performance specifications of ASTM D
6216-98.
13.3 Field Audit Performance Specifications. The installed COMS must
comply with the following performance specifications:
(1) Optical Alignment. Objectively indicate proper alignment
relative to reference marks (e.g., bull's-eye) or conditions.
(2) Calibration Error. The calibration error must be 3
percent opacity for each of the three calibration attenuators.
(3) System Response Time. The COMS upscale and downscale response
times must be 10 seconds as measured at the COMS data
recorder.
(4) Averaging Period Calculation and Recording. The COMS data
recorder must average and record each calibration attenuator value to
within 2 percent opacity of the certified value of the attenuator.
(5) Operational Test Period. The COMS must be able to measure and
record opacity and to perform daily calibration drift assessments for
168 hours without unscheduled maintenance, repair, or adjustment.
(6) Zero and Upscale Calibration Drift Error. The COMS zero and
upscale calibration drift error must not exceed 2 percent opacity over a
24 hour period.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Which references are relevant to this method?

1. Experimental Statistics. Department of Commerce. National Bureau
of Standards Handbook 91. Paragraph 3-3.1.4. 1963. 3-31 p.
2. Performance Specifications for Stationary Source Monitoring
Systems for Gases and Visible Emissions, EPA-650/2-74-013, January 1974,
U. S. Environmental Protection Agency, Research Triangle Park, NC.
3. Koontz, E.C., Walton, J. Quality Assurance Programs for Visible
Emission Evaluations. Tennessee Division of Air Pollution Control.
Nashville, TN. 78th Meeting of the Air Pollution Control Association.
Detroit, MI. June 16-21, 1985.
4. Evaluation of Opacity CEMS Reliability and Quality Assurance
Procedures. Volume 1. U. S. Environmental Protection Agency. Research
Triangle Park, NC. EPA-340/1-86-009a.
5. Nimeroff, I. ``Colorimetry Precision Measurement and
Calibration.'' NBS Special Publication 300. Volume 9. June 1972.
6. Technical Assistance Document: Performance Audit Procedures for
Opacity Monitors. U. S. Environmental Protection Agency. Research
Triangle Park, NC. EPA-600/8-87-025. April 1987.
7. Technical Assistance Document: Performance Audit Procedures for
Opacity Monitors. U. S. Environmental Protection Agency. Research
Triangle Park, NC. EPA-450/4-92-010. April 1992.
8. ASTM D 6216-98: Standard Practice for Opacity Monitor
Manufacturers to Certify Conformance with Design and Performance
Specifications. American Society for Testing and Materials (ASTM). April
1998.

17.0 What tables and diagrams are relevant to this method?

17.1 Reference Tables.

Table 1-1--Source C, Human Eye Response Factor
----------------------------------------------------------------------------------------------------------------
Wavelength nanometers Weighting factor \a\ Wavelength nanometers Weighting factor \a\
----------------------------------------------------------------------------------------------------------------
380.................................. 0 590 6627
390.................................. 0 600 5316

[[Page 681]]

400.................................. 2 610 4176
410.................................. 9 620 3153
420.................................. 37 630 2190
430.................................. 122 640 1443
440.................................. 262 650 886
450.................................. 443 660 504
460.................................. 694 670 259
470.................................. 1058 680 134
480.................................. 1618 690 62
490.................................. 2358 700 29
500.................................. 3401 720 14
510.................................. 4833 720 6
520.................................. 6462 730 3
530.................................. 7934 740 2
540.................................. 9194 750 1
550.................................. 9832 760 1
560.................................. 9841 770 0
570.................................. 9147 780 0
580.................................. 7992 ....................... .......................
----------------------------------------------------------------------------------------------------------------
\1\ Total of weighting factors = 100,000.

Table 1-2 \T\ Values
----------------------------------------------------------------------------------------------------------------
n \a\ \t\ 0.975 n \a\ \t\ 0.975 n \a\ \t\ 0.975
----------------------------------------------------------------------------------------------------------------
2.............................................. 12.706 7 2.447 12 2.201
3.............................................. 4.303 8 2.365 13 2.179
4.............................................. 3.182 9 2.306 14 2.160
5.............................................. 2.776 10 2.262 15 2.145
6.............................................. 2.571 11 2.228 16 2.131
----------------------------------------------------------------------------------------------------------------
\a\ The values in this table are already corrected for n-1 degrees of freedom. Use n equal to the number of
individual values.

17.2 Diagrams.

[[Page 682]]

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[[Page 683]]

[GRAPHIC] [TIFF OMITTED] TR10AU00.019

[[Page 684]]

[GRAPHIC] [TIFF OMITTED] TR10AU00.020

[[Page 685]]

[GRAPHIC] [TIFF OMITTED] TR10AU00.021

[[Page 686]]

Performance Specification 2--Specifications and Test Procedures for
SO2 and NOX Continuous Emission Monitoring Systems
in Stationary Sources

1.0 Scope and Application

1.1 Analytes

------------------------------------------------------------------------
Analyte CAS Nos.
------------------------------------------------------------------------
Sulfur Dioxide (SO2)................................ 7449-09-5
Nitrogen Oxides (NOX)............................... 10102-44-0 (NO2),
10024-97-2 (NO)
------------------------------------------------------------------------

1.2 Applicability.
1.2.1 This specification is for evaluating the acceptability of
SO2 and NOX continuous emission monitoring systems
(CEMS) at the time of installation or soon after and whenever specified
in the regulations. The CEMS may include, for certain stationary
sources, a diluent (O2 or CO2) monitor.
1.2.2 This specification is not designed to evaluate the installed
CEMS performance over an extended period of time nor does it identify
specific calibration techniques and other auxiliary procedures to assess
the CEMS performance. The source owner or operator is responsible to
calibrate, maintain, and operate the CEMS properly. The Administrator
may require, under section 114 of the Act, the operator to conduct CEMS
performance evaluations at other times besides the initial test to
evaluate the CEMS performance. See 40 CFR Part 60, Sec. 60.13(c).

2.0 Summary of Performance Specification

Procedures for measuring CEMS relative accuracy and calibration
drift are outlined. CEMS installation and measurement location
specifications, equipment specifications, performance specifications,
and data reduction procedures are included. Conformance of the CEMS with
the Performance Specification is determined.

3.0 Definitions

3.1 Calibration Drift (CD) means the difference in the CEMS output
readings from the established reference value after a stated period of
operation during which no unscheduled maintenance, repair, or adjustment
took place.
3.2 Centroidal Area means a concentric area that is geometrically
similar to the stack or duct cross section and is no greater than l
percent of the stack or duct cross-sectional area.
3.3 Continuous Emission Monitoring System means the total equipment
required for the determination of a gas concentration or emission rate.
The sample interface, pollutant analyzer, diluent analyzer, and data
recorder are the major subsystems of the CEMS.
3.4 Data Recorder means that portion of the CEMS that provides a
permanent record of the analyzer output. The data recorder may include
automatic data reduction capabilities.
3.5 Diluent Analyzer means that portion of the CEMS that senses the
diluent gas (i.e., CO2 or O2) and generates an
output proportional to the gas concentration.
3.6 Path CEMS means a CEMS that measures the gas concentration along
a path greater than 10 percent of the equivalent diameter of the stack
or duct cross section.
3.7 Point CEMS means a CEMS that measures the gas concentration
either at a single point or along a path equal to or less than 10
percent of the equivalent diameter of the stack or duct cross section.
3.8 Pollutant Analyzer means that portion of the CEMS that senses
the pollutant gas and generates an output proportional to the gas
concentration.
3.9 Relative Accuracy (RA) means the absolute mean difference
between the gas concentration or emission rate determined by the CEMS
and the value determined by the reference method (RM), plus the 2.5
percent error confidence coefficient of a series of tests, divided by
the mean of the RM tests or the applicable emission limit.
3.10 Sample Interface means that portion of the CEMS used for one or
more of the following: sample acquisition, sample delivery, sample
conditioning, or protection of the monitor from the effects of the stack
effluent.
3.11 Span Value means the concentration specified for the affected
source category in an applicable subpart of the regulations that is used
to set the calibration gas concentration and in determining calibration
drift.

4.0 Interferences [Reserved]

5.0 Safety

The procedures required under this performance specification may
involve hazardous materials, operations, and equipment. This performance
specification may not address all of the safety problems associated with
these procedures. It is the responsibility of the user to establish
appropriate safety and health practices and determine the applicable
regulatory limitations prior to performing these procedures. The CEMS
user's manual and materials recommended by the reference method should
be consulted for specific precautions to be taken.

6.0 Equipment and Supplies

6.1 CEMS Equipment Specifications.
6.1.1 Data Recorder Scale. The CEMS data recorder output range must
include zero and a high-level value. The high-level value is chosen by
the source owner or operator and is defined as follows:
6.1.1.1 For a CEMS intended to measure an uncontrolled emission
(e.g., SO2 measurements at the inlet of a flue gas

[[Page 687]]

desulfurization unit), the high-level value should be between 1.25 and 2
times the maximum potential emission level over the appropriate
averaging time, unless otherwise specified in an applicable subpart of
the regulations.
6.1.1.2 For a CEMS installed to measure controlled emissions or
emissions that are in compliance with an applicable regulation, the
high-level value between 1.5 times the pollutant concentration
corresponding to the emission standard level and the span value given in
the applicable regulations is adequate.
6.1.1.3 Alternative high-level values may be used, provided the
source can measure emissions which exceed the full-scale limit in
accordance with the requirements of applicable regulations.
6.1.1.4 If an analog data recorder is used, the data recorder output
must be established so that the high-level value would read between 90
and 100 percent of the data recorder full scale. (This scale requirement
may not be applicable to digital data recorders.) The zero and high
level calibration gas, optical filter, or cell values should be used to
establish the data recorder scale.
6.1.2 The CEMS design should also allow the determination of
calibration drift at the zero and high-level values. If this is not
possible or practical, the design must allow these determinations to be
conducted at a low-level value (zero to 20 percent of the high-level
value) and at a value between 50 and 100 percent of the high-level
value. In special cases, the Administrator may approve a single-point
calibration-drift determination.
6.2 Other equipment and supplies, as needed by the applicable
reference method(s) (see section 8.4.2 of this Performance
Specification), may be required.

7.0 Reagents and Standards

7.1 Reference Gases, Gas Cells, or Optical Filters. As specified by
the CEMS manufacturer for calibration of the CEMS (these need not be
certified).
7.2 Reagents and Standards. May be required as needed by the
applicable reference method(s) (see section 8.4.2 of this Performance
Specification).

8.0 Performance Specification Test Procedure

8.1 Installation and Measurement Location Specifications.
8.1.1 CEMS Installation. Install the CEMS at an accessible location
where the pollutant concentration or emission rate measurements are
directly representative or can be corrected so as to be representative
of the total emissions from the affected facility or at the measurement
location cross section. Then select representative measurement points or
paths for monitoring in locations that the CEMS will pass the RA test
(see section 8.4). If the cause of failure to meet the RA test is
determined to be the measurement location and a satisfactory correction
technique cannot be established, the Administrator may require the CEMS
to be relocated. Suggested measurement locations and points or paths
that are most likely to provide data that will meet the RA requirements
are listed below.
8.1.2 CEMS Measurement Location. It is suggested that the
measurement location be (1) at least two equivalent diameters downstream
from the nearest control device, the point of pollutant generation, or
other point at which a change in the pollutant concentration or emission
rate may occur and (2) at least a half equivalent diameter upstream from
the effluent exhaust or control device.
8.1.2.1 Point CEMS. It is suggested that the measurement point be
(1) no less than 1.0 meter (3.3 ft) from the stack or duct wall or (2)
within or centrally located over the centroidal area of the stack or
duct cross section.
8.1.2.2 Path CEMS. It is suggested that the effective measurement
path (1) be totally within the inner area bounded by a line 1.0 meter
(3.3 ft) from the stack or duct wall, or (2) have at least 70 percent of
the path within the inner 50 percent of the stack or duct cross-
sectional area, or (3) be centrally located over any part of the
centroidal area.
8.1.3 Reference Method Measurement Location and Traverse Points.
8.1.3.1 Select, as appropriate, an accessible RM measurement point
at least two equivalent diameters downstream from the nearest control
device, the point of pollutant generation, or other point at which a
change in the pollutant concentration or emission rate may occur, and at
least a half equivalent diameter upstream from the effluent exhaust or
control device. When pollutant concentration changes are due solely to
diluent leakage (e.g., air heater leakages) and pollutants and diluents
are simultaneously measured at the same location, a half diameter may be
used in lieu of two equivalent diameters. The CEMS and RM locations need
not be the same.
8.1.3.2 Select traverse points that assure acquisition of
representative samples over the stack or duct cross section. The minimum
requirements are as follows: Establish a ``measurement line'' that
passes through the centroidal area and in the direction of any expected
stratification. If this line interferes with the CEMS measurements,
displace the line up to 30 cm (12 in.) (or 5 percent of the equivalent
diameter of the cross section, whichever is less) from the centroidal
area. Locate three traverse points at 16.7, 50.0, and 83.3 percent of
the measurement line. If the measurement line is longer than 2.4 meters

[[Page 688]]

(7.8 ft) and pollutant stratification is not expected, the three
traverse points may be located on the line at 0.4, 1.2, and 2.0 meters
from the stack or duct wall. This option must not be used after wet
scrubbers or at points where two streams with different pollutant
concentrations are combined. If stratification is suspected, the
following procedure is suggested. For rectangular ducts, locate at least
nine sample points in the cross section such that sample points are the
centroids of similarly-shaped, equal area divisions of the cross
section. Measure the pollutant concentration, and, if applicable, the
diluent concentration at each point using appropriate reference methods
or other appropriate instrument methods that give responses relative to
pollutant concentrations. Then calculate the mean value for all sample
points. For circular ducts, conduct a 12-point traverse (i.e., six
points on each of the two perpendicular diameters) locating the sample
points as described in 40 CFR 60, Appendix A, Method 1. Perform the
measurements and calculations as described above. Determine if the mean
pollutant concentration is more than 10% different from any single
point. If so, the cross section is considered to be stratified, and the
tester may not use the alternative traverse point locations (...0.4,
1.2, and 2.0 meters from the stack or duct wall.) but must use the three
traverse points at 16.7, 50.0, and 83.3 percent of the entire
measurement line. Other traverse points may be selected, provided that
they can be shown to the satisfaction of the Administrator to provide a
representative sample over the stack or duct cross section. Conduct all
necessary RM tests within 3 cm (1.2 in.) of the traverse points, but no
closer than 3 cm (1.2 in.) to the stack or duct wall.
8.2 Pretest Preparation. Install the CEMS, prepare the RM test site
according to the specifications in section 8.1, and prepare the CEMS for
operation according to the manufacturer's written instructions.
8.3 Calibration Drift Test Procedure.
8.3.1 CD Test Period. While the affected facility is operating,
determine the magnitude of the CD once each day (at 24-hour intervals)
for 7 consecutive calendar days according to the procedure given in
sections 8.3.2 through 8.3.4. Alternatively, the CD test may be
conducted over 7 consecutive unit operating days.
8.3.2 The purpose of the CD measurement is to verify the ability of
the CEMS to conform to the established CEMS calibration used for
determining the emission concentration or emission rate. Therefore, if
periodic automatic or manual adjustments are made to the CEMS zero and
calibration settings, conduct the CD test immediately before these
adjustments, or conduct it in such a way that the CD can be determined.
8.3.3 Conduct the CD test at the two points specified in section
6.1.2. Introduce to the CEMS the reference gases, gas cells, or optical
filters (these need not be certified). Record the CEMS response and
subtract this value from the reference value (see example data sheet in
Figure 2-1).
8.4 Relative Accuracy Test Procedure.
8.4.1 RA Test Period. Conduct the RA test according to the procedure
given in sections 8.4.2 through 8.4.6 while the affected facility is
operating at more than 50 percent of normal load, or as specified in an
applicable subpart. The RA test may be conducted during the CD test
period.
8.4.2 Reference Methods. Unless otherwise specified in an applicable
subpart of the regulations, Methods 3B, 4, 6, and 7, or their approved
alternatives, are the reference methods for diluent (O2 and
CO2), moisture, SO2, and NOX,
respectively.
8.4.3 Sampling Strategy for RM Tests. Conduct the RM tests in such a
way that they will yield results representative of the emissions from
the source and can be correlated to the CEMS data. It is preferable to
conduct the diluent (if applicable), moisture (if needed), and pollutant
measurements simultaneously. However, diluent and moisture measurements
that are taken within an hour of the pollutant measurements may be used
to calculate dry pollutant concentration and emission rates. In order to
correlate the CEMS and RM data properly, note the beginning and end of
each RM test period of each run (including the exact time of day) on the
CEMS chart recordings or other permanent record of output. Use the
following strategies for the RM tests:
8.4.3.1 For integrated samples (e.g., Methods 6 and Method 4), make
a sample traverse of at least 21 minutes, sampling for an equal time at
each traverse point (see section 8.1.3.2 for discussion of traverse
points.
8.4.3.2 For grab samples (e.g., Method 7), take one sample at each
traverse point, scheduling the grab samples so that they are taken
simultaneously (within a 3-minute period) or at an equal interval of
time apart over the span of time the CEM pollutant is measured. A test
run for grab samples must be made up of at least three separate
measurements.

Note: At times, CEMS RA tests are conducted during new source
performance standards performance tests. In these cases, RM results
obtained during CEMS RA tests may be used to determine compliance as
long as the source and test conditions are consistent with the
applicable regulations.

8.4.4 Number of RM Tests. Conduct a minimum of nine sets of all
necessary RM test runs.

Note: More than nine sets of RM tests may be performed. If this
option is chosen, a maximum of three sets of the test results may be
rejected so long as the total number of test results used to determine
the RA is greater

[[Page 689]]

than or equal to nine. However, all data must be reported, including the
rejected data.

8.4.5 Correlation of RM and CEMS Data. Correlate the CEMS and the RM
test data as to the time and duration by first determining from the CEMS
final output (the one used for reporting) the integrated average
pollutant concentration or emission rate for each pollutant RM test
period. Consider system response time, if important, and confirm that
the pair of results are on a consistent moisture, temperature, and
diluent concentration basis. Then, compare each integrated CEMS value
against the corresponding average RM value. Use the following guidelines
to make these comparisons.
8.4.5.1 If the RM has an integrated sampling technique, make a
direct comparison of the RM results and CEMS integrated average value.
8.4.5.2 If the RM has a grab sampling technique, first average the
results from all grab samples taken during the test run, and then
compare this average value against the integrated value obtained from
the CEMS chart recording or output during the run. If the pollutant
concentration is varying with time over the run, the arithmetic average
of the CEMS value recorded at the time of each grab sample may be used.
8.4.6 Calculate the mean difference between the RM and CEMS values
in the units of the emission standard, the standard deviation, the
confidence coefficient, and the relative accuracy according to the
procedures in section 12.0.
8.5 Reporting. At a minimum (check with the appropriate regional
office, State, or Local agency for additional requirements, if any),
summarize in tabular form the results of the CD tests and the RA tests
or alternative RA procedure, as appropriate. Include all data sheets,
calculations, charts (records of CEMS responses), cylinder gas
concentration certifications, and calibration cell response
certifications (if applicable) necessary to confirm that the performance
of the CEMS met the performance specifications.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this Performance
Specification (see section 8.0). Refer to the RM for specific analytical
procedures.

12.0 Calculations and Data Analysis

Summarize the results on a data sheet similar to that shown in
Figure 2-2 (in section 18.0).
12.1 All data from the RM and CEMS must be on a consistent dry basis
and, as applicable, on a consistent diluent basis and in the units of
the emission standard. Correct the RM and CEMS data for moisture and
diluent as follows:
12.1.1 Moisture Correction (as applicable). Correct each wet RM run
for moisture with the corresponding Method 4 data; correct each wet CEMS
run using the corresponding CEMS moisture monitor date using Equation 2-
1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.453

12.1.2 Correction to Units of Standard (as applicable). Correct each
dry RM run to the units of the emission standard with the corresponding
Method 3B data; correct each dry CEMS run using the corresponding CEMS
diluent monitor data as follows:
12.1.2.1 Correct to Diluent Basis. The following is an example of
concentration (ppm) correction to 7% oxygen.
[GRAPHIC] [TIFF OMITTED] TR17OC00.454

The following is an example of mass/gross calorific value (lbs/
million Btu) correction.

lbs/MMBtu = Conc(dry) (F-factor) (20.9/20.9-%02)

[[Page 690]]

12.2 Arithmetic Mean. Calculate the arithmetic mean of the
difference, d, of a data set as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.455

Where:

n = Number of data points.
[GRAPHIC] [TIFF OMITTED] TR17OC00.456

12.3 Standard Deviation. Calculate the standard deviation,
Sd, as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.457

12.4 Confidence Coefficient. Calculate the 2.5 percent error
confidence coefficient (one-tailed), CC, as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.458

Where:

t0.975 = t-value (see Table 2-1).

12.5 Relative Accuracy. Calculate the RA of a set of data as
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.459

Where:

d = Absolute value of the mean differences (from Equation 2-3).
CC = Absolute value of the confidence coefficient (from Equation 2-3).
RM = Average RM value. In cases where the average emissions for the test
are less than 50 percent of the applicable standard,
substitute the emission standard value in the denominator of
Eq. 2-6 in place of RM. In all other cases, use RM.

13.0 Method Performance

13.1 Calibration Drift Performance Specification. The CEMS
calibration must not drift or deviate from the reference value of the
gas cylinder, gas cell, or optical filter by more than 2.5 percent of
the span value. If the CEMS includes pollutant and diluent monitors, the
CD must be determined separately for each in terms of concentrations
(See Performance Specification 3 for the diluent specifications), and
none of the CDs may exceed the specification.
13.2 Relative Accuracy Performance Specification. The RA of the CEMS
must be no greater than 20 percent when RM is used in the denominator of
Eq. 2-6 (average emissions during test are greater than 50 percent of
the emission standard) or 10 percent when the applicable emission
standard is used in the denominator of Eq. 2-6 (average emissions during
test are less than 50 percent of the emission standard). For
SO2 emission standards of 130 to and including 86 ng/J (0.30
and 0.20 lb/million Btu), inclusive, use 15 percent of the applicable
standard; below 86 ng/J (0.20 lb/million Btu), use 20 percent of the
emission standard.
13.3 For instruments that use common components to measure more than
one effluent gas constituent, all channels must simultaneously pass the
RA requirement, unless it can be demonstrated that any adjustments made
to one channel did not affect the others.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

Paragraphs 60.13(j)(1) and (2) of 40 CFR part 60 contain criteria
for which the reference method procedure for determining relative
accuracy (see section 8.4 of this Performance Specification) may be
waived and the following procedure substituted.
16.1 Conduct a complete CEMS status check following the
manufacturer's written instructions. The check should include operation
of the light source, signal receiver, timing mechanism functions, data
acquisition and data reduction functions, data recorders, mechanically
operated functions (mirror movements, zero pipe operation,

[[Page 691]]

calibration gas valve operations, etc.), sample filters, sample line
heaters, moisture traps, and other related functions of the CEMS, as
applicable. All parts of the CEMS shall be functioning properly before
proceeding to the alternative RA procedure.
16.2 Alternative RA Procedure.
16.2.1 Challenge each monitor (both pollutant and diluent, if
applicable) with cylinder gases of known concentrations or calibration
cells that produce known responses at two measurement points within the
ranges shown in Table 2-2 (Section 18).
16.2.2 Use a separate cylinder gas (for point CEMS only) or
calibration cell (for path CEMS or where compressed gas cylinders can
not be used) for measurement points 1 and 2. Challenge the CEMS and
record the responses three times at each measurement point. The
Administrator may allow dilution of cylinder gas using the performance
criteria in Test Method 205, 40 CFR Part 51, Appendix M. Use the average
of the three responses in determining relative accuracy.
16.2.3 Operate each monitor in its normal sampling mode as nearly as
possible. When using cylinder gases, pass the cylinder gas through all
filters, scrubbers, conditioners, and other monitor components used
during normal sampling and as much of the sampling probe as practical.
When using calibration cells, the CEMS components used in the normal
sampling mode should not be by-passed during the RA determination. These
include light sources, lenses, detectors, and reference cells. The CEMS
should be challenged at each measurement point for a sufficient period
of time to assure adsorption-desorption reactions on the CEMS surfaces
have stabilized.
16.2.4 Use cylinder gases that have been certified by comparison to
National Institute of Standards and Technology (NIST) gaseous standard
reference material (SRM) or NIST/EPA approved gas manufacturer's
certified reference material (CRM) (See Reference 2 in section 17.0)
following EPA Traceability Protocol Number 1 (See Reference 3 in section
17.0). As an alternative to Protocol Number 1 gases, CRM's may be used
directly as alternative RA cylinder gases. A list of gas manufacturers
that have prepared approved CRM's is available from EPA at the address
shown in Reference 2. Procedures for preparation of CRM's are described
in Reference 2.
16.2.5 Use calibration cells certified by the manufacturer to
produce a known response in the CEMS. The cell certification procedure
shall include determination of CEMS response produced by the calibration
cell in direct comparison with measurement of gases of known
concentration. This can be accomplished using SRM or CRM gases in a
laboratory source simulator or through extended tests using reference
methods at the CEMS location in the exhaust stack. These procedures are
discussed in Reference 4 in section 17.0. The calibration cell
certification procedure is subject to approval of the Administrator.
16.3 The differences between the known concentrations of the
cylinder gases and the concentrations indicated by the CEMS are used to
assess the accuracy of the CEMS. The calculations and limits of
acceptable relative accuracy are as follows:
16.3.1 For pollutant CEMS:
[GRAPHIC] [TIFF OMITTED] TR17OC00.460

Where:

d = Average difference between responses and the concentration/responses
(see section 16.2.2).
AC = The known concentration/response of the cylinder gas or calibration
cell.

16.3.2 For diluent CEMS:

RA=d O.7 percent O2 or CO2, as
applicable.

Note: Waiver of the relative accuracy test in favor of the
alternative RA procedure does not preclude the requirements to complete
the CD tests nor any other requirements specified in an applicable
subpart for reporting CEMS data and performing CEMS drift checks or
audits.

17.0 References

1. Department of Commerce. Experimental Statistics. Handbook 91.
Washington, D.C. p. 3-31, paragraphs 3-3.1.4.
2. ``A Procedure for Establishing Traceability of Gas Mixtures to
Certain National Bureau of Standards Standard Reference Materials.''
Joint publication by NBS and EPA. EPA 600/7-81-010. Available from U.S.
Environmental Protection Agency, Quality Assurance Division (MD-77),
Research Triangle Park, North Carolina 27711.
3. ``Traceability Protocol for Establishing True Concentrations of
Gases Used for Calibration and Audits of Continuous Source Emission
Monitors. (Protocol Number 1).'' June 1978. Protocol Number 1 is
included in

[[Page 692]]

the Quality Assurance Handbook for Air Pollution Measurement Systems,
Volume III, Stationary Source Specific Methods. EPA-600/4-77-027b.
August 1977.
4. ``Gaseous Continuous Emission Monitoring Systems--Performance
Specification Guidelines for SO2, NOX,
CO2, O2, and TRS.'' EPA-450/3-82-026. Available
from the U.S. EPA, Emission Measurement Center, Emission Monitoring and
Data Analysis Division (MD-19), Research Triangle Park, North Carolina
27711.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

Figure 2-1. Calibration Drift Determination

Table 2-1--t-Values
----------------------------------------------------------------------------------------------------------------
n \a\ t0.975 n \a\ t0.975 n \a\ t0.975
----------------------------------------------------------------------------------------------------------------
2.............................................. 12.706 7 2.447 12 2.201
3.............................................. 4.303 8 2.365 13 2.179
4.............................................. 3.182 9 2.306 14 2.160
5.............................................. 2.776 10 2.262 15 2.145
6.............................................. 2.571 11 2.228 16 2.131
----------------------------------------------------------------------------------------------------------------
\a\ The values in this table are already corrected for n-1 degrees of freedom. Use n equal to the number of
individual values.

Table 2-2--Measurement Range
----------------------------------------------------------------------------------------------------------------
Diluent monitor for
Measurement point Pollutant monitor -------------------------------------------------
CO2 O2
----------------------------------------------------------------------------------------------------------------
1.................................... 20-30% of span value... 5-8% by volume......... 4-6% by volume.
2.................................... 50-60% of span value... 10-14% by volume....... 8-12% by volume.

--------------------------------------------------------------------------------------------------------------------------------------------------------
Calibration value Percent of span value (C-
Day Date and time (C) Monitor value (M) Difference (C-M) M)/span value x 100
--------------------------------------------------------------------------------------------------------------------------------------------------------
Low-level.......................

High-level......................

--------------------------------------------------------------------------------------------------------------------------------------------------------

Figure 2-2. Relative Accuracy Determination.
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
SO2 NOX \b\ CO2 or O2 \a\ SO2 \a\ NOX \a\
Run No. Date and time ----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
RM CEMS Diff RM CEMS Diff RM CEMS RM CEMS Diff RM CEMS Diff
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
ppm \c\
ppm \c\ % \c\ % \c\ mass/GCV
mass/GCV
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
1.............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
2.............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
3.............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
4.............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
5.............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
6.............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
7.............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
8.............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

[[Page 693]]

9.............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
10............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
11............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
12............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Average
Confidence Interval
Accuracy
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
\a\ For steam generators.
\b\ Average of three samples.
\c\ Make sure that RM and CEMS data are on a consistent basis, either wet or dry.

Performance Specification 3--Specifications and Test Procedures for
O2 and CO2 Continuous Emission Monitoring Systems
in Stationary Sources

1.0 Scope and Application

1.1 Analytes.

1.2 Applicability.
1.2.1 This specification is for evaluating acceptability of
O2 and CO2 continuous emission monitoring systems
(CEMS) at the time of installation or soon after and whenever specified
in an applicable subpart of the regulations. This specification applies
to O2 or CO2 monitors that are not included under
Performance Specification 2 (PS 2).
1.2.2 This specification is not designed to evaluate the installed
CEMS performance over an extended period of time, nor does it identify
specific calibration techniques and other auxiliary procedures to assess
the CEMS performance. The source owner or operator, is responsible to
calibrate, maintain, and operate the CEMS properly. The Administrator
may require, under section 114 of the Act, the operator to conduct CEMS
performance evaluations at other times besides the initial test to
evaluate the CEMS performance. See 40 CFR part 60, section 60.13(c).
1.2.3 The definitions, installation and measurement location
specifications, calculations and data analysis, and references are the
same as in PS 2, sections 3, 8.1, 12, and 17, respectively, and also
apply to O2 and CO2 CEMS under this specification.
The performance and equipment specifications and the relative accuracy
(RA) test procedures for O2 and CO2 CEMS do not
differ from those for SO2 and NOX CEMS (see PS 2),
except as noted below.

2.0 Summary of Performance Specification

The RA and calibration drift (CD) tests are conducted to determine
conformance of the CEMS to the specification.

3.0 Definitions

Same as in section 3.0 of PS 2.

4.0 Interferences [Reserved]

5.0 Safety

This performance specification may involve hazardous materials,
operations, and equipment. This performance specification may not
address all of the safety problems associated with its use. It is the
responsibility of the user to establish appropriate safety and health
practices and determine the applicable regulatory limitations prior to
performing this performance specification. The CEMS users manual should
be consulted for specific precautions to be taken with regard to the
analytical procedures.

6.0 Equipment and Supplies

Same as section 6.0 of PS2.

7.0 Reagents and Standards

Same as section 7.0 of PS2.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Relative Accuracy Test Procedure. Sampling Strategy for
reference method (RM) Tests, Correlation of RM and CEMS Data, and Number
of RM Tests. Same as PS 2, sections 8.4.3, 8.4.5, and 8.4.4,
respectively.
8.2 Reference Method. Unless otherwise specified in an applicable
subpart of the regulations, Method 3B or other approved alternative is
the RM for O2 or CO2.

[[Page 694]]

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure

Sample collection and analyses are concurrent for this performance
specification (see section 8). Refer to the RM for specific analytical
procedures.

12.0 Calculations and Data Analysis

Summarize the results on a data sheet similar to that shown in
Figure 2.2 of PS2. Calculate the arithmetic difference between the RM
and the CEMS output for each run. The average difference of the nine (or
more) data sets constitute the RA.

13.0 Method Performance

13.1 Calibration Drift Performance Specification. The CEMS
calibration must not drift by more than 0.5 percent O2 or
CO2 from the reference value of the gas, gas cell, or optical
filter.
13.2 CEMS Relative Accuracy Performance Specification. The RA of the
CEMS must be no greater than 20 percent of the mean value of the
reference method (RM) data. The results are also acceptable if the
absolute value of the difference between the mean RM value and the mean
CEMS value is less than or equal to 1.0 percent O2 (or
CO2).

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as in section 17.0 of PS 2.

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Performance Specification 4--Specifications and Test Procedures for
Carbon Monoxide Continuous Emission Monitoring Systems in Stationary
Sources

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Carbon Monoxide (CO)................................... 630-08-0
------------------------------------------------------------------------

1.2 Applicability.
1.2.1 This specification is for evaluating the acceptability of
carbon monoxide (CO) continuous emission monitoring systems (CEMS) at
the time of installation or soon after and whenever specified in an
applicable subpart of the regulations. This specification was developed
primarily for CEMS having span values of 1,000 ppmv CO.
1.2.2 This specification is not designed to evaluate the installed
CEMS performance over an extended period of time nor does it identify
specific calibration techniques and other auxiliary procedures to assess
CEMS performance. The source owner or operator, is responsible to
calibrate, maintain, and operate the CEMS. The Administrator may
require, under section 114 of the Act, the source owner or operator to
conduct CEMS performance evaluations at other times besides the initial
test to evaluate the CEMS performance. See 40 CFR part 60, section
60.13(c).
1.2.3 The definitions, performance specification test procedures,
calculations, and data analysis procedures for determining calibration
drift (CD) and relative accuracy (RA) of Performance Specification 2 (PS
2), sections 3, 8.0, and 12, respectively, apply to this specification.

2.0 Summary of Performance Specification

The CD and RA tests are conducted to determine conformance of the
CEMS to the specification.

3.0 Definitions

Same as in section 3.0 of PS 2.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Same as section 6.0 of PS 2.

7.0 Reagents and Standards

Same as section 7.0 of PS 2.

8.0 Sample Collection, Preservation, Storage, and Transport

[[Page 695]]

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this performance
specification (see section 8.0). Refer to the RM for specific analytical
procedures.

12.0 Calculations and Data Analysis

Same as section 12.0 of PS 2.

13.0 Method Performance

13.1 Calibration Drift. The CEMS calibration must not drift or
deviate from the reference value of the calibration gas, gas cell, or
optical filter by more than 5 percent of the established span value for
6 out of 7 test days (e.g., the established span value is 1000 ppm for
Subpart J affected facilities).
13.2 Relative Accuracy. The RA of the CEMS must be no greater than
10 percent when the average RM value is used to calculate RA or 5
percent when the applicable emission standard is used to calculate RA.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures [Reserved]

17.0 References

1. Ferguson, B.B., R.E. Lester, and W.J. Mitchell. Field Evaluation
of Carbon Monoxide and Hydrogen Sulfide Continuous Emission Monitors at
an Oil Refinery. U.S. Environmental Protection Agency. Research Triangle
Park, N.C. Publication No. EPA-600/4-82-054. August 1982. 100 p.
2. ``Gaseous Continuous Emission Monitoring Systems--Performance
Specification Guidelines for SO2, NOX,
CO2, O2, and TRS.'' EPA-450/3-82-026. U.S.
Environmental Protection Agency, Technical Support Division (MD-19),
Research Triangle Park, NC 27711.
3. Repp, M. Evaluation of Continuous Monitors for Carbon Monoxide in
Stationary Sources. U.S. Environmental Protection Agency. Research
Triangle Park, N.C. Publication No. EPA-600/2-77-063. March 1977. 155 p.
4. Smith, F., D.E. Wagoner, and R.P. Donovan. Guidelines for
Development of a Quality Assurance Program: Volume VIII--Determination
of CO Emissions from Stationary Sources by NDIR Spectrometry. U.S.
Environmental Protection Agency. Research Triangle Park, N.C.
Publication No. EPA-650/4-74-005-h. February 1975. 96 p.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

Same as section 18.0 of PS 2.

Performance Specification 4A--Specifications and Test Procedures for
Carbon Monoxide Continuous Emission Monitoring Systems in Stationary
Sources

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Carbon Monoxide (CO)................................... 630-80-0
------------------------------------------------------------------------

1.2 Applicability.
1.2.1 This specification is for evaluating the acceptability of
carbon monoxide (CO) continuous emission monitoring systems (CEMS) at
the time of installation or soon after and whenever specified in an
applicable subpart of the regulations. This specification was developed
primarily for CEMS that comply with low emission standards (less than
200 ppmv).
1.2.2 This specification is not designed to evaluate the installed
CEMS performance over an extended period of time nor does it identify
specific calibration techniques and other auxiliary procedures to assess
CEMS performance. The source owner or operator is responsible to
calibrate, maintain, and operate the CEMS. The Administrator may
require, under section 114 of the Act, the source owner or operator to
conduct CEMS performance evaluations at other times besides the initial
test to evaluate CEMS performance. See 40 CFR Part 60, section 60.13(c).
1.2.3 The definitions, performance specification, test procedures,
calculations and data analysis procedures for determining calibration
drifts (CD) and relative accuracy (RA), of Performance Specification 2
(PS 2), sections 3, 8.0, and 12, respectively, apply to this
specification.

2.0 Summary of Performance Specification

The CD and RA tests are conducted to determine conformance of the
CEMS to the specification.

3.0 Definitions

Same as in section 3.0 of PS 2.

4.0 Interferences [Reserved]

5.0 Safety

[[Page 696]]

6.0 Equipment and Supplies

Same as section 6.0 of PS 2 with the following additions.
6.1 Data Recorder Scale.
6.1.1 This specification is the same as section 6.1 of PS 2. The
CEMS shall be capable of measuring emission levels under normal
conditions and under periods of short-duration peaks of high
concentrations. This dual-range capability may be met using two separate
analyzers (one for each range) or by using dual-range units which have
the capability of measuring both levels with a single unit. In the
latter case, when the reading goes above the full-scale measurement
value of the lower range, the higher-range operation shall be started
automatically. The CEMS recorder range must include zero and a high-
level value. Under applications of consistent low emissions, a single-
range analyzer is allowed provided normal and spike emissions can be
quantified. In this case, set an appropriate high-level value to include
all emissions.
6.1.2 For the low-range scale of dual-range units, the high-level
value shall be between 1.5 times the pollutant concentration
corresponding to the emission standard level and the span value. For the
high-range scale, the high-level value shall be set at 2000 ppm, as a
minimum, and the range shall include the level of the span value. There
shall be no concentration gap between the low-and high-range scales.

7.0 Reagents and Standards

Same as section 7.0 of PS 2.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Relative Accuracy Test Procedure. Sampling Strategy for
reference method (RM) Tests, Number of RM Tests, and Correlation of RM
and CEMS Data are the same as PS 2, sections 8.4.3, 8.4.4, and 8.4.5,
respectively.
8.2 Reference Methods. Unless otherwise specified in an applicable
subpart of the regulation, Methods 10, 10A, 10B, or other approved
alternative is the RM for this PS. When evaluating nondispersive
infrared CEMS using Method 10 as the RM, the alternative interference
trap specified in section 16.0 of Method 10 shall be used.
8.3 Response Time Test Procedure. The response time test applies to
all types of CEMS, but will generally have significance only for
extractive systems.
8.3.1 Introduce zero gas into the analyzer. When the system output
has stabilized (no change greater than 1 percent of full scale for 30
sec), introduce an upscale calibration gas and wait for a stable value.
Record the time (upscale response time) required to reach 95 percent of
the final stable value. Next, reintroduce the zero gas and wait for a
stable reading before recording the response time (downscale response
time). Repeat the entire procedure three times and determine the mean
upscale and downscale response times. The slower or longer of the two
means is the system response time.
8.4 Interference Check. The CEMS must be shown to be free from the
effects of any interferences.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this performance
specification (see section 8.0). Refer to the RM for specific analytical
procedures.

12.0 Calculations and Data Analysis. Same as section 12.0 of PS 2

13.0 Method Performance

13.1 Calibration Drift. The CEMS calibration must not drift or
deviate from the reference value of the calibration gas, gas cell, or
optical filter by more than 5 percent of the established span value for
6 out of 7 test days.
13.2 Relative Accuracy. The RA of the CEMS must be no greater than
10 percent when the average RM value is used to calculate RA, 5 percent
when the applicable emission standard is used to calculate RA, or within
5 ppmv when the RA is calculated as the absolute average difference
between the RM and CEMS plus the 2.5 percent confidence coefficient.
13.3 Response Time. The CEMS response time shall not exceed 1.5 min
to achieve 95 percent of the final stable value.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 Under conditions where the average CO emissions are less than
10 percent of the standard and this is verified by Method 10, a cylinder
gas audit may be performed in place of the RA test to determine
compliance with these limits. In this case, the cylinder gas shall
contain CO in 12 percent carbon dioxide as an interference check. If
this option is exercised, Method 10 must be used to verify that emission
levels are less than 10 percent of the standard.

17.0 References

Same as section 17 of PS 4.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

Same as section 18.0 of PS 2.

[[Page 697]]

Performance Specification 4B--Specifications and Test Procedures for
Carbon Monoxide and Oxygen Continuous Monitoring Systems in Stationary
Sources

a. Applicability and Principle

1.1 Applicability. a. This specification is to be used for
evaluating the acceptability of carbon monoxide (CO) and oxygen
(O2) continuous emission monitoring systems (CEMS) at the
time of or soon after installation and whenever specified in the
regulations. The CEMS may include, for certain stationary sources, (a)
flow monitoring equipment to allow measurement of the dry volume of
stack effluent sampled, and (b) an automatic sampling system.
b. This specification is not designed to evaluate the installed
CEMS' performance over an extended period of time nor does it identify
specific calibration techniques and auxiliary procedures to assess the
CEMS' performance. The source owner or operator, however, is responsible
to properly calibrate, maintain, and operate the CEMS. To evaluate the
CEMS' performance, the Administrator may require, under section 114 of
the Act, the operator to conduct CEMS performance evaluations at times
other than the initial test.
c. The definitions, installation and measurement location
specifications, test procedures, data reduction procedures, reporting
requirements, and bibliography are the same as in PS 3 (for
O2) and PS 4A (for CO) except as otherwise noted below.
1.2 Principle. Installation and measurement location specifications,
performance specifications, test procedures, and data reduction
procedures are included in this specification. Reference method tests,
calibration error tests, calibration drift tests, and interferant tests
are conducted to determine conformance of the CEMS with the
specification.

b. Definitions

2.1 Continuous Emission Monitoring System (CEMS). This definition is
the same as PS 2 section 2.1 with the following addition. A continuous
monitor is one in which the sample to be analyzed passes the measurement
section of the analyzer without interruption.
2.2 Response Time. The time interval between the start of a step
change in the system input and when the pollutant analyzer output
reaches 95 percent of the final value.
2.3 Calibration Error (CE). The difference between the concentration
indicated by the CEMS and the known concentration generated by a
calibration source when the entire CEMS, including the sampling
interface is challenged. A CE test procedure is performed to document
the accuracy and linearity of the CEMS over the entire measurement
range.

3. Installation and Measurement Location Specifications

3.1 The CEMS Installation and Measurement Location. This
specification is the same as PS 2 section 3.1 with the following
additions. Both the CO and O2 monitors should be installed at
the same general location. If this is not possible, they may be
installed at different locations if the effluent gases at both sample
locations are not stratified and there is no in-leakage of air between
sampling locations.
3.1.1 Measurement Location. Same as PS 2 section 3.1.1.
3.1.2 Point CEMS. The measurement point should be within or
centrally located over the centroidal area of the stack or duct cross
section.
3.1.3 Path CEMS. The effective measurement path should: (1) Have at
least 70 percent of the path within the inner 50 percent of the stack or
duct cross sectional area, or (2) be centrally located over any part of
the centroidal area.
3.2 Reference Method (RM) Measurement Location and Traverse Points.
This specification is the same as PS 2 section 3.2 with the following
additions. When pollutant concentration changes are due solely to
diluent leakage and CO and O2 are simultaneously measured at
the same location, one half diameter may be used in place of two
equivalent diameters.
3.3 Stratification Test Procedure. Stratification is defined as the
difference in excess of 10 percent between the average concentration in
the duct or stack and the concentration at any point more than 1.0 meter
from the duct or stack wall. To determine whether effluent
stratification exists, a dual probe system should be used to determine
the average effluent concentration while measurements at each traverse
point are being made. One probe, located at the stack or duct centroid,
is used as a stationary reference point to indicate change in the
effluent concentration over time. The second probe is used for sampling
at the traverse points specified in Method 1 (40 CFR part 60 appendix
A). The monitoring system samples sequentially at the reference and
traverse points throughout the testing period for five minutes at each
point.

d. Performance and Equipment Specifications

4.1 Data Recorder Scale. For O2, same as specified in PS
3, except that the span must be 25 percent. The span of the
O2 may be higher if the O2 concentration at the
sampling point can be greater than 25 percent. For CO, same as specified
in PS 4A, except that the low-range span must be 200 ppm and the high
range span must be 3000 ppm. In addition, the scale for both CEMS must
record all readings within a measurement range with a resolution of 0.5
percent.

[[Page 698]]

4.2 Calibration Drift. For O2, same as specified in PS 3.
For CO, the same as specified in PS 4A except that the CEMS calibration
must not drift from the reference value of the calibration standard by
more than 3 percent of the span value on either the high or low range.
4.3 Relative Accuracy (RA). For O2, same as specified in
PS 3. For CO, the same as specified in PS 4A.
4.4 Calibration Error (CE). The mean difference between the CEMS and
reference values at all three test points (see Table I) must be no
greater than 5 percent of span value for CO monitors and 0.5 percent for
O2 monitors.
4.5 Response Time. The response time for the CO or O2
monitor must not exceed 2 minutes.

e. Performance Specification Test Procedure

5.1 Calibration Error Test and Response Time Test Periods. Conduct
the CE and response time tests during the CD test period.

F. The CEMS Calibration Drift and Response Time Test Procedures

The response time test procedure is given in PS 4A, and must be
carried out for both the CO and O2 monitors.
7. Relative Accuracy and Calibration Error Test Procedures
7.1 Calibration Error Test Procedure. Challenge each monitor (both
low and high range CO and O2) with zero gas and EPA Protocol
1 cylinder gases at three measurement points within the ranges specified
in Table I.

Table I. Calibration Error Concentration Ranges
------------------------------------------------------------------------
CO Low
Measurement point range CO High O2 (%)
(ppm) range (ppm)
------------------------------------------------------------------------
1................................. 0-40 0-600 0-2
2................................. 60-80 900-1200 8-10
3................................. 140-160 2100-2400 14-16
------------------------------------------------------------------------

Operate each monitor in its normal sampling mode as nearly as possible.
The calibration gas must be injected into the sample system as close to
the sampling probe outlet as practical and should pass through all CEMS
components used during normal sampling. Challenge the CEMS three non-
consecutive times at each measurement point and record the responses.
The duration of each gas injection should be sufficient to ensure that
the CEMS surfaces are conditioned.
7.1.1 Calculations. Summarize the results on a data sheet. Average
the differences between the instrument response and the certified
cylinder gas value for each gas. Calculate the CE results for the CO
monitor according to:

CE = | d/FS | x 100 (1)

Where d is the mean difference between the CEMS response and the known
reference concentration, and FS is the span value. The CE for the
O2 monitor is the average percent O2 difference
between the O2 monitor and the certified cylinder gas value
for each gas.

7.2 Relative Accuracy Test Procedure. Follow the RA test procedures
in PS 3 (for O2) section 3 and PS 4A (for CO) section 4.
7.3 Alternative RA Procedure. Under some operating conditions, it
may not be possible to obtain meaningful results using the RA test
procedure. This includes conditions where consistent, very low CO
emission or low CO emissions interrupted periodically by short duration,
high level spikes are observed. It may be appropriate in these
circumstances to waive the RA test and substitute the following
procedure.
Conduct a complete CEMS status check following the manufacturer's
written instructions. The check should include operation of the light
source, signal receiver, timing mechanism functions, data acquisition
and data reduction functions, data recorders, mechanically operated
functions, sample filters, sample line heaters, moisture traps, and
other related functions of the CEMS, as applicable. All parts of the
CEMS must be functioning properly before the RA requirement can be
waived. The instrument must also successfully passed the CE and CD
specifications. Substitution of the alternate procedure requires
approval of the Regional Administrator.
8. Bibliography
1. 40 CFR Part 266, Appendix IX, section 2, ``Performance
Specifications for Continuous Emission Monitoring Systems.''

Performance Specification 5--Specifications and Test Procedures for TRS
Continuous Emission Monitoring Systems in Stationary Sources

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Total Reduced Sulfur (TRS)............................. NA
------------------------------------------------------------------------

1.2 Applicability. This specification is for evaluating the
applicability of TRS continuous emission monitoring systems (CEMS) at
the time of installation or soon after and whenever specified in an
applicable subpart of the regulations. The CEMS may include oxygen
monitors which are subject to Performance Specification 3 (PS 3).
1.3 The definitions, performance specification, test procedures,
calculations and data analysis procedures for determining calibration
drifts (CD) and relative accuracy (RA) of PS 2, sections 3.0, 8.0, and
12.0, respectively, apply to this specification.

[[Page 699]]

2.0 Summary of Performance Specification

The CD and RA tests are conducted to determine conformance of the
CEMS to the specification.

3.0 Definitions

Same as in section 3.0 of PS 2.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Same as section 6.0 of PS 2.

7.0 Reagents and Standards

Same as section 7.0 of PS 2.

8.0 Sample Collection, Preservation, Storage, and Transport

Note: For Method 16, a sample is made up of at least three separate
injects equally space over time. For Method 16A, a sample is collected
for at least 1 hour.

8.2 Reference Methods. Unless otherwise specified in the applicable
subpart of the regulations, Method 16, Method 16A, 16B or other approved
alternative is the RM for TRS.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this performance
specification (see section 8.0). Refer to the reference method for
specific analytical procedures.

12.0 Calculations and Data Analysis

Same as section 12.0 of PS 2.

13.0 Method Performance

13.1 Calibration Drift. The CEMS detector calibration must not drift
or deviate from the reference value of the calibration gas by more than
5 percent of the established span value for 6 out of 7 test days. This
corresponds to 1.5 ppm drift for Subpart BB sources where the span value
is 30 ppm. If the CEMS includes pollutant and diluent monitors, the CD
must be determined separately for each in terms of concentrations (see
PS 3 for the diluent specifications).
13.2 Relative Accuracy. The RA of the CEMS must be no greater than
20 percent when the average RM value is used to calculate RA or 10
percent when the applicable emission standard is used to calculate RA.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures [Reserved]

17.0 References

1. Department of Commerce. Experimental Statistics, National Bureau
of Standards, Handbook 91. 1963. Paragraphs 3-3.1.4, p. 3-31.
2. A Guide to the Design, Maintenance and Operation of TRS
Monitoring Systems. National Council for Air and Stream Improvement
Technical Bulletin No. 89. September 1977.
3. Observation of Field Performance of TRS Monitors on a Kraft
Recovery Furnace. National Council for Air and Stream Improvement
Technical Bulletin No. 91. January 1978.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

Same as section 18.0 of PS 2.

Performance Specification 6--Specifications and Test Procedures for
Continuous Emission Rate Monitoring Systems in Stationary Sources

1.0 Scope and Application

1.1 Applicability. This specification is used for evaluating the
acceptability of continuous emission rate monitoring systems (CERMSs).
1.2 The installation and measurement location specifications,
performance specification test procedure, calculations, and data
analysis procedures, of Performance Specifications (PS 2), sections 8.0
and 12, respectively, apply to this specification.

2.0 Summary of Performance Specification

The calibration drift (CD) and relative accuracy (RA) tests are
conducted to determine conformance of the CERMS to the specification.

3.0 Definitions

The definitions are the same as in section 3 of PS 2, except this
specification refers to the continuous emission rate monitoring

[[Page 700]]

system rather than the continuous emission monitoring system. The
following definitions are added:
3.1 Continuous Emission Rate Monitoring System (CERMS). The total
equipment required for the determining and recording the pollutant mass
emission rate (in terms of mass per unit of time).
3.2 Flow Rate Sensor. That portion of the CERMS that senses the
volumetric flow rate and generates an output proportional to that flow
rate. The flow rate sensor shall have provisions to check the CD for
each flow rate parameter that it measures individually (e.g., velocity,
pressure).

4.0 Interferences [Reserved]

5.0 Safety

This performance specification may involve hazardous materials,
operations, and equipment. This performance specification may not
address all of the safety problems associated with its use. It is the
responsibility of the user to establish appropriate safety and health
practices and determine the applicable regulatory limitations prior to
performing this performance specification. The CERMS users manual should
be consulted for specific precautions to be taken with regard to the
analytical procedures.

6.0 Equipment and Supplies

Same as section 6.0 of PS 2.

7.0 Reagents and Standards

Same as section 7.0 of PS 2.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Calibration Drift Test Procedure.
8.1.1 The CD measurements are to verify the ability of the CERMS to
conform to the established CERMS calibrations used for determining the
emission rate. Therefore, if periodic automatic or manual adjustments
are made to the CERMS zero and calibration settings, conduct the CD
tests immediately before these adjustments, or conduct them in such a
way that CD can be determined.
8.1.2 Conduct the CD tests for pollutant concentration at the two
values specified in section 6.1.2 of PS 2. For other parameters that are
selectively measured by the CERMS (e.g., velocity, pressure, flow rate),
use two analogous values (e.g., Low: 0-20% of full scale, High: 50-100%
of full scale). Introduce to the CERMS the reference signals (these need
not be certified). Record the CERMS response to each and subtract this
value from the respective reference value (see example data sheet in
Figure 6-1).
8.2 Relative Accuracy Test Procedure.
8.2.1 Sampling Strategy for reference method (RM) Tests, Correlation
of RM and CERMS Data, and Number of RM Tests are the same as PS 2,
sections 8.4.3, 8.4.5, and 8.4.4, respectively. Summarize the results on
a data sheet. An example is shown in Figure 6-1. The RA test may be
conducted during the CD test period.
8.2.2 Reference Methods. Unless otherwise specified in the
applicable subpart of the regulations, the RM for the pollutant gas is
the Appendix A method that is cited for compliance test purposes, or its
approved alternatives. Methods 2, 2A, 2B, 2C, or 2D, as applicable, are
the RMs for the determination of volumetric flow rate.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure

Same as section 11.0 of PS 2.

12.0 Calculations and Data Analysis

Same as section 12.0 of PS 2.

13.0 Method Performance

13.1 Calibration Drift. Since the CERMS includes analyzers for
several measurements, the CD shall be determined separately for each
analyzer in terms of its specific measurement. The calibration for each
analyzer associated with the measurement of flow rate shall not drift or
deviate from each reference value of flow rate by more than 3 percent of
the respective high-level value. The CD specification for each analyzer
for which other PSs have been established (e.g., PS 2 for SO2
and NOX), shall be the same as in the applicable PS.
13.2 CERMS Relative Accuracy. The RA of the CERMS shall be no
greater than 20 percent of the mean value of the RM's test data in terms
of the units of the emission standard, or 10 percent of the applicable
standard, whichever is greater.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

Same as in section 16.0 of PS 2.

17.0 References

1. Brooks, E.F., E.C. Beder, C.A. Flegal, D.J. Luciani, and R.
Williams. Continuous Measurement of Total Gas Flow Rate from Stationary
Sources. U.S. Environmental Protection Agency. Research Triangle Park,
North Carolina. Publication No. EPA-650/2-75-020. February 1975. 248 p.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 701]]

----------------------------------------------------------------------------------------------------------------
Emission rate (kg/hr)a
--------------------------------------------------------------------
Run No. Date and time Difference (RMs-
CERMS RMs CERMS)
----------------------------------------------------------------------------------------------------------------
1 .....................
----------------------------------------------------------------------------------------------------------------
2 .....................
----------------------------------------------------------------------------------------------------------------
3 .....................
----------------------------------------------------------------------------------------------------------------
4 .....................
----------------------------------------------------------------------------------------------------------------
5 .....................
----------------------------------------------------------------------------------------------------------------
6 .....................
----------------------------------------------------------------------------------------------------------------
7 .....................
----------------------------------------------------------------------------------------------------------------
8 .....................
----------------------------------------------------------------------------------------------------------------
9 .....................
----------------------------------------------------------------------------------------------------------------
\a\ The RMs and CERMS data as corrected to a consistent basis (i.e., moisture, temperature, and pressure
conditions).

Figure 6-1--Emission Rate Determinations

Performance Specification 7--Specifications and Test Procedures for
Hydrogen Sulfide Continuous Emission Monitoring Systems in Stationary
Sources

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Hydrogen Sulfide........................................ 7783-06-4
------------------------------------------------------------------------

1.2 Applicability.
1.2.1 This specification is to be used for evaluating the
acceptability of hydrogen sulfide (H2S) continuous emission
monitoring systems (CEMS) at the time of or soon after installation and
whenever specified in an applicable subpart of the regulations.
1.2.2 This specification is not designed to evaluate the installed
CEMS performance over an extended period of time nor does it identify
specific calibration techniques and other auxiliary procedures to assess
CEMS performance. The source owner or operator, however, is responsible
to calibrate, maintain, and operate the CEMS. To evaluate CEMS
performance, the Administrator may require, under section 114 of the
Act, the source owner or operator to conduct CEMS performance
evaluations at other times besides the initial test. See section
60.13(c).

2.0 Summary

Calibration drift (CD) and relative accuracy (RA) tests are
conducted to determine that the CEMS conforms to the specification.

3.0 Definitions

Same as section 3.0 of PS 2.

4.0 Interferences [Reserved]

5.0 Safety

The procedures required under this performance specification may
involve hazardous materials, operations, and equipment. This performance
specification may not address all of the safety problems associated with
these procedures. It is the responsibility of the user to establish
appropriate safety problems associated with these procedures. It is the
responsibility of the user to establish appropriate safety and health
practices and determine the application regulatory limitations prior to
performing these procedures. The CEMS user's manual and materials
recommended by the reference method should be consulted for specific
precautions to be taken.

6.0 Equipment and Supplies

6.1 Instrument Zero and Span. This specification is the same as
section 6.1 of PS 2.
6.2 Calibration Drift. The CEMS calibration must not drift or
deviate from the reference value of the calibration gas or reference
source by more than 5 percent of the established span value for 6 out of
7 test days (e.g., the established span value is 300 ppm for Subpart J
fuel gas combustion devices).
6.3 Relative Accuracy. The RA of the CEMS must be no greater than 20
percent when the average reference method (RM) value is used to
calculate RA or 10 percent when the applicable emission standard is used
to calculate RA.

7.0 Reagents and Standards

Same as section 7.0 of PS 2.

[[Page 702]]

8.0 Sample Collection, Preservation, Storage, and Transport.

8.1 Installation and Measurement Location Specification. Same as
section 8.1 of PS 2.
8.2 Pretest Preparation. Same as section 8.2 of PS 2.
8.3 Calibration Drift Test Procedure. Same as section 8.3 of PS 2.
8.4 Relative Accuracy Test Procedure.
8.4.1 Sampling Strategy for RM Tests, Number of RM Tests,
Correlation of RM and CEMS Data, and Calculations. These are the same as
that in PS-2, Sections 8.4.3 (except as specified below), 8.4.4, 8.4.5,
and 8.4.6, respectively.
8.4.2 Reference Methods. Unless otherwise specified in an applicable
subpart of the regulation, Methods 11, 15, and 16 may be used for the RM
for this PS.
8.4.2.1 Sampling Time Per Run--Method 11. A sampling run, when
Method 11 (integrated sampling) is used, shall consist of a single
measurement for at least 10 minutes and 0.010 dscm (0.35 dscf). Each
sample shall be taken at approximately 30-minute intervals.
8.4.2.2 Sampling Time Per Run--Methods 15 and 16. The sampling run
shall consist of two injections equally spaced over a 30-minute period
following the procedures described in the particular method. Note:
Caution! Heater or non-approved electrical probes should not be used
around explosive or flammable sources.
8.5 Reporting. Same as section 8.5 of PS 2.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardizations [Reserved]

11.0 Analytical Procedures

Sample Collection and analysis are concurrent for this PS (see
section 8.0). Refer to the RM for specific analytical procedures.

12.0 Data Analysis and Calculations

Same as section 12.0 of PS 2.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. U.S. Environmental Protection Agency. Standards of Performance
for New Stationary Sources; Appendix B; Performance Specifications 2 and
3 for SO2, NOX, CO2, and O2
Continuous Emission Monitoring Systems; Final Rule. 48 CFR 23608.
Washington, D.C. U.S. Government Printing Office. May 25, 1983.
2. U.S. Government Printing Office. Gaseous Continuous Emission
Monitoring Systems--Performance Specification Guidelines for
SO2, NOX, CO2, O2, and TRS.
U.S. Environmental Protection Agency. Washington, D.C. EPA-450/3-82-026.
October 1982. 26 p.
3. Maines, G.D., W.C. Kelly (Scott Environmental Technology, Inc.),
and J.B. Homolya. Evaluation of Monitors for Measuring H2S in
Refinery Gas. Prepared for the U.S. Environmental Protection Agency.
Research Triangle Park, N.C. Contract No. 68-02-2707. 1978. 60 p.
4. Ferguson, B.B., R.E. Lester (Harmon Engineering and Testing), and
W.J. Mitchell. Field Evaluation of Carbon Monoxide and Hydrogen Sulfide
Continuous Emission Monitors at an Oil Refinery. Prepared for the U.S.
Environmental Protection Agency. Research Triangle Park, N.C.
Publication No. EPA-600/4-82-054. August 1982. 100 p.
5. Letter to RAMCON Environmental Corp. from Robert Kellam, December
27, 1992.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Same as section 18.0 of PS 2.

Performance Specification 8--Performance Specifications for Volatile
Organic Compound Continuous Emission Monitoring Systems in Stationary
Sources

1.0 Scope and Application

1.1 Analytes. Volatile Organic Compounds (VOCs).
1.2 Applicability.
1.2.1 This specification is to be used for evaluating a continuous
emission monitoring system (CEMS) that measures a mixture of VOC's and
generates a single combined response value. The VOC detection principle
may be flame ionization (FI), photoionization (PI), non-dispersive
infrared absorption (NDIR), or any other detection principle that is
appropriate for the VOC species present in the emission gases and that
meets this performance specification. The performance specification
includes procedures to evaluate the acceptability of the CEMS at the
time of or soon after its installation and whenever specified in
emission regulations or permits. This specification is not designed to
evaluate the installed CEMS performance over an extended period of time,
nor does it identify specific calibration techniques and other auxiliary
procedures to assess the CEMS performance. The source owner or operator,
however, is responsible to calibrate, maintain, and operate the CEMS
properly. To evaluate the CEMS performance, the Administrator may
require, under section 114 of the Act, the operator to conduct CEMS
performance evaluations in addition to the initial test. See section
60.13(c).
1.2.2 In most emission circumstances, most VOC monitors can provide
only a relative measure of the total mass or volume concentration of a
mixture of organic gases, rather than an accurate quantification. This

[[Page 703]]

problem is removed when an emission standard is based on a total VOC
measurement as obtained with a particular detection principle. In those
situations where a true mass or volume VOC concentration is needed, the
problem can be mitigated by using the VOC CEMS as a relative indicator
of total VOC concentration if statistical analysis indicates that a
sufficient margin of compliance exists for this approach to be
acceptable. Otherwise, consideration can be given to calibrating the
CEMS with a mixture of the same VOC's in the same proportions as they
actually occur in the measured source. In those circumstances where only
one organic species is present in the source, or where equal incremental
amounts of each of the organic species present generate equal CEMS
responses, the latter choice can be more easily achieved.

2.0 Summary of Performance Specification

2.1 Calibration drift and relative accuracy tests are conducted to
determine adherence of the CEMS with specifications given for those
items. The performance specifications include criteria for installation
and measurement location, equipment and performance, and procedures for
testing and data reduction.

3.0 Definitions.

Same as section 3.0 of PS 2.

4.0 Interferences [Reserved]

5.0 Safety

The procedures required under this performance specification may
involve hazardous materials, operations, and equipment. This performance
specification may not address all of the safety problems associated with
these procedures. It is the responsibility of the user to establish
appropriate safety problems associated with these procedures. It is the
responsibility of the user to establish appropriate safety and health
practices and determine the application regulatory limitations prior to
performing these procedures. The CEMS user's manual and materials
recommended by the reference method should be consulted for specific
precautions to be taken.

6.0 Equipment and Supplies

6.1 VOC CEMS Selection. When possible, select a VOC CEMS with the
detection principle of the reference method specified in the regulation
or permit (usually either FI, NDIR, or PI). Otherwise, use knowledge of
the source process chemistry, previous emission studies, or gas
chromatographic analysis of the source gas to select an appropriate VOC
CEMS. Exercise extreme caution in choosing and installing any CEMS in an
area with explosive hazard potential.
6.2 Data Recorder Scale. Same as section 6.1 of PS 2.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Installation and Measurement Location Specifications. Same as
section 8.1 of PS 2.
8.2 Pretest Preparation. Same as section 8.2 of PS 2.
8.3 Reference Method (RM). Use the method specified in the
applicable regulation or permit, or any approved alternative, as the RM.
8.4 Sampling Strategy for RM Tests, Correlation of RM and CEMS Data,
and Number of RM Tests. Follow PS 2, sections 8.4.3, 8.4.5, and 8.4.4,
respectively.
8.5 Reporting. Same as section 8.5 of PS 2.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this PS (see
section 8.0). Refer to the RM for specific analytical procedures.

12.0 Calculations and Data Analysis

Same as section 12.0 of PS 2.

13.0 Method Performance

13.1 Calibration Drift. The CEMS calibration must not drift by more
than 2.5 percent of the span value.
13.2 CEMS Relative Accuracy. Unless stated otherwise in the
regulation or permit, the RA of the CEMS must not be greater than 20
percent of the mean value of the RM test data in terms of the units of
the emission standard, or 10 percent of the applicable standard,
whichever is greater.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as section 17.0 of PS 2.

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Performance Specification 8A--Specifications and Test Procedures for
Total Hydrocarbon Continuous Monitoring Systems in Stationary Sources

1. Applicability and Principle

1.1 Applicability. These performance specifications apply to
hydrocarbon (HC) continuous emission monitoring systems (CEMS)

[[Page 704]]

installed on stationary sources. The specifications include procedures
which are intended to be used to evaluate the acceptability of the CEMS
at the time of its installation or whenever specified in regulations or
permits. The procedures are not designed to evaluate CEMS performance
over an extended period of time. The source owner or operator is
responsible for the proper calibration, maintenance, and operation of
the CEMS at all times.
1.2 Principle. A gas sample is extracted from the source through a
heated sample line and heated filter to a flame ionization detector
(FID). Results are reported as volume concentration equivalents of
propane. Installation and measurement location specifications,
performance and equipment specifications, test and data reduction
procedures, and brief quality assurance guidelines are included in the
specifications. Calibration drift, calibration error, and response time
tests are conducted to determine conformance of the CEMS with the
specifications.

2. Definitions

2.1 Continuous Emission Monitoring System (CEMS). The total
equipment used to acquire data, which includes sample extraction and
transport hardware, analyzer, data recording and processing hardware,
and software. The system consists of the following major subsystems:
2.1.1 Sample Interface. That portion of the system that is used for
one or more of the following: Sample acquisition, sample transportation,
sample conditioning, or protection of the analyzer from the effects of
the stack effluent.
2.1.2 Organic Analyzer. That portion of the system that senses
organic concentration and generates an output proportional to the gas
concentration.
2.1.3 Data Recorder. That portion of the system that records a
permanent record of the measurement values. The data recorder may
include automatic data reduction capabilities.
2.2 Instrument Measurement Range. The difference between the minimum
and maximum concentration that can be measured by a specific instrument.
The minimum is often stated or assumed to be zero and the range
expressed only as the maximum.
2.3 Span or Span Value. Full scale instrument measurement range. The
span value must be documented by the CEMS manufacturer with laboratory
data.
2.4 Calibration Gas. A known concentration of a gas in an
appropriate diluent gas.
2.5 Calibration Drift (CD). The difference in the CEMS output
readings from the established reference value after a stated period of
operation during which no unscheduled maintenance, repair, or adjustment
takes place. A CD test is performed to demonstrate the stability of the
CEMS calibration over time.
2.6 Response Time. The time interval between the start of a step
change in the system input (e.g., change of calibration gas) and the
time when the data recorder displays 95 percent of the final value.
2.7 Accuracy. A measurement of agreement between a measured value
and an accepted or true value, expressed as the percentage difference
between the true and measured values relative to the true value. For
these performance specifications, accuracy is checked by conducting a
calibration error (CE) test.
2.8 Calibration Error (CE). The difference between the concentration
indicated by the CEMS and the known concentration of the cylinder gas. A
CE test procedure is performed to document the accuracy and linearity of
the monitoring equipment over the entire measurement range.
2.9 Performance Specification Test (PST) Period. The period during
which CD, CE, and response time tests are conducted.
2.10 Centroidal Area. A concentric area that is geometrically
similar to the stack or duct cross section and is no greater than 1
percent of the stack or duct cross-sectional area.

3. Installation and Measurement Location Specifications

3.1 CEMS Installation and Measurement Locations. The CEMS must be
installed in a location in which measurements representative of the
source's emissions can be obtained. The optimum location of the sample
interface for the CEMS is determined by a number of factors, including
ease of access for calibration and maintenance, the degree to which
sample conditioning will be required, the degree to which it represents
total emissions, and the degree to which it represents the combustion
situation in the firebox (where applicable). The location should be as
free from in-leakage influences as possible and reasonably free from
severe flow disturbances. The sample location should be at least two
equivalent duct diameters downstream from the nearest control device,
point of pollutant generation, or other point at which a change in the
pollutant concentration or emission rate occurs and at least 0.5
diameter upstream from the exhaust or control device. The equivalent
duct diameter is calculated as per 40 CFR part 60, appendix A, method 1,
section 2.1. If these criteria are not achievable or if the location is
otherwise less than optimum, the possibility of stratification should be
investigated as described in section 3.2. The measurement point must be
within the centroidal area of the stack or duct cross section.
3.2 Stratification Test Procedure. Stratification is defined as a
difference in excess of 10 percent between the average concentration in
the duct or stack and the concentration at any point more than 1.0 meter
from the duct

[[Page 705]]

or stack wall. To determine whether effluent stratification exists, a
dual probe system should be used to determine the average effluent
concentration while measurements at each traverse point are being made.
One probe, located at the stack or duct centroid, is used as a
stationary reference point to indicate the change in effluent
concentration over time. The second probe is used for sampling at the
traverse points specified in 40 CFR part 60 appendix A, method 1. The
monitoring system samples sequentially at the reference and traverse
points throughout the testing period for five minutes at each point.

4. CEMS Performance and Equipment Specifications

If this method is applied in highly explosive areas, caution and
care must be exercised in choice of equipment and installation.
4.1 Flame Ionization Detector (FID) Analyzer. A heated FID analyzer
capable of meeting or exceeding the requirements of these
specifications. Heated systems must maintain the temperature of the
sample gas between 150 [deg]C (300 [deg]F) and 175 [deg]C (350 [deg]F)
throughout the system. This requires all system components such as the
probe, calibration valve, filter, sample lines, pump, and the FID to be
kept heated at all times such that no moisture is condensed out of the
system. The essential components of the measurement system are described
below:
4.1.1 Sample Probe. Stainless steel, or equivalent, to collect a gas
sample from the centroidal area of the stack cross-section.
4.1.2 Sample Line. Stainless steel or Teflon tubing to transport the
sample to the analyzer.

Note: Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.

4.1.3 Calibration Valve Assembly. A heated three-way valve assembly
to direct the zero and calibration gases to the analyzer is recommended.
Other methods, such as quick-connect lines, to route calibration gas to
the analyzers are applicable.
4.1.4 Particulate Filter. An in-stack or out-of-stack sintered
stainless steel filter is recommended if exhaust gas particulate loading
is significant. An out-of-stack filter must be heated.
4.1.5 Fuel. The fuel specified by the manufacturer (e.g., 40 percent
hydrogen/60 percent helium, 40 percent hydrogen/60 percent nitrogen gas
mixtures, or pure hydrogen) should be used.
4.1.6 Zero Gas. High purity air with less than 0.1 parts per million
by volume (ppm) HC as methane or carbon equivalent or less than 0.1
percent of the span value, whichever is greater.
4.1.7 Calibration Gases. Appropriate concentrations of propane gas
(in air or nitrogen). Preparation of the calibration gases should be
done according to the procedures in EPA Protocol 1. In addition, the
manufacturer of the cylinder gas should provide a recommended shelf life
for each calibration gas cylinder over which the concentration does not
change by more than 2 percent from the certified value.
4.2 CEMS Span Value. 100 ppm propane. The span value must be
documented by the CEMS manufacturer with laboratory data.
4.3 Daily Calibration Gas Values. The owner or operator must choose
calibration gas concentrations that include zero and high-level
calibration values.
4.3.1 The zero level may be between zero and 0.1 ppm (zero and 0.1
percent of the span value).
4.3.2 The high-level concentration must be between 50 and 90 ppm (50
and 90 percent of the span value).
4.4 Data Recorder Scale. The strip chart recorder, computer, or
digital recorder must be capable of recording all readings within the
CEMS' measurement range and must have a resolution of 0.5 ppm (0.5
percent of span value).
4.5 Response Time. The response time for the CEMS must not exceed 2
minutes to achieve 95 percent of the final stable value.
4.6 Calibration Drift. The CEMS must allow the determination of CD
at the zero and high-level values. The CEMS calibration response must
not differ by more than 3 ppm (3 percent of the span value) after each
24-hour period of the 7-day test at both zero and high levels.
4.7 Calibration Error. The mean difference between the CEMS and
reference values at all three test points listed below must be no
greater than 5 ppm (5 percent of the span value).
4.7.1 Zero Level. Zero to 0.1 ppm (0 to 0.1 percent of span value).
4.7.2 Mid-Level. 30 to 40 ppm (30 to 40 percent of span value).
4.7.3 High-Level. 70 to 80 ppm (70 to 80 percent of span value).
4.8 Measurement and Recording Frequency. The sample to be analyzed
must pass through the measurement section of the analyzer without
interruption. The detector must measure the sample concentration at
least once every 15 seconds. An average emission rate must be computed
and recorded at least once every 60 seconds.
4.9 Hourly Rolling Average Calculation. The CEMS must calculate
every minute an hourly rolling average, which is the arithmetic mean of
the 60 most recent 1-minute average values.
4.10 Retest. If the CEMS produces results within the specified
criteria, the test is successful. If the CEMS does not meet one or more
of the criteria, necessary corrections must be made and the performance
tests repeated.

[[Page 706]]

5. Performance Specification Test (PST) Periods

5.1 Pretest Preparation Period. Install the CEMS, prepare the PTM
test site according to the specifications in section 3, and prepare the
CEMS for operation and calibration according to the manufacturer's
written instructions. A pretest conditioning period similar to that of
the 7-day CD test is recommended to verify the operational status of the
CEMS.
5.2 Calibration Drift Test Period. While the facility is operating
under normal conditions, determine the magnitude of the CD at 24-hour
intervals for seven consecutive days according to the procedure given in
section 6.1. All CD determinations must be made following a 24-hour
period during which no unscheduled maintenance, repair, or adjustment
takes place. If the combustion unit is taken out of service during the
test period, record the onset and duration of the downtime and continue
the CD test when the unit resumes operation.
5.3 Calibration Error Test and Response Time Test Periods. Conduct
the CE and response time tests during the CD test period.

6. Performance Specification Test Procedures

6.1 Relative Accuracy Test Audit (RATA) and Absolute Calibration
Audits (ACA). The test procedures described in this section are in lieu
of a RATA and ACA.
6.2 Calibration Drift Test.
6.2.1 Sampling Strategy. Conduct the CD test at 24-hour intervals
for seven consecutive days using calibration gases at the two daily
concentration levels specified in section 4.3. Introduce the two
calibration gases into the sampling system as close to the sampling
probe outlet as practical. The gas must pass through all CEM components
used during normal sampling. If periodic automatic or manual adjustments
are made to the CEMS zero and calibration settings, conduct the CD test
immediately before these adjustments, or conduct it in such a way that
the CD can be determined. Record the CEMS response and subtract this
value from the reference (calibration gas) value. To meet the
specification, none of the differences may exceed 3 percent of the span
of the CEM.
6.2.2 Calculations. Summarize the results on a data sheet. An
example is shown in Figure 1. Calculate the differences between the CEMS
responses and the reference values.
6.3 Response Time. The entire system including sample extraction and
transport, sample conditioning, gas analyses, and the data recording is
checked with this procedure.
6.3.1 Introduce the calibration gases at the probe as near to the
sample location as possible. Introduce the zero gas into the system.
When the system output has stabilized (no change greater than 1 percent
of full scale for 30 sec), switch to monitor stack effluent and wait for
a stable value. Record the time (upscale response time) required to
reach 95 percent of the final stable value.
6.3.2 Next, introduce a high-level calibration gas and repeat the
above procedure. Repeat the entire procedure three times and determine
the mean upscale and downscale response times. The longer of the two
means is the system response time.
6.4 Calibration Error Test Procedure.
6.4.1 Sampling Strategy. Challenge the CEMS with zero gas and EPA
Protocol 1 cylinder gases at measurement points within the ranges
specified in section 4.7.
6.4.1.1 The daily calibration gases, if Protocol 1, may be used for
this test.

[[Page 707]]

[GRAPHIC] [TIFF OMITTED] TR30SE99.011

6.4.1.2 Operate the CEMS as nearly as possible in its normal
sampling mode. The calibration gas should be injected into the sampling
system as close to the sampling probe outlet as practical and must pass
through all filters, scrubbers, conditioners, and other monitor
components used during normal sampling. Challenge the CEMS three non-
consecutive times at each measurement point and record the responses.
The duration of each gas injection should be for a sufficient period of
time to ensure that the CEMS surfaces are conditioned.
6.4.2 Calculations. Summarize the results on a data sheet. An
example data sheet is shown in Figure 2. Average the differences between
the instrument response and the certified cylinder gas value for each
gas. Calculate three CE results according to Equation 1. No confidence
coefficient is used in CE calculations.

7. Equations

Calibration Error. Calculate CE using Equation 1.
[GRAPHIC] [TIFF OMITTED] TR30SE99.012

Where:

d = Mean difference between CEMS response and the known reference
concentration, determined using Equation 2.

[[Page 708]]

[GRAPHIC] [TIFF OMITTED] TR30SE99.013

Where:

di = Individual difference between CEMS response and the
known reference concentration.

8. Reporting

At a minimum, summarize in tabular form the results of the CD,
response time, and CE test, as appropriate. Include all data sheets,
calculations, CEMS data records, and cylinder gas or reference material
certifications.
[GRAPHIC] [TIFF OMITTED] TR30SE99.014

9. References

1. Measurement of Volatile Organic Compounds-Guideline Series. U.S.
Environmental Protection Agency, Research Triangle Park, North Carolina,
27711, EPA-450/2-78-041, June 1978.
2. Traceability Protocol for Establishing True Concentrations of
Gases Used for Calibration and Audits of Continuous Source Emission
Monitors (Protocol No. 1). U.S. Environmental Protection Agency ORD/
EMSL, Research Triangle Park, North Carolina, 27711, June 1978.
3. Gasoline Vapor Emission Laboratory Evaluation-Part 2. U.S.
Environmental Protection Agency, OAQPS, Research Triangle Park, North
Carolina, 27711, EMB Report No. 76-GAS-6, August 1975.

[[Page 709]]

Performance Specification 9--Specifications and Test Procedures for Gas
Chromatographic Continuous Emission Monitoring Systems in Stationary
Sources

1.0 Scope and Application

1.1 Applicability. These requirements apply to continuous emission
monitoring systems (CEMSs) that use gas chromatography (GC) to measure
gaseous organic compound emissions. The requirements include procedures
intended to evaluate the acceptability of the CEMS at the time of its
installation and whenever specified in regulations or permits. Quality
assurance procedures for calibrating, maintaining, and operating the
CEMS properly at all times are also given in this procedure.

2.0 Summary of Performance Specification

2.1 Calibration precision, calibration error, and performance audit
tests are conducted to determine conformance of the CEMS with these
specifications. Daily calibration and maintenance requirements are also
specified.

3.0 Definitions

3.1 Gas Chromatograph (GC). That portion of the system that
separates and detects organic analytes and generates an output
proportional to the gas concentration. The GC must be temperature
controlled.

Note: The term temperature controlled refers to the ability to
maintain a certain temperature around the column. Temperature-
programmable GC is not required for this performance specification, as
long as all other requirements for precision, linearity and accuracy
listed in this performance specification are met. It should be noted
that temperature programming a GC will speed up peak elution, thus
allowing increased sampling frequency.

3.1.1 Column. Analytical column capable of separating the analytes
of interest.
3.1.2 Detector. A detection system capable of detecting and
quantifying all analytes of interest.
3.1.3 Integrator. That portion of the system that quantifies the
area under a particular sample peak generated by the GC.
3.1.4 Data Recorder. A strip chart recorder, computer, or digital
recorder capable of recording all readings within the instrument's
calibration range.
3.2 Calibration Precision. The error between triplicate injections
of each calibration standard.

4.0 Interferences [Reserved]

5.0 Safety

The procedures required under this performance specification may
involve hazardous materials, operations, and equipment. This performance
specification does not purport to address all of the safety problems
associated with these procedures. It is the responsibility of the user
to establish appropriate safety problems associated with these
procedures. It is the responsibility of the user to establish
appropriate safety and health practices and determine the application
regulatory limitations prior to performing these procedures. The CEMS
user's manual and materials recommended by the reference method should
be consulted for specific precautions to be taken.

6.0 Equipment and Supplies

6.1 Presurvey Sample Analysis and GC Selection. Determine the
pollutants to be monitored from the applicable regulation or permit and
determine the approximate concentration of each pollutant (this
information can be based on past compliance test results). Select an
appropriate GC configuration to measure the organic compounds. The GC
components should include a heated sample injection loop (or other
sample introduction systems), separatory column, temperature-controlled
oven, and detector. If the source chooses dual column and/or dual
detector configurations, each column/detector is considered a separate
instrument for the purpose of this performance specification and thus
the procedures in this performance specification shall be carried out on
each system. If this method is applied in highly explosive areas,
caution should be exercised in selecting the equipment and method of
installation.
6.2 Sampling System. The sampling system shall be heat traced and
maintained at a minimum of 120 [deg]C with no cold spots. All system
components shall be heated, including the probe, calibration valve,
sample lines, sampling loop (or sample introduction system), GC oven,
and the detector block (when appropriate for the type of detector being
utilized, e.g., flame ionization detector).

7.0 Reagents and Standards

7.1 Calibration Gases. Obtain three concentrations of calibration
gases certified by the manufacturer to be accurate to within 2 percent
of the value on the label. A gas dilution system may be used to prepare
the calibration gases from a high concentration certified standard if
the gas dilution system meets the requirements specified in Test Method
205, 40 CFR Part 51, Appendix M. The performance test specified in Test
Method 205 shall be repeated quarterly, and the results of the Method
205 test shall be included in the report. The calibration gas
concentration of each target analyte shall be as follows (measured
concentration is based on the presurvey concentration determined in
section 6.1).

[[Page 710]]

Note: If the low level calibration gas concentration falls at or
below the limit of detection for the instrument for any target
pollutant, a calibration gas with a concentration at 4 to 5 times the
limit of detection for the instrument may be substituted for the low-
level calibration gas listed in section 7.1.1.

7.1.1 Low-level. 40-60 percent of measured concentration.
7.1.2 Mid-level. 90-110 percent of measured concentration.
7.1.3 High-level. 140-160 percent of measured concentration, or
select highest expected concentration.
7.2 Performance Audit Gas. A certified EPA audit gas shall be used,
when possible. A gas mixture containing all the target compounds within
the calibration range and certified by EPA's Traceability Protocol for
Assay and Certification of Gaseous Calibration Standards may be used
when EPA performance audit materials are not available. The instrument
relative error shall be 10 percent of the certified value of
the audit gas.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Installation and Measurement Location Specifications. Install
the CEMs in a location where the measurements are representative of the
source emissions. Consider other factors, such as ease of access for
calibration and maintenance purposes. The location should not be close
to air in-leakages. The sampling location should be at least two
equivalent duct diameters downstream from the nearest control device,
point of pollutant generation, or other point at which a change in the
pollutant concentration or emission rate occurs. The location should be
at least 0.5 diameter upstream from the exhaust or control device. To
calculate equivalent duct diameter, see section 12.2 of Method 1 (40 CFR
Part 60, Appendix A). Sampling locations not conforming to the
requirements in this section may be used if necessary upon approval of
the Administrator.
8.2 Pretest Preparation Period. Using the procedures described in
Method 18
(40 CFR Part 60, Appendix A), perform initial tests to determine GC
conditions that provide good resolution and minimum analysis time for
compounds of interest. Resolution interferences that may occur can be
eliminated by appropriate GC column and detector choice or by shifting
the retention times through changes in the column flow rate and the use
of temperature programming.
8.3 7-Day Calibration Error (CE) Test Period. At the beginning of
each 24-hour period, set the initial instrument setpoints by conducting
a multi-point calibration for each compound. The multi-point calibration
shall meet the requirements in section 13.3. Throughout the 24-hour
period, sample and analyze the stack gas at the sampling intervals
prescribed in the regulation or permit. At the end of the 24 hour
period, inject the three calibration gases for each compound in
triplicate and determine the average instrument response. Determine the
CE for each pollutant at each level using the equation in section 9-2.
Each CE shall be 10 percent. Repeat this procedure six
more times for a total of 7 consecutive days.
8.4 Performance Audit Test Periods. Conduct the performance audit
once during the initial 7-day CE test and quarterly thereafter. Sample
and analyze the EPA audit gas(es) (or the gas mixture prepared by EPA's
traceability protocol if an EPA audit gas is not available) three times.
Calculate the average instrument response. Report the audit results as
part of the reporting requirements in the appropriate regulation or
permit (if using a gas mixture, report the certified cylinder
concentration of each pollutant).
8.5 Reporting. Follow the reporting requirements of the applicable
regulation or permit. If the reporting requirements include the results
of this performance specification, summarize in tabular form the results
of the CE tests. Include all data sheets, calculations, CEMS data
records, performance audit results, and calibration gas concentrations
and certifications.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization

10.1 Initial Multi-Point Calibration. After initial startup of the
GC, after routine maintenance or repair, or at least once per month,
conduct a multi-point calibration of the GC for each target analyte. The
multi-point calibration for each analyte shall meet the requirements in
section 13.3.
10.2 Daily Calibration. Once every 24 hours, analyze the mid-level
calibration standard for each analyte in triplicate. Calculate the
average instrument response for each analyte. The average instrument
response shall not vary more than 10 percent from the certified
concentration value of the cylinder for each analyte. If the difference
between the analyzer response and the cylinder concentration for any
target compound is greater than 10 percent, immediately inspect the
instrument making any necessary adjustments, and conduct an initial
multi-point calibration as described in section 10.1.

11.0 Analytical Procedure. Sample Collection and Analysis Are Concurrent
for This Performance Specification (See section 8.0)

12.0 Calculations and Data Analysis

12.1 Nomenclature.

Cm = average instrument response, ppm.

[[Page 711]]

Ca = cylinder gas value, ppm.
F = Flow rate of stack gas through sampling system, in Liters/min.
n = Number of measurement points.
r\2\ = Coefficient of determination.
V = Sample system volume, in Liters, which is the volume inside the
sample probe and tubing leading from the stack to the sampling
loop.
x = CEMS response.
y = Actual value of calibration standard.

12.2 Coefficient of Determination. Calculate r\2\ using linear
regression analysis and the average concentrations obtained at three
calibration points as shown in Equation 9-1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.461

12.3 Calibration Error Determination. Determine the percent
calibration error (CE) at each concentration for each pollutant using
the following equation.
[GRAPHIC] [TIFF OMITTED] TR17OC00.462

12.4 Sampling System Time Constant (T).
[GRAPHIC] [TIFF OMITTED] TR17OC00.463

13.0 Method Performance

13.1 Calibration Error (CE). The CEMS must allow the determination
of CE at all three calibration levels. The average CEMS calibration
response must not differ by more than 10 percent of calibration gas
value at each level after each 24-hour period of the initial test.
13.2 Calibration Precision and Linearity. For each triplicate
injection at each concentration level for each target analyte, any one
injection shall not deviate more than 5 percent from the average
concentration measured at that level. The linear regression curve for
each organic compound at all three levels shall have an r\2\
0.995 (using Equation 9-1).
13.3 Measurement Frequency. The sample to be analyzed shall flow
continuously through the sampling system. The sampling system time
constant shall be 5 minutes or the sampling frequency
specified in the applicable regulation, whichever is less. Use Equation
9-3 to determine T. The analytical system shall be capable of measuring
the effluent stream at the frequency specified in the appropriate
regulation or permit.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References [Reserved]

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Performance Specification 11--Specifications and Test Procedures for
Particulate Matter Continuous Emission Monitoring Systems at Stationary
Sources

1.0 What Are the Purpose and Applicability of Performance Specification
11?

The purpose of Performance Specification 11 (PS-11) is to establish
the initial installation and performance procedures that are required
for evaluating the acceptability of a particulate matter (PM) continuous
emission monitoring system (CEMS); it is not to evaluate the ongoing
performance of your PM CEMS over an extended period of time, nor to
identify specific calibration techniques and auxiliary procedures to
assess CEMS performance. You will find procedures for evaluating the
ongoing performance of a PM CEMS in Procedure 2 of Appendix F--Quality
Assurance Requirements for Particulate Matter Continuous Emission
Monitoring Systems Used at Stationary Sources.
1.1 Under what conditions does PS-11 apply to my PM CEMS? The PS-11
applies to your PM CEMS if you are required by any provision of Title 40
of the Code of Federal Regulations (CFR) to install and operate PM CEMS.
1.2 When must I comply with PS-11? You must comply with PS-11 when
directed by the applicable rule that requires you to install and operate
a PM CEMS.
1.3 What other monitoring must I perform? To report your PM
emissions in units of the emission standard, you may need to monitor
additional parameters to correct the PM concentration reported by your
PM CEMS. Your CEMS may include the components

[[Page 712]]

listed in paragraphs (1) through (3) of this section:
(1) A diluent monitor (i.e., O2, CO2, or other
CEMS specified in the applicable regulation), which must meet its own
performance specifications (also found in this appendix),
(2) Auxiliary monitoring equipment to allow measurement,
determination, or input of the flue gas temperature, pressure, moisture
content, and/or dry volume of stack effluent sampled, and
(3) An automatic sampling system. The performance of your PM CEMS
and the establishment of its correlation to manual reference method
measurements must be determined in units of mass concentration as
measured by your PM CEMS (e.g., milligrams per actual cubic meter (mg/
acm) or milligrams per dry standard cubic meter (mg/dscm)).

2.0 What Are the Basic Requirements of PS-11?

The PS-11 requires you to perform initial installation and
calibration procedures that confirm the acceptability of your CEMS when
it is installed and placed into operation. You must develop a site-
specific correlation of your PM CEMS response against manual gravimetric
reference method measurements (including those made using EPA Methods 5,
5I, or 17).
2.1 What types of PM CEMS technologies are covered? Several
different types of PM CEMS technologies (e.g., light scattering, Beta
attenuation, etc.) can be designed with in-situ or extractive sample gas
handling systems. Each PM CEMS technology and sample gas handling
technology has certain site-specific advantages. You should select and
install a PM CEMS that is appropriate for the flue gas conditions at
your source.
2.2 How is PS-11 different from other performance specifications?
The PS-11 is based on a technique of correlating PM CEMS responses
relative to emission concentrations determined by the reference method.
This technique is called ``the correlation.'' This differs from CEMS
used to measure gaseous pollutants that have available calibration gases
of known concentration. Because the type and characteristics of PM vary
from source to source, a single PM correlation, applicable to all
sources, is not possible.
2.3 How are the correlation data handled? You must carefully review
your manual reference method data and your PM CEMS responses to include
only valid, high-quality data. For the correlation, you must convert the
manual reference method data to measurement conditions (e.g., wet or dry
basis) that are consistent with your PM CEMS. Then, you must correlate
the manual method and PM CEMS data in terms of the output as received
from the monitor (e.g., milliamps). At the appropriate PM CEMS response
specified in section 13.2 of this performance specification, you must
calculate the confidence interval half range and tolerance interval half
range as a percentage of the applicable PM concentration emission limit
and compare the confidence interval and tolerance interval percentages
with the performance criteria. Also, you must calculate the correlation
coefficient and compare the correlation coefficient with the applicable
performance criterion specified in section 13.2 of this performance
specification.
Situations may arise where you will need two or more correlations.
If you need multiple correlations, you must collect sufficient data for
each correlation, and each correlation must satisfy the performance
criteria specified in section 13.2 of this performance specification.
2.4 How do I design my PM CEMS correlation program? When planning
your PM CEMS correlation effort, you must address each of the items in
paragraphs (1) through (7) of this section to enhance the probability of
success. You will find each of these elements further described in this
performance specification or in the applicable reference method
procedure.
(1) What type of PM CEMS should I select? You should select a PM
CEMS that is appropriate for your source with technical consideration
for potential factors such as interferences, site-specific
configurations, installation location, flue gas conditions, PM
concentration range, and other PM characteristics. You can find guidance
on which technology is best suited for specific situations in our report
``Current Knowledge of Particulate Matter (PM) Continuous Emission
Monitoring'' (PM CEMS Knowledge Document, see section 16.5).
(2) Where should I install my PM CEMS? Your PM CEMS must be
installed in a location that is most representative of PM emissions, as
determined by the reference method, such that the correlation between PM
CEMS response and emissions determined by the reference method will meet
these performance specifications. Care must be taken in selecting a
location and measurement point to minimize problems due to flow
disturbances, cyclonic flow, and varying PM stratification.
(3) How should I record my CEMS data? You need to ensure that your
PM CEMS and data logger are set up to collect and record all normal
emission levels and excursions. You must ensure that your data logger
and PM CEMS have been properly programmed to accept and transfer status
signals of valid monitor operation (e.g., flags for internal
calibration, suspect data, or maintenance periods).
(4) What CEMS data should I review? You must review drift data daily
to document proper operation. You must also ensure that any audit
material is appropriate for the typical operating range of your PM CEMS.

[[Page 713]]

(5) How long should I operate my PM CEMS before conducting the
initial correlation test? You should allow sufficient time for your PM
CEMS to operate for you to become familiar with your PM CEMS.
(i) You should observe PM CEMS response over time during normal and
varying process conditions. This will ensure that your PM CEMS has been
properly set up to operate at a range that is compatible with the
concentrations and characteristics of PM emissions for your source. You
should use this information to establish the range of operating
conditions necessary to determine the correlations of PM CEMS data to
manual reference method measurements over a wide operating range.
(ii) You must determine the types of process changes that will
influence, on a definable and repeatable basis, flue gas PM
concentrations and the resulting PM CEMS responses. You may find this
period useful to make adjustments to your planned approach for operating
your PM CEMS at your source. For instance, you may change the
measurement range or batch sampling period to something other than those
you initially planned to use.
(6) How do I conduct the initial correlation test? When conducting
the initial correlation test of your PM CEMS response to PM emissions
determined by the reference method, you must pay close attention to
accuracy and details. Your PM CEMS must be operating properly. You must
perform the manual reference method testing accurately, with attention
to eliminating site-specific systemic errors. You must coordinate the
timing of the manual reference method testing with the sampling cycle of
your PM CEMS. You must complete a minimum of 15 manual reference method
tests. You must perform the manual reference method testing over the
full range of PM CEMS responses that correspond to normal operating
conditions for your source and control device and will result in the
widest range of emission concentrations.
(7) How should I perform the manual reference method testing? You
must perform the manual reference method testing in accordance with
specific rule requirements, coordinated closely with PM CEMS and process
operations. It is highly recommended that you use paired trains for the
manual reference method testing. You must perform the manual reference
method testing over a suitable PM concentration range that corresponds
to the full range of normal process and control device operating
conditions. Because the manual reference method testing for this
correlation test is not for compliance reporting purposes, you may
conduct the reference method test runs for less than the typical minimum
test run duration of 1 hour.
(8) What do I do with the manual reference method data and PM CEMS
data? You must complete each of the activities in paragraphs (8)(i)
through (v) of this section.
(i) Screen the manual reference method data for validity (e.g.,
isokinetics, leak checks), quality assurance, and quality control (e.g.,
outlier identification).
(ii) Screen your PM CEMS data for validity (e.g., daily drift check
requirements) and quality assurance (e.g., flagged data).
(iii) Convert the manual reference method test data into measurement
units (e.g., mg/acm) consistent with the measurement conditions of your
PM CEMS.
(iv) Calculate the correlation equation(s) as specified in section
12.3.
(v) Calculate the correlation coefficient, confidence interval half
range, and tolerance interval half range for the complete set of PM CEMS
and reference method correlation data for comparison with the
correlation performance criteria specified in section 13.2.
2.5 What other procedures must I perform? Before conducting the
initial correlation test, you must successfully complete a 7-day drift
test (See section 8.5).

3.0 What Special Definitions Apply to PS-11?

3.1 ``Appropriate Measurement Range of your PM CEMS'' means a
measurement range that is capable of recording readings over the
complete range of your source's PM emission concentrations during
routine operations. The appropriate range is determined during the
pretest preparations as specified in section 8.4.
3.2 ``Appropriate Data Range for PM CEMS Correlation'' means the
data range that reflects the full range of your source's PM emission
concentrations recorded by your PM CEMS during the correlation test
planning period or other normal operations as defined in the applicable
regulations.
3.3 ``Batch Sampling'' means that gas is sampled on an intermittent
basis and concentrated on a collection medium before intermittent
analysis and follow-up reporting. Beta gauge PM CEMS are an example of
batch sampling devices.
3.4 ``Confidence Interval Half Range (CI)'' is a statistical term
and means one-half of the width of the 95 percent confidence interval
around the predicted mean PM concentration (y value) calculated at the
PM CEMS response value (x value) where the confidence interval is
narrowest. Procedures for calculating CI are specified in section 12.3.
The CI as a percent of the emission limit value (CI%) is calculated at
the appropriate PM CEMS response value and must satisfy the criteria
specified in section 13.2 (2).
3.5 ``Continuous Emission Monitoring System (CEMS)'' means all of
the equipment required for determination of PM mass concentration in
units of the emission standard.

[[Page 714]]

The sample interface, pollutant monitor, diluent monitor, other
auxiliary data monitor(s), and data recorder are the major subsystems of
your CEMS.
3.6 ``Correlation'' means the primary mathematical relationship for
correlating the output from your PM CEMS to a PM concentration, as
determined by the PM reference method. The correlation is expressed in
the measurement units that are consistent with the measurement
conditions (e.g., mg/dscm, mg/acm) of your PM CEMS.
3.7 ``Correlation Coefficient (r)'' means a quantitative measure of
the association between your PM CEMS outputs and the reference method
measurements. Equations for calculating the r value are provided in
section 12.3(1)(iv) for linear correlations and in section 12.3(2)(iv)
for polynomial correlations.
3.8 ``Cycle Time'' means the time required to complete one sampling,
measurement, and reporting cycle. For a batch sampling PM CEMS, the
cycle time would start when sample gas is first extracted from the
stack/duct and end when the measurement of that batch sample is complete
and a new result for that batch sample is produced on the data recorder.
3.9 ``Data Recorder'' means the portion of your CEMS that provides a
permanent record of the monitor output in terms of response and status
(flags). The data recorder may also provide automatic data reduction and
CEMS control capabilities (see section 6.6).
3.10 ``Diluent Monitor and Other Auxiliary Data Monitor(s) (if
applicable)'' means the portion of your CEMS that provides the diluent
gas concentration (such as O2 or CO2, as specified
by the applicable regulations), temperature, pressure, and/or moisture
content, and generates an output proportional to the diluent gas
concentration or gas property.
3.11 ``Drift Check'' means a check of the difference between your PM
CEMS output readings and the established reference value of a reference
standard or procedure after a stated period of operation during which no
unscheduled maintenance, repair, or adjustment took place. The
procedures used to determine drift are specific to the operating
principles of your specific PM CEMS. A drift check includes both a zero
drift check and an upscale drift check.
3.12 ``Exponential Correlation'' means an exponential equation used
to define the relationship between your PM CEMS output and the reference
method PM concentration, as indicated by Equation 11-37.
3.13 ``Flagged Data'' means data marked by your CEMS indicating that
the response value(s) from one or more CEMS subsystems is suspect or
invalid or that your PM CEMS is not in source-measurement operating
mode.
3.14 ``Linear Correlation'' means a first-order mathematical
relationship between your PM CEMS output and the reference method PM
concentration that is linear in form, as indicated by Equation 11-3.
3.15 ``Logarithmic Correlation'' means a first-order mathematical
relationship between the natural logarithm of your PM CEMS output and
the reference method PM concentration that is linear in form, as
indicated by Equation 11-34.
3.16 ``Low-Emitting Source'' means a source that operated at no more
than 50 percent of the emission limit during the most recent performance
test, and, based on the PM CEMS correlation, the daily average emissions
for the source, measured in the units of the applicable emission limit,
have not exceeded 50 percent of the emission limit for any day since the
most recent performance test.
3.17 ``Paired Trains'' means two reference method trains that are
used to conduct simultaneous measurements of PM concentrations. Guidance
on the use of paired sampling trains can be found in the PM CEMS
Knowledge Document (see section 16.5).
3.18 ``Polynomial Correlation'' means a second-order equation used
to define the relationship between your PM CEMS output and reference
method PM concentration, as indicated by Equation 11-16.
3.19 ``Power Correlation'' means an equation used to define a power
function relationship between your PM CEMS output and the reference
method concentration, as indicated by Equation 11-42.
3.20 ``Reference Method'' means the method defined in the applicable
regulations, but commonly refers to those methods collectively known as
EPA Methods 5, 5I, and 17 (for particulate matter), found in Appendix A
of 40 CFR 60. Only the front half and dry filter catch portions of the
reference method can be correlated to your PM CEMS output.
3.21 ``Reference Standard'' means a reference material or procedure
that produces a known and unchanging response when presented to the
pollutant monitor portion of your CEMS. You must use these standards to
evaluate the overall operation of your PM CEMS, but not to develop a PM
CEMS correlation.
3.22 ``Response Time'' means the time interval between the start of
a step change in the system input and the time when the pollutant
monitor output reaches 95 percent of the final value (see sections 6.5
and 13.3 for procedures and acceptance criteria).
3.23 ``Sample Interface'' means the portion of your CEMS used for
one or more of the following: sample acquisition, sample delivery,
sample conditioning, or protection of the monitor from the effects of
the stack effluent.
3.24 ``Sample Volume Check'' means a check of the difference between
your PM

[[Page 715]]

CEMS sample volume reading and the sample volume reference value.
3.25 ``Tolerance Interval half range (TI)'' means one-half of the
width of the tolerance interval with upper and lower limits, within
which a specified percentage of the future data population is contained
with a given level of confidence, as defined by the respective tolerance
interval half range equations in section 12.3(1)(iii) for linear
correlations and in section 12.3(2)(iii) for polynomial correlations.
The TI as a percent of the emission limit value (TI%) is calculated at
the appropriate PM CEMS response value specified in section 13.2(3).
3.26 ``Upscale Check Value'' means the expected response to a
reference standard or procedure used to check the upscale response of
your PM CEMS.
3.27 ``Upscale Drift (UD) Check'' means a check of the difference
between your PM CEMS output reading and the upscale check value.
3.28 ``Zero Check Value'' means the expected response to a reference
standard or procedure used to check the response of your PM CEMS to
particulate-free or low-particulate concentration conditions.
3.29 ``Zero Drift (ZD) Check'' means a check of the difference
between your PM CEMS output reading and the zero check value.
3.30 ``Zero Point Correlation Value'' means a value added to PM CEMS
correlation data to represent low or near zero PM concentration data
(see section 8.6 for rationale and procedures).

4.0 Are There Any Potential Interferences for My PM CEMS?

Yes, condensible water droplets or condensible acid gas aerosols
(i.e., those with condensation temperatures above those specified by the
reference method) at the measurement location can be interferences for
your PM CEMS if the necessary precautions are not met.
4.1 Where are interferences likely to occur? Interferences may
develop if your CEMS is installed downstream of a wet air pollution
control system or any other conditions that produce flue gases, which,
at your PM CEMS measurement point, normally or occasionally contain
entrained water droplets or condensible salts before release to the
atmosphere.
4.2 How do I deal with interferences? We recommend that you use a PM
CEMS that extracts and heats representative samples of the flue gas for
measurement to simulate results produced by the reference method for
conditions such as those described in section 4.1. Independent of your
PM CEMS measurement technology and extractive technique, you should have
a configuration simulating the reference method to ensure that:
(1) No formation of new PM or deposition of PM occurs in sample
delivery from the stack or duct; and
(2) No condensate accumulates in the sample flow measurement
apparatus.
4.3 What PM CEMS measurement technologies should I use? You should
use a PM CEMS measurement technology that is free of interferences from
any condensible constituent in the flue gas.

5.0 What Do I Need To Know To Ensure the Safety of Persons Using PS-11?

People using the procedures required under PS-11 may be exposed to
hazardous materials, operations, site conditions, and equipment. This
performance specification does not purport to address all of the safety
issues associated with its use. It is your responsibility to establish
appropriate safety and health practices and determine the applicable
regulatory limitations before performing these procedures. You must
consult your CEMS user's manual and other reference materials
recommended by the reference method for specific precautions to be
taken.

6.0 What Equipment and Supplies Do I Need?

Different types of PM CEMS use different operating principles. You
should select an appropriate PM CEMS based on your site-specific
configurations, flue gas conditions, and PM characteristics.
(1) Your PM CEMS must sample the stack effluent continuously or, for
batch sampling PM CEMS, intermittently.
(2) You must ensure that the averaging time, the number of
measurements in an average, the minimum data availability, and the
averaging procedure for your CEMS conform with those specified in the
applicable emission regulation.
(3) Your PM CEMS must include, as a minimum, the equipment described
in sections 6.1 through 6.7.
6.1 What equipment is needed for my PM CEMS's sample interface? Your
PM CEMS's sample interface must be capable of delivering a
representative sample of the flue gas to your PM CEMS. This subsystem
may be required to heat the sample gas to avoid PM deposition or
moisture condensation, provide dilution air, perform other gas
conditioning to prepare the sample for analysis, or measure the sample
volume or flow rate.
(1) If your PM CEMS is installed downstream of a wet air pollution
control system such that the flue gases normally or occasionally contain
entrained water droplets, we recommend that you select a sampling system
that includes equipment to extract and heat a representative sample of
the flue gas for measurement so that the pollutant monitor portion of
your CEMS measures only dry PM. Heating should be sufficient to raise
the temperature of the extracted flue

[[Page 716]]

gas above the water condensation temperature and should be maintained at
all times and at all points in the sample line from where the flue gas
is extracted, including the pollutant monitor and any sample flow
measurement devices.
(2) You must consider the measured conditions of the sample gas
stream to ensure that manual reference method test data are converted to
units of PM concentration that are appropriate for the correlation
calculations. Additionally, you must identify what, if any, additional
auxiliary data from other monitoring and handling systems are necessary
to convert your PM CEMS response into the units of the PM standard.
(3) If your PM CEMS is an extractive type and your source's flue gas
volumetric flow rate varies by more than 10 percent from nominal, your
PM CEMS should maintain an isokinetic sampling rate (within 10 percent
of true isokinetic). If your extractive-type PM CEMS does not maintain
an isokinetic sampling rate, you must use actual site-specific data or
data from a similar installation to prove to us, the State, and/or local
enforcement agency that isokinetic sampling is not necessary.
6.2 What type of equipment is needed for my PM CEMS? Your PM CEMS
must be capable of providing an electronic output that can be correlated
to the PM concentration.
(1) Your PM CEMS must be able to perform zero and upscale drift
checks. You may perform these checks manually, but performing these
checks automatically is preferred.
(2) We recommend that you select a PM CEMS that is capable of
performing automatic diagnostic checks and sending instrument status
signals (flags) to the data recorder.
(3) If your PM CEMS is an extractive type that measures the sample
volume and uses the measured sample volume as part of calculating the
output value, your PM CEMS must be able to perform a check of the sample
volume to verify the accuracy of the sample volume measuring equipment.
The sample volume check must be conducted daily and at the normal
sampling rate of your PM CEMS.
6.3 What is the appropriate measurement range for my PM CEMS?
Initially, your PM CEMS must be set up to measure over the expected
range of your source's PM emission concentrations during routine
operations. You may change the measurement range to a more appropriate
range prior to correlation testing.
6.4 What if my PM CEMS does automatic range switching? Your PM CEMS
may be equipped to perform automatic range switching so that it is
operating in a range most sensitive to the detected concentrations. If
your PM CEMS does automatic range switching, you must configure the data
recorder to handle the recording of data values in multiple ranges
during range-switching intervals.
6.5 What averaging time and sample intervals should be used? Your
CEMS must sample the stack effluent such that the averaging time, the
number of measurements in an average, the minimum sampling time, and the
averaging procedure for reporting and determining compliance conform
with those specified in the applicable regulation. Your PM CEMS must be
designed to meet the specified response time and cycle time established
in this performance specification (see section 13.3).
6.6 What type of equipment is needed for my data recorder? Your CEMS
data recorder must be able to accept and record electronic signals from
all the monitors associated with your PM CEMS.
(1) Your data recorder must record the signals from your PM CEMS
that can be correlated to PM mass concentrations. If your PM CEMS uses
multiple ranges, your data recorder must identify what range the
measurement was made in and provide range-adjusted results.
(2) Your data recorder must accept and record monitor status signals
(flagged data).
(3) Your data recorder must accept signals from auxiliary data
monitors, as appropriate.
6.7 What other equipment and supplies might I need? You may need
other supporting equipment as defined by the applicable reference
method(s) (see section 7) or as specified by your CEMS manufacturer.

7.0 What Reagents and Standards Do I Need?

You will need reference standards or procedures to perform the zero
drift check, the upscale drift check, and the sample volume check.
7.1 What is the reference standard value for the zero drift check?
You must use a zero check value that is no greater than 20 percent of
the PM CEMS's response range. You must obtain documentation on the zero
check value from your PM CEMS manufacturer.
7.2 What is the reference standard value for the upscale drift
check? You must use an upscale check value that produces a response
between 50 and 100 percent of the PM CEMS's response range. For a PM
CEMS that produces output over a range of 4 mA to 20 mA, the upscale
check value must produce a response in the range of 12 mA to 20 mA. You
must obtain documentation on the upscale check value from your PM CEMS
manufacturer.
7.3 What is the reference standard value for the sample volume
check? You must use a reference standard value or procedure that
produces a sample volume value equivalent to the normal sampling rate.
You must obtain documentation on the sample volume value from your PM
CEMS manufacturer.

[[Page 717]]

8.0 What Performance Specification Test Procedure Do I Follow?

You must complete each of the activities in sections 8.1 through 8.8
for your performance specification test.
8.1 How should I select and set up my equipment? You should select a
PM CEMS that is appropriate for your source, giving consideration to
potential factors such as flue gas conditions, interferences, site-
specific configuration, installation location, PM concentration range,
and other PM characteristics. Your PM CEMS must meet the equipment
specifications in sections 6.1 and 6.2.
(1) You should select a PM CEMS that is appropriate for the flue gas
conditions at your source. If your source's flue gas contains entrained
water droplets, we recommend that your PM CEMS include a sample delivery
and conditioning system that is capable of extracting and heating a
representative sample.
(i) Your PM CEMS must maintain the sample at a temperature
sufficient to prevent moisture condensation in the sample line before
analysis of PM.
(ii) If condensible PM is an issue, we recommend that you operate
your PM CEMS to maintain the sample gas temperature at the same
temperature as the reference method filter.
(iii) Your PM CEMS must avoid condensation in the sample flow rate
measurement lines.
(2) Some PM CEMS do not have a wide measurement range capability.
Therefore, you must select a PM CEMS that is capable of measuring the
full range of PM concentrations expected from your source from normal
levels through the emission limit concentration.
(3) Some PM CEMS are sensitive to particle size changes, water
droplets in the gas stream, particle charge, stack gas velocity changes,
or other factors. Therefore, you should select a PM CEMS appropriate for
the emission characteristics of your source.
(4) We recommend that you consult your PM CEMS vendor to obtain
basic recommendations on the instrument capabilities and setup
configuration. You are ultimately responsible for setup and operation of
your PM CEMS.
8.2 Where do I install my PM CEMS? You must install your PM CEMS at
an accessible location downstream of all pollution control equipment.
You must perform your PM CEMS concentration measurements from a location
considered representative or be able to provide data that can be
corrected to be representative of the total PM emissions as determined
by the manual reference method.
(1) You must select a measurement location that minimizes problems
due to flow disturbances, cyclonic flow, and varying PM stratification
(refer to Method 1 for guidance).
(2) If you plan to achieve higher emissions for correlation test
purposes by adjusting the performance of the air pollution control
device (per section 8.6(4)(i)), you must locate your PM CEMS and
reference method sampling points well downstream of the control device
(e.g., downstream of the induced draft fan), in order to minimize PM
stratification that may be created in these cases.
8.3 How do I select the reference method measurement location and
traverse points? You must follow EPA Method 1 for identifying manual
reference method traverse points. Ideally, you should perform your
manual reference method measurements at locations that satisfy the
measurement site selection criteria specified in EPA Method 1 of at
least eight duct diameters downstream and at least two duct diameters
upstream of any flow disturbance. Where necessary, you may conduct
testing at a location that is two diameters downstream and 0.5 diameters
upstream of flow disturbances. If your location does not meet the
minimum downstream and upstream requirements, you must obtain approval
from us to test at your location.
8.4 What are my pretest preparation steps? You must install your
CEMS and prepare the reference method test site according to the
specifications in sections 8.2 and 8.3.
(1) After completing the initial field installation, we recommend
that you operate your PM CEMS according to the manufacturer's
instructions to familiarize yourself with its operation before you begin
correlation testing.
(i) During this initial period of operation, we recommend that you
conduct daily checks (zero and upscale drift and sample volume, as
appropriate), and, when any check exceeds the daily specification (see
section 13.1), make adjustments and perform any necessary maintenance to
ensure reliable operation.
(2) When you are confident that your PM CEMS is operating properly,
we recommend that you operate your CEMS over a correlation test planning
period of sufficient duration to identify the full range of operating
conditions and PM emissions to be used in your PM CEMS correlation test.
(i) During the correlation test planning period, you should operate
the process and air pollution control equipment over the normal range of
operating conditions, except when you attempt to produce higher
emissions.
(ii) Your data recorder should record PM CEMS response during the
full range of routine process operating conditions.
(iii) You should try to establish the relationships between
operating conditions and PM CEMS response, especially those conditions
that produce the highest PM CEMS response over 15-minute averaging
periods, and

[[Page 718]]

the lowest PM CEMS response as well. The objective is to be able to
reproduce the conditions for purposes of the actual correlation testing
discussed in section 8.6.
(3) You must set the response range of your PM CEMS such that the
instrument measures the full range of responses that correspond to the
range of source operating conditions that you will implement during
correlation testing.
(4) We recommend that you perform preliminary reference method
testing after the correlation test planning period. During this
preliminary testing, you should measure the PM emission concentration
corresponding to the highest PM CEMS response observed during the full
range of normal operation, when perturbing the control equipment, or as
the result of PM spiking.
(5) Before performing correlation testing, you must perform a 7-day
zero and upscale drift test (see section 8.5).
(6) You must not change the response range of the monitor once the
response range has been set and the drift test successfully completed.
8.5 How do I perform the 7-day drift test? You must check the zero
(or low-level value between 0 and 20 percent of the response range of
the instrument) and upscale (between 50 and 100 percent of the
instrument's response range) drift. You must perform this check at least
once daily over 7 consecutive days. Your PM CEMS must quantify and
record the zero and upscale measurements and the time of the
measurements. If you make automatic or manual adjustments to your PM
CEMS zero and upscale settings, you must conduct the drift test
immediately before these adjustments, or conduct it in such a way that
you can determine the amount of drift. You will find the calculation
procedures for drift in section 12.1 and the acceptance criteria for
allowable drift in section 13.1.
(1) What is the purpose of 7-day drift tests? The purpose of the 7-
day drift test is to demonstrate that your system is capable of
operating in a stable manner and maintaining its calibration for at
least a 7-day period.
(2) How do I conduct the 7-day drift test? To conduct the 7-day
drift test, you must determine the magnitude of the drift once each day,
at 24-hour intervals, for 7 consecutive days while your source is
operating normally.
(i) You must conduct the 7-day drift test at the two points
specified in section 8.5. You may perform the 7-day drift tests
automatically or manually by introducing to your PM CEMS suitable
reference standards (these need not be certified) or by using other
appropriate procedures.
(ii) You must record your PM CEMS zero and upscale response and
evaluate them against the zero check value and upscale check value.
(3) When must I conduct the 7-day drift test? You must complete a
valid 7-day drift test before attempting the correlation test.
8.6 How do I conduct my PM CEMS correlation test? You must conduct
the correlation test according to the procedure given in paragraphs (1)
through (5) of this section. If you need multiple correlations, you must
conduct testing and collect at least 15 sets of reference method and PM
CEMS data for calculating each separate correlation.
(1) You must use the reference method for PM (usually EPA Methods 5,
5I, or 17) that is prescribed by the applicable regulations. You may
need to perform other reference methods or performance specifications
(e.g., Method 3 for oxygen, Method 4 for moisture, etc.) depending on
the units in which your PM CEMS reports PM concentration.
(i) We recommend that you use paired reference method trains when
collecting manual PM data to identify and screen the reference method
data for imprecision and bias. Procedures for checking reference method
data for bias and precision can be found in the PM CEMS Knowledge
Document (see section 16.5).
(ii) You may use test runs that are shorter than 60 minutes in
duration (e.g., 20 or 30 minutes). You may perform your PM CEMS
correlation tests during new source performance standards performance
tests or other compliance tests subject to the Clean Air Act or other
statutes, such as the Resource Conservation and Recovery Act. In these
cases, your reference method results obtained during the PM CEMS
correlation test may be used to determine compliance so long as your
source and the test conditions and procedures (e.g., reference method
sample run durations) are consistent with the applicable regulations and
the reference method.
(iii) You must convert the reference method results to units
consistent with the conditions of your PM CEMS measurements. For
example, if your PM CEMS measures and reports PM emissions in the units
of mass per actual volume of stack gas, you must convert your reference
method results to those units (e.g., mg/acm). If your PM CEMS extracts
and heats the sample gas to eliminate water droplets, then measures and
reports PM emissions under those actual conditions, you must convert
your reference method results to those same conditions (e.g., mg/acm at
160 [deg]C).
(2) During each test run, you must coordinate process operations,
reference method sampling, and PM CEMS operations. For example, you must
ensure that the process is operating at the targeted conditions, both
reference method trains are sampling simultaneously (if paired sampling
trains are being used), and your PM CEMS and data logger are operating
properly.

[[Page 719]]

(i) You must coordinate the start and stop times of each run between
the reference method sampling and PM CEMS operation. For a batch
sampling PM CEMS, you must start the reference method at the same time
as your PM CEMS sampling.
(ii) You must note the times for port changes (and other periods
when the reference method sampling may be suspended) on the data sheets
so that you can adjust your PM CEMS data accordingly, if necessary.
(iii) You must properly align the time periods for your PM CEMS and
your reference method measurements to account for your PM CEMS response
time.
(3) You must conduct a minimum of 15 valid runs each consisting of
simultaneous PM CEMS and reference method measurement sets.
(i) You may conduct more than 15 sets of CEMS and reference method
measurements. If you choose this option, you may reject certain test
results so long as the total number of valid test results you use to
determine the correlation is greater than or equal to 15.
(ii) You must report all data, including the rejected data.
(iii) You may reject the results of up to five test runs without
explanation.
(iv) If you reject the results of more than five test runs, the
basis for rejecting the results of the additional test runs must be
explicitly stated in the reference method, this performance
specification, Procedure 2 of appendix F, or your quality assurance
plan.
(4) Simultaneous PM CEMS and reference method measurements must be
performed in a manner to ensure that the range of data that will be used
to establish the correlation for your PM CEMS is maximized. You must
first attempt to maximize your correlation range by following the
procedures described in paragraphs (4)(i) through (iv) of this section.
If you cannot obtain the three levels as described in paragraphs (i)
through (iv), then you must use the procedure described in section
8.6(5).
(i) You must attempt to obtain the three different levels of PM mass
concentration by varying process operating conditions, varying PM
control device conditions, or by means of PM spiking.
(ii) The three PM concentration levels you use in the correlation
tests must be distributed over the complete operating range experienced
by your source.
(iii) At least 20 percent of the minimum 15 measured data points you
use should be contained in each of the following levels:
Level 1: From no PM (zero concentration) emissions to 50
percent of the maximum PM concentration;
Level 2: 25 to 75 percent of the maximum PM concentration;
and
Level 3: 50 to 100 percent of the maximum PM concentration.
(iv) Although the above levels overlap, you may only apply
individual run data to one level.
(5) If you cannot obtain three distinct levels of PM concentration
as described, you must perform correlation testing over the maximum
range of PM concentrations that is practical for your PM CEMS. To ensure
that the range of data used to establish the correlation for your PM
CEMS is maximized, you must follow one or more of the steps in
paragraphs (5)(i) through (iv) of this section.
(i) Zero point data for in-situ instruments should be obtained, to
the extent possible, by removing the instrument from the stack and
monitoring ambient air on a test bench.
(ii) Zero point data for extractive instruments should be obtained
by removing the extractive probe from the stack and drawing in clean
ambient air.
(iii) Zero point data also can be obtained by performing manual
reference method measurements when the flue gas is free of PM emissions
or contains very low PM concentrations (e.g., when your process is not
operating, but the fans are operating or your source is combusting only
natural gas).
(iv) If none of the steps in paragraphs (5)(i) through (iii) of this
section are possible, you must estimate the monitor response when no PM
is in the flue gas (e.g., 4 mA = 0 mg/acm).
8.7 What do I do with the initial correlation test data for my PM
CEMS? You must calculate and report the results of the correlation
testing, including the correlation coefficient, confidence interval, and
tolerance interval for the PM CEMS response and reference method
correlation data that are use to establish the correlation, as specified
in section 12. You must include all data sheets, calculations, charts
(records of PM CEMS responses), process data records including PM
control equipment operating parameters, and reference media
certifications necessary to confirm that your PM CEMS met the
requirements of this performance specification. In addition, you must:
(1) Determine the integrated (arithmetic average) PM CEMS output
over each reference method test period;
(2) Adjust your PM CEMS outputs and reference method test data to
the same clock time (considering response time of your PM CEMS);
(3) Confirm that the reference method results are consistent with
your PM CEMS response in terms of, where applicable, moisture,
temperature, pressure, and diluent concentrations; and
(4) Determine whether any of the reference method test results do
not meet the test method criteria.
8.8 What is the limitation on the range of my PM CEMS correlation?
Although the data you collect during the correlation testing should be
representative of the full range of normal operating conditions at your

[[Page 720]]

source, you must conduct additional correlation testing if either of the
conditions specified in paragraphs (1) and (2) of this section occurs.
(1) If your source is a low-emitting source, as defined in section
3.16 of this specification, you must conduct additional correlation
testing if either of the events specified in paragraphs (1)(i) or (ii)
of this section occurs while your source is operating under normal
conditions.
(i) Your source generates 24 consecutive hourly average PM CEMS
responses that are greater than 125 percent of the highest PM CEMS
response (e.g., mA reading) used for the correlation curve or are
greater than the PM CEMS response that corresponds to 50 percent of the
emission limit, whichever is greater, or
(ii) The cumulative hourly average PM CEMS responses generated by
your source are greater than 125 percent of the highest PM CEMS response
used for the correlation curve or are greater than the PM CEMS response
that corresponds to 50 percent of the emission limit, whichever is
greater, for more than 5 percent of your PM CEMS operating hours for the
previous 30-day period.
(2) If your source is not a low-emitting source, as defined in
section 3.16 of this specification, you must conduct additional
correlation testing if either of the events specified in paragraph (i)
or (ii) of this section occurs while your source is operating under
normal conditions.
(i) Your source generates 24 consecutive hourly average PM CEMS
responses that are greater than 125 percent of the highest PM CEMS
response (e.g., mA reading) used for the correlation curve, or
(ii) The cumulative hourly average PM CEMS responses generated by
your source are greater than 125 percent of the highest PM CEMS response
used for the correlation curve for more than 5 percent of your PM CEMS
operating hours for the previous 30-day period.
(3) If additional correlation testing is required, you must conduct
at least three additional test runs under the conditions that caused the
higher PM CEMS response.
(i) You must complete the additional testing and use the resulting
new data along with the previous data to calculate a revised correlation
equation within 60 days after the occurrence of the event that requires
additional testing, as specified in paragraphs 8.8(1) and (2).
(4) If your source generates consecutive PM CEMS hourly responses
that are greater than 125 percent of the highest PM CEMS response used
to develop the correlation curve for 24 hours or for a cumulative period
that amounts to more than 5 percent of the PM CEMS operating hours for
the previous 30-day period, you must report the reason for the higher PM
CEMS responses.

9.0 What Quality Control Measures Are Required?

Quality control measures for PM CEMS are specified in 40 CFR 60,
Appendix F, Procedure 2.

10.0 What Calibration and Standardization Procedures Must I Perform?
[Reserved]

11.0 What Analytical Procedures Apply to This Procedure?

Specific analytical procedures are outlined in the applicable
reference method(s).

12.0 What Calculations and Data Analyses Are Needed?

You must determine the primary relationship for correlating the
output from your PM CEMS to a PM concentration, typically in units of
mg/acm or mg/dscm of flue gas, using the calculations and data analysis
process in sections 12.2 and 12.3. You develop the correlation by
performing an appropriate regression analysis between your PM CEMS
response and your reference method data.
12.1 How do I calculate upscale drift and zero drift? You must
determine the difference in your PM CEMS output readings from the
established reference values (zero and upscale check values) after a
stated period of operation during which you performed no unscheduled
maintenance, repair, or adjustment.
(1) Calculate the upscale drift (UD) using Equation 11-1:
[GRAPHIC] [TIFF OMITTED] TR27FE14.017

Where:

UD = The upscale (high-level) drift of your PM CEMS in percent,
RCEM = The measured PM CEMS response to the upscale reference
standard, and
RU = The pre-established numerical value of the upscale
reference standard.

[[Page 721]]

FS= Full-scale value.
(2) Calculate the zero drift (ZD) using Equation 11-2:
[GRAPHIC] [TIFF OMITTED] TR27FE14.018

Where:

ZD = The zero (low-level) drift of your PM CEMS in percent,
RCEM = The measured PM CEMS response to the zero reference
standard,
RL = The pre-established numerical value of the zero
reference standard, and
FS = Full-scale value.

(3) Summarize the results on a data sheet similar to that shown in
Table 2 (see section 17).
12.2 How do I perform the regression analysis? You must couple each
reference method PM concentration measurement, y, in the appropriate
units, with an average PM CEMS response, x, over corresponding time
periods. You must complete your PM CEMS correlation calculations using
data deemed acceptable by quality control procedures identified in 40
CFR 60, Appendix F, Procedure 2.
(1) You must evaluate all flagged or suspect data produced during
measurement periods and determine whether they should be excluded from
your PM CEMS's average.
(2) You must assure that the reference method and PM CEMS results
are on a consistent moisture, temperature, and diluent basis. You must
convert the reference method PM concentration measurements (dry standard
conditions) to the units of your PM CEMS measurement conditions. The
conditions of your PM CEMS measurement are monitor-specific. You must
obtain from your PM CEMS vendor or instrument manufacturer the
conditions and units of measurement for your PM CEMS.
(i) If your sample gas contains entrained water droplets and your PM
CEMS is an extractive system that measures at actual conditions (i.e.,
wet basis), you must use the measured moisture content determined from
the impinger analysis when converting your reference method PM data to
PM CEMS conditions; do not use the moisture content calculated from a
psychrometric chart based on saturated conditions.
12.3 How do I determine my PM CEMS correlation? To predict PM
concentrations from PM CEMS responses, you must use the calculation
method of least squares presented in paragraphs (1) through (5) of this
section. When performing the calculations, each reference method PM
concentration measurement must be treated as a discrete data point; if
using paired sampling trains, do not average reference method data pairs
for any test run.
This performance specification describes procedures for evaluating
five types of correlation models: linear, polynomial, logarithmic,
exponential, and power. Procedures for selecting the most appropriate
correlation model are presented in section 12.4 of this specification.
(1) How do I evaluate a linear correlation for my correlation test
data? To evaluate a linear correlation, follow the procedures described
in paragraphs (1)(i) through (iv) of this section.
(i) Calculate the linear correlation equation, which gives the
predicted PM concentration () as a function of the PM CEMS response (x),
as indicated by Equation 11-3:
[GRAPHIC] [TIFF OMITTED] TR12JA04.005

Where:

y = the predicted PM concentration,
b0 = the intercept for the correlation curve, as calculated
using Equation 11-4,
b1 = the slope of the correlation curve, as calculated using
Equation 11-6, and
x = the PM CEMS response value.

Calculate the y intercept (b0) of the correlation curve
using Equation 11-4:
[GRAPHIC] [TIFF OMITTED] TR12JA04.006

Where:

x = the mean value of the PM CEMS response data, as calculated using
Equation 11-5, and
y = the mean value of the PM concentration data, as calculated using
Equation 11-5:
[GRAPHIC] [TIFF OMITTED] TR12JA04.007

Where:

xi = the PM CEMS response value for run i,
yi = the PM concentration value for run i, and
n = the number of data points.

Calculate the slope (b1) of the correlation curve using
Equation 11-6:

[[Page 722]]

[GRAPHIC] [TIFF OMITTED] TR12JA04.008

Where:

Sxx, Sxy = as calculated using Equation 11-7:
[GRAPHIC] [TIFF OMITTED] TR12JA04.009

(ii) Calculate the half range of the 95 percent confidence interval
(CI) for the predicted PM concentration () at the mean value of x, using
Equation 11-8:
[GRAPHIC] [TIFF OMITTED] TR25MR09.063

Where:

CI = the half range of the 95 percent confidence interval for the
predicted PM concentration at the mean x value,
tdf,1-a/2 = the value for the t statistic provided in Table 1
for df = (n - 2), and
SL = the scatter or deviation of values about the correlation
curve, which is determined using Equation 11-9:

[GRAPHIC] [TIFF OMITTED] TR25MR09.064

Calculate the confidence interval half range for the predicted PM
concentration () at the mean x value as a percentage of the emission
limit (CI%) using Equation 11-10:
[GRAPHIC] [TIFF OMITTED] TR25MR09.065

Where:

CI = the half range of the 95 percent confidence interval for the
predicted PM concentration at the mean x value, and
EL = PM emission limit, as described in section 13.2.

(iii) Calculate the half range of the tolerance interval (TI) for
the predicted PM concentration () at the mean x value using Equation 11-
11:
[GRAPHIC] [TIFF OMITTED] TR25MR09.066

Where:

TI = the half range of the tolerance interval for the predicted PM
concentration () at the mean x value,
kT = as calculated using Equation 11-12, and
SL = as calculated using Equation 11-9:

[GRAPHIC] [TIFF OMITTED] TR25MR09.067

Where:

n' = the number of test runs (n),
un' = the tolerance factor for 75 percent coverage at 95
percent confidence provided in Table 1 for df = (n-2), and
vdf = the value from Table 1 for df = (n-2).

Calculate the half range of the tolerance interval for the predicted
PM concentration () at the mean x value as a percentage of the emission
limit (TI%) using Equation 11-13:
[GRAPHIC] [TIFF OMITTED] TR25MR09.068

Where:

TI = the half range of the tolerance interval for the predicted PM
concentration () at the mean x value, and
EL = PM emission limit, as described in section 13.2.

(iv) Calculate the linear correlation coefficient (r) using Equation
11-14:
[GRAPHIC] [TIFF OMITTED] TR12JA04.016

Where:

SL = as calculated using Equation 11-9, and
Sy = as calculated using Equation 11-15:
[GRAPHIC] [TIFF OMITTED] TR12JA04.017

(2) How do I evaluate a polynomial correlation for my correlation
test data? To evaluate a polynomial correlation, follow the procedures
described in paragraphs (2)(i) through (iv) of this section.
(i) Calculate the polynomial correlation equation, which is
indicated by Equation 11-16, using Equations 11-17 through 11-22:
[GRAPHIC] [TIFF OMITTED] TR25MR09.069

Where:

[[Page 723]]

= the PM CEMS concentration predicted by the polynomial correlation
equation, and
b0, b1, b2 = the coefficients
determined from the solution to the matrix equation Ab = B

Where:
[GRAPHIC] [TIFF OMITTED] TR25MR09.070

Where:

Xi = the PM CEMS response for run i,
Yi = the reference method PM concentration for run i, and
n = the number of test runs.

Calculate the polynomial correlation curve coefficients
(b0, b1, and b2) using Equations 11-19
through 11-21, respectively:
[GRAPHIC] [TIFF OMITTED] TR25MR09.071

Where:
[GRAPHIC] [TIFF OMITTED] TR25MR09.072

(ii) Calculate the 95 percent confidence interval half range (CI) by
first calculating the C coefficients (Co to C5)
using Equations 11-23 and 11-24:

[[Page 724]]

[GRAPHIC] [TIFF OMITTED] TR25MR09.073

Where:
[GRAPHIC] [TIFF OMITTED] TR25MR09.074

Calculate F using Equation 11-25 for each x value:
[GRAPHIC] [TIFF OMITTED] TR25MR09.075

Determine the x value that corresponds to the minimum value of F
(Fmin). Determine the scatter or deviation of values about
the polynomial correlation curve (SP) using Equation 11-26:
[GRAPHIC] [TIFF OMITTED] TR25MR09.076

Calculate the half range of the 95 percent confidence interval (CI) for
the predicted PM concentration () at the x value that corresponds to
Fmin using Equation 11-27:
[GRAPHIC] [TIFF OMITTED] TR25MR09.077

Where:

df = (n-3), and
tdf = as listed in Table 1 (see section 17).

Calculate the half range of the 95 percent confidence interval for the
predicted PM concentration at the x value that corresponds to
Fmin as a percentage of the emission limit (CI%) using
Equation 11-28:
[GRAPHIC] [TIFF OMITTED] TR25MR09.078

Where:

CI = the half range of the 95 percent confidence interval for the
predicted PM concentration at the x value that corresponds to
Fmin, and
EL = PM emission limit, as described in section 13.2.

(iii) Calculate the tolerance interval half range (TI) for the
predicted PM concentration at the x value that corresponds to
Fmin, as indicated in Equation 11-29 for the polynomial
correlation, using Equations 11-30 and 11-31:
[GRAPHIC] [TIFF OMITTED] TR25MR09.079

Where:
[GRAPHIC] [TIFF OMITTED] TR25MR09.080

un' = the value indicated in Table 1 for df = (n'-3), and

[[Page 725]]

vdf = the value indicated in Table 1 for df = (n'--3).

Calculate the tolerance interval half range for the predicted PM
concentration at the x value that corresponds to Fmin as a
percentage of the emission limit (TI%) using Equation 11-32:
[GRAPHIC] [TIFF OMITTED] TR25MR09.081

Where:

TI = the tolerance interval half range for the predicted PM
concentration at the x value that corresponds to
Fmin, and
EL = PM emission limit, as described in section 13.2.

(iv) Calculate the polynomial correlation coefficient (r) using
Equation 11-33:
[GRAPHIC] [TIFF OMITTED] TR25MR09.082

Where:

SP = as calculated using Equation 11-26, and
Sy = as calculated using Equation 11-15.

(3) How do I evaluate a logarithmic correlation for my correlation
test data? To evaluate a logarithmic correlation, which has the form
indicated by Equation 11-34, follow the procedures described in
paragraphs (3)(i) through (iii) of this section.
[GRAPHIC] [TIFF OMITTED] TR12JA04.034

(i) Perform a logarithmic transformation of each PM CEMS response
value (x values) using Equation 11-35:
[GRAPHIC] [TIFF OMITTED] TR12JA04.035

Where:

xi' = is the transformed value of xi, and
Ln(xi) = the natural logarithm of the PM CEMS response for
run i.

(ii) Using the values for xi' in place of the values for
xi, perform the same procedures used to develop the linear
correlation equation described in paragraph (1)(i) of this section. The
resulting equation has the form indicated by Equation 11-36:
[GRAPHIC] [TIFF OMITTED] TR12JA04.036

Where:

x' = the natural logarithm of the PM CEMS response, and the variables ,
b0, and b1 are as defined in paragraph
(1)(i) of this section.

(iii) Using the values for xi' in place of the values for
xi, calculate the confidence interval half range at the mean
x' value as a percentage of the emission limit (CI%), the tolerance
interval half range at the mean x' value as a percentage of the emission
limit (TI%), and the correlation coefficient (r) using the procedures
described in paragraphs (1)(ii) through (iv) of this section.
(4) How do I evaluate an exponential correlation for my correlation
test data? To evaluate an exponential correlation, which has the form
indicated by Equation 11-37, follow the procedures described in
paragraphs (4)(i) through (v) of this section:
[GRAPHIC] [TIFF OMITTED] TR25MR09.083

(i) Perform a logarithmic transformation of each PM concentration
measurement (y values) using Equation 11-38:
[GRAPHIC] [TIFF OMITTED] TR25MR09.084

Where:

y'i = is the transformed value of yi, and
Ln(yi) = the natural logarithm of the PM concentration
measurement for run i.

(ii) Using the values for y'i in place of the values for
yi, perform the same procedures used to develop the linear
correlation equation described in paragraph (1)(i) of this section. The
resulting equation will have the form indicated by Equation 11-39.
[GRAPHIC] [TIFF OMITTED] TR25MR09.085

Where:

' = the predicted log PM concentration value,
b'0 = the natural logarithm of b0, and the
variables b0, b1, and x are as defined
in paragraph (1)(i) of this section.

(iii) Using the values for yi in place of the values for
yi, calculate the half range of the 95 percent confidence interval
(CI'), as described in paragraph (1)(ii) of this section for CI. Note
that CI' is on the log scale. Next, calculate the upper and lower 95
percent confidence limits for the mean value y' using Equations 11-40
and 11-41:
[GRAPHIC] [TIFF OMITTED] TR25MR09.086

[GRAPHIC] [TIFF OMITTED] TR25MR09.087

Where:

LCL' = the lower 95 percent confidence limit for the mean value y',
UCL' = the upper 95 percent confidence limit for the mean value y',
y' = the mean value of the log-transformed PM concentrations, and
CI' = the half range of the 95 percent confidence interval for the
predicted PM concentration ('), as calculated in Equation 11-
8.

[[Page 726]]

Calculate the half range of the 95 percent confidence interval (CI) on
the original PM concentration scale using Equation 11-42:
[GRAPHIC] [TIFF OMITTED] TR25MR09.088

Where:

CI = the half range of the 95 percent confidence interval on the
original PM concentration scale, and UCL' and LCL' are as
defined previously.

Calculate the half range of the 95 percent confidence interval for the
predicted PM concentration corresponding to the mean value of x as a
percentage of the emission limit (CI%) using Equation 11-10.
(iv) Using the values for y'i in place of the values for yi,
calculate the half range tolerance interval (TI'), as described in
paragraph (1)(iii) of this section for TI. Note that TI' is on the log
scale. Next, calculate the half range tolerance limits for the mean
value y' using Equations 11-43 and 11-44:
[GRAPHIC] [TIFF OMITTED] TR25MR09.089

[GRAPHIC] [TIFF OMITTED] TR25MR09.090

Where:

LTL' = the lower 95 percent tolerance limit for the mean value y',
UTL' = the upper 95 percent tolerance limit for the mean value y',
y', = the mean value of the log-transformed PM concentrations, and
TI' = the half range of the 95 percent tolerance interval for the
predicted PM concentration ('), as calculated in Equation 11-
11.

Calculate the half range tolerance interval (TI) on the original PM
concentration scale using Equation 11-45:
[GRAPHIC] [TIFF OMITTED] TR25MR09.091

TI = the half range of the 95 percent tolerance interval on the original
PM scale, and UTL' and LTL' are as defined previously.

Calculate the tolerance interval half range for the predicted PM
concentration corresponding to the mean value of x as a percentage of
the emission limit (TI%) using Equation 11-13.
(v) Using the values for y i in place of the values for
yi, calculate the correlation coefficient (r) using the procedure
described in paragraph (1)(iv) of this section.
(5) How do I evaluate a power correlation for my correlation test
data? To evaluate a power correlation, which has the form indicated by
Equation 11-46, follow the procedures described in paragraphs (5)(i)
through (v) of this section.
[GRAPHIC] [TIFF OMITTED] TR25MR09.092

(i) Perform logarithmic transformations of each PM CEMS response (x
values) and each PM concentration measurement (y values) using Equations
11-35 and 11-38, respectively.
(ii) Using the values for xi in place of the values for
xi, and the values for yi in place of the values for yi,
perform the same procedures used to develop the linear correlation
equation described in paragraph (1)(i) of this section. The resulting
equation will have the form indicated by Equation 11-47:
[GRAPHIC] [TIFF OMITTED] TR25MR09.093

Where:

' = the predicted log PM concentration value, and
x' = the natural logarithm of the PM CEMS response values,
b'0 = the natural logarithm of b0, and the
variables b0, b1, and x are as defined
in paragraph (1)(i) of this section.

(iii) Using the same procedure described for exponential models in
paragraph (4)(iii) of this section, calculate the half range of the 95
percent confidence interval for the predicted PM concentration
corresponding to the mean value of x' as a percentage of the emission
limit.
(iv) Using the same procedure described for exponential models in
paragraph (4)(iv) of this section, calculate the tolerance interval half
range for the predicted PM concentration corresponding to the mean value
of x' as a percentage of the emission limit.
(v) Using the values for y'i in place of the values for yi,
calculate the correlation coefficient (r) using the procedure described
in paragraph (1)(iv) of this section.
Note: PS-11 does not address the application of correlation
equations to calculate PM emission concentrations using PM CEMS response
data during normal operations of a PM CEMS. However, we will provide
guidance on the use of specific correlation models (i.e., logarithmic,
exponential, and power models) to calculate PM concentrations in an
operating PM CEMS in situations when the PM CEMS response values are
equal to or less than zero, and the correlation model is undefined.
12.4 Which correlation model should I use? Follow the procedures
described in paragraphs (1) through (4) of this section to determine
which correlation model you should use.
(1) For each correlation model that you develop using the procedures
described in section 12.3 of this specification, compare the confidence
interval half range percentage, tolerance interval half range
percentage, and

[[Page 727]]

correlation coefficient to the performance criteria specified in section
13.2 of this specification. You can use the linear, logarithmic,
exponential, or power correlation model if the model satisfies all of
the performance criteria specified in section 13.2 of this
specification. However, to use the polynomial model you first must check
that the polynomial correlation curve satisfies the criteria for minimum
and maximum values specified in paragraph (3) of this section.
(2) If you develop more than one correlation curve that satisfy the
performance criteria specified in section 13.2 of this specification,
you should use the correlation curve with the greatest correlation
coefficient. If the polynomial model has the greatest correlation
coefficient, you first must check that the polynomial correlation curve
satisfies the criteria for minimum and maximum values specified in
paragraph (3) of this section.
(3) You can use the polynomial model that you develop using the
procedures described in section 12.3(2) if the model satisfies the
performance criteria specified in section 13.2 of this specification,
and the minimum or maximum value of the polynomial correlation curve
does not occur within the expanded data range. The minimum or maximum
value of the polynomial correlation curve is the point where the slope
of the curve equals zero. To determine if the minimum or maximum value
occurs within the expanded data range, follow the procedure described in
paragraphs (3)(i) through (iv) of this section.
(i) Determine if your polynomial correlation curve has a minimum or
maximum point by comparing the polynomial coefficient b2 to
zero. If b2 is less than zero, the curve has a maximum value.
If b2 is greater than zero, the curve has a minimum value.
(Note: If b2 equals zero, the correlation curve is linear.)
(ii) Calculate the minimum value using Equation 11-48.
[GRAPHIC] [TIFF OMITTED] TR25MR09.106

(iii) If your polynomial correlation curve has a minimum point, you
must compare the minimum value to the minimum PM CEMS response used to
develop the correlation curve. If the correlation curve minimum value is
less than or equal to the minimum PM CEMS response value, you can use
the polynomial correlation curve, provided the correlation curve also
satisfies all of the performance criteria specified in section 13.2 of
this specification. If the correlation curve minimum value is greater
than the minimum PM CEMS response value, you cannot use the polynomial
correlation curve to predict PM concentrations.
(iv) If your polynomial correlation curve has a maximum, the maximum
value must be greater than the allowable extrapolation limit. If your
source is not a low-emitting source, as defined in section 3.16 of this
specification, the allowable extrapolation limit is 125 percent of the
highest PM CEMS response used to develop the correlation curve. If your
source is a low-emitting source, the allowable extrapolation limit is
125 percent of the highest PM CEMS response used to develop the
correlation curve or the PM CEMS response that corresponds to 50 percent
of the emission limit, whichever is greater. If the polynomial
correlation curve maximum value is greater than the extrapolation limit,
and the correlation curve satisfies all of the performance criteria
specified in section 13.2 of this specification, you can use the
polynomial correlation curve to predict PM concentrations. If the
correlation curve maximum value is less than the extrapolation limit,
you cannot use the polynomial correlation curve to predict PM
concentrations.
(4) You may petition the Administrator for alternative solutions or
sampling recommendations if the correlation models described in section
12.3 of this specification do not satisfy the performance criteria
specified in section 13.2 of this specification.

13.0 What Are the Performance Criteria for My PM CEMS?

You must evaluate your PM CEMS based on the 7-day drift check, the
accuracy of the correlation, and the sampling periods and cycle/response
time.
13.1 What is the 7-day drift check performance specification? Your
daily PM CEMS internal drift checks must demonstrate that the average
daily drift of your PM CEMS does not deviate from the value of the
reference light, optical filter, Beta attenuation signal, or other
technology-suitable reference standard by more than 2 percent of the
upscale value. If your CEMS includes diluent and/or auxiliary monitors
(for temperature, pressure, and/or moisture) that are employed as a
necessary part of this performance specification, you must determine the
calibration drift separately for each ancillary monitor in terms of its
respective output (see the appropriate performance specification for the
diluent CEMS specification). None of the calibration drifts may exceed
their individual specification.
13.2 What performance criteria must my PM CEMS correlation satisfy?
Your PM CEMS correlation must meet each of the minimum specifications in
paragraphs (1), (2), and (3) of this section. Before confidence and
tolerance interval half range percentage calculations are made, you must
convert the emission limit to the appropriate units of your PM CEMS
measurement conditions using the average of emissions gas property

[[Page 728]]

values (e.g., diluent concentration, temperature, pressure, and
moisture) measured during the correlation test.
(1) The correlation coefficient must satisfy the criterion specified
in paragraph (1)(i) or (ii), whichever applies.
(i) If your source is not a low-emitting source, as defined in
section 3.16 of this specification, the correlation coefficient (r) must
be greater than or equal to 0.85.
(ii) If your source is a low-emitting source, as defined in section
3.16 of this specification, the correlation coefficient (r) must be
greater than or equal to 0.75.
(2) The confidence interval half range must satisfy the applicable
criterion specified in paragraph (2)(i), (ii), or (iii) of this section,
based on the type of correlation model.
(i) For linear or logarithmic correlations, the 95 percent
confidence interval half range at the mean PM CEMS response value from
the correlation test must be within 10 percent of the PM emission limit
value specified in the applicable regulation. Therefore, the CI%
calculated using Equation 11-10 must be less than or equal to 10
percent.
(ii) For polynomial correlations, the 95 percent confidence interval
half range at the PM CEMS response value from the correlation test that
corresponds to the minimum value for F must be within 10 percent of the
PM emission limit value specified in the applicable regulation.
Therefore, the CI% calculated using Equation 11-28 must be less than or
equal to 10 percent.
(iii) For exponential or power correlations, the 95 percent
confidence interval half range at the mean of the logarithm of the PM
CEMS response values from the correlation test must be within 10 percent
of the PM emission limit value specified in the applicable regulation.
Therefore, the CI% calculated using Equation 11-10 must be less than or
equal to 10 percent.
(3) The tolerance interval half range must satisfy the applicable
criterion specified in paragraph (3)(i), (ii), or (iii) of this section,
based on the type of correlation model.
(i) For linear or logarithmic correlations, the half range tolerance
interval with 95 percent confidence and 75 percent coverage at the mean
PM CEMS response value from the correlation test must be within 25
percent of the PM emission limit value specified in the applicable
regulation. Therefore, the TI% calculated using Equation 11-13 must be
less than or equal to 25 percent.
(ii) For polynomial correlations, the half range tolerance interval
with 95 percent confidence and 75 percent coverage at the PM CEMS
response value from the correlation test that corresponds to the minimum
value for F must be within 25 percent of the PM emission limit value
specified in the applicable regulation. Therefore, the TI% calculated
using Equation 11-32 must be less than or equal to 25 percent.
(iii) For exponential or power correlations, the half range
tolerance interval with 95 percent confidence and 75 percent coverage at
the mean of the logarithm of the PM CEMS response values from the
correlation test must be within 25 percent of the PM emission limit
value specified in the applicable regulation. Therefore, the TI%
calculated using Equation 11-13 must be less than or equal to 25
percent.
13.3 What are the sampling periods and cycle/response time? You must
document and maintain the response time and any changes in the response
time following installation.
(1) If you have a batch sampling PM CEMS, you must evaluate the
limits presented in paragraphs (1)(i) and (ii) of this section.
(i) The response time of your PM CEMS, which is equivalent to the
cycle time, must be no longer than 15 minutes. In addition, the delay
between the end of the sampling time and reporting of the sample
analysis must be no greater than 3 minutes. You must document any
changes in the response time following installation.
(ii) The sampling time of your PM CEMS must be no less than 30
percent of the cycle time. If you have a batch sampling PM CEMS,
sampling must be continuous except during pauses when the collected
pollutant on the capture media is being analyzed and the next capture
medium starts collecting a new sample.
13.4 What PM compliance monitoring must I do? You must report your
CEMS measurements in the units of the standard expressed in the
regulations (e.g., mg/dscm @ 7 percent oxygen, pounds per million Btu
(lb/mmBtu), etc.). You may need to install auxiliary data monitoring
equipment to convert the units reported by your PM CEMS into units of
the PM emission standard.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Which References Are Relevant to This Performance Specification?

16.1 Technical Guidance Document: Compliance Assurance Monitoring.
U.S. Environmental Protection Agency Office of Air Quality Planning and
Standards Emission Measurement Center. August 1998.
16.2 40 CFR 60, Appendix B, ``Performance Specification 2--
Specifications and Test Procedures for SO2, and
NOX, Continuous Emission Monitoring Systems in Stationary
Sources.''
16.3 40 CFR 60, Appendix B, ``Performance Specification 1--
Specification and Test Procedures for Opacity Continuous Emission
Monitoring Systems in Stationary Sources.''
16.4 40 CFR 60, Appendix A, ``Method 1--Sample and Velocity
Traverses for Stationary Sources.''

[[Page 729]]

16.5 ``Current Knowledge of Particulate Matter (PM) Continuous
Emission Monitoring.'' EPA-454/R-00-039. U.S. Environmental Protection
Agency, Research Triangle Park, NC. September 2000.
16.6 40 CFR 266, Appendix IX, section 2, ``Performance
Specifications for Continuous Emission Monitoring Systems.''
16.7 ISO 10155, ``Stationary Source Emissions--Automated Monitoring
of Mass Concentrations of Particles: Performance Characteristics, Test
Procedures, and Specifications.'' American National Standards Institute,
New York City. 1995.
16.8 Snedecor, George W. and Cochran, William G. (1989), Statistical
Methods, Eighth Edition, Iowa State University Press.
16.9 Wallis, W. A. (1951) ``Tolerance Intervals for Linear
Regression,'' in Second Berkeley Symposium on Mathematical Statistics
and Probability, ed. J. Neyman, Berkeley: University of California
Press, pp. 43-51.

17.0 What Reference Tables and Validation Data Are Relevant to PS-11?

Use the information in Table 1 for determining the confidence and
tolerance interval half ranges. Use Table 2 to record your 7-day drift
test data.

Table 1--Factors for Calculation of Confidence and Tolerance Interval Half Ranges
----------------------------------------------------------------------------------------------------------------
Tolerance interval with 75% coverage and 95%
Student's t, confidence level
df tdf -----------------------------------------------
vdf (95%) un' (75%) kT
----------------------------------------------------------------------------------------------------------------
3............................................... 3.182 2.920 1.266 3.697
4............................................... 2.776 2.372 1.247 2.958
5............................................... 2.571 2.089 1.233 2.576
6............................................... 2.447 1.915 1.223 2.342
7............................................... 2.365 1.797 1.214 2.183
8............................................... 2.306 1.711 1.208 2.067
9............................................... 2.262 1.645 1.203 1.979
10.............................................. 2.228 1.593 1.198 1.909
11.............................................. 2.201 1.551 1.195 1.853
12.............................................. 2.179 1.515 1.192 1.806
13.............................................. 2.160 1.485 1.189 1.766
14.............................................. 2.145 1.460 1.186 1.732
15.............................................. 2.131 1.437 1.184 1.702
16.............................................. 2.120 1.418 1.182 1.676
17.............................................. 2.110 1.400 1.181 1.653
18.............................................. 2.101 1.384 1.179 1.633
19.............................................. 2.093 1.370 1.178 1.614
20.............................................. 2.086 1.358 1.177 1.597
21.............................................. 2.080 1.346 1.175 1.582
22.............................................. 2.074 1.335 1.174 1.568
23.............................................. 2.069 1.326 1.173 1.555
24.............................................. 2.064 1.316 1.172 1.544
25.............................................. 2.060 1.308 1.172 1.533
26.............................................. 2.056 1.300 1.171 1.522
27.............................................. 2.052 1.293 1.170 1.513
28.............................................. 2.048 1.286 1.170 1.504
29.............................................. 2.045 1.280 1.169 1.496
30.............................................. 2.042 1.274 1.168 1.488
31.............................................. 2.040 1.268 1.168 1.481
32.............................................. 2.037 1.263 1.167 1.474
33.............................................. 2.035 1.258 1.167 1.467
34.............................................. 2.032 1.253 1.166 1.461
35.............................................. 2.030 1.248 1.166 1.455
36.............................................. 2.028 1.244 1.165 1.450
37.............................................. 2.026 1.240 1.165 1.444
38.............................................. 2.024 1.236 1.165 1.439
39.............................................. 2.023 1.232 1.164 1.435
40.............................................. 2.021 1.228 1.164 1.430
41.............................................. 2.020 1.225 1.164 1.425
42.............................................. 2.018 1.222 1.163 1.421
43.............................................. 2.017 1.218 1.163 1.417
44.............................................. 2.015 1.215 1.163 1.413
45.............................................. 2.014 1.212 1.163 1.410
46.............................................. 2.013 1.210 1.162 1.406
47.............................................. 2.012 1.207 1.162 1.403
48.............................................. 2.011 1.204 1.162 1.399
49.............................................. 2.010 1.202 1.162 1.396
50.............................................. 2.009 1.199 1.161 1.393
51.............................................. 2.008 1.197 1.161 1.390
52.............................................. 2.007 1.195 1.161 1.387

[[Page 730]]

53.............................................. 2.006 1.192 1.161 1.384
54.............................................. 2.005 1.190 1.161 1.381
55.............................................. 2.004 1.188 1.160 1.379
56.............................................. 2.003 1.186 1.160 1.376
57.............................................. 2.002 1.184 1.160 1.374
58.............................................. 2.002 1.182 1.160 1.371
59.............................................. 2.001 1.180 1.160 1.369
60.............................................. 2.000 1.179 1.160 1.367
----------------------------------------------------------------------------------------------------------------
References 16.8 (t values) and 16.9 (vdf and un' values).

Table 2--7-Day Drift Test Data
----------------------------------------------------------------------------------------------------------------
Zero drift
Zero drift day # Date and time Zero check value PM CEMS response Difference (RCEMS- ((RCEMS-RL) /RU)
(RL) (RCEMS) RL) x 100
----------------------------------------------------------------------------------------------------------------
1
----------------------------------------------------------------------------------------------------------------
2
----------------------------------------------------------------------------------------------------------------
3
----------------------------------------------------------------------------------------------------------------
4
----------------------------------------------------------------------------------------------------------------
5
----------------------------------------------------------------------------------------------------------------
6
----------------------------------------------------------------------------------------------------------------
7
----------------------------------------------------------------------------------------------------------------

Upscale drift
Upscale drift day Date and time Upscale check PM CEMS response Difference (RCEMS- ((RCEMS-RU)/RU) x
# value (RU) (RCEMS) RU) 100%
----------------------------------------------------------------------------------------------------------------
1
----------------------------------------------------------------------------------------------------------------
2
----------------------------------------------------------------------------------------------------------------
3
----------------------------------------------------------------------------------------------------------------
4
----------------------------------------------------------------------------------------------------------------
5
----------------------------------------------------------------------------------------------------------------
6
----------------------------------------------------------------------------------------------------------------
7
----------------------------------------------------------------------------------------------------------------

Performance Specification 12A--Specifications and Test Procedures for
Total Vapor Phase Mercury Continuous Emission Monitoring Systems in
Stationary Sources

1.0 Scope and Application

1.1 Analyte. The analyte measured by these procedures and
specifications is total vapor phase mercury (Hg) in the flue gas, which
represents the sum of elemental Hg (Hg[deg], CAS Number 7439-97-6) and
oxidized forms of gaseous Hg (Hg⁺²), in concentration units
of micrograms per cubic meter (g/m\3\).
1.2 Applicability.
1.2.1 This specification is for evaluating the acceptability of
total vapor phase Hg continuous emission monitoring systems (CEMS)
installed at stationary sources at the time of or soon after
installation and whenever specified in the regulations. The Hg CEMS must
be capable of measuring the total concentration in g/m\3\ of
vapor phase Hg, regardless of speciation, and recording that
concentration at standard conditions on a wet or dry basis. These
specifications do not address measurement of particle bound Hg.

[[Page 731]]

1.2.2 This specification is not designed to evaluate an installed
CEMS's performance over an extended period of time nor does it identify
specific calibration techniques and auxiliary procedures to assess the
CEMS's performance. The source owner or operator, however, is
responsible to calibrate, maintain, and operate the CEMS properly. The
Administrator may require, under section 114 of the Clean Air Act, the
operator to conduct CEMS performance evaluations at other times besides
the initial performance evaluation test. See Sec. Sec. 60.13(c) and
63.8(e)(1).
1.2.3 Mercury monitoring approaches not entirely suited to these
specifications may be approvable under the alternative monitoring or
alternative test method provisions of Sec. 60.13(i) and Sec. 63.8(f)
or Sec. 60.8(b)(3) and Sec. 63.7(f), respectively.

2.0 Summary of Performance Specification

Procedures for determining CEMS relative accuracy, linearity, and
calibration drift are outlined. CEMS installation and measurement
location specifications, data reduction procedures, and performance
criteria are included.

3.0 Definitions

3.1 Continuous Emission Monitoring System (CEMS) means the total
equipment required to measure a pollutant concentration. The system
generally consists of the following three major subsystems:
3.2 Sample Interface means that portion of the CEMS used for one or
more of the following: sample acquisition, sample transport, sample
conditioning, and protection of the monitor from the effects of the
stack effluent.
3.3 Hg Analyzer means that portion of the Hg CEMS that measures the
total vapor phase Hg mass concentration and generates a proportional
output.
3.4 Data Recorder means that portion of the CEMS that provides a
permanent electronic record of the analyzer output. The data recorder
may provide automatic data reduction and CEMS control capabilities.
3.5 Span Value means the measurement range as specified in the
applicable regulation or other requirement. If the span is not specified
in the applicable regulation or other requirement, then it must be a
value approximately equivalent to two times the emission standard.
Unless otherwise specified, the span value may be rounded up to the
nearest multiple of 10.
3.6 Measurement Error Test means a test procedure in which the
accuracy of the concentrations measured by a CEMS at three or more
points over its measurement range is evaluated using reference gases.
For Hg CEMS, elemental and oxidized Hg (Hg\0\ and mercuric chloride,
HgCl2) gas standards of known concentration are used for this
procedure.
3.7 Measurement Error (ME) means the absolute value of the
difference between the concentration indicated by the CEMS and the known
concentration of a reference gas, expressed as a percentage of the span
value, when the entire CEMS, including the sampling interface, is
challenged.
3.8 Calibration Drift (CD) means the absolute value of the
difference between the CEMS output response and either an upscale Hg
reference gas or a zero-level Hg reference gas, expressed as a
percentage of the span value, when the entire CEMS, including the
sampling interface, is challenged after a stated period of operation
during which no unscheduled maintenance or repair took place.
3.9 Relative Accuracy Test Procedure means a test procedure
consisting of at least nine test runs, in which the accuracy of the
concentrations measured by a CEMS is evaluated by comparison against
concurrent measurements made with a reference method (RM). Relative
accuracy tests repeated on a regular, on-going basis are referred to as
relative accuracy test audits or RATAs.
3.10 Relative Accuracy (RA) means the absolute mean difference
between the pollutant concentrations determined by the CEMS and the
values determined by the RM plus the 2.5 percent error confidence
coefficient of a series of tests divided by the mean of the RM tests.
Alternatively, for sources with an average RM concentration less than
5.0 micrograms per standard cubic meter (g/scm), the RA may be
expressed as the absolute value of the difference between the mean CEMS
and RM values.

4.0 Interferences [Reserved]

5.0 Safety

The procedures required under this performance specification may
involve hazardous materials, operations, and equipment. This performance
specification may not address all of the safety problems associated with
these procedures. It is the responsibility of the user to establish
appropriate safety and health practices and determine the applicable
regulatory limitations prior to performing these procedures. The CEMS
user's manual and materials recommended by the RM should be consulted
for specific precautions to be taken.

6.0 Equipment and Supplies

6.1 CEMS Equipment Specifications.
6.1.1 Data Recorder Scale. The Hg CEMS data recorder output range
must include the full range of expected Hg concentration values in the
gas stream to be sampled including zero and the span value.
6.1.2 The Hg CEMS design should also provide for the determination
of CD and ME at

[[Page 732]]

a zero value (zero to 20 percent of the span value) and at upscale
values (between 50 and 100 percent of the span value). The Hg CEMS must
be constructed to permit the introduction of known concentrations of Hg
and HgCl2 separately into the sampling system of the CEMS
immediately preceding the sample extraction filtration system such that
the entire CEMS can be challenged.
6.2 Reference Gas Delivery System. The reference gas delivery system
must be designed so that the flowrate exceeds the sampling system flow
requirements of the CEMS and that the gas is delivered to the CEMS at
atmospheric pressure.
6.3 Other equipment and supplies, as needed by the reference method
used for the Relative Accuracy Test Procedure. See section 8.6.2.

7.0 Reagents and Standards

7.1 Reference Gases. Reference gas standards are required for both
elemental and oxidized Hg (Hg and mercuric chloride, HgCl2).
The use of National Institute of Standards and Technology (NIST)-
traceable standards and reagents is required. The following gas
concentrations are required.
7.1.1 Zero-level. 0 to 20 percent of the span value.
7.1.2 Mid-level. 50 to 60 percent of the span value.
7.1.3 High-level. 80 to 100 percent of the span value.
7.2 Reference gas standards may also be required for the reference
methods. See section 8.6.2.

8.0 Performance Specification Test Procedure

8.1 Installation and Measurement Location Specifications.
8.1.1 CEMS Installation. Install the CEMS at an accessible location
downstream of all pollution control equipment. Place the probe outlet or
other sampling interface at a point or location in the stack (or vent)
representative of the stack gas concentration of Hg. Since the Hg CEMS
sample system normally extracts gas from a single point in the stack, a
location that has been shown to be free of stratification for Hg or,
alternatively, SO2 is recommended. If the cause of failure to
meet the RA test requirement is determined to be the measurement
location and a satisfactory correction technique cannot be established,
the Administrator may require the CEMS to be relocated. Measurement
locations and points or paths that are most likely to provide data that
will meet the RA requirements are described in sections 8.1.2 and 8.1.3
below.
8.1.2 Measurement Location. The measurement location should be (1)
at least two equivalent diameters downstream of the nearest control
device, point of pollutant generation or other point at which a change
of pollutant concentration may occur, and (2) at least half an
equivalent diameter upstream from the effluent exhaust. The equivalent
duct diameter is calculated according to Method 1 in appendix A-1 to
this part.
8.1.3 Hg CEMS Sample Extraction Point. Use a sample extraction point
either (1) no less than 1.0 meter from the stack or duct wall, or (2)
within the centroidal velocity traverse area of the stack or duct cross
section. This does not apply to cross-stack, in-situ measurement
systems.
8.2 Measurement Error (ME) Test Procedure. Sequentially inject each
of at least three elemental Hg reference gases (zero, mid-level, and
high level, as defined in section 7.1), three times each for a total of
nine injections. Inject the gases in such a manner that the entire CEMS
is challenged. Do not inject the same gas concentration twice in
succession. At each reference gas concentration, determine the average
of the three CEMS responses and subtract the average response from the
reference gas value. Calculate the measurement error (ME) using Equation
12-1 by expressing the absolute value of the difference between the
average CEMS response (A) and the reference gas value (R) as a
percentage of the span (see example data sheet in Figure 12A-1). For
each elemental Hg reference gas, the absolute value of the difference
between the CEMS response and the reference value must not exceed 5
percent of the span value. If this specification is not met, identify
and correct the problem before proceeding. Repeat the measurement error
test procedure using oxidized Hg reference gases. For each oxidized Hg
reference gas, the absolute value of the difference between the CEMS
response and the reference value shall not exceed 10 percent of the span
value. If this specification is not met, identify and correct the
problem before proceeding.
[GRAPHIC] [TIFF OMITTED] TR09SE10.009

8.3 Seven-Day Calibration Drift (CD) Test Procedure.
8.3.1 CD Test Period. While the affected facility is operating
normally, or as specified

[[Page 733]]

in an applicable regulation, determine the magnitude of the CD once each
day (at 24-hour intervals, to the extent practicable) for 7 consecutive
unit operating days according to the procedures in sections 8.3.2 and
8.3.3. The 7 consecutive unit operating days need not be 7 consecutive
calendar days. Use either Hg[deg] or HgCl2 standards for this
test.
8.3.2 The purpose of the CD measurement is to verify the ability of
the CEMS to conform to the established CEMS response used for
determining emission concentrations or emission rates. Therefore, if
periodic automatic or manual adjustments are made to the CEMS zero and
upscale response settings, conduct the CD test immediately before these
adjustments, or conduct it in such a way that the CD can be determined.
8.3.3 Conduct the CD test using the zero gas specified and either
the mid-level or high-level gas as specified in section 7.1.
Sequentially introduce the reference gases to the CEMS at the sampling
system of the CEMS immediately preceding the sample extraction
filtration system. Record the CEMS response (A) for each reference gas
and, using Equation 12A-2, subtract the corresponding reference value
(R) from the CEMS value, and express the absolute value of the
difference as a percentage of the span value (see also example data
sheet in Figure 12A-2). For each reference gas, the absolute value of
the difference between the CEMS response and the reference value must
not exceed 5 percent of the span value. If these specifications are not
met, identify and correct the problem before proceeding.
[GRAPHIC] [TIFF OMITTED] TR09SE10.010

8.4 Relative Accuracy (RA) Test Procedure.
8.4.1 RA Test Period. Conduct the RA test according to the procedure
given in sections 8.4.2 through 8.4.6 while the affected facility is
operating normally, or as specified in an applicable subpart. The RA
test may be conducted during the CD test period.
8.4.2 Reference Methods (RM). Unless otherwise specified in an
applicable subpart of the regulations, use Method 29, Method 30A, or
Method 30B in appendix A-8 to this part or American Society of Testing
and Materials (ASTM) Method D6784-02 (incorporated by reference, see
Sec. 60.17) as the RM for Hg concentration. For Method 29 and ASTM
Method D6784-02 only, the filterable portion of the sample need not be
included when making comparisons to the CEMS results. When Method 29,
Method 30B, or ASTM D6784-02 is used, conduct the RM test runs with
paired or duplicate sampling systems and use the average of the vapor
phase Hg concentrations measured by the two trains. When Method 30A is
used, paired sampling systems are not required. If the RM and CEMS
measure on a different moisture basis, data derived with Method 4 in
appendix A-3 to this part must also be obtained during the RA test.
8.4.3 Sampling Strategy for RM Tests. Conduct the RM tests in such a
way that they will yield results representative of the emissions from
the source and can be compared to the CEMS data. The RM and CEMS
locations need not be immediately adjacent. Locate the RM measurement
points in accordance with section 8.1.3 of Performance Specification 2
(PS 2) in this appendix. It is preferable to conduct moisture
measurements (if needed) and Hg measurements simultaneously, although
moisture measurements that are taken within an hour of the Hg
measurements may be used to adjust the Hg concentrations to a consistent
moisture basis. In order to correlate the CEMS and RM data properly,
note the beginning and end of each RM test period for each paired RM run
(including the exact time of day) on the CEMS chart recordings or other
permanent record of output.
8.4.4 Number and Length of RM Test Runs. Conduct a minimum of nine
RM test runs. When Method 29, Method 30B, or ASTM D6784-02 is used, only
test runs for which the paired RM trains meet the relative deviation
criteria (RD) of this PS must be used in the RA calculations. In
addition, for Method 29 and ASTM D6784-02, use a minimum sample time of
2 hours and for Methods 30A and 30B use a minimum sample time of 30
minutes.
Note: More than nine sets of RM test runs may be performed. If this
option is chosen, RM test run results may be excluded so long as the
total number of RM test run results used to determine the CEMS RA is
greater than or equal to nine. However, all data must be reported
including the excluded test run data.
8.4.5 Correlation of RM and CEMS Data. Correlate the CEMS and the RM
test data as to the time and duration by first determining from the CEMS
final output (the one used for reporting) the integrated average
pollutant concentration for each RM test period. Consider system
response time, if important, and confirm that the results are on

[[Page 734]]

a consistent moisture basis with the RM test. Then, compare each
integrated CEMS value against the corresponding RM value. When Method
29, Method 30B, or ASTM D6784-02 is used, compare each CEMS value
against the corresponding average of the paired RM values.
8.4.6 Paired RM Outliers.
8.4.6.1 When Method 29, Method 30B, or ASTM D6784-02 is used,
outliers are identified through the determination of relative deviation
(RD) of the paired RM tests. Data that do not meet the RD criteria must
be flagged as a data quality problem and may not be used in the
calculation of RA. The primary reason for performing paired RM sampling
is to ensure the quality of the RM data. The percent RD of paired data
is the parameter used to quantify data quality. Determine RD for paired
data points as follows:
[GRAPHIC] [TIFF OMITTED] TR09SE10.011

Where:

Ca and Cb are the Hg concentration values
determined from the paired samples.

8.4.6.2 The minimum performance criteria for RM Hg data is that RD
for any data pair must be 10 percent as long as the mean Hg
concentration is greater than 1.0 g/m\3\. If the mean Hg
concentration is less than or equal to 1.0 g/m\3\, the RD must
be 20 percent or 0.2 g/m\3\ absolute
difference. Pairs of RM data exceeding these RD criteria should be
eliminated from the data set used to develop a Hg CEMS correlation or to
assess CEMS RA.
8.4.7 Calculate the mean difference between the RM and CEMS values
in the units of micrograms per cubic meter (g/m\3\), the
standard deviation, the confidence coefficient, and the RA according to
the procedures in section 12.0.
8.5 Reporting. At a minimum (check with the appropriate EPA Regional
Office, State or local Agency for additional requirements, if any),
summarize in tabular form the results of the CD tests, the linearity
tests, and the RA test or alternative RA procedure, as appropriate.
Include all data sheets, calculations, charts (records of CEMS
responses), reference gas concentration certifications, and any other
information necessary to confirm that the CEMS meets the performance
criteria.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure

For Method 30A, sample collection and analysis are concurrent. For
the other RM, post-run sample analyses are performed. Refer to the RM
employed for specific analytical procedures.

12.0 Calculations and Data Analysis

Calculate and summarize the RA test results on a data sheet similar
to Figure 12A-3.
12.1 Consistent Basis. All data from the RM and CEMS must be
compared in units of micrograms per standard cubic meter (g/
scm), on a consistent and identified moisture basis. The values must be
standardized to 20 [deg]C, 760 mm Hg.
12.1.1 Moisture Correction (as applicable). If the RM and CEMS
measure Hg on a different moisture basis, they will need to be corrected
to a consistent basis. Use Equation 12A-4a to correct data from a wet
basis to a dry basis.
[GRAPHIC] [TIFF OMITTED] TR09SE10.012

Use Equation 12A-4b to correct data from a dry basis to a wet basis.
[GRAPHIC] [TIFF OMITTED] TR09SE10.013

[[Page 735]]

Where:

Bws is the moisture content of the flue gas from Method 4,
expressed as a decimal fraction (e.g., for 8.0 percent
H2O, Bws= 0.08).

12.2 Arithmetic Mean. Calculate d, the arithmetic mean of the
differences (di) of a data set as follows:
[GRAPHIC] [TIFF OMITTED] TR09SE10.014

Where:

n = Number of data points.

12.3 Standard Deviation. Calculate the standard deviation,
Sd, as follows:
[GRAPHIC] [TIFF OMITTED] TR09SE10.015

12.3 Confidence Coefficient (CC). Calculate the 2.5 percent error
confidence coefficient (one-tailed), CC, as follows:
[GRAPHIC] [TIFF OMITTED] TR09SE10.016

12.4 Relative Accuracy. Calculate the RA of a set of data as
follows:
[GRAPHIC] [TIFF OMITTED] TR09SE10.017

[[Page 736]]

Where:

d = Absolute value of the mean of the differences (from Equation 12A-
5)
CC = Absolute value of the confidence coefficient (from Equation 12A-
7)
RM = Average reference method value

13.0 Method Performance

13.1 Measurement Error (ME). For Hg⁰, the ME must not
exceed 5 percent of the span value at the zero-, mid-, and high-level
reference gas concentrations. For HgCl2, the ME must not
exceed 10 percent of the span value at the zero-, mid-, and high-level
reference gas concentrations.
13.2 Calibration Drift (CD). The CD must not exceed 5 percent of the
span value on any of the 7 days of the CD test.
13.3 Relative Accuracy (RA). The RA of the CEMS must be no greater
than 20 percent of the mean value of the RM test data in terms of units
of g/scm. Alternatively, if the mean RM is less than 5.0
g/scm, the results are acceptable if the absolute value of the
difference between the mean RM and CEMS values does not exceed 1.0
g/scm.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures [Reserved]

17.0 Bibliography

17.1 40 CFR part 60, appendix B, ``Performance Specification 2--
Specifications and Test Procedures for SO2 and NOX
Continuous Emission Monitoring Systems in Stationary Sources.''
17.2 40 CFR part 60, appendix A, ``Method 29--Determination of
Metals Emissions from Stationary Sources.''
17.3 40 CFR part 60, appendix A, ``Method 30A--Determination of
Total Vapor Phase Mercury Emissions From Stationary Sources
(Instrumental Analyzer Procedure).
17.4 40 CFR part 60, appendix A, ``Method 30B--Determination of
Total Vapor Phase Mercury Emissions From Coal-Fired Combustion Sources
Using Carbon Sorbent Traps.''
17.5 ASTM Method D6784-02, ``Standard Test Method for Elemental,
Oxidized, Particle-Bound and Total Mercury in Flue Gas Generated from
Coal-Fired Stationary Sources (Ontario Hydro Method).''

18.0 Tables and Figures

Table 12A-1--T-Values
--------------------------------------------------------------------------------------------------------------------------------------------------------
n\a\ t0.975 n\a\ t0.975 n\a\ t0.975
--------------------------------------------------------------------------------------------------------------------------------------------------------
2...................................... 12.706 7........................ 2.447 12....................... 2.201
3...................................... 4.303 8........................ 2.365 13....................... 2.179
4...................................... 3.182 9........................ 2.306 14....................... 2.160
5...................................... 2.776 10....................... 2.262 15....................... 2.145
6...................................... 2.571 11....................... 2.228 16....................... 2.131
--------------------------------------------------------------------------------------------------------------------------------------------------------
\a\ The values in this table are already corrected for n-1 degrees of freedom. Use n equal to the number of individual values.

Figure 12A-1--ME Determination
----------------------------------------------------------------------------------------------------------------
Reference gas CEMS measured Absolute
value (g/ value (g/ difference ME (% of
Date Time m\3\) m\3\) (g/m\3\) span
value)
----------------------------------------------------------------------------------------------------------------
Zero level
----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------

[[Page 737]]

Figure 12A-2--7-Day Calibration Drift Determination
----------------------------------------------------------------------------------------------------------------
Reference gas CEMS measured Absolute
value (g/ value (g/ difference CD (% of
Date Time m\3\) m\3\) (g/m\3\) span
value)
----------------------------------------------------------------------------------------------------------------
Zero level
----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------
Upscale
(Mid or High)
----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------

[[Page 738]]

Figure 12A-3--Relative Accuracy Test Data
--------------------------------------------------------------------------------------------------------------------------------------------------------
RM value (g/m\3\) m>g/m\3\) (g/m\3\) Run used? (Yes/ RD\1\
No)
--------------------------------------------------------------------------------------------------------------------------------------------------------
1 .............. .............. .............. .................. .................. ................. ..............
--------------------------------------------------------------------------------------------------------------------------------------------------------
2 .............. .............. .............. .................. .................. ................. ..............
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3 .............. .............. .............. .................. .................. ................. ..............
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4 .............. .............. .............. .................. .................. ................. ..............
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5 .............. .............. .............. .................. .................. ................. ..............
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6 .............. .............. .............. .................. .................. ................. ..............
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7 .............. .............. .............. .................. .................. ................. ..............
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8 .............. .............. .............. .................. .................. ................. ..............
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9 .............. .............. .............. .................. .................. ................. ..............
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10 .............. .............. .............. .................. .................. ................. ..............
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11 .............. .............. .............. .................. .................. ................. ..............
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12 .............. .............. .............. .................. .................. ................. ..............
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Average Values .................. ..................
--------------------------------------------------------------------------------------------------------------------------------------------------------
Arithmetic Mean Difference:
Standard Deviation:
Confidence Coefficient:
T-Value:
% Relative Accuracy:
| (RM)avg - (CEMS)avg | :
--------------------------------------------------------------------------------------------------------------------------------------------------------
\1\ Calculate the RD only if paired samples are taken using RM 30B, RM 29, or ASTM 6784-08. Express RD as a percentage or, for very low RM
concentrations (1.0 g/m\3\), as the absolute difference between Ca and Cb.

[[Page 739]]

Performance Specification 12B--Specifications and Test Procedures for
Monitoring Total Vapor Phase Mercury Emissions From Stationary Sources
Using a Sorbent Trap Monitoring System

1.0 Scope and Application

The purpose of Performance Specification 12B (PS 12B) is to
establish performance benchmarks for, and to evaluate the acceptability
of, sorbent trap monitoring systems used to monitor total vapor-phase
mercury (Hg) emissions in stationary source flue gas streams. These
monitoring systems involve continuous repetitive in-stack sampling using
paired sorbent media traps with periodic analysis of the time-integrated
samples. Persons using PS 12B should have a thorough working knowledge
of Methods 1, 2, 3, 4, 5 and 30B in appendices A-1 through A-3 and A-8
to this part.
1.1 Analyte. The analyte measured by these procedures and
specifications is total vapor phase Hg in the flue gas, which represents
the sum of elemental Hg (Hg\0\, CAS Number 7439-97-6) and gaseous forms
of oxidized Hg (i.e., Hg⁺²) in mass concentration units of
micrograms per dry standard cubic meter (g/dscm).

1.2 Applicability

1.2.1 These procedures are only intended for use under relatively
low particulate conditions (e.g., monitoring after all pollution control
devices). This specification is for evaluating the acceptability of
total vapor phase Hg sorbent trap monitoring systems installed at
stationary sources at the time of, or soon after, installation and
whenever specified in the regulations. The Hg monitoring system must be
capable of measuring the total concentration of vapor phase Hg
(regardless of speciation), in units of g/dscm.
1.2.2 This specification contains routine procedures and
specifications designed to evaluate an installed sorbent trap monitoring
system's performance over time; Procedure 5 of appendix F to this part
contains additional procedures and specifications which may be required
for long term operation. In addition, the source owner or operator is
responsible to calibrate, maintain, and operate the monitoring system
properly. The Administrator may require the owner or operator, under
section 114 of the Clean Air Act, to conduct performance evaluations at
other times besides the initial test to evaluate the CEMS performance.
See Sec. 60.13(c) and 63.8(e)(1).

2.0 Principle

Known volumes of flue gas are continuously extracted from a stack or
duct through paired, in-stack, pre-spiked sorbent media traps at
appropriate nominal flow rates. The sorbent traps in the sampling system
are periodically exchanged with new ones, prepared for analysis as
needed, and analyzed by any technique that can meet the performance
criteria. For quality-assurance purposes, a section of each sorbent trap
is spiked with Hg\0\ prior to sampling. Following sampling, this section
is analyzed separately and a specified minimum percentage of the spike
must be recovered. Paired train sampling is required to determine method
precision.

3.0 Definitions

3.1 Sorbent Trap Monitoring System means the total equipment
required for the collection of gaseous Hg samples using paired three-
partition sorbent traps.
3.2 Relative Accuracy Test Procedure means a test procedure
consisting of at least nine runs, in which the accuracy of the total
vapor phase Hg concentrations measured by the sorbent trap monitoring
system is evaluated by comparison against concurrent measurements made
with a reference method (RM). Relative accuracy tests repeated on a
regular, on-going basis are referred to as relative accuracy test audits
or RATAs.
3.3 Relative Accuracy (RA) means the absolute mean difference
between the pollutant (Hg) concentrations determined by the sorbent trap
monitoring system and the values determined by the reference method (RM)
plus the 2.5 percent error confidence coefficient of a series of tests
divided by the mean of the RM tests. Alternatively, for low
concentration sources, the RA may be expressed as the absolute value of
the difference between the mean sorbent trap monitoring system and RM
values.
3.4 Relative Deviation (RD) means the absolute difference of the Hg
concentration values obtained with a pair of sorbent traps divided by
the sum of those concentrations, expressed as a percentage. RD is used
to assess the precision of the sorbent trap monitoring system.
3.5 Spike Recovery means the mass of Hg recovered from the spiked
trap section, expressed as a percentage of the amount spiked. Spike
recovery is used to assess sample matrix interference.

4.0 Interferences [Reserved]

5.0 Safety

[[Page 740]]

6.0 Equipment and Supplies

6.1 Sorbent Trap Monitoring System Equipment Specifications.
6.1.1 Monitoring System. The equipment described in Method 30B in
appendix A-8 to this part must be used to continuously sample for Hg
emissions, with the substitution of three-section traps in place of two-
section traps, as described below. A typical sorbent trap monitoring
system is shown in Figure 12B-1.
6.1.2 Three-Section Sorbent Traps. The sorbent media used to collect
Hg must be configured in traps with three distinct and identical
segments or sections, connected in series, to be separately analyzed.
section 1 is designated for primary capture of gaseous Hg. section 2 is
designated as a backup section for determination of vapor-phase Hg
breakthrough. section 3 is designated for quality assurance/quality
control (QA/QC) purposes. section 3 must be spiked with a known amount
of gaseous Hg\0\ prior to sampling and later analyzed to determine the
spike (and hence sample) recovery efficiency.
[GRAPHIC] [TIFF OMITTED] TR09SE10.005

6.1.3 Gaseous Hg\0\ Sorbent Trap Spiking System. A known mass of
gaseous Hg\0\ must be spiked onto section 3 of each sorbent trap prior
to sampling. Any approach capable of quantitatively delivering known
masses of Hg\0\ onto sorbent traps is acceptable. Several technologies
or devices are available to meet this objective. Their practicality is a
function of Hg mass spike levels. For low levels, NIST-certified or
NIST-traceable gas generators or tanks may be suitable, but will likely
require long preparation times. A more practical, alternative system,
capable of delivering almost any mass required, employs NIST-certified
or NIST-traceable Hg salt solutions (e.g.,
Hg(NO3)2). With this system, an aliquot of known
volume and concentration is added to a reaction vessel containing a
reducing agent (e.g., stannous chloride); the Hg salt solution is
reduced to Hg\0\ and purged onto section 3 of the sorbent trap by using
an impinger sparging system.

[[Page 741]]

6.1.4 Sample Analysis Equipment. Any analytical system capable of
quantitatively recovering and quantifying total gaseous Hg from sorbent
media is acceptable provided that the analysis can meet the performance
criteria in Table 12B-1 in section 9 of this performance specification.
Candidate recovery techniques include leaching, digestion, and thermal
desorption. Candidate analytical techniques include ultraviolet atomic
fluorescence (UV AF); ultraviolet atomic absorption (UV AA), with and
without gold trapping; and in-situ X-ray fluorescence (XRF).

7.0 Reagents and Standards

Only NIST-certified or NIST-traceable calibration gas standards and
reagents must be used for the tests and procedures required under this
performance specification. The sorbent media may be any collection
material (e.g., carbon, chemically treated filter, etc.) capable of
quantitatively capturing and recovering for subsequent analysis, all
gaseous forms of Hg in the emissions from the intended application.
Selection of the sorbent media must be based on the material's ability
to achieve the performance criteria contained in this method as well as
the sorbent's vapor phase Hg capture efficiency for the emissions matrix
and the expected sampling duration at the test site.

8.0 Performance Specification Test Procedure

8.1 Installation and Measurement Location Specifications.
8.1.1 Selection of Monitoring Site. Sampling site information should
be obtained in accordance with Method 1 in appendix A-1 to this part.
Place the probe inlet at a point or location in the stack (or vent)
downstream of all pollution control equipment and representative of the
stack gas concentration of Hg. A location that has been shown to be free
of stratification for Hg or, alternatively, SO2 is
recommended. An estimation of the expected stack Hg concentration is
required to establish a target sample flow rate, total gas sample
volume, and the mass of Hg\0\ to be spiked onto section 3 of each
sorbent trap.
8.1.2 Pre-sampling Spiking of Sorbent Traps. Based on the estimated
Hg concentration in the stack, the target sample rate and the target
sampling duration, calculate the expected mass loading for section 1 of
each sorbent trap (see section 12.1 of this performance specification).
The pre-sampling spike to be added to section 3 of each sorbent trap
must be within 50 percent of the expected section 1 mass loading. Spike
section 3 of each sorbent trap at this level, as described in section
6.1.3 of this performance specification. For each sorbent trap, keep a
record of the mass of Hg\0\ added to section 3. This record must
include, at a minimum, the identification number of the trap, the date
and time of the spike, the name of the analyst performing the procedure,
the method of spiking, the mass of Hg \0\ added to section 3 of the trap
(g), and the supporting calculations.
8.1.3 Pre-monitoring Leak Check. Perform a leak check with the
sorbent traps in place in the sampling system. Draw a vacuum in each
sample train. Adjust the vacuum in each sample train to \15'' Hg. Use
the gas flow meter to determine leak rate. The leakage rate must not
exceed 4 percent of the target sampling rate. Once the leak check passes
this criterion, carefully release the vacuum in the sample train, then
seal the sorbent trap inlet until the probe is ready for insertion into
the stack or duct.
8.1.4 Determination of Flue Gas Characteristics. Determine or
measure the flue gas measurement environment characteristics (gas
temperature, static pressure, gas velocity, stack moisture, etc.) in
order to determine ancillary requirements such as probe heating
requirements (if any), sampling rate, proportional sampling conditions,
moisture management, etc.
8.2 Monitoring.
8.2.1 System Preparation and Initial Data Recording. Remove the plug
from the end of each sorbent trap and store each plug in a clean sorbent
trap storage container. Remove the stack or duct port cap and insert the
probe(s) with the inlet(s) aligned perpendicular to the stack gas flow.
Secure the probe(s) and ensure that no leakage occurs between the duct
and environment. Record initial data including the sorbent trap ID,
start time, starting gas flow meter readings, initial temperatures, set
points, and any other appropriate information.
8.2.2 Flow Rate Control. Set the initial sample flow rate at the
target value from section 8.1.1 of this performance specification. Then,
for every operating hour during the sampling period, record the date and
time, the sample flow rate, the gas flow meter reading, the stack
temperature (if needed), the flow meter temperatures (if needed),
temperatures of heated equipment such as the vacuum lines and the probes
(if heated), and the sampling system vacuum readings. Also, record the
stack gas flow rate and the ratio of the stack gas flow rate to the
sample flow rate. Adjust the sampling flow rate to maintain proportional
sampling, i.e., keep the ratio of the stack gas flow rate to sample flow
rate within 25 percent of the reference ratio from the first hour of
the data collection period (see section 12.2 of this performance
specification). The sample flow rate through a sorbent trap monitoring
system during any hour (or portion of an hour) that the unit is not
operating must be zero.

[[Page 742]]

8.2.3 Stack Gas Moisture Determination. If data from the sorbent
trap monitoring system will be used to calculate Hg mass emissions,
determine the stack gas moisture content using a continuous moisture
monitoring system or other means acceptable to the Administrator, such
as the ones described in Sec. 75.11(b) of this chapter. Alternatively,
for combustion of coal, wood, or natural gas in boilers only, a default
moisture percentage from Sec. 75.11(b) of this chapter may be used.
8.2.4 Essential Operating Data. Obtain and record any essential
operating data for the facility during the test period, e.g., the
barometric pressure for correcting the sample volume measured by a dry
gas meter to standard conditions. At the end of the data collection
period, record the final gas flow meter reading and the final values of
all other essential parameters.
8.2.5 Post-monitoring Leak Check. When the monitoring period is
completed, turn off the sample pump, remove the probe/sorbent trap from
the port and carefully re-plug the end of each sorbent trap. Perform a
leak check with the sorbent traps in place, at the maximum vacuum
reached during the monitoring period. Use the same general approach
described in section 8.1.3 of this performance specification. Record the
leakage rate and vacuum. The leakage rate must not exceed 4 percent of
the average sampling rate for the monitoring period. Following the leak
check, carefully release the vacuum in the sample train.
8.2.6 Sample Recovery. Recover each sampled sorbent trap by removing
it from the probe and seal both ends. Wipe any deposited material from
the outside of the sorbent trap. Place the sorbent trap into an
appropriate sample storage container and store/preserve it in an
appropriate manner.
8.2.7 Sample Preservation, Storage, and Transport. While the
performance criteria of this approach provide for verification of
appropriate sample handling, it is still important that the user
consider, determine, and plan for suitable sample preservation, storage,
transport, and holding times for these measurements. Therefore,
procedures in recognized voluntary consensus standards such as those in
ASTM D6911-03 ``Standard Guide for Packaging and Shipping Environmental
Samples for Laboratory Analysis'' should be followed for all samples.
8.2.8 Sample Custody. Proper procedures and documentation for sample
chain of custody are critical to ensuring data integrity. Chain of
custody procedures in recognized voluntary consensus standards such as
those in ASTM D4840-99 ``Standard Guide for Sample Chain-of-Custody
Procedures'' should be followed for all samples (including field samples
and blanks).
8.3 Relative Accuracy (RA) Test Procedure
8.3.1 For the initial certification of a sorbent trap monitoring
system, a RA Test is required. Follow the basic RA test procedures and
calculation methodology described in sections 8.4.1 through 8.4.7 and
12.4 of PS 12A in this appendix, replacing the term ``CEMS'' with
``sorbent trap monitoring system''.
8.3.2 Special Considerations. The type of sorbent material used in
the traps must be the same as that used for daily operation of the
monitoring system; however, the size of the traps used for the RA test
may be smaller than the traps used for daily operation of the system.
Spike the third section of each sorbent trap with elemental Hg, as
described in section 8.1.2 of this performance specification. Install a
new pair of sorbent traps prior to each test run. For each run, the
sorbent trap data must be validated according to the quality assurance
criteria in Table 12B-1 in section 9.0, below.
8.3.3 Acceptance Criteria. The RA of the sorbent trap monitoring
system must be no greater than 20 percent of the mean value of the RM
test data in terms of units of g/scm. Alternatively, if the RM
concentration is less than or equal to 5.0 g/scm, then the RA
results are acceptable if the absolute difference between the means of
the RM and sorbent trap monitoring system values does not exceed 1.0
g/scm.

9.0 Quality Assurance and Quality Control (QA/QC)

Table 12B-1 summarizes the QA/QC performance criteria that are used
to validate the Hg emissions data from a sorbent trap monitoring system.
Failure to achieve these performance criteria will result in
invalidation of Hg emissions data, except where otherwise noted.

Table 12B-1--QA/QC Criteria for Sorbent Trap Monitoring Systems
----------------------------------------------------------------------------------------------------------------
QA/QC test or specification Acceptance criteria Frequency Consequences if not met
----------------------------------------------------------------------------------------------------------------
Pre-test leak check.................. 4% of target Prior to monitoring.... Monitoring must not
sampling rate. commence until the
leak check is passed.

[[Page 743]]

Post-test leak check................. 4% of After monitoring....... Invalidate the data
average sampling rate. from the paired traps
or, if certain
conditions are met,
report adjusted data
from a single trap
(see Section 12.8.3).
Ratio of stack gas flow rate to No more than 5% of the Every hour throughout Invalidate the data
sample flow rate. hourly ratios or 5 monitoring period. from the paired traps
hourly ratios or, if certain
(whichever is less conditions are met,
restrictive) may report adjusted data
deviate from the from a single trap
reference ratio by (see Section 12.8.3).
more than 25%.
Sorbent trap section 2 breakthrough.. 5% of Every sample........... Invalidate the data
Section 1 Hg mass. from the paired traps
10% of or, if certain
Section 1 Hg mass if conditions are met,
average Hg report adjusted data
concentration is 0.5 g/ (see Section 12.8.3).
scm.
No criterion when Hg
concentration for trap
less than 10% of the
applicable emission
limit (must meet all
other QA/QC
specifications).
Paired sorbent trap agreement........ 10% Relative Every sample........... Either invalidate the
Deviation (RD) if the data from the paired
average concentration traps or report the
is > 1.0 g/ results from the trap
m\3\. with the higher Hg
20% RD if concentration.
the average
concentration is 1.0 g/
m\3\.
Results also acceptable
if absolute difference
between concentrations
from paired traps is
0.03
g/m\3\.
Spike Recovery Study................. Average recovery Prior to analyzing Field samples must not
between 85% and 115% field samples and be analyzed until the
for each of the 3 prior to use of new percent recovery
spike concentration sorbent media. criteria have been
levels. met.
Multipoint analyzer calibration...... Each analyzer reading On the day of analysis, Recalibrate until
within 10% of true before analyzing any successful.
value and r\2\ 0.99.
Analysis of independent calibration Within 10% of true Following daily Recalibrate and repeat
standard. value. calibration, prior to independent standard
analyzing field analysis until
samples. successful.
Spike recovery from section 3 of both 75-125% of spike amount Every sample........... Invalidate the data
sorbent traps. from the paired traps
or, if certain
conditions are met,
report adjusted data
from a single trap
(see Section 12.8.3).
Relative Accuracy.................... RA 20.0% of RA specification must Data from the system
RM mean value; or if be met for initial are invalid until a RA
RM mean value 5.0 g/scm,
absolute difference
between RM and sorbent
trap monitoring system
mean values 1.0 g/scm.
Gas flow meter calibration........... An initial calibration At 3 settings prior to Recalibrate meter at 3
factor (Y) has been initial use and at settings to determine
determined at 3 least quarterly at one a new value of Y.
settings; for mass setting thereafter.
flow meters, initial
calibration with stack
gas has been
performed. For
subsequent
calibrations, Y within
5% of average value
from the most recent 3-
point calibration.
Temperature sensor calibration....... Absolute temperature Prior to initial use Recalibrate; sensor may
measured by sensor and at least quarterly not be used until
within 1.5% of a thereafter. specification is met.
reference sensor.
Barometer calibration................ Absolute pressure Prior to initial use Recalibrate; instrument
measured by instrument and at least quarterly may not be used until
within 10 mm Hg of thereafter. specification is met.
reading with a NIST-
traceable barometer.
----------------------------------------------------------------------------------------------------------------

[[Page 744]]

10.0 Calibration and Standardization

10.1 Gaseous and Liquid Standards. Only NIST certified or NIST-
traceable calibration standards (i.e., calibration gases, solutions,
etc.) must be used for the spiking and analytical procedures in this
performance specification.
10.2 Gas Flow Meter Calibration. The manufacturer or supplier of the
gas flow meter should perform all necessary set-up, testing,
programming, etc., and should provide the end user with any necessary
instructions, to ensure that the meter will give an accurate readout of
dry gas volume in standard cubic meters for the particular field
application.
10.2.1 Initial Calibration. Prior to its initial use, a calibration
of the flow meter must be performed. The initial calibration may be done
by the manufacturer, by the equipment supplier, or by the end user. If
the flow meter is volumetric in nature (e.g., a dry gas meter), the
manufacturer, equipment supplier, or end user may perform a direct
volumetric calibration using any gas. For a mass flow meter, the
manufacturer, equipment supplier, or end user may calibrate the meter
using a bottled gas mixture containing 12 0.5% CO2, 7 0.5%
O2, and balance N2, or these same gases in
proportions more representative of the expected stack gas composition.
Mass flow meters may also be initially calibrated on-site, using actual
stack gas.
10.2.1.1 Initial Calibration Procedures. Determine an average
calibration factor (Y) for the gas flow meter, by calibrating it at
three sample flow rate settings covering the range of sample flow rates
at which the sorbent trap monitoring system typically operates. Either
the procedures in section 10.3.1 of Method 5 in appendix A-3 to this
part or the procedures in section 16 of Method 5 in appendix A-3 to this
part may be followed. If a dry gas meter is being calibrated, use at
least five revolutions of the meter at each flow rate.
10.2.1.2 Alternative Initial Calibration Procedures. Alternatively,
the initial calibration of the gas flow meter may be performed using a
reference gas flow meter (RGFM). The RGFM may be either: (1) A wet test
meter calibrated according to section 10.3.1 of Method 5 in appendix A-3
to this part; (2) A gas flow metering device calibrated at multiple flow
rates using the procedures in section 16 of Method 5 in appendix A-3 to
this part; or (3) A NIST-traceable calibration device capable of
measuring volumetric flow to an accuracy of 1 percent. To calibrate the
gas flow meter using the RGFM, proceed as follows: While the sorbent
trap monitoring system is sampling the actual stack gas or a compressed
gas mixture that simulates the stack gas composition (as applicable),
connect the RGFM to the discharge of the system. Care should be taken to
minimize the dead volume between the sample flow meter being tested and
the RGFM. Concurrently measure dry gas volume with the RGFM and the flow
meter being calibrated for a minimum of 10 minutes at each of three flow
rates covering the typical range of operation of the sorbent trap
monitoring system. For each 10-minute (or longer) data collection
period, record the total sample volume, in units of dry standard cubic
meters (dscm), measured by the RGFM and the gas flow meter being tested.
10.2.1.3 Initial Calibration Factor. Calculate an individual
calibration factor Yi at each tested flow rate from section 10.2.1.1 or
10.2.1.2 of this performance specification (as applicable), by taking
the ratio of the reference sample volume to the sample volume recorded
by the gas flow meter. Average the three Yi values, to determine Y, the
calibration factor for the flow meter. Each of the three individual
values of Yi must be within 0.02 of Y. Except as otherwise provided in
sections 10.2.1.4 and 10.2.1.5 of this performance specification, use
the average Y value from the three level calibration to adjust all
subsequent gas volume measurements made with the gas flow meter.
10.2.2 Initial On-Site Calibration Check. For a mass flow meter that
was initially calibrated using a compressed gas mixture, an on-site
calibration check must be performed before using the flow meter to
provide data. While sampling stack gas, check the calibration of the
flow meter at one intermediate flow rate typical of normal operation of
the monitoring system. Follow the basic procedures in section 10.2.1.1
or 10.2.1.2 of this performance specification. If the onsite calibration
check shows that the value of Yi, the calibration factor at the tested
flow rate, differs by more than 5 percent from the value of Y obtained
in the initial calibration of the meter, repeat the full 3-level
calibration of the meter using stack gas to determine a new value of Y,
and apply the new Y value to all subsequent gas volume measurements made
with the gas flow meter.
10.2.3 Ongoing Quality Control. Recalibrate the gas flow meter
quarterly at one intermediate flow rate setting representative of normal
operation of the monitoring system. Follow the basic procedures in
section 10.2.1.1 or 10.2.1.2 of this performance specification. If a
quarterly recalibration shows that the value of Yi, the calibration
factor at the tested flow rate, differs from the current value of Y by
more than 5 percent, repeat the full 3-level calibration of the meter to
determine a new value of Y, and apply the new Y value to all subsequent
gas volume measurements made with the gas flow meter.
10.3 Calibration of Thermocouples and Other Temperature Sensors. Use
the procedures and criteria in section 10.3 of Method 2 in appendix A-1
to this part to calibrate in-

[[Page 745]]

stack temperature sensors and thermocouples. Calibrations must be
performed prior to initial use and at least quarterly thereafter. At
each calibration point, the absolute temperature measured by the
temperature sensor must agree to within 1.5 percent of the temperature
measured with the reference sensor, otherwise the sensor may not
continue to be used.
10.4 Barometer Calibration. Calibrate the barometer against another
barometer that has a NIST-traceable calibration. This calibration must
be performed prior to initial use and at least quarterly thereafter. At
each calibration point, the absolute pressure measured by the barometer
must agree to within 10 mm Hg of the pressure measured by the NIST-
traceable barometer, otherwise the barometer may not continue to be
used.
10.5 Calibration of Other Sensors and Gauges. Calibrate all other
sensors and gauges according to the procedures specified by the
instrument manufacturer(s).
10.6 Analytical System Calibration. See section 11.1 of this
performance specification.

11.0 Analytical Procedures

The analysis of the Hg samples may be conducted using any instrument
or technology capable of quantifying total Hg from the sorbent media and
meeting the performance criteria in section 9 of this performance
specification.
11.1 Analyzer System Calibration. Perform a multipoint calibration
of the analyzer at three or more upscale points over the desired
quantitative range (multiple calibration ranges must be calibrated, if
necessary). The field samples analyzed must fall within a calibrated,
quantitative range and meet the necessary performance criteria. For
samples that are suitable for aliquotting, a series of dilutions may be
needed to ensure that the samples fall within a calibrated range.
However, for sorbent media samples that are consumed during analysis
(e.g., thermal desorption techniques), extra care must be taken to
ensure that the analytical system is appropriately calibrated prior to
sample analysis. The calibration curve range(s) should be determined
based on the anticipated level of Hg mass on the sorbent media.
Knowledge of estimated stack Hg concentrations and total sample volume
may be required prior to analysis. The calibration curve for use with
the various analytical techniques (e.g., UV AA, UV AF, and XRF) can be
generated by directly introducing standard solutions into the analyzer
or by spiking the standards onto the sorbent media and then introducing
into the analyzer after preparing the sorbent/standard according to the
particular analytical technique. For each calibration curve, the value
of the square of the linear correlation coefficient, i.e., r\2\, must be
0.99, and the analyzer response must be within 10 percent of
reference value at each upscale calibration point. Calibrations must be
performed on the day of the analysis, before analyzing any of the
samples. Following calibration, an independently prepared standard (not
from same calibration stock solution) must be analyzed. The measured
value of the independently prepared standard must be within 10 percent
of the expected value.
11.2 Sample Preparation. Carefully separate the three sections of
each sorbent trap. Combine for analysis all materials associated with
each section, i.e., any supporting substrate that the sample gas passes
through prior to entering a media section (e.g., glass wool,
polyurethane foam, etc.) must be analyzed with that segment.
11.3 Spike Recovery Study. Before analyzing any field samples, the
laboratory must demonstrate the ability to recover and quantify Hg from
the sorbent media by performing the following spike recovery study for
sorbent media traps spiked with elemental mercury. Using the procedures
described in sections 6.2 and 12.1 of this performance specification,
spike the third section of nine sorbent traps with gaseous Hg\0\, i.e.,
three traps at each of three different mass loadings, representing the
range of masses anticipated in the field samples. This will yield a 3 x
3 sample matrix. Prepare and analyze the third section of each spiked
trap, using the techniques that will be used to prepare and analyze the
field samples. The average recovery for each spike concentration must be
between 85 and 115 percent. If multiple types of sorbent media are to be
analyzed, a separate spike recovery study is required for each sorbent
material. If multiple ranges are calibrated, a separate spike recovery
study is required for each range.
11.4 Field Sample Analyses. Analyze the sorbent trap samples
following the same procedures that were used for conducting the spike
recovery study. The three sections of each sorbent trap must be analyzed
separately (i.e., section 1, then section 2, then section 3). Quantify
the total mass of Hg for each section based on analytical system
response and the calibration curve from section 11.1 of this performance
specification. Determine the spike recovery from sorbent trap section 3.
The spike recovery must be no less than 75 percent and no greater than
125 percent. To report the final Hg mass for each trap, add together the
Hg masses collected in trap sections 1 and 2.

12.0 Calculations, Data Reduction, and Data Analysis

12.1 Calculation of Pre-Sampling Spiking Level. Determine sorbent
trap section 3 spiking level using estimates of the stack Hg
concentration, the target sample flow rate, and the expected monitoring
period. Calculate Mexp, the expected Hg mass that will

[[Page 746]]

be collected in section 1 of the trap, using Equation 12B-1. The pre-
sampling spike must be within 50 percent of this mass.
[GRAPHIC] [TIFF OMITTED] TR09SE10.018

Where:

Mexp = Expected sample mass (g)
Qs = Sample flow rate (L/min)
ts = Expected monitoring period (min)
Cest = Estimated Hg concentration in stack gas (g/
m\3\)
10^-3 = Conversion factor (m\3\/L)

Example calculation: For an estimated stack Hg concentration of 5
g/m\3\, a target sample rate of 0.30 L/min, and a monitoring
period of 5 days:

Mexp = (0.30 L/min)(1440 min/day)(5 days)(10^-3
m\3\/L)(5 g/m\3\) = 10.8 g

A pre-sampling spike of 10.8 g 50 percent is, therefore,
appropriate.
12.2 Calculations for Flow-Proportional Sampling. For the first hour
of the data collection period, determine the reference ratio of the
stack gas volumetric flow rate to the sample flow rate, as follows:
[GRAPHIC] [TIFF OMITTED] TR09SE10.019

Where:

Rref = Reference ratio of hourly stack gas flow rate to
hourly sample flow rate
Qref = Average stack gas volumetric flow rate for first hour
of collection period (scfh)
Fref = Average sample flow rate for first hour of the
collection period, in appropriate units (e.g., liters/min, cc/
min, dscm/min)
K = Power of ten multiplier, to keep the value of Rref
between 1 and 100. The appropriate K value will depend on the
selected units of measure for the sample flow rate.

Then, for each subsequent hour of the data collection period,
calculate ratio of the stack gas flow rate to the sample flow rate using
Equation 12B-3:
[GRAPHIC] [TIFF OMITTED] TR09SE10.020

Where:

Rh = Ratio of hourly stack gas flow rate to hourly sample
flow rate
Qh = Average stack gas volumetric flow rate for the hour
(scfh)
Fh = Average sample flow rate for the hour, in appropriate
units (e.g., liters/min, cc/min, dscm/min)
K = Power of ten multiplier, to keep the value of Rh between
1 and 100. The appropriate K value will depend on the selected
units of measure for the sample flow rate and the range of
expected stack gas flow rates.

Maintain the value of Rh within 25 percent of
Rref throughout the data collection period.
12.3 Calculation of Spike Recovery. Calculate the percent recovery
of each section 3 spike, as follows:
[GRAPHIC] [TIFF OMITTED] TR09SE10.021

[[Page 747]]

Where:

%R = Percentage recovery of the pre-sampling spike
M3 = Mass of Hg recovered from section 3 of the sorbent trap,
(g)
Ms = Calculated Hg mass of the pre-sampling spike, from
section 8.1.2 of this performance specification, (g)

12.4 Calculation of Breakthrough. Calculate the percent breakthrough
to the second section of the sorbent trap, as follows:
[GRAPHIC] [TIFF OMITTED] TR09SE10.022

Where:

%B = Percent breakthrough
M2 = Mass of Hg recovered from section 2 of the sorbent trap,
(g)
M1 = Mass of Hg recovered from section 1 of the sorbent trap,
(g)

12.5 Calculation of Hg Concentration. Calculate the Hg concentration
for each sorbent trap, using the following equation:
[GRAPHIC] [TIFF OMITTED] TR09SE10.023

Where:

C = Concentration of Hg for the collection period, (g/dscm)
M* = Total mass of Hg recovered from sections 1 and 2 of the sorbent
trap, (g)
Vt = Total volume of dry gas metered during the collection
period, (dscm). For the purposes of this performance
specification, standard temperature and pressure are defined
as 20 [deg]C and 760 mm Hg, respectively.

12.6 Calculation of Paired Trap Agreement. Calculate the relative
deviation (RD) between the Hg concentrations measured with the paired
sorbent traps:
[GRAPHIC] [TIFF OMITTED] TR09SE10.024

Where:

RD = Relative deviation between the Hg concentrations from traps ``a''
and ``b'' (percent)
Ca = Concentration of Hg for the collection period, for
sorbent trap ``a'' (g/dscm)
Cb = Concentration of Hg for the collection period, for
sorbent trap ``b'' (g/dscm)

12.7 Calculation of Relative Accuracy. Calculate the relative
accuracy as described in section 12.4 of PS 12A in this appendix.
12.8 Data Reduction. Typical monitoring periods for normal, day-to-
day operation of a sorbent trap monitoring system range from about 24
hours to 168 hours. For the required RA tests of the system, smaller
sorbent traps are often used, and the ``monitoring period'' or time per
run is considerably shorter (e.g., 1 hour or less). Generally speaking,
to validate sorbent trap monitoring system data, the acceptance criteria
for the following five QC specifications in Table 12B-1 above must be
met for both traps: (a) the post-monitoring leak check; (b) the ratio of
stack gas flow rate to sample flow rate; (c) section 2 breakthrough; (d)
paired trap agreement; and (e) section 3 spike recovery.
12.8.1 For routine day-to-day operation of a sorbent trap monitoring
system, when both traps meet the acceptance criteria for all five QC
specifications, the two measured Hg concentrations must be averaged
arithmetically and the average value must be applied to each hour of the
data collection period.
12.8.2 To validate a RA test run, both traps must meet the
acceptance criteria for all five QC specifications. However, as
specified

[[Page 748]]

in section 12.8.3 below, for routine day-to-day operation of the
monitoring system, a monitoring period may, in certain instances, be
validated based on the results from one trap.
12.8.3 For the routine, day-to-day operation of the monitoring
system, when one of the two sorbent trap samples or sampling systems
either: (a) Fails the post-monitoring leak check; or (b) has excessive
section 2 breakthrough; or (c) fails to maintain the proper stack flow-
to-sample flow ratio; or (d) fails to achieve the required section 3
spike recovery; or (e) is lost, broken, or damaged, provided that the
other trap meets the acceptance criteria for all four of these QC
specifications, the Hg concentration measured by the valid trap may be
multiplied by a factor of 1.111 and then used for reporting purposes.
Further, if both traps meet the acceptance criteria for all four of
these QC specifications, but the acceptance criterion for paired trap
agreement is not met, the owner or operator may report the higher of the
two Hg concentrations measured by the traps, in lieu of invalidating the
data from the paired traps.
12.8.4 Whenever the data from a pair of sorbent traps must be
invalidated and no quality-assured data from a certified backup Hg
monitoring system or Hg reference method are available to cover the
hours in the data collection period, treat those hours in the manner
specified in the applicable regulation (i.e., use missing data
substitution procedures or count the hours as monitoring system down
time, as appropriate).

13.0 Monitoring System Performance

These monitoring criteria and procedures have been successfully
applied to coal-fired utility boilers (including units with post-
combustion emission controls), having vapor-phase Hg concentrations
ranging from 0.03 g/dscm to approximately 100 g/dscm.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures [Reserved]

17.0 Bibliography

17.1 40 CFR Part 60, Appendix B, ``Performance Specification 2--
Specifications and Test Procedures for SO2 and NOX
Continuous Emission Monitoring Systems in Stationary Sources.''
17.2 40 CFR Part 60, Appendix B, ``Performance Specification 12A--
Specifications and Test Procedures for Total Vapor Phase Mercury
Continuous Emission Monitoring Systems in Stationary Sources.''

Performance Specification 15--Performance Specification for Extractive
FTIR Continuous Emissions Monitor Systems in Stationary Sources

1.0 Scope and Application

1.1 Analytes. This performance specification is applicable for
measuring all hazardous air pollutants (HAPs) which absorb in the
infrared region and can be quantified using Fourier Transform Infrared
Spectroscopy (FTIR), as long as the performance criteria of this
performance specification are met. This specification is to be used for
evaluating FTIR continuous emission monitoring systems for measuring
HAPs regulated under Title III of the 1990 Clean Air Act Amendments.
This specification also applies to the use of FTIR CEMs for measuring
other volatile organic or inorganic species.
1.2 Applicability. A source which can demonstrate that the
extractive FTIR system meets the criteria of this performance
specification for each regulated pollutant may use the FTIR system to
continuously monitor for the regulated pollutants.

2.0 Summary of Performance Specification

For compound-specific sampling requirements refer to FTIR sampling
methods (e.g., reference 1). For data reduction procedures and
requirements refer to the EPA FTIR Protocol (reference 2), hereafter
referred to as the ``FTIR Protocol.'' This specification describes
sampling and analytical procedures for quality assurance. The infrared
spectrum of any absorbing compound provides a distinct signature. The
infrared spectrum of a mixture contains the superimposed spectra of each
mixture component. Thus, an FTIR CEM provides the capability to
continuously measure multiple components in a sample using a single
analyzer. The number of compounds that can be speciated in a single
spectrum depends, in practice, on the specific compounds present and the
test conditions.

3.0 Definitions

For a list of definitions related to FTIR spectroscopy refer to
Appendix A of the FTIR Protocol. Unless otherwise specified,
spectroscopic terms, symbols and equations in this performance
specification are taken from the FTIR Protocol or from documents cited
in the Protocol. Additional definitions are given below.
3.1 FTIR Continuous Emission Monitoring System (FTIR CEM).
3.1.1 FTIR System. Instrument to measure spectra in the mid-infrared
spectral region (500 to 4000 cm^-1). It contains an infrared
source, interferometer, sample gas containment cell, infrared detector,
and computer. The interferometer consists of a beam splitter that
divides the beam into two paths, one

[[Page 749]]

path a fixed distance and the other a variable distance. The computer is
equipped with software to run the interferometer and store the raw
digitized signal from the detector (interferogram). The software
performs the mathematical conversion (the Fourier transform) of the
interferogram into a spectrum showing the frequency dependent sample
absorbance. All spectral data can be stored on computer media.
3.1.2 Gas Cell. A gas containment cell that can be evacuated. It
contains the sample as the infrared beam passes from the interferometer,
through the sample, and to the detector. The gas cell may have multi-
pass mirrors depending on the required detection limit(s) for the
application.
3.1.3 Sampling System. Equipment used to extract sample from the
test location and transport the gas to the FTIR analyzer. Sampling
system components include probe, heated line, heated non-reactive pump,
gas distribution manifold and valves, flow measurement devices and any
sample conditioning systems.
3.2 Reference CEM. An FTIR CEM, with sampling system, that can be
used for comparison measurements.
3.3 Infrared Band (also Absorbance Band or Band). Collection of
lines arising from rotational transitions superimposed on a vibrational
transition. An infrared absorbance band is analyzed to determine the
analyte concentration.
3.4 Sample Analysis. Interpreting infrared band shapes, frequencies,
and intensities to obtain sample component concentrations. This is
usually performed by a software routine using a classical least squares
(cls), partial least squares (pls), or K- or P- matrix method.
3.5 (Target) Analyte. A compound whose measurement is required,
usually to some established limit of detection and analytical
uncertainty.
3.6 Interferant. A compound in the sample matrix whose infrared
spectrum overlaps at least part of an analyte spectrum complicating the
analyte measurement. The interferant may not prevent the analyte
measurement, but could increase the analytical uncertainty in the
measured concentration. Reference spectra of interferants are used to
distinguish the interferant bands from the analyte bands. An interferant
for one analyte may not be an interferant for other analytes.
3.7 Reference Spectrum. Infrared spectra of an analyte, or
interferant, prepared under controlled, documented, and reproducible
laboratory conditions (see section 4.6 of the FTIR Protocol). A suitable
library of reference spectra can be used to measure target analytes in
gas samples.
3.8 Calibration Spectrum. Infrared spectrum of a compound suitable
for characterizing the FTIR instrument configuration (Section 4.5 in the
FTIR Protocol).
3.9 One hundred percent line. A double beam transmittance spectrum
obtained by combining two successive background single beam spectra.
Ideally, this line is equal to 100 percent transmittance (or zero
absorbance) at every point in the spectrum. The zero absorbance line is
used to measure the RMS noise of the system.
3.10 Background Deviation. Any deviation (from 100 percent) in the
one hundred percent line (or from zero absorbance). Deviations greater
than 5 percent in any analytical region are unacceptable. Such
deviations indicate a change in the instrument throughput relative to
the single-beam background.
3.11 Batch Sampling. A gas cell is alternately filled and evacuated.
A Spectrum of each filled cell (one discreet sample) is collected and
saved.
3.12 Continuous Sampling. Sample is continuously flowing through a
gas cell. Spectra of the flowing sample are collected at regular
intervals.
3.13 Continuous Operation. In continuous operation an FTIR CEM
system, without user intervention, samples flue gas, records spectra of
samples, saves the spectra to a disk, analyzes the spectra for the
target analytes, and prints concentrations of target analytes to a
computer file. User intervention is permitted for initial set-up of
sampling system, initial calibrations, and periodic maintenance.
3.14 Sampling Time. In batch sampling--the time required to fill the
cell with flue gas. In continuous sampling--the time required to collect
the infrared spectrum of the sample gas.
3.15 PPM-Meters. Sample concentration expressed as the
concentration-path length product, ppm (molar) concentration multiplied
by the path length of the FTIR gas cell. Expressing concentration in
these units provides a way to directly compare measurements made using
systems with different optical configurations. Another useful expression
is (ppm-meters)/K, where K is the absolute temperature of the sample in
the gas cell.
3.16 CEM Measurement Time Constant. The Time Constant (TC, minutes
for one cell volume to flow through the cell) determines the minimum
interval for complete removal of an analyte from the FTIR cell. It
depends on the sampling rate (Rs in Lpm), the FTIR cell
volume (Vcell in L) and the chemical and physical properties
of an analyte.
[GRAPHIC] [TIFF OMITTED] TR17OC00.464

For example, if the sample flow rate (through the FTIR cell) is 5 Lpm
and the cell volume is 7 liters, then TC is equal to 1.4

[[Page 750]]

minutes (0.71 cell volumes per minute). This performance specification
defines 5 * TC as the minimum interval between independent samples.
3.17 Independent Measurement. Two independent measurements are
spectra of two independent samples. Two independent samples are
separated by, at least 5 cell volumes. The interval between independent
measurements depends on the cell volume and the sample flow rate
(through the cell). There is no mixing of gas between two independent
samples. Alternatively, estimate the analyte residence time empirically:
(1) Fill cell to ambient pressure with a (known analyte concentration)
gas standard, (2) measure the spectrum of the gas standard, (3) purge
the cell with zero gas at the sampling rate and collect a spectrum every
minute until the analyte standard is no longer detected
spectroscopically. If the measured time corresponds to less than 5 cell
volumes, use 5 * TC as the minimum interval between independent
measurements. If the measured time is greater than 5 * TC, then use this
time as the minimum interval between independent measurements.
3.18 Test Condition. A period of sampling where all process, and
sampling conditions, and emissions remain constant and during which a
single sampling technique and a single analytical program are used. One
Run may include results for more than one test condition. Constant
emissions means that the composition of the emissions remains
approximately stable so that a single analytical program is suitable for
analyzing all of the sample spectra. A greater than two-fold change in
analyte or interferant concentrations or the appearance of additional
compounds in the emissions, may constitute a new test condition and may
require modification of the analytical program.
3.19 Run. A single Run consists of spectra (one spectrum each) of at
least 10 independent samples over a minimum of one hour. The
concentration results from the spectra can be averaged together to give
a run average for each analyte measured in the test run.

4.0 Interferences

Several compounds, including water, carbon monoxide, and carbon
dioxide, are known interferences in the infrared region in which the
FTIR instrument operates. Follow the procedures in the FTIR protocol for
subtracting or otherwise dealing with these and other interferences.

5.0 Safety

The procedures required under this performance specification may
involve hazardous materials, operations, and equipment. This performance
specification may not address all of the safety problems associated with
these procedures. It is the responsibility of the user to establish
appropriate safety and health practices and determine the applicable
regulatory limitations prior to performing these procedures. The CEMS
users manual and materials recommended by this performance specification
should be consulted for specific precautions to be taken.

6.0 Equipment and Supplies

6.1 Installation of sampling equipment should follow requirements of
FTIR test Methods such as references 1 and 3 and the EPA FTIR Protocol
(reference 2). Select test points where the gas stream composition is
representative of the process emissions. If comparing to a reference
method, the probe tips for the FTIR CEM and the RM should be positioned
close together using the same sample port if possible.
6.2 FTIR Specifications. The FTIR CEM must be equipped with
reference spectra bracketing the range of path length-concentrations
(absorbance intensities) to be measured for each analyte. The effective
concentration range of the analyzer can be adjusted by changing the path
length of the gas cell or by diluting the sample. The optical
configuration of the FTIR system must be such that maximum absorbance of
any target analyte is no greater than 1.0 and the minimum absorbance of
any target analyte is at least 10 times the RMSD noise in the analytical
region. For example, if the measured RMSD in an analytical region is
equal to 10^-3, then the peak analyte absorbance is required
to be at least 0.01. Adequate measurement of all of the target analytes
may require changing path lengths during a run, conducting separate runs
for different analytes, diluting the sample, or using more than one gas
cell.
6.3 Data Storage Requirements. The system must have sufficient
capacity to store all data collected in one week of routine sampling.
Data must be stored to a write-protected medium, such as write-once-
read-many (WORM) optical storage medium or to a password protected
remote storage location. A back-up copy of all data can be temporarily
saved to the computer hard drive. The following items must be stored
during testing.
At least one sample interferogram per sampling Run or one
interferogram per hour, whichever is greater. This assumes that no
sampling or analytical conditions have changed during the run.
All sample absorbance spectra (about 12 per hr, 288 per
day).
All background spectra and interferograms (variable, but
about 5 per day).
All CTS spectra and interferograms (at least 2 each 24 hour
period).
Documentation showing a record of resolution, path length,
apodization, sampling

[[Page 751]]

time, sampling conditions, and test conditions for all sample, CTS,
calibration, and background spectra.
Using a resolution of 0.5 cm^-1, with analytical range of
3500 cm^-1, assuming about 65 Kbytes per spectrum and 130 Kb
per interferogram, the storage requirement is about 164 Mb for one week
of continuous sampling. Lower spectral resolution requires less storage
capacity. All of the above data must be stored for at least two weeks.
After two weeks, storage requirements include: (1) all analytical
results (calculated concentrations), (2) at least 1 sample spectrum with
corresponding background and sample interferograms for each test
condition, (3) CTS and calibration spectra with at least one
interferogram for CTS and all interferograms for calibrations, (4) a
record of analytical input used to produce results, and (5) all other
documentation. These data must be stored according to the requirements
of the applicable regulation.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection, Preservation, Storage, and Transport [Reserved]

9.0 Quality Control

These procedures shall be used for periodic quarterly or semiannual
QA/QC checks on the operation of the FTIR CEM. Some procedures test only
the analytical program and are not intended as a test of the sampling
system.
9.1 Audit Sample. This can serve as a check on both the sampling
system and the analytical program.
9.1.1 Sample Requirements. The audit sample can be a mixture or a
single component. It must contain target analyte(s) at approximately the
expected flue gas concentration(s). If possible, each mixture component
concentration should be NIST traceable (2 percent accuracy). If a
cylinder mixture standard(s) cannot be obtained, then, alternatively, a
gas phase standard can be generated from a condensed phase analyte
sample. Audit sample contents and concentrations are not revealed to the
FTIR CEM operator until after successful completion of procedures in
5.3.2.
9.1.2 Test Procedure. An audit sample is obtained from the
Administrator. Spike the audit sample using the analyte spike procedure
in section 11. The audit sample is measured directly by the FTIR system
(undiluted) and then spiked into the effluent at a known dilution ratio.
Measure a series of spiked and unspiked samples using the same
procedures as those used to analyze the stack gas. Analyze the results
using sections 12.1 and 12.2. The measured concentration of each analyte
must be within 5 percent of the expected concentration (plus the
uncertainty), i.e., the calculated correction factor must be within 0.93
and 1.07 for an audit with an analyte uncertainty of 2 percent.
9.2 Audit Spectra. Audit spectra can be used to test the analytical
program of the FTIR CEM, but provide no test of the sampling system.
9.2.1 Definition and Requirements. Audit spectra are absorbance
spectra that; (1) have been well characterized, and (2) contain
absorbance bands of target analyte(s) and potential interferants at
intensities equivalent to what is expected in the source effluent. Audit
spectra are provided by the administrator without identifying
information. Methods of preparing Audit spectra include; (1)
mathematically adding sample spectra or adding reference and interferant
spectra, (2) obtaining sample spectra of mixtures prepared in the
laboratory, or (3) they may be sample spectra collected previously at a
similar source. In the last case it must be demonstrated that the
analytical results are correct and reproducible. A record associated
with each Audit spectrum documents its method of preparation. The
documentation must be sufficient to enable an independent analyst to
reproduce the Audit spectra.
9.2.2 Test Procedure. Audit spectra concentrations are measured
using the FTIR CEM analytical program. Analytical results must be within
5 percent of the certified audit concentration for each analyte (plus
the uncertainty in the audit concentration). If the condition is not
met, demonstrate how the audit spectra are unrepresentative of the
sample spectra. If the audit spectra are representative, modify the FTIR
CEM analytical program until the test requirement is met. Use the new
analytical program in subsequent FTIR CEM analyses of effluent samples.
9.3 Submit Spectra For Independent Analysis. This procedure tests
only the analytical program and not the FTIR CEM sampling system. The
analyst can submit FTIR CEM spectra for independent analysis by EPA.
Requirements for submission include; (1) three representative absorbance
spectra (and stored interferograms) for each test period to be reviewed,
(2) corresponding CTS spectra, (3) corresponding background spectra and
interferograms, (4) spectra of associated spiked samples if applicable,
and (5) analytical results for these sample spectra. The analyst will
also submit documentation of process times and conditions, sampling
conditions associated with each spectrum, file names and sampling times,
method of analysis and reference spectra used, optical configuration of
FTIR CEM including cell path length and temperature, spectral resolution
and apodization used for every spectrum. Independent analysis can also
be performed on site in conjunction with the FTIR CEM sampling and
analysis. Sample spectra are stored on the independent analytical system

[[Page 752]]

as they are collected by the FTIR CEM system. The FTIR CEM and the
independent analyses are then performed separately. The two analyses
will agree to within 120 percent for each analyte using the procedure
in section 12.3. This assumes both analytical routines have properly
accounted for differences in optical path length, resolution, and
temperature between the sample spectra and the reference spectra.

10.0 Calibration and Standardization

10.1 Calibration Transfer Standards. For CTS requirements see
section 4.5 of the FTIR Protocol. A well characterized absorbance band
in the CTS gas is used to measure the path length and line resolution of
the instrument. The CTS measurements made at the beginning of every 24
hour period must agree to within 5 percent after correction for
differences in pressure.
Verify that the frequency response of the instrument and CTS
absorbance intensity are correct by comparing to other CTS spectra or by
referring to the literature.
10.2 Analyte Calibration. If EPA library reference spectra are not
available, use calibration standards to prepare reference spectra
according to section 6 of the FTIR Protocol. A suitable set of analyte
reference data includes spectra of at least 2 independent samples at
each of at least 2 different concentrations. The concentrations bracket
a range that includes the expected analyte absorbance intensities. The
linear fit of the reference analyte band areas must have a fractional
calibration uncertainty (FCU in Appendix F of the FTIR Protocol) of no
greater than 10 percent. For requirements of analyte standards refer to
section 4.6 of the FTIR Protocol.
10.3 System Calibration. The calibration standard is introduced at a
point on the sampling probe. The sampling system is purged with the
calibration standard to verify that the absorbance measured in this way
is equal to the absorbance in the analyte calibration. Note that the
system calibration gives no indication of the ability of the sampling
system to transport the target analyte(s) under the test conditions.
10.4 Analyte Spike. The target analyte(s) is spiked at the outlet of
the sampling probe, upstream of the particulate filter, and combined
with effluent at a ratio of about 1 part spike to 9 parts effluent. The
measured absorbance of the spike is compared to the expected absorbance
of the spike plus the analyte concentration already in the effluent.
This measures sampling system bias, if any, as distinguished from
analyzer bias. It is important that spiked sample pass through all of
the sampling system components before analysis.
10.5 Signal-to-Noise Ratio (S/N). The measure of S/N in this
performance specification is the root-mean-square (RMS) noise level as
given in Appendix C of the FTIR Protocol. The RMS noise level of a
contiguous segment of a spectrum is defined as the RMS difference (RMSD)
between the n contiguous absorbance values (Ai) which form
the segment and the mean value (AM) of that segment.
[GRAPHIC] [TIFF OMITTED] TR17OC00.465

A decrease in the S/N may indicate a loss in optical throughput, or
detector or interferometer malfunction.
10.6 Background Deviation. The 100 percent baseline must be between
95 and 105 percent transmittance (absorbance of 0.02 to -0.02) in every
analytical region. When background deviation exceeds this range, a new
background spectrum must be collected using nitrogen or other zero gas.
10.7 Detector Linearity. Measure the background and CTS at three
instrument aperture settings; one at the aperture setting to be used in
the testing, and one each at settings one half and twice the test
aperture setting. Compare the three CTS spectra. CTS band areas should
agree to within the uncertainty of the cylinder standard. If test
aperture is the maximum aperture, collect CTS spectrum at maximum
aperture, then close the aperture to reduce the IR through-put by half.
Collect a second background and CTS at the smaller aperture setting and
compare the spectra as above. Instead of changing the aperture neutral
density filters can be used to attenuate the infrared beam. Set up the
FTIR system as it will be used in the test measurements. Collect a CTS
spectrum. Use a neutral density filter to attenuate the infrared beam
(either immediately after the source or the interferometer) to
approximately \1/2\ its original intensity. Collect a second CTS
spectrum. Use another filter to attenuate the infrared beam to
approximately \1/4\ its original intensity. Collect a third background
and CTS spectrum. Compare the CTS spectra as above. Another check on
linearity is to observe the single beam background in frequency regions
where the optical configuration is known to have a zero response. Verify
that the detector response is ``flat'' and equal to zero in these
regions. If detector response is not linear, decrease aperture, or
attenuate the infrared beam. Repeat the linearity check until system
passes the requirement.

11.0 Analytical Procedure

11.1 Initial Certification. First, perform the evaluation procedures
in section 6.0 of the FTIR Protocol. The performance of an FTIR CEM can
be certified upon installation using EPA Method 301 type validation (40
CFR, Part 63, Appendix A), or by comparison to a

[[Page 753]]

reference Method if one exists for the target analyte(s). Details of
each procedure are given below. Validation testing is used for initial
certification upon installation of a new system. Subsequent performance
checks can be performed with more limited analyte spiking. Performance
of the analytical program is checked initially, and periodically as
required by EPA, by analyzing audit spectra or audit gases.
11.1.1 Validation. Use EPA Method 301 type sampling (reference 4,
section 5.3 of Method 301) to validate the FTIR CEM for measuring the
target analytes. The analyte spike procedure is as follows: (1) a known
concentration of analyte is mixed with a known concentration of a non-
reactive tracer gas, (2) the undiluted spike gas is sent directly to the
FTIR cell and a spectrum of this sample is collected, (3) pre-heat the
spiked gas to at least the sample line temperature, (4) introduce spike
gas at the back of the sample probe upstream of the particulate filter,
(5) spiked effluent is carried through all sampling components
downstream of the probe, (6) spike at a ratio of roughly 1 part spike to
9 parts flue gas (or more dilute), (7) the spike-to-flue gas ratio is
estimated by comparing the spike flow to the total sample flow, and (8)
the spike ratio is verified by comparing the tracer concentration in
spiked flue gas to the tracer concentration in undiluted spike gas. The
analyte flue gas concentration is unimportant as long as the spiked
component can be measured and the sample matrix (including
interferences) is similar to its composition under test conditions.
Validation can be performed using a single FTIR CEM analyzing sample
spectra collected sequentially. Since flue gas analyte (unspiked)
concentrations can vary, it is recommended that two separate sampling
lines (and pumps) are used; one line to carry unspiked flue gas and the
other line to carry spiked flue gas. Even with two sampling lines the
variation in unspiked concentration may be fast compared to the interval
between consecutive measurements. Alternatively, two FTIR CEMs can be
operated side-by-side, one measuring spiked sample, the other unspiked
sample. In this arrangement spiked and unspiked measurements can be
synchronized to minimize the affect of temporal variation in the
unspiked analyte concentration. In either sampling arrangement, the
interval between measured concentrations used in the statistical
analysis should be, at least, 5 cell volumes (5 * TC in equation 1). A
validation run consists of, at least, 24 independent analytical results,
12 spiked and 12 unspiked samples. See section 3.17 for definition of an
``independent'' analytical result. The results are analyzed using
sections 12.1 and 12.2 to determine if the measurements passed the
validation requirements. Several analytes can be spiked and measured in
the same sampling run, but a separate statistical analysis is performed
for each analyte. In lieu of 24 independent measurements, averaged
results can be used in the statistical analysis. In this procedure, a
series of consecutive spiked measurements are combined over a sampling
period to give a single average result. The related unspiked
measurements are averaged in the same way. The minimum 12 spiked and 12
unspiked result averages are obtained by averaging measurements over
subsequent sampling periods of equal duration. The averaged results are
grouped together and statistically analyzed using section 12.2.
11.1.1.1 Validation with a Single Analyzer and Sampling Line. If one
sampling line is used, connect the sampling system components and purge
the entire sampling system and cell with at least 10 cell volumes of
sample gas. Begin sampling by collecting spectra of 2 independent
unspiked samples. Introduce the spike gas into the back of the probe,
upstream of the particulate filter. Allow 10 cell volumes of spiked flue
gas to purge the cell and sampling system. Collect spectra of 2
independent spiked samples. Turn off the spike flow and allow 10 cell
volumes of unspiked flue gas to purge the FTIR cell and sampling system.
Repeat this procedure 6 times until the 24 samples are collected. Spiked
and unspiked samples can also be measured in groups of 4 instead of in
pairs. Analyze the results using sections 12.1 and 12.2. If the
statistical analysis passes the validation criteria, then the validation
is completed. If the results do not pass the validation, the cause may
be that temporal variations in the analyte sample gas concentration are
fast relative to the interval between measurements. The difficulty may
be avoided by: (1) Averaging the measurements over long sampling periods
and using the averaged results in the statistical analysis, (2)
modifying the sampling system to reduce TC by, for example, using a
smaller volume cell or increasing the sample flow rate, (3) using two
sample lines (4) use two analyzers to perform synchronized measurements.
This performance specification permits modifications in the sampling
system to minimize TC if the other requirements of the validation
sampling procedure are met.
11.1.1.2 Validation With a Single Analyzer and Two Sampling Lines.
An alternative sampling procedure uses two separate sample lines, one
carrying spiked flue gas, the other carrying unspiked gas. A valve in
the gas distribution manifold allows the operator to choose either
sample. A short heated line connects the FTIR cell to the 3-way valve in
the manifold. Both sampling lines are continuously purged. Each sample
line has a rotameter and a bypass vent line after the rotameter,
immediately upstream of the valve, so that the spike and unspiked sample
flows can each be continuously monitored. Begin

[[Page 754]]

sampling by collecting spectra of 2 independent unspiked samples. Turn
the sampling valve to close off the unspiked gas flow and allow the
spiked flue gas to enter the FTIR cell. Isolate and evacuate the cell
and fill with the spiked sample to ambient pressure. (While the
evacuated cell is filling, prevent air leaks into the cell by making
sure that the spike sample rotameter always indicates that a portion of
the flow is directed out the by-pass vent.) Open the cell outlet valve
to allow spiked sample to continuously flow through the cell. Measure
spectra of 2 independent spiked samples. Repeat this procedure until at
least 24 samples are collected.
11.1.1.3 Synchronized Measurements With Two Analyzers. Use two FTIR
analyzers, each with its own cell, to perform synchronized spiked and
unspiked measurements. If possible, use a similar optical configuration
for both systems. The optical configurations are compared by measuring
the same CTS gas with both analyzers. Each FTIR system uses its own
sampling system including a separate sampling probe and sampling line. A
common gas distribution manifold can be used if the samples are never
mixed. One sampling system and analyzer measures spiked effluent. The
other sampling system and analyzer measures unspiked flue gas. The two
systems are synchronized so that each measures spectra at approximately
the same times. The sample flow rates are also synchronized so that both
sampling rates are approximately the same (TC1 \
TC2 in equation 1). Start both systems at the same time.
Collect spectra of at least 12 independent samples with each (spiked and
unspiked) system to obtain the minimum 24 measurements. Analyze the
analytical results using sections 12.1 and 12.2. Run averages can be
used in the statistical analysis instead of individual measurements.
11.1.1.4 Compare to a Reference Method (RM). Obtain EPA approval
that the method qualifies as an RM for the analyte(s) and the source to
be tested. Follow the published procedures for the RM in preparing and
setting up equipment and sampling system, performing measurements, and
reporting results. Since FTIR CEMS have multicomponent capability, it is
possible to perform more than one RM simultaneously, one for each target
analyte. Conduct at least 9 runs where the FTIR CEM and the RM are
sampling simultaneously. Each Run is at least 30 minutes long and
consists of spectra of at least 5 independent FTIR CEM samples and the
corresponding RM measurements. If more than 9 runs are conducted, the
analyst may eliminate up to 3 runs from the analysis if at least 9 runs
are used.
11.1.1.4.1 RMs Using Integrated Sampling. Perform the RM and FTIR
CEM sampling simultaneously. The FTIR CEM can measure spectra as
frequently as the analyst chooses (and should obtain measurements as
frequently as possible) provided that the measurements include spectra
of at least 5 independent measurements every 30 minutes. Concentration
results from all of the FTIR CEM spectra within a run may be averaged
for use in the statistical comparison even if all of the measurements
are not independent. When averaging the FTIR CEM concentrations within a
run, it is permitted to exclude some measurements from the average
provided the minimum of 5 independent measurements every 30 minutes are
included: The Run average of the FTIR CEM measurements depends on both
the sample flow rate and the measurement frequency (MF). The run average
of the RM using the integrated sampling method depends primarily on its
sampling rate. If the target analyte concentration fluctuates
significantly, the contribution to the run average of a large
fluctuation depends on the sampling rate and measurement frequency, and
on the duration and magnitude of the fluctuation. It is, therefore,
important to carefully select the sampling rate for both the FTIR CEM
and the RM and the measurement frequency for the FTIR CEM. The minimum
of 9 run averages can be compared according to the relative accuracy
test procedure in Performance Specification 2 for SO2 and
NOX CEMs (40 CFR, Part 60, App. B).
11.1.1.4.2 RMs Using a Grab Sampling Technique. Synchronize the RM
and FTIR CEM measurements as closely as possible. For a grab sampling
RM, record the volume collected and the exact sampling period for each
sample. Synchronize the FTIR CEM so that the FTIR measures a spectrum of
a similar cell volume at the same time as the RM grab sample was
collected. Measure at least five independent samples with both the FTIR
CEM and the RM for each of the minimum nine runs. Compare the run
concentration averages by using the relative accuracy analysis procedure
in Performance Specification 2 of appendix B of 40 CFR part 60.
11.1.1.4.3 Continuous Emission Monitors as RMs. If the RM is a CEM,
synchronize the sampling flow rates of the RM and the FTIR CEM. Each run
is at least 1 hour long and consists of at least 10 FTIR CEM
measurements and the corresponding 10 RM measurements (or averages). For
the statistical comparison, use the relative accuracy analysis procedure
in Performance Specification 2 of appendix B of 40 CFR part 60. If the
RM time constant is < \1/2\ the FTIR CEM time constant, brief
fluctuations in analyte concentrations that are not adequately measured
with the slower FTIR CEM time constant can be excluded from the run
average along with the corresponding RM measurements. However, the FTIR
CEM run average must still include at least 10 measurements over a 1-
hour period.

[[Page 755]]

12.0 Calculations and Data Analysis

12.1 Spike Dilution Ratio, Expected Concentration. The Method 301
bias is calculated as follows.
[GRAPHIC] [TIFF OMITTED] TR17OC00.466

Where:

B = Bias at the spike level
Sm = Mean of the observed spiked sample concentrations
Mm = Mean of the observed unspiked sample concentrations
CS = Expected value of the spiked concentration.

The CS is determined by comparing the SF6 tracer
concentration in undiluted spike gas to the SF6 tracer
concentrations in the spiked samples;
[GRAPHIC] [TIFF OMITTED] TR17OC00.467

The expected concentration (CS) is the measured concentration of the
analyte in undiluted spike gas divided by the dilution factor
[GRAPHIC] [TIFF OMITTED] TR17OC00.468

Where:

[anal]dir = The analyte concentration in undiluted spike gas
measured directly by filling the FTIR cell with the spike gas.

If the bias is statistically significant (Section 12.2), Method 301
requires that a correction factor, CF, be multiplied by the analytical
results, and that 0.7 CF 1.3.
[GRAPHIC] [TIFF OMITTED] TR17OC00.469

12.2 Statistical Analysis of Validation Measurements. Arrange the
independent measurements (or measurement averages) as in Table 1. More
than 12 pairs of measurements can be analyzed. The statistical analysis
follows EPA Method 301, section 6.3. section 12.1 of this performance
specification shows the calculations for the bias, expected spike
concentration, and correction factor. This section shows the
determination of the statistical significance of the bias. Determine the
statistical significance of the bias at the 95 percent confidence level
by calculating the t-value for the set of measurements. First, calculate
the differences, di, for each pair of spiked and each pair of
unspiked measurements. Then calculate the standard deviation of the
spiked pairs of measurements.
[GRAPHIC] [TIFF OMITTED] TR17OC00.470

Where:

di = The differences between pairs of spiked measurements.
SDs = The standard deviation in the di values.
n = The number of spiked pairs, 2n = 12 for the minimum of 12 spiked and
12 unspiked measurements.

Calculate the relative standard deviation, RSD, using SDs and
the mean of the spiked concentrations, Sm. The RSD must be
50%.
[GRAPHIC] [TIFF OMITTED] TR17OC00.471

[[Page 756]]

Repeat the calculations in equations 7 and 8 to determine SDu
and RSD, respectively, for the unspiked samples. Calculate the standard
deviation of the mean using SDs and SDu from
equation 7.
[GRAPHIC] [TIFF OMITTED] TR17OC00.472

The t-statistic is calculated as follows to test the bias for
statistical significance;
[GRAPHIC] [TIFF OMITTED] TR17OC00.473

where the bias, B, and the correction factor, CF, are given in section
12.1. For 11 degrees of freedom, and a one-tailed distribution, Method
301 requires that t 2.201. If the t-statistic indicates the
bias is statistically significant, then analytical measurements must be
multiplied by the correction factor. There is no limitation on the
number of measurements, but there must be at least 12 independent spiked
and 12 independent unspiked measurements. Refer to the t-distribution
(Table 2) at the 95 percent confidence level and appropriate degrees of
freedom for the critical t-value.

16.0 References

1. Method 318, 40 CFR, Part 63, Appendix A (Draft), ``Measurement of
Gaseous Formaldehyde, Phenol and Methanol Emissions by FTIR
Spectroscopy,'' EPA Contract No. 68D20163, Work Assignment 2-18,
February, 1995.
2. ``EPA Protocol for the Use of Extractive Fourier Transform
Infrared (FTIR) Spectrometry in Analyses of Gaseous Emissions from
Stationary Industrial Sources,'' February, 1995.
3. ``Measurement of Gaseous Organic and Inorganic Emissions by
Extractive FTIR Spectroscopy,'' EPA Contract No. 68-D2-0165, Work
Assignment 3-08.
4. ``Method 301--Field Validation of Pollutant Measurement Methods
from Various Waste Media,'' 40 CFR 63, App A.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Table 1--Arrangement of Validation Measurements for Statistical Analysis
----------------------------------------------------------------------------------------------------------------
Measurement (or average) Time Spiked (ppm) di spiked Unspiked (ppm) di unspiked
----------------------------------------------------------------------------------------------------------------
1........................... .............. S1 ............... U1
-------------------------------------------------------------- -----------------
2........................... .............. S2 S2-S1 U2 U2-U1
----------------------------------------------------------------------------------------------------------------
3........................... .............. S3 ............... U3
-------------------------------------------------------------- -----------------
4........................... .............. S4 S4-S3 U4 U4-U3
----------------------------------------------------------------------------------------------------------------
5........................... .............. S5 ............... U5
-------------------------------------------------------------- -----------------
6........................... .............. S6 S6-S5 U6 U6-U5
----------------------------------------------------------------------------------------------------------------
7........................... .............. S7 ............... U7
-------------------------------------------------------------- -----------------
8........................... .............. S8 S8-S7 U8 U8-U7
----------------------------------------------------------------------------------------------------------------
9........................... .............. S9 ............... U9
-------------------------------------------------------------- -----------------
10.......................... .............. S10 S10-S9 U10 U10-U9
----------------------------------------------------------------------------------------------------------------
11.......................... .............. S11 ............... U11
-------------------------------------------------------------- -----------------
12.......................... .............. S12 S12-S11 U12 U12-U11
----------------------------------------------------------------------------------------------------------------
Average ->.................. .............. Sm ............... Mm
----------------------------------------------------------------------------------------------------------------

[[Page 757]]

Table 2--t = Values
----------------------------------------------------------------------------------------------------------------
n-1 \a\ t-value n-1 \a\ t-value n-1 \a\ t-value n-1 \a\ t-value
----------------------------------------------------------------------------------------------------------------
11 2.201 17 2.110 23 2.069 29 2.045
12 2.179 18 2.101 24 2.064 30 2.042
13 2.160 19 2.093 25 2.060 40 2.021
14 2.145 20 2.086 26 2.056 60 2.000
15 2.131 21 2.080 27 2.052 120 1.980
16 2.120 22 2.074 28 2.048 8 1.960
----------------------------------------------------------------------------------------------------------------
\a\ n is the number of independent pairs of measurements (a pair consists of one spiked and its corresponding
unspiked measurement). Either discreet (independent) measurements in a single run, or run averages can be
used.

Performance Specification 16--Specifications and Test Procedures for
Predictive Emission Monitoring Systems in Stationary Sources

1.0 Scope and Application

1.1 Does this performance specification apply to me? If you, the
source owner or operator, intend to use (with any necessary approvals) a
predictive emission monitoring system (PEMS) to show compliance with
your emission limitation under 40 CFR 60, 61, or 63, you must use the
procedures in this performance specification (PS) to determine whether
your PEMS is acceptable for use in demonstrating compliance with
applicable requirements. Use these procedures to certify your PEMS after
initial installation and periodically thereafter to ensure the PEMS is
operating properly. If your PEMS contains a diluent (O2 or
CO2) measuring component and your emissions limitation is in
units that require a diluent measurement (e.g. lbs/mm Btu), the diluent
component must be tested as well. These specifications apply to PEMS
that are installed under 40 CFR 60, 61, and 63 after the effective date
of this performance specification. These specifications do not apply to
parametric monitoring systems, these are covered under PS-17.
1.1.1 How do I certify my PEMS after it is installed? PEMS must pass
a relative accuracy (RA) test and accompanying statistical tests in the
initial certification test to be acceptable for use in demonstrating
compliance with applicable requirements. Ongoing quality assurance tests
also must be conducted to ensure the PEMS is operating properly. An
ongoing sensor evaluation procedure must be in place before the PEMS
certification is complete. The amount of testing and data validation
that is required depends upon the regulatory needs, i.e., whether
precise quantification of emissions will be needed or whether indication
of exceedances of some regulatory threshold will suffice. Performance
criteria are more rigorous for PEMS used in determining continual
compliance with an emission limit than those used to measure excess
emissions. You must perform the initial certification test on your PEMS
before reporting any PEMS data as quality-assured.
1.1.2 Is other testing required after certification? After you
initially certify your PEMS, you must pass additional periodic
performance checks to ensure the long-term quality of data. These
periodic checks are listed in the table in section 9. You are always
responsible for properly maintaining and operating your PEMS.

2.0 Summary of Performance Specification

The following performance tests are required in addition to other
equipment and measurement location requirements.
2.1 Initial PEMS Certification.
2.1.1 Excess Emissions PEMS. For a PEMS that is used for excess
emission reporting, the owner or operator must perform a minimum 9-run,
3-level (3 runs at each level) RA test (see section 8.2).
2.1.2 Compliance PEMS. For a PEMS that is used for continual
compliance standards, the owner or operator must perform a minimum 27-
run, 3-level (9 runs at each level) RA test (see section 8.2).
Additionally, the data must be evaluated for bias and by F-test and
correlation analysis.
2.2 Periodic Quality Assurance (QA) Assessments. Owners and
operators of all PEMS are required to conduct quarterly relative
accuracy audits (RAA) and yearly relative accuracy test audits (RATA) to
assess ongoing PEMS operation. The frequency of these periodic
assessments may be shortened by successful operation during a prior
year.

3.0 Definitions

The following definitions apply:
3.1 Centroidal Area means that area in the center of the stack (or
duct) comprising no more than 1 percent of the stack cross-sectional
area and having the same geometric shape as the stack.
3.2 Data Recorder means the equipment that provides a permanent
record of the PEMS output. The data recorder may include automatic data
reduction capabilities and may include electronic data records, paper
records, or a combination of electronic data and paper records.
3.3 Defective sensor means a sensor that is responsible for PEMS
malfunction or that

[[Page 758]]

operates outside the approved operating envelope. A defective sensor may
be functioning properly, but because it is operating outside the
approved operating envelope, the resulting predicted emission is not
validated.
3.4 Diluent PEMS means the total equipment required to predict a
diluent gas concentration or emission rate.
3.5 Operating envelope means the defined range of a parameter input
that is established during PEMS development. Emission data generated
from parameter inputs that are beyond the operating envelope are not
considered quality assured and are therefore unacceptable.
3.6 PEMS means all of the equipment required to predict an emission
concentration or emission rate. The system may consist of any of the
following major subsystems: sensors and sensor interfaces, emission
model, algorithm, or equation that uses process data to generate an
output that is proportional to the emission concentration or emission
rate, diluent emission model, data recorder, and sensor evaluation
system. Systems that use fewer than 3 variables do not qualify as PEMS
unless the system has been specifically approved by the Administrator
for use as a PEMS. A PEMS may predict emissions data that are corrected
for diluent if the relative accuracy and relevant QA tests are passed in
the emission units corrected for diluent. Parametric monitoring systems
that serve as indicators of compliance and have parametric limits but do
not predict emissions to comply with an emissions limit are not included
in this definition.
3.7 PEMS training means the process of developing or confirming the
operation of the PEMS against a reference method under specified
conditions.
3.8 Quarter means a quarter of a calendar year in which there are at
least 168 unit operating hours.
3.9 Reconciled Process Data means substitute data that are generated
by a sensor evaluation system to replace that of a failed sensor.
Reconciled process data may not be used without approval from the
Administrator.
3.10 Relative Accuracy means the accuracy of the PEMS when compared
to a reference method (RM) at the source. The RA is the average
difference between the pollutant PEMS and RM data for a specified number
of comparison runs plus a 2.5 percent confidence coefficient, divided by
the average of the RM tests. For a diluent PEMS, the RA may be expressed
as a percentage of absolute difference between the PEMS and RM.
Alternative specifications are given for units that have very low
emissions.
3.11 Relative Accuracy Audit means a quarterly audit of the PEMS
against a portable analyzer meeting the requirements of ASTM D6522-00 or
a RM for a specified number of runs. A RM may be used in place of the
portable analyzer for the RAA.
3.12 Relative Accuracy Test Audit means a RA test that is performed
at least once every four calendar quarters after the initial
certification test while the PEMS is operating at the normal operating
level.
3.13 Reference Value means a PEMS baseline value that may be
established by RM testing under conditions when all sensors are
functioning properly. This reference value may then be used in the
sensor evaluation system or in adjusting new sensors.
3.14 Sensor Evaluation System means the equipment or procedure used
to periodically assess the quality of sensor input data. This system may
be a sub-model that periodically cross-checks sensor inputs among
themselves or any other procedure that checks sensor integrity at least
daily (when operated for more than one hour in any calendar day).
3.15 Sensors and Sensor Interface means the equipment that measures
the process input signals and transports them to the emission prediction
system.

4.0 Interferences [Reserved]

5.0 Safety [Reserved]

6.0 Equipment and Supplies

6.1 PEMS Design. You must detail the design of your PEMS and make
this available in reports and for on-site inspection. You must also
establish the following, as applicable:
6.1.1 Number of Input Parameters. An acceptable PEMS will normally
use three or more input parameters. You must obtain the Administrator's
permission on a case-by-case basis if you desire to use a PEMS having
fewer than three input parameters.
6.1.2 Parameter Operating Envelopes. Before you evaluate your PEMS
through the certification test, you must specify the input parameters
your PEMS uses, define their range of minimum and maximum values
(operating envelope), and demonstrate the integrity of the parameter
operating envelope using graphs and data from the PEMS development
process, vendor information, or engineering calculations, as
appropriate. If you operate the PEMS beyond these envelopes at any time
after the certification test, the data generated during this condition
will not be acceptable for use in demonstrating compliance with
applicable requirements. If these parameter operating envelopes are not
clearly defined and supported by development data, the PEMS operation
will be limited to the range of parameter inputs encountered during the
certification test until the PEMS has a new operating envelope
established.

[[Page 759]]

6.1.3 Source-Specific Operating Conditions. Identify any source-
specific operating conditions, such as fuel type, that affect the output
of your PEMS. You may only use the PEMS under the source-specific
operating conditions it was certified for.
6.1.4 Ambient Conditions. You must explain whether and how ambient
conditions and seasonal changes affect your PEMS. Some parameters such
as absolute ambient humidity cannot be manipulated during a test. The
effect of ambient conditions such as humidity on the pollutant
concentration must be determined and this effect extrapolated to include
future anticipated conditions. Seasonal changes and their effects on the
PEMS must be evaluated unless you can show that such effects are
negligible.
6.1.5 PEMS Principle of Operation. If your PEMS is developed on the
basis of known physical principles, you must identify the specific
physical assumptions or mathematical manipulations that support its
operation. If your PEMS is developed on the basis of linear or nonlinear
regression analysis, you must make available the paired data (preferably
in graphic form) used to develop or train the model.
6.1.6 Data Recorder Scale. If you are not using a digital recorder,
you must choose a recorder scale that accurately captures the desired
range of potential emissions. The lower limit of your data recorder's
range must be no greater than 20 percent of the applicable emission
standard (if subject to an emission standard). The upper limit of your
data recorder's range must be determined using the following table. If
you obtain approval first, you may use other lower and upper recorder
limits.

------------------------------------------------------------------------
Then your upper
If PEMS is measuring. . . And if. . . limit. . .
------------------------------------------------------------------------
Uncontrolled emissions, such No other regulation Must be 1.25 to 2
as NOX at the stack of a sets an upper limit times the average
natural gas-fired boiler. for the data potential emission
recorder's range. level
Uncontrolled emissions, such Another regulation Must follow the
as NOX at the stack of a sets an upper limit other regulation
natural gas-fired boiler. for the data
recorder's range.
Controlled emissions........ Must be 1.5 to 2.0
times concentration
of the emission
standard that
applies to your
emission unit.
Continual compliance Must be 1.1 to 1.5
emissions for an applicable times the
regulation. concentration of
the emission
standard that
applies to your
emission unit.
------------------------------------------------------------------------

6.1.7 Sensor Location and Repair. We recommend you install sensors
in an accessible location in order to perform repairs and replacements.
Permanently-installed platforms or ladders may not be needed. If you
install sensors in an area that is not accessible, you may be required
to shut down the emissions unit to repair or replace a sensor. Conduct a
new RATA after replacing a sensor that supplies a critical PEMS
parameter if the new sensor provides a different output or scaling or
changes the historical training dataset of the PEMS. Replacement of a
non-critical sensor that does not cause an impact in the accuracy of the
PEMS does not trigger a RATA. All sensors must be calibrated as often as
needed but at least as often as recommended by the manufacturers.
6.1.8 Sensor Evaluation System. Your PEMS must be designed to
perform automatic or manual determination of defective sensors on at
least a daily basis. This sensor evaluation system may consist of a
sensor validation sub-model, a comparison of redundant sensors, a spot
check of sensor input readings at a reference value, operation, or
emission level, or other procedure that detects faulty or failed
sensors. Some sensor evaluation systems generate substitute values
(reconciled data) that are used when a sensor is perceived to have
failed. You must obtain prior approval before using reconciled data.
6.1.9 Parameter Envelope Exceedances. Your PEMS must include a plan
to detect and notify the operator of parameter envelope exceedances.
Emission data collected outside the ranges of the sensor envelopes will
not be considered quality assured.
6.2 Recordkeeping. All valid data recorded by the PEMS must be used
to calculate the emission value.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Initial Certification. Use the following procedure to certify
your PEMS. Complete all PEMS training before the certification begins.
8.2 Relative Accuracy Test.
8.2.1 Reference Methods. Unless otherwise specified in the
applicable regulations, you must use the test methods in appendix A of
this part for the RM test. Conduct the RM tests at three operating
levels. The RM tests shall be performed at a low-load (or production)
level between the minimum safe, stable load and 50 percent of the
maximum level load, at the mid-load level (an intermediary level between
the low and high levels), and at a high-load level between 80 percent
and

[[Page 760]]

the maximum load. Alternatively, if practicable, you may test at three
levels of the key operating parameter (e.g. selected based on a
covariance analysis between each parameter and the PEMS output) equally
spaced within the normal range of the parameter.
8.2.2 Number of RM Tests for Excess Emission PEMS. For PEMS used for
excess emission reporting, conduct at least the following number of RM
tests at the following key parameter operating levels:
(1) Three at a low level.
(2) Three at a mid level.
(3) Three at a high level.
You may choose to perform more than nine total RM tests. If you
perform more than nine tests, you may reject a maximum of three tests as
long as the total number of test results used to determine the RA is
nine or greater and each operating level has at least three tests. You
must report all data, including the rejected data.
8.2.3 Number of RM Tests for Continual Compliance PEMS. For PEMS
used to determine compliance, conduct at least the following number of
RM tests at the following key parameter operating levels:
(1) Nine at a low level.
(2) Nine at a mid level.
(3) Nine at a high level.
You may choose to perform more than 9 RM runs at each operating
level. If you perform more than 9 runs, you may reject a maximum of
three runs per level as long as the total number of runs used to
determine the RA at each operating level is 9 or greater.
8.2.4 Reference Method Measurement Location. Select an accessible
measurement point for the RM that will ensure you measure emissions
representatively. Ensure the location is at least two equivalent stack
diameters downstream and half an equivalent diameter upstream from the
nearest flow disturbance such as the control device, point of pollutant
generation, or other place where the pollutant concentration or emission
rate can change. You may use a half diameter downstream instead of the
two diameters if you meet both of the following conditions:
(1) Changes in the pollutant concentration are caused solely by
diluent leakage, such as leaks from air heaters.
(2) You measure pollutants and diluents simultaneously at the same
locations.
8.2.5 Traverse Points. Select traverse points that ensure
representative samples. Conduct all RM tests within 3 cm of each
selected traverse point but no closer than 3 cm to the stack or duct
wall. The minimum requirement for traverse points are as follows:
(1) Establish a measurement line across the stack that passes
through the center and in the direction of any expected stratification.
(2) Locate a minimum of three traverse points on the line at 16.7,
50.0, and 83.3 percent of the stack inside diameter.
(3) Alternatively, if the stack inside diameter is greater than 2.4
meters, you may locate the three traverse points on the line at 0.4,
1.2, and 2.0 meters from the stack or duct wall. You may not use this
alternative option after wet scrubbers or at points where two streams
with different pollutant concentrations are combined. You may select
different traverse points if you demonstrate and provide verification
that it provides a representative sample. You may also use the traverse
point specifications given the RM.
8.2.6 Relative Accuracy Procedure. Perform the number of RA tests at
the levels required in sections 8.2.2 and 8.2.3. For integrated samples
(e.g., Method 3A or 7E), make a sample traverse of at least 21 minutes,
sampling for 7 minutes at each traverse point. For grab samples (e.g.,
Method 3 or 7), take one sample at each traverse point, scheduling the
grab samples so that they are taken simultaneously (within a 3-minute
period) or at an equal interval of time apart over a 21-minute period. A
test run for grab samples must be made up of at least three separate
measurements. Where multiple fuels are used in the monitored unit and
the fuel type affects the predicted emissions, determine a RA for each
fuel unless the effects of the alternative fuel on predicted emissions
or diluent were addressed in the model training process. The unit may
only use fuels that have been evaluated this way.
8.2.7 Correlation of RM and PEMS Data. Mark the beginning and end of
each RM test run (including the exact time of day) on the permanent
record of PEMS output. Correlate the PEMS and the RM test data by the
time and duration using the following steps:
A. Determine the integrated pollutant concentration for the PEMS for
each corresponding RM test period.
B. Consider system response time, if important, and confirm that the
pair of results is on a consistent moisture, temperature, and diluent
concentration basis.
C. Compare each average PEMS value to the corresponding average RM
value. Use the following guidelines to make these comparisons.

------------------------------------------------------------------------
If . . . Then . . . And then . . .
------------------------------------------------------------------------
The RM has an instrumental Directly compare RM
or integrated non- and PEMS results.
instrumental sampling
technique.

[[Page 761]]

The RM has a grab sampling Average the results Compare this average
technique. from all grab RM result with the
samples taken PEMS result
during the test obtained during the
run. The test run run.
must include 3 separate
grab measurements.
------------------------------------------------------------------------

Use the paired PEMS and RM data and the equations in section 12.2 to
calculate the RA in the units of the applicable emission standard. For
this 3-level RA test, calculate the RA at each operation level.
8.3 Statistical Tests for PEMS that are Used for Continual
Compliance. In addition to the RA determination, evaluate the paired RA
and PEMS data using the following statistical tests.
8.3.1 Bias Test. From the RA data taken at the mid-level, determine
if a bias exists between the RM and PEMS. Use the equations in section
12.3.1.
8.3.2 F-test. Perform a separate F-test for the RA paired data from
each operating level to determine if the RM and PEMS variances differ by
more than might be expected from chance. Use the equations in section
12.3.2.
8.3.3 Correlation Analysis. Perform a correlation analysis using the
RA paired data from all operating levels combined to determine how well
the RM and PEMS correlate. Use the equations in section 12.3.3. The
correlation is waived if the process cannot be varied to produce a
concentration change sufficient for a successful correlation test
because of its technical design. In such cases, should a subsequent RATA
identify a variation in the RM measured values by more than 30 percent,
the waiver will not apply, and a correlation analysis test must be
performed at the next RATA.
8.4 Reporting. Summarize in tabular form the results of the RA and
statistical tests. Include all data sheets, calculations, and charts
(records of PEMS responses) necessary to verify that your PEMS meets the
performance specifications. Include in the report the documentation used
to establish your PEMS parameter envelopes.
8.5 Reevaluating Your PEMS After a Failed Test, Change in
Operations, or Change in Critical PEMS Parameter. After initial
certification, if your PEMS fails to pass a quarterly RAA or yearly
RATA, or if changes occur or are made that could result in a significant
change in the emission rate (e.g., turbine aging, process modification,
new process operating modes, or changes to emission controls), your PEMS
must be recertified using the tests and procedures in section 8.1. For
example, if you initially developed your PEMS for the emissions unit
operating at 80-100 percent of its range, you would have performed the
initial test under these conditions. Later, if you wanted to operate the
emission unit at 50-100 percent of its range, you must conduct another
RA test and statistical tests, as applicable, to verify that the new
conditions of 50-100 percent of range are functional. These tests must
demonstrate that your PEMS provides acceptable data when operating in
the new range or with the new critical PEMS parameter(s). The
requirements of section 8.1 must be completed by the earlier of 60 unit
operating days or 180 calendar days after the failed RATA or after the
change that caused a significant change in emission rate.

9.0 Quality Control

You must incorporate a QA plan beyond the initial PEMS certification
test to verify that your system is generating quality-assured data. The
QA plan must include the components of this section.
9.1 QA/QC Summary. Conduct the applicable ongoing tests listed
below.

Ongoing Quality Assurance Tests
----------------------------------------------------------------------------------------------------------------
PEMS regulatory
Test purpose Acceptability Frequency
----------------------------------------------------------------------------------------------------------------
Sensor Evaluation.................... All.................... ....................... Daily.
RAA.................................. Compliance............. 3-test avg 10% of simultaneous quarter when RATA
analyzer or RM average. performed.
RATA................................. All.................... Same as for RA in Sec. Yearly in quarter when
13.1. RAA not performed.
Bias Correction...................... All.................... If davg Bias test passed (no
|cc|. correction factor
needed).
PEMS Training........................ All.................... If Fcritical F. and subsequent RATAs.
r 0.8.......
Sensor Evaluation Alert Test All.................... See Section 6.1.8...... After each PEMS
(optional). training.
----------------------------------------------------------------------------------------------------------------

[[Page 762]]

9.2 Daily Sensor Evaluation Check. Your sensor evaluation system
must check the integrity of each PEMS input at least daily.
9.3 Quarterly Relative Accuracy Audits. In the first year of
operation after the initial certification, perform a RAA consisting of
at least three 30-minute portable analyzer or RM determinations each
quarter a RATA is not performed. To conduct a RAA, follow the procedures
in Section 8.2 for the relative accuracy test, except that only three
sets of measurement data are required, and the statistical tests are not
required. The average of the three or more portable analyzer or RM
determinations must not exceed the limits given in Section 13.5. Report
the data from all sets of measurement data. If a PEMS passes all
quarterly RAAs in the first year and also passes the subsequent yearly
RATA in the second year, you may elect to perform a single mid-year RAA
in the second year in place of the quarterly RAAs. This option may be
repeated, but only until the PEMS fails either a mid-year RAA or a
yearly RATA. When such a failure occurs, you must resume quarterly RAAs
in the quarter following the failure and continue conducting quarterly
RAAs until the PEMS successfully passes both a year of quarterly RAAs
and a subsequent RATA.
9.4 Yearly Relative Accuracy Test. Perform a minimum 9-run RATA at
the normal operating level on a yearly basis in the quarter that the RAA
is not performed. The statistical tests in Section 8.3 are not required
for the yearly RATA.

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure [Reserved]

12.0 Calculations and Data Analysis

12.1 Nomenclature

B = PEMS bias adjustment factor.
cc = Confidence coefficient.
di = Difference between each RM and PEMS run.
d = Arithmetic mean of differences for all runs.
ei = Individual measurement provided by the PEMS or RM at a
particular level.
em = Mean of the PEMS or RM measurements at a particular
level.
ep = Individual measurement provided by the PEMS.
ev = Individual measurement provided by the RM.
F = Calculated F-value.
n = Number of RM runs.
PEMSi = Individual measurement provided by the PEMS.
PEMSiAdjusted = Individual measurement provided by the PEMS
adjusted for bias.
PEMS = Mean of the values provided by the PEMS at the normal operating
range during the bias test.
r = Coefficient of correlation.
RA = Relative accuracy.
RAA = Relative accuracy audit.
RM = Average RM value (or in the case of the RAA, the average portable
analyzer value). In cases where the average emissions for the
test are less than 50 percent of the applicable standard,
substitute the emission standard value here in place of the
average RM value.
Sd = Standard deviation of differences.
S\2\ = Variance of your PEMS or RM.
t0.025 = t-value for a one-sided, 97.5 percent confidence
interval (see Table 16-1).

12.2 Relative Accuracy Calculations. Calculate the mean of the RM
values. Calculate the differences between the pairs of observations for
the RM and the PEMS output sets. Finally, calculate the mean of the
differences, standard deviation, confidence coefficient, and PEMS RA,
using Equations 16-1, 16-2, 16-3, and 16-4, respectively. For compliance
PEMS, calculate the RA at each test level. The PEMS must pass the RA
criterion at each test level.
12.2.1 Arithmetic Mean. Calculate the arithmetic mean of the
differences between paired RM and PEMS observations using Equation 16-1.
[GRAPHIC] [TIFF OMITTED] TR25MR09.094

12.2.2 Standard Deviation. Calculate the standard deviation of the
differences using Equation 16-2 (positive square root).
[GRAPHIC] [TIFF OMITTED] TR25MR09.095

12.2.3 Confidence Coefficient. Calculate the confidence coefficient
using Equation 16-3 and Table 16-1.
[GRAPHIC] [TIFF OMITTED] TR25MR09.096

12.2.4 Relative Accuracy. Calculate the RA of your data using
Equation 16-4.
[GRAPHIC] [TIFF OMITTED] TR25MR09.097

12.3 Compliance PEMS Statistical Tests. If your PEMS will be used
for continual compliance purposes, conduct the following tests using the
information obtained during the RA tests. For the pollutant measurements
at any one test level, if the mean value of the

[[Page 763]]

RM is less than either 10 ppm or 5 percent of the emission standard, all
statistical tests are waived at that specific test level. For diluent
measurements at any one test level, if the mean value of the RM is less
than 3 percent of span, all statistical tests are waived for that
specific test level.
12.3.1 Bias Test. Conduct a bias test to determine if your PEMS is
biased relative to the RM. Determine the PEMS bias by comparing the
confidence coefficient obtained from Equation 16-3 to the arithmetic
mean of the differences determined in Equation 16-1. If the arithmetic
mean of the differences (d) is greater than the absolute value of the
confidence coefficient (cc), your PEMS must incorporate a bias factor to
adjust future PEMS values as in Equation 16-5.
[GRAPHIC] [TIFF OMITTED] TR25MR09.098

Where:
[GRAPHIC] [TIFF OMITTED] TR25MR09.099

12.3.2 F-test. Conduct an F-test for each of the three RA data sets
collected at different test levels. Calculate the variances of the PEMS
and the RM using Equation 16-6.
[GRAPHIC] [TIFF OMITTED] TR25MR09.100

Determine if the variance of the PEMS data is significantly different
from that of the RM data at each level by calculating the F-value using
Equation 16-7.
[GRAPHIC] [TIFF OMITTED] TR25MR09.101

Compare the calculated F-value with the critical value of F at the 95
percent confidence level with n-1 degrees of freedom. The critical value
is obtained from Table 16-2 or a similar table for F-distribution. If
the calculated F-value is greater than the critical value at any level,
your proposed PEMS is unacceptable. For pollutant PEMS measurements, if
the standard deviation of the RM is less than either 3 percent of the
span or 5 ppm, use a RM standard deviation of either 5 ppm or 3 percent
of span. For diluent PEMS measurements, if the standard deviation of the
reference method is less than 3 percent of span, use a RM standard
deviation of 3 percent of span.
12.3.3 Correlation Analysis. Calculate the correlation coefficient
either manually using Eq. 16-8, on a graph, or by computer using all of
the paired data points from all operating levels. Your PEMS correlation
must be 0.8 or greater to be acceptable. If during the initial
certification test, your PEMS data are determined to be auto-correlated
according to the procedures in 40 CFR 75.41(b)(2), or if the signal-to-
noise ratio of the data is less than 4, then the correlation analysis is
permanently waived.
[GRAPHIC] [TIFF OMITTED] TR25MR09.102

12.4 Relative Accuracy Audit. Calculate the quarterly RAA using
Equation 16-9.
[GRAPHIC] [TIFF OMITTED] TR27FE14.019

13.0 Method Performance

13.1 PEMS Relative Accuracy. The RA must not exceed 10 percent if
the PEMS measurements are greater than 100 ppm or 0.2 lbs/mm Btu. The RA
must not exceed 20 percent if the PEMS measurements are between 100 ppm
(or 0.2 lb/mm Btu) and 10 ppm (or 0.05 lb/mm Btu). For measurements
below 10 ppm, the absolute mean difference between the PEMS measurements
and the RM measurements must not exceed 2 pppm. For diluent PEMS, an
alternative criterion of 1 percent absolute difference between the PEMS
and RM may be used if less stringent.

[[Page 764]]

13.2 PEMS Bias. Your PEMS data is considered biased and must be
adjusted if the arithmetic mean (d) is greater than the absolute value
of the confidence coefficient (cc) in Equations 16.1 and 16.3. In such
cases, a bias factor must be used to correct your PEMS data.
13.3 PEMS Variance. Your calculated F-value must not be greater than
the critical F-value at the 95-percent confidence level for your PEMS to
be acceptable.
13.4 PEMS Correlation. Your calculated r-value must be greater than
or equal to 0.8 for your PEMS to be acceptable.
13.5 Relative Accuracy Audits. The average of the three portable
analyzer or RM determinations must not differ from the simultaneous PEMS
average value by more than 10 percent of the analyzer or RM for
concentrations greater than 100 ppm or 20 percent for concentrations
between 100 and 20 ppm, or the test is failed. For measurements at 20
ppm or less, this difference must not exceed 2 ppm for a pollutant PEMS
and 1 percent absolute for a diluents PEMS.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References [Reserved]

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Table 16-1--t-Values for One-sided, 97.5 Percent Confidence Intervals for Selected Sample Sizes*
----------------------------------------------------------------------------------------------------------------
n-1 t0.025 n-1 t0.025
----------------------------------------------------------------------------------------------------------------
2............................................................... 12.706 16 2.131
3............................................................... 4.303 17 2.120
4............................................................... 3.182 18 2.110
5............................................................... 2.776 19 2.101
6............................................................... 2.571 20 2.093
7............................................................... 2.447 21 2.086
8............................................................... 2.365 22 2.080
9............................................................... 2.306 23 2.074
10.............................................................. 2.262 24 2.069
11.............................................................. 2.228 25 2.064
12.............................................................. 2.201 26 2.060
13.............................................................. 2.179 27 2.056
14.............................................................. 2.160 28 2.052
15.............................................................. 2.145 >29 t-Table
----------------------------------------------------------------------------------------------------------------
* Use n equal to the number of data points (n-1 equals the degrees of freedom).

[[Page 765]]

[GRAPHIC] [TIFF OMITTED] TR25MR09.107

Performance Specification 17 [Reserved]

Performance Specification 18--Performance Specifications and Test
Procedures for Gaseous Hydrogen Chloride (HCI) Continuous Emission
Monitoring Systems at Stationary Sources

1.0 Scope and Application

1.1 Analyte. This performance specification (PS) is applicable for
measuring gaseous concentrations of hydrogen chloride (HCl), CAS: 7647-
01-0, on a continuous basis in the units of the applicable standard or
in units that can be converted to units of the applicable standard(s).
1.2 Applicability.
1.2.1 This specification is used to evaluate the acceptability of
HCl continuous emission monitoring systems (CEMS) at the time of

[[Page 766]]

installation or soon after and whenever specified in the regulations.
The specification includes requirements for initial acceptance including
instrument accuracy and stability assessments and use of audit samples
if they are available.
1.2.2 The Administrator may require the operator, under section 114
of the Clean Air Act, to conduct CEMS performance evaluations at other
times besides the initial test to evaluate the CEMS performance. See 40
CFR part 60, Sec. Sec. 60.13(c) and 63.8(e)(1).
1.2.3 A source that demonstrates their CEMS meets the criteria of
this PS may use the system to continuously monitor gaseous HCl under any
regulation or permit that requires compliance with this PS. If your CEMS
is capable of reporting the HCl concentration in the units of the
applicable standard, no additional CEMS components are necessary. If
your CEMS does not report concentrations in the units of the existing
standard, then other CEMS components (e.g., oxygen (O2),
temperature, stack gas flow, moisture and pressure) may be necessary to
convert the units reported by your CEMS to the units of the standard.
1.2.4 These specification test results are intended to be valid for
the life of the system. As a result, the HCl measurement system must be
tested and operated in a configuration consistent with the configuration
that will be used for ongoing continuous emissions monitoring.
1.2.5 Substantive changes to the system configuration require
retesting according to this PS. Examples of such conditions include, but
are not limited to: major changes in dilution ratio (for dilution based
systems); changes in sample conditioning and transport, if used, such as
filtering device design or materials; changes in probe design or
configuration and changes in materials of construction. Changes
consistent with instrument manufacturer upgrade that fall under
manufacturer's certification do not require additional field
verification. Manufacturer's upgrades require recertification by the
manufacturer for those requirements allowed by this PS, including
interference, level of detection (LOD), and light intensity
qualification.
1.2.6 This specification is not designed to evaluate the ongoing
CEMS performance nor does it identify specific calibration techniques
and auxiliary procedures to assess CEMS performance over an extended
period of time. The requirements in appendix F, Procedure 6 are designed
to provide a way to assess CEMS performance over an extended period of
time. The source owner or operator is responsible to calibrate,
maintain, and operate the CEMS properly.

2.0 Summary of Performance Specification

2.1 This specification covers the procedures that each CEMS must
meet during the performance evaluation test. Installation and
measurement location specifications, data reduction procedures, and
performance criteria are included.
2.2 The technology used to measure gaseous HCl must provide a
distinct response and address any appropriate interference
correction(s). It must accurately measure gaseous HCl in a
representative sample (path or point sampling) of stack effluent.
2.3 The relative accuracy (RA) must be established against a
reference method (RM) (i.e., Method 26A, Method 320, ASTM International
(ASTM) D6348-12, including mandatory annexes, or Method 321, as
appropriate for the source concentration and category). Method 26 may be
approved as a RM by the Administrator on a case-by-case basis if not
otherwise allowed or denied in an applicable subpart of the regulations.
2.4 A standard addition (SA) procedure using a reference standard is
included in appendix A to this performance specification for use in
verifying LOD. For extractive CEMS, where the SA is done by dynamic
spiking (DS), the appendix A procedure is allowed as an option for
assessing calibration drift and is also referenced by Procedure 6 of
appendix F to this part for ongoing quality control tests.

3.0 Definitions

3.1 Calibration Cell means a gas containment cell used with cross
stack or integrated path (IP) CEMS for calibration and to perform many
of the test procedures required by this performance specification. The
cell may be a removable sealed cell or an evacuated and/or purged cell
capable of exchanging reference and other calibration gases as well as
zero gas standards. When charged, it contains a known concentration of
HCl and/or interference gases. The calibration cell is filled with zero
gas or removed from the optical path during stack gas measurement.
3.2 Calibration Drift (CD) means the absolute value of the
difference between the CEMS output response and an upscale reference gas
or a zero-level gas, expressed as a percentage of the span value, when
the CEMS is challenged after a stated period of operation during which
no unscheduled adjustments, maintenance or repairs took place.
3.3 Centroidal Area means a central area that is geometrically
similar to the stack or duct cross section and is no greater than 10
percent of the stack or duct cross-sectional area.
3.4 Continuous Emission Monitoring System (CEMS) means the total
equipment required to measure the pollutant concentration or emission
rate continuously. The system generally consists of the following three
major subsystems:

[[Page 767]]

3.4.1 Sample Interface means that portion of the CEMS used for one
or more of the following: sample acquisition, sample transport, sample
conditioning, defining the optical measurement path, and protection of
the monitor from the effects of the stack effluent.
3.4.2 HCl Analyzer means that portion of the HCl CEMS that measures
the total vapor phase HCl concentration and generates a proportional
output.
3.4.3 Data Recorder means that portion of the CEMS that provides a
permanent electronic record of the analyzer output. The data recorder
may record other pertinent data such as effluent flow rates, various
instrument temperatures or abnormal CEMS operation. The data recorder
may also include automatic data reduction capabilities and CEMS control
capabilities.
3.5 Diluent Gas means a major gaseous constituent in a gaseous
pollutant mixture. For combustion sources, either carbon dioxide (CO2)
or oxygen (O2) or a combination of these two gases are the major gaseous
diluents of interest.
3.6 Dynamic Spiking (DS) means the procedure where a known
concentration of HCl gas is injected into the probe sample gas stream
for extractive CEMS at a known flow rate to assess the performance of
the measurement system in the presence of potential interference from
the flue gas sample matrix.
3.7 Independent Measurement(s) means the series of CEMS data values
taken during sample gas analysis separated by two times the procedure
specific response time (RT) of the CEMS.
3.8 Integrated Path CEMS (IP-CEMS) means an in-situ CEMS that
measures the gas concentration along an optical path in the stack or
duct cross section.
3.9 Interference means a compound or material in the sample matrix
other than HCl whose characteristics may bias the CEMS measurement
(positively or negatively). The interference may not prevent the sample
measurement, but could increase the analytical uncertainty in the
measured HCl concentration through reaction with HCl or by changing the
electronic signal generated during HCl measurement.
3.10 Interference Test means the test to detect CEMS responses to
interferences that are not adequately accounted for in the calibration
procedure and may cause measurement bias.
3.11 Level of Detection (LOD) means the lowest level of pollutant
that the CEMS can detect in the presence of the source gas matrix
interferents with 99 percent confidence.
3.12 Liquid Evaporative Standard means a reference gas produced by
vaporizing National Institute of Standards and Technology (NIST)
traceable liquid standards of known HCl concentration and quantitatively
diluting the resultant vapor with a carrier gas.
3.13 Measurement Error (ME) is the mean difference between the
concentration measured by the CEMS and the known concentration of a
reference gas standard, divided by the span, when the entire CEMS,
including the sampling interface, is challenged.
3.14 Optical Path means the route light travels from the light
source to the receiver used to make sample measurements.
3.15 Path Length means, for an extractive optical CEMS, the distance
in meters of the optical path within a gas measurement cell. For an IP-
CEMS, path length means the distance in meters of the optical path that
passes through the source gas in the stack or duct.
3.16 Point CEMS means a CEMS that measures the source gas
concentration, either at a single point at the sampling probe tip or
over a path length for IP-CEMS less than 10 percent of the equivalent
diameter of the stack or duct cross section.
3.17 Stack Pressure Measurement Device means a NIST-traceable gauge
or monitor that measures absolute pressure and conforms to the design
requirements of ASME B40.100-2010, ``Pressure Gauges and Gauge
Attachments'' (incorporated by reference--see Sec. 60.17).
3.18 Reference Gas Standard means a NIST-traceable gas standard
containing a known concentration of HCl certified in accordance with an
EPA traceability protocol in section 7.1 of this PS.
3.19 Relative Accuracy (RA) means the absolute mean difference
between the gas concentration or the emission rate determined by the
CEMS and the value determined by the RM, plus the confidence coefficient
of a series of nine test runs, divided by the average of the RM or the
applicable emission standard.
3.20 Response Time (RT) means the time it takes for the measurement
system, while operating normally at its target sample flow rate,
dilution ratio, or data collection rate to respond to a known step
change in gas concentration, either from a low- or zero-level to a high-
level gas concentration or from a high-level to a low or zero-level gas
concentration, and to read 95 percent of the change to the stable
instrument response. There may be several response times (RTs) for an
instrument related to different functions or procedures (e.g., DS, LOD,
and ME).
3.21 Span Value means an HCl concentration approximately equal to
two times the concentration equivalent to the emission standard unless
otherwise specified in the applicable regulation, permit or other
requirement. Unless otherwise specified, the span may be rounded up to
the nearest multiple of 5.

[[Page 768]]

3.22 Standard Addition means the addition of known amounts of HCl
gas (either statically or dynamically) to the actual measurement path or
measured sample gas stream.
3.23 Zero gas means a gas or liquid with an HCl concentration that
is below the LOD of the measurement system.

4.0 Interferences

Sample gas interferences will vary depending on the instrument or
technology used to make the measurement. Interferences must be evaluated
through the interference test in this PS. Several compounds including
carbon dioxide (CO2), carbon monoxide (CO), formaldehyde
(CH2O), methane (CH4), and water (H2O)
are potential optical interferences with certain types of HCl monitoring
technology. Ammonia is a potential chemical interference with HCl.

5.0 Safety

The procedures required under this PS may involve hazardous
materials, operations, and equipment. This PS may not address all of the
safety issues associated with these procedures. It is the responsibility
of the user to establish appropriate safety and health practices and
determine the applicable regulatory limitations prior to performing
these procedures. The CEMS user's manual and materials recommended by
the RM should be consulted for specific precautions to be taken.

6.0 Equipment and Supplies

Equipment and supplies for CEMS will vary depending on the
measurement technology and equipment vendors. This section provides a
description of the equipment and supplies typically found in one or more
types of CEMS.
6.1 Sample Extraction System. The portion of an extractive CEMS that
collects and transports the sample to the pressure regulation and sample
conditioning module. The extraction system must deliver a representative
sample to the measurement instrument. The sample extraction system
typically consists of a sample probe and a heated umbilical line.
6.2 Sample Conditioning Module. The portion of an extractive CEMS
that removes particulate matter and moisture from the gas stream and
provides a sample gas stream to the CEMS analysis module or analyzer.
You must keep the particle-free gas sample above the dew point
temperature of its components.
6.3 HClAnalyzer. The portion of the CEMS that detects, quantifies
and generates an output proportional to the sample gas HCl
concentration.
6.4 System Controller. The portion of the CEMS that provides control
of the analyzer and other sub-systems (e.g., sample extraction, sample
conditioning, reference gas) as necessary for continuous operation and
periodic maintenance/QC activities.
6.5 Data Recorder. The portion of the CEMS that provides a record of
analyzer output. The data recorder may record other pertinent data such
as effluent flow rates, various instrument temperatures or abnormal CEMS
operation. The data recorder output range must include the full range of
expected HCl concentration values in the gas stream to be sampled
including zero and span value.
6.6 Reference Gas System(s). Gas handling system(s) needed to
introduce reference and other gases into the measurement system. For
extractive CEMS, the system must be able to introduce gas flow
sufficient to flood the sampling probe and prevent entry of gas from the
effluent stream. For IP-CEMS, the system must be able to introduce a
known concentration of HCl, at known cell length, pressure and
temperature, into the optical path used to measure HCl gas
concentration.
6.7 Moisture Measurement System. If correction of the measured HCl
emissions for moisture is required, you must install, operate, maintain,
and quality assure a continuous moisture monitoring system for measuring
and recording the moisture content of the flue gases. The following
continuous moisture monitoring systems are acceptable: An FTIR system
validated according to Method 301 or section 13.0 of Method 320 in
appendix A to part 63 of this chapter; a continuous moisture sensor; an
oxygen analyzer (or analyzers) capable of measuring O2 both
on a wet basis and on a dry basis; a stack temperature sensor and a
moisture look-up table, i.e., a psychrometric chart (for saturated gas
streams following wet scrubbers or other demonstrably saturated gas
streams, only); or other continuous moisture measurement methods
approved by the Administrator. Alternatively, for any type of fuel, you
may determine an appropriate site-specific default moisture value (or
values), using measurements made with Method 4--Determination of
Moisture Content In Stack Gases, in appendix A-3 to of this part. If
this option is selected, the site-specific moisture default value(s)
must represent the fuel(s) or fuel blends that are combusted in the unit
during normal, stable operation, and must account for any distinct
difference(s) in the stack gas moisture content associated with
different process operating conditions. At least nine Method 4 runs are
required for determining each site-specific default moisture percentage.
Calculate each site-specific default moisture value by taking the
arithmetic average of the Method 4 runs. Each site-specific moisture
default value shall be updated whenever the current value is non-
representative, due to changes in unit or process operation, but in any
event no less frequently than annually.

[[Page 769]]

7.0 Reagents and Standards

7.1 Reference Gases. Reference gases (e.g., cylinder gases or liquid
evaporative standards) used to meet the requirements of this PS must be
NIST certified or NIST-traceable and vendor certified to 5.0 percent
accuracy. HCl cylinder gases must be certified according to Reference 5
in section 16 of this PS through a documented unbroken chain of
comparisons each contributing to the reported uncertainty. Liquid
evaporative standards must be certified using the gravimetrically-based
procedures of the latest version of the EPA Traceability Protocol for
Qualification and Certification of Evaporative HCl Gas Standards and
Humidification of HCl Gas Standards from Cylinders (see EPA-HQ-OAR-2013-
0696-0026.pdf).
7.2 Cylinder gas and/or liquid evaporative standards must be used
within their certification periods.
7.3 High concentration cylinder gas or liquid evaporative HCl
standards may be diluted for use in this specification. You must
document the quantitative introduction of HCl standards into the system
using Method 205, found in 40 CFR part 51, appendix M, or other
procedure approved by the Administrator.

8.0 CEMS Measurement Location Specifications and Pretest Preparation

8.1 Prior to the start of your initial PS tests, you must ensure
that the CEMS is installed according to the manufacturer's
specifications and the requirements in this section. You may use either
point or IP sampling technology.
8.2 CEMS Installation. Install the CEMS at an accessible location
where the pollutant concentration or emission rate measurements are
directly representative of the HCl emissions or can be corrected so as
to be representative of the total emissions from the affected facility.
The CEMS need not be installed at the same location as the relative
accuracy test location. If you fail the RA requirements in this
specification due to the CEMS measurement location and a satisfactory
correction technique cannot be established, the Administrator may
require the CEMS to be relocated.
8.2.1 Single point sample gas extraction should be (1) no less than
1.0 m (3.3 ft.) from the stack or duct wall or (2) within the centroidal
area of the stack or duct cross section.
8.2.2 IP-CEMS measurements should (1) be conducted totally within
the inner area bounded by a line 1.0 m (3.3 ft.) from the stack or duct
wall, (2) have at least 70 percent of the path within the inner 50
percent of the stack or duct cross-sectional area, or (3) be located
over any part of the centroidal area.
8.2.2.1 You must measure the IP-CEMS path length from the inner
flange of the sampling ports or the inner end of the instrument
insertion into the stack cavity using a laser tape measure, mechanical
measurement tape, or similar device accurate to 1.5 mm (0.059 in).
8.2.2.2 You must ensure that any purge flow used to protect IP-CEMS
instrument windows from stack gas does not alter the measurement path
length. Purge flow of less than or equal to 10 percent of the gas
velocity in the duct meets this requirement.
8.2.3 CEMS and Data Recorder Scale Check. After CEMS installation,
record and document the measurement range of the HCl CEMS. The CEMS
operating range and the range of the data recording device must
encompass all potential and expected HCl concentrations, including the
concentration equivalent to the applicable emission limit and the span
value.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Performance Specification Test Procedure

After completing the CEMS installation, setup and calibration, you
must complete the PS test procedures in this section. You must perform
the following procedures and meet the performance requirements for the
initial demonstration of your CEMS:
a. Interference Test;
b. Beam Intensity Test (IP-CEMS only);
c. Temperature Verification Procedure (IP-CEMS only);
d. Pressure Verification Procedure (IP-CEMS only);
e. Level of Detection Determination;
f. Response Time Test;
g. Measurement Error Test;
h. Calibration Drift Test; and
i. Relative Accuracy Test.

11.1 Interference Test

11.1.1 Prior to its initial use in the field, you must demonstrate
that your monitoring system meets the performance requirements of the
interference test in section 13.5 to verify that the candidate system
measures HCl accurately in the presence of common interferences in
emission matrices.
11.1.2 Your interference test must be conducted in a controlled
environment. The equipment you test for interference must include the
combination of the analyzer, related analysis software, and any sample
conditioning equipment (e.g., dilution module, moisture removal
equipment or other interferent scrubber) used to control interferents.
11.1.3 If you own multiple measurement systems with components of
the same make and model numbers, you need only perform

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this interference test on one analyzer and associated interference
conditioning equipment combination. You may also rely on an interference
test conducted by the manufacturer or a continuous measurement system
integrator on a system having components of the same make and model(s)
of the system that you use.
11.1.4 Perform the interference check using an HCl reference gas
concentration of approximately five times the LOD.
11.1.5 Introduce the interference test gases listed in Table 1 in
section 17.0 of this PS to the analyzer/conditioning system separately
or in any combination. The interference test gases need not be of
reference gas quality.
11.1.5.1 For extractive CEMS, the interference test gases may be
introduced directly into the inlet to the analyzer/conditioning system
after the probe extension coupling.
11.1.5.2 For IP-CEMS, the interference test gases may be added with
the HCl in a calibration cell or separately in a temperature-controlled
cell. The effective concentration of the gas in the cell must meet the
requirements in Table 1 corrected for absolute pressure, temperature and
the nominal stack sampling path length of the CEMS.
11.1.6 The interference test must be performed by combining an HCl
reference gas with each interference test gas (or gas mixture). You must
measure the baseline HCl response, followed by the response after adding
the interference test gas(es) while maintaining a constant HCl
concentration. You must perform each interference gas injection and
evaluation in triplicate.
Note: The baseline HCl gas may include interference gases at
concentrations typical of ambient air (e.g., 21 percent O2,
400 parts per million (ppm) CO2, 2 percent H2O),
but these concentrations must be brought to the concentrations listed in
Table 1 when their interference effects are being evaluated.
11.1.7 You should document the gas volume/rate, temperature, and
pressure used to conduct the interference test. A gas blending system or
manifold may be used.
11.1.8 Ensure the duration of each interference test is sufficient
to condition the HCl measurement system surfaces before a stable
measurement is obtained.
11.1.9 Measure the HCl response of the analyzer/sample conditioning
system combination to the test gases in ppmv. Record the responses and
determine the overall interference response using Table 2 in section
17.0.
11.1.10 For each interference gas (or mixture), calculate the mean
difference (FMCavg) between the measurement system responses
with and without the interference test gas(es) using Equation 1 in
section 12.2. Summarize the results following the format contained in
Table 2 in section 17.
11.1.11 Calculate the percent interference (I) for the gas runs
using Equation 2 in section 12.2.
11.1.12 The total interference response (i.e., the sum of the
interference responses of all tested gaseous components) must not exceed
the criteria set forth in section 13.5 of this PS.

11.2 Beam Intensity Test for IP-CEMS

11.2.1 For IP-CEMS, you must establish the tolerance of your system
to beam intensity attenuation.
11.2.1.1 Your beam intensity test may be conducted in either a
controlled environment or on-site during initial setup and demonstration
of your CEMS.
11.2.1.2 If you have multiple measurement systems with components of
the same make and model numbers, you need only perform this attenuation
check on one system and you may also rely on an attenuation test
conducted by the manufacturer on a system having components of the same
make and model(s) of the system that you use.
11.2.2 Insert one or more neutral density filter(s) or otherwise
attenuate the beam intensity by a known percentage (e.g., 90 percent of
the beam intensity).
11.2.3 Perform a high-level HCl reference gas measurement.
11.2.4 Record and report the attenuated beam intensity, the measured
HCl calibration gas concentration at full beam intensity, the measured
HCl gas concentration with attenuated beam intensity, and the percent
difference between the two HCl measurements with and without attenuation
of the beam intensity. The percent difference must not exceed the
criteria set forth in section 13.6 of this PS.
11.2.5 In the future, you may not operate your IP-CEMS at a beam
intensity lower than that established based on the attenuation used
during this test. However, you may repeat the test to establish a lower
beam intensity limit or level.

11.3 Temperature Measurement Verification Procedure for IP-CEMS

11.3.1 Any measurement instrument or device that is used as a
reference in verification of temperature measurement must have an
accuracy that is traceable to NIST.
11.3.2 You must verify the temperature sensor used in IP-CEMS
measurements on-site as part of the initial installation and
verification procedures.
11.3.3 Comparison to Calibrated Temperature Measurement Device.
11.3.3.1 Place the sensor of a calibrated temperature reference
device adjacent to the sensor used to measure stack temperature

[[Page 771]]

for your IP-CEMS. The calibrated temperature reference device must
satisfy the accuracy requirements specified in Table 3 of this PS. The
calibrated temperature reference device must also have a range equal to
or greater than the range of your IP-CEMS temperature sensor.
11.3.3.2 Allow sufficient time for the response of the calibrated
temperature reference device to reach equilibrium. With the process and
control device operating under normal conditions, concurrently record
the temperatures measured by your IP-CEMS system (Mt) and the
calibrated temperature reference device (Vt). You must meet
the accuracy requirements specified in section 13.7 of this PS.
11.3.3.3 If your IP-CEMS temperature sensor does not satisfy the
accuracy requirement of this PS, check all system components and take
any corrective action that is necessary to achieve the required minimum
accuracy. Repeat this verification procedure until the accuracy
requirement of this specification is satisfied.

11.4 Pressure Measurement Verification Procedure for IP-CEMS

11.4.1 For stack pressure measurement verification, you must select
a NIST-traceable gauge or monitor that conforms to the design
requirements of ASME B40.100-2010, ``Pressure Gauges and Gauge
Attachments,'' (incorporated by reference--see Sec. 60.17) as a
reference device.
11.4.2 As an alternative for a calibrated pressure reference device
with NIST-traceable accuracy, you may use a water-in-glass U-tube
manometer to verify your IP-CEMS pressure measurement equipment,
provided there is also an accurate measurement of absolute atmospheric
pressure at the manometer location.
11.4.3 Allow sufficient time for the response of the reference
pressure measurement device to reach equilibrium. With the process and
control device operating under normal conditions, concurrently record
the pressures measured by your IP-CEMS system (MP) and the
pressure reference device (Vp). You must meet the accuracy
requirements specified in section 13.8 of this PS.
11.4.4 If your IP-CEMS pressure sensor does not satisfy the accuracy
requirement of this PS, check all system components and take any
corrective action that is necessary to achieve the required minimum
accuracy. Repeat this verification procedure until the accuracy
requirement of this specification is satisfied.

11.5 Level of Detection Determination

11.5.1 You must determine the minimum amount of HCl that can be
detected above the background in a representative gas matrix.
11.5.2 You must perform the LOD determination in a controlled
environment such as a laboratory or manufacturer's facility.
11.5.3 You must add interference gases listed in Table 1 of this PS
to a constant concentration of HCl reference gas.
11.5.3.1 You may not use an effective reference HCl gas
concentration greater than five times the estimated instrument LOD.
11.5.3.2 For extractive CEMS, inject the HCl and interferents
described in section 11.1.5 directly into the inlet to the analyzer.
11.5.3.3 For IP-CEMS, the HCl and interference test gases may be
added to a calibration cell or separately in a temperature-controlled
cell that is part of the measurement path. The effective concentration
of the gas in the cell must meet the requirements in Table 1 corrected
for absolute pressure, temperature and the nominal stack sampling path
length of the CEMS.
11.5.4 Collect seven or more consecutive measurements separated by
twice the RT (described in section 11.6) to determine the LOD.
11.5.5 Calculate the standard deviation of the measured values and
define the LOD as three times the standard deviation of these
measurements.
11.5.5.1 The LOD for extractive units must be determined and
reported in ppmv.
11.5.5.2 The LOD for IP units must be determined and reported on a
ppm-meter basis and the site- or installation-specific LOD must be
calculated based on the actual measurement path length and gas density
of the emissions at the specific site installation in ppmv.
11.5.6 You must verify the controlled environment LOD of section
11.5.2 of this PS for your CEMS during initial setup and field
certification testing. You must use the SA procedure in appendix A of
this PS with the following exceptions:
11.5.6.1 For the LOD verification in the field, you must make three
independent SA measurements spiking the native source concentration by
no more than three times the controlled environment LOD concentration
determined in section 11.5.5.
11.5.6.2 For extractive CEMS, you must perform the SA as a dynamic
spike by passing the spiked source gas sample through all filters,
scrubbers, conditioners and other monitoring system components used
during normal sampling, and as much of the sampling probe as practical.
For IP-CEMS, you must perform the SA procedure by adding or passing a
known concentration reference gas into a calibration cell in the optical
path of the CEMS; you must also include the source measurement optical
path while performing the SA measurement.

[[Page 772]]

11.5.6.3 The amount detected, or standard addition response (SAR),
is based on the average difference of the native HCl concentration in
the stack or duct relative to the native stack concentration plus the
SA. You must be able to detect the effective spike addition (ESA) above
the native HCl present in the stack gas matrix. For extractive CEMS, the
ESA is calculated using Equation A7 in appendix A of this PS. For IP-
CEMS, the ESA is calculated as Ci,eff using Equation 4 of
this PS.
11.5.6.4 For extractive CEMS, calculate the SAR using Equation A4 in
appendix A of this PS. For IP-CEMS, calculate the SAR using Equation A8.
11.5.6.5 If your system LOD field verification does not demonstrate
a SAR greater than or equal to your initial controlled environment LOD,
you must increase the SA concentration incrementally and repeat the
field verification procedure until the SAR is equal to or greater than
LOD. The site-specific standard addition detection level (SADL) is equal
to the standard addition needed to achieve the acceptable SAR, and SADL
replaces the controlled environment LOD. For extractive CEMS, the SADL
is calculated as the ESA using Equation A7 in appendix A of this PS. For
IP-CEMS, the SADL is the SA calculated using Equation A8 in appendix A
of this PS. As described in section 13.1 of this PS, the SADL must be
less than 20 percent of the applicable emission limit.

11.6 Response Time Determination. You must determine ME-, LOD- and SA-RT

11.6.1 For ME- or LOD-RT, start the upscale RT determination by
injecting zero gas into the measurement system as required by the
procedures in section 11.7 or 11.5, respectively. You may use humidified
zero gas. For standard addition RT, start the upscale RT determination
by measuring the native stack gas concentration of HCl.
11.6.1.1 For extractive CEMS measuring ME- or LOD-RT, the output has
stabilized when there is no change greater than 1.0 percent of full
scale for 30 seconds.
11.6.1.2 For standard addition RT that includes the stack gas matrix
the final stable response may continue to vary by more than 1 percent,
but may be considered stable if the variability is random and not
continuously rising or falling.
11.6.2 When the CEMS output has stabilized, record the response in
ppmv and introduce an upscale (high level) or spike reference gas as
required by the relevant procedure.
11.6.3 Record the time (upscale RT) required to reach 95 percent of
the change to the final stable value.
11.6.4 Next, for ME or LOD RT, reintroduce the zero gas and record
the time required to reach 95 percent of the change to the stable
instrument response at the zero gas reading. For SA RT, introduce zero
gas to the IP-CEMS cell or stop the spike gas flow to the extractive
CEMS as required by the specified procedure and record the time required
to reach 95 percent of the change to the stable instrument response of
the native gas reading. This time is the downscale RT.
(Note: For CEMS that perform a series of operations (purge, blow
back, sample integration, analyze, etc.), you must start adding
reference or zero gas immediately after these procedures are complete.)
11.6.5 Repeat the entire procedure until you have three sets of
data, then determine the mean upscale and mean downscale RTs for each
relevant procedure. Report the greater of the average upscale or average
downscale RTs as the RT for the system.

11.7 Measurement Error (ME) Test

11.7.1 On the same day and as close in time as practicable to when
the ME test is conducted, perform and meet requirements for a
calibration drift (CD) test using a zero gas as used in the Seven-Day
Drift Test (see section 11.8) and document and report the results. To
meet this requirement, the ME test may be conducted during the Seven-Day
CD Test.
11.7.2 Extractive CEMS ME Test.
11.7.2.1 Introduce reference gases to the CEMS probe, prior to the
sample conditioning and filtration system.
11.7.2.2 Measure three upscale HCl reference gas concentrations in
the range shown in Table 4 of this PS.
11.7.2.3 Introduce the gases into the sampling probe with sufficient
flow rate to replace the entire source gas sample.
11.7.2.4 Continue to add the reference gas until the response is
stable as evidenced when the difference between two consecutive
measurements is less than the LOD or within five percent of each other.
11.7.2.5 Make triplicate measurements for each reference gas for a
total of nine measurements. Introduce different reference gas
concentrations in any order but do not introduce the same gas
concentration twice in succession.
11.7.2.6 At each reference gas concentration, determine the average
of the three CEMS responses (MCl). Calculate the ME using Equation 3A in
section 12.3.
11.7.2.7 If you desire to determine the system RT during this test,
you must inject zero gas immediately before and after each injection of
the high-level gas standard.
11.7.2.8 For non-dilution systems, you may adjust the system to
maintain the correct flow rate at the analyzer during the test, but you
may not make adjustments for any other purpose. For dilution systems,
you must operate the measurement system at the appropriate dilution
ratio during all system ME checks, and you may make only the

[[Page 773]]

adjustments necessary to maintain the proper ratio.
11.7.3 IP-CEMS ME Test.
11.7.3.1 Conduct a 3-level system ME test by individually adding the
known concentrations of HCl reference gases into a calibration cell of
known volume, temperature, pressure and path length.
Note: The optical path used for IP-CEMS ME checks must include the
native HCl measurement path. You must also collect native stack
concentration HCl measurements before and after each HCl standard
measurement. Bracketing HCl reference gas measurements with native stack
HCl measurements must be used in the calculations in Equation 5 in
section 12.4.2 to correct the upscale measurements for stack gas HCl
concentration changes.
11.7.3.2 Introduce HCl reference gas into your calibration cell in a
range of concentrations that produce responses equivalent to the source
concentrations shown in Table 4 of this PS for your path length.
11.7.3.3 Make triplicate measurements for each reference gas
standard for a total of nine measurements. Introduce different
calibration concentrations in any order but do not introduce the same
reference gas concentration twice in succession.
11.7.3.4 You must calculate the effective concentration
(Ci,eff) of the HCl reference gas equivalent to the stack
concentration by correcting for calibration cell temperature, pressure,
path length, line strength factor (LSF) and, if necessary, the native
stack gas HCl concentration using Equation 4 in section 12.0.
11.7.3.5 You may use the LSF provided by your instrument
manufacturer or determine an instrument-specific LSF as a function of
temperature using a heated gas cell and equivalent concentrations
(Ci,eff) between 50 and 150 percent of the emission limit.
11.7.3.6 At each reference gas concentration, average the three
independent CEMS measurement responses corrected for native HCl stack
concentration. Calculate the ME using Equation 6A in section 12.4.3.
11.7.4 You may use Figure 1 in section 17.0 to record and report
your ME test results.
11.7.5 If the ME specification in section 13.3 is not met for all
three reference gas concentrations, take corrective action and repeat
the test until an acceptable 3-level ME test is achieved.

11.8 Seven-Day Calibration Drift (CD) Test

11.8.1 The CD Test Period. Prior to the start of the RA tests, you
must perform a seven-day CD test. The purpose of the seven-day CD test
is to verify the ability of the CEMS to maintain calibration for each of
seven consecutive unit operating days as specified in section 11.8.5 of
this PS.
11.8.2 The CD tests must be performed using the zero gas and mid-
level reference gas standards as defined in Table 4 of this PS.
11.8.3 Conduct the CD test on each day during continuous operation
of the CEMS and normal facility operations following the procedures in
section 11.7 of this PS, except that the zero gas and mid-level gas need
only be introduced to the measurement system once each.
11.8.4 If periodic automatic or manual adjustments are made to the
CEMS zero and upscale response factor settings, conduct the CD test
immediately before these adjustments.
Note: Automatic signal or mathematical processing of all measurement
data to determine emission results may be performed throughout the
entire CD process.
11.8.5 Determine the magnitude of the CD at approximately 24-hour
intervals, for 7 consecutive unit operating days. The 7 consecutive unit
operating days need not be 7 consecutive calendar days.
11.8.6 Record the CEMS response for single measurements of zero gas
and mid-level reference gas. You may use Figure 2 in section 17 of this
PS to record and report the results of your 7-day CD test.
11.8.6.1 For extractive CEMS, calculate the CD using Equation 3B in
section 12.3. Report the absolute value of the differences as a
percentage of the span value.
11.8.6.2 For IP-CEMS, you must include the source measurement
optical path while performing the upscale CD measurement; you must
exclude the source measurement optical path when determining the zero
gas concentration. Calculate the CD for IP CEMS using Equations 4, 5,
6B, and 7 in section 12.4.
11.8.7 The zero-level and mid-level CD for each day must be less
than 5.0 percent of the span value as specified in section 13.2 of this
PS. You must meet this criterion for 7 consecutive operating days past
the 7-day CD test.
11.8.8 Dynamic Spiking Option for Seven-Day CD Test. For extractive
CEMS, you have the option to conduct a mid-level dynamic spiking
procedure for each of the 7 days in lieu of the mid-level reference gas
injection described in sections 11.8.2 and 11.8.3. If this option is
selected, the daily zero CD check is still required.
11.8.8.1 To conduct each of the seven daily mid-level dynamic
spikes, you must use the DS procedure described in appendix A of this PS
using a single spike of the mid-level reference gas (see Table 4).
11.8.8.2 You must perform the dynamic spike procedure by passing the
spiked source gas sample through all filters, scrubbers, conditioners
and other monitoring system components used during normal sampling, and
as much of the sampling probe as practical.

[[Page 774]]

11.8.8.3 Calculate the mid-level CD as a percent of span using
Equation A6 of appendix A to this PS and calculate the zero drift using
Equation 3B in section 12.3. Record and report the results as described
in sections 11.8.6 and 11.8.7.

11.9 Relative Accuracy Test

11.9.1 Unless otherwise specified in an applicable regulation, use
Method 26A in 40 CFR part 60, appendix A-8, Method 320 or Method 321,
both found in 40 CFR part 63, appendix A, or ASTM D6348-12 including all
annexes, as applicable, as the RMs for HCl measurement. Obtain and
analyze RM audit samples, if they are available, concurrently with RM
test samples according to the same procedure specified for performance
tests in the general provisions of the applicable part. If Method 26 is
not specified in an applicable subpart of the regulations, you may
request approval to use Method 26 in appendix A-8 to this part as the RM
on a site-specific basis under Sec. Sec. 63.7(f) or 60.8(b). Other RMs
for moisture, O2, etc., may be necessary. Conduct the RM
tests in such a way that they will yield results representative of the
emissions from the source and can be compared to the CEMS data.
11.9.1.1 When Method 26A is used as the RM, you must sample
sufficient gas to reach three times your method detection limit for
Method 26A in 40 CFR part 60, appendix A-8, or for a minimum of one
hour, whichever is greater.
11.9.1.2 When Method 320 or Method 321, both found in 40 CFR part
63, appendix A, or ASTM D6348-12, are used as the RM, you must collect
gas samples that are at stack conditions (hot and wet) and you must
traverse as required in section 11.9.3.
11.9.2 Conduct the diluent (if applicable), moisture (if needed),
and pollutant measurements simultaneously. However, diluent and moisture
measurements that are taken within an hour of the pollutant measurements
may be used to calculate dry pollutant concentration and emission rates.
11.9.3 Reference Method Measurement Location and Traverse Point(s)
Selection.
11.9.3.1 Measurement Location. Select, as appropriate, an accessible
RM measurement location at least two equivalent diameters downstream
from the nearest control device, point of pollutant generation, or other
point at which a change in the pollutant concentration or emission rate
may occur, and at least one half equivalent diameter upstream from the
effluent exhaust or a control device. When pollutant concentration
changes are due solely to diluent leakage (e.g., air heater leakages)
and pollutants and diluents are simultaneously measured at the same
location, a half diameter may be used in lieu of two equivalent
diameters. The equivalent duct diameter is calculated according to
Method 1 in appendix A-1 to this part. The CEMS and RM sampling
locations need not be the same.
11.9.3.2 Traverse Point Selection. Select traverse points that
assure acquisition of representative RM samples over the stack or duct
cross section according to one of the following options: (a) sample at
twelve traverse points located according to section 11.3 of Method 1 in
appendix A-1 to this part, (b) sample at 6 Method 1 traverse points
according to section 6.5.6(b)(1) of appendix A to part 75 of this
chapter, or (c) sample at three points on a measurement line (``3-point
long line'') that passes through the centroidal area of the duct in the
direction of any potential stratification. If this line interferes with
the CEMS measurements, you may displace the line up to 20 cm (12 in.) or
5.0 percent of the equivalent diameter of the cross section, whichever
is less, from the centroidal area. Locate the three traverse points at
16.7, 50.0, and 83.3 percent of the measurement line. Alternatively, you
may conduct a stratification test following the procedures in sections
11.9.3.2.1 through 11.9.3.2.4 to justify sampling at a single point or
three points located on the measurement line at 0.4, 1.2, and 2.0 m from
the stack wall (``3-point short line''). Stratification testing must be
conducted at the sampling location to be used for the RM measurements
during the RA test and must be made during normal facility operating
conditions. You must evaluate the stratification by measuring the gas on
the same moisture basis as the HCl CEMS (wet or dry). Stratification
testing must be repeated for each RA test program to justify single
point or ``3-point short line'' sampling.
11.9.3.2.1 Use a probe of appropriate length to measure the HCl
concentration or an alternative analyte, as described in this section,
using 12 traverse points located according to section 11.3 of Method 1
in appendix A-1 to 40 CFR part 60 for a circular stack or nine points at
the centroids of similarly-shaped, equal area divisions of the cross
section of a rectangular stack.
11.9.3.2.2 You may substitute a stratification test for
SO2 for the HCl stratification test. If you select this
option, you must follow the test procedures in Method 6C of appendix A-4
to 40 CFR part 60 or Method 320 of appendix A of 40 CFR part 63.
11.9.3.2.3 Calculate the mean measured concentration for all
sampling points (MNavg).
11.9.3.2.4 Calculate the percent stratification (St) of
each traverse point using Equation 8 in section 12.5.
11.9.3.2.5 The gas stream is considered to be unstratified and you
may perform the RA testing at a single point that most closely matches
the mean if the concentration at each traverse point differs from the
mean concentration for all traverse points by: (a)

[[Page 775]]

No more than 5.0 percent of the mean concentration; or (b) 0.2 ppm (for
HCl) or 3 ppm (for SO2) absolute, whichever is less
restrictive.
11.9.3.2.6 If the criterion for single point sampling (5.0 percent,
0.2 ppm for HCl or 3 ppm for SO2 are not met, but the
concentration at each traverse point differs from the mean concentration
for all traverse points by no more than 10.0 percent of the mean, the
gas stream is considered to be minimally stratified, and you may take RA
samples using the ``3-point short line''. Alternatively, you may use the
3-point short line if each traverse point differs from the mean value by
no more than 0.4 ppm (for HCl) or 5 ppm (for SO2).
11.9.3.2.7 If the concentration at any traverse point differs from
the mean concentration by more than 10 percent, the gas stream is
considered stratified and you must sample using one of the options in
section 11.9.3.2 above.
11.9.3.3 Conduct all necessary RM tests within 3 cm (1.2 in.) of the
traverse points, but no closer than 3 cm (1.2 in.) to the stack or duct
wall.
11.9.4 In order to correlate the CEMS and RM data properly, record
the beginning and end of each RM run (including the time of day in
hours, minutes, and seconds) using a clock synchronized with the CEM
clock used to create a permanent time record with the CEMS output.
11.9.5 You must conduct the RATA during representative process and
control operating conditions or as specified in an applicable
regulation, permit or subpart.
11.9.6 Conduct a minimum of nine RM test runs. NOTE: More than nine
RM test runs may be performed. If this option is chosen, up to three
test run results may be excluded so long as the total number of test run
results used to determine the CEMS RA is greater than or equal to nine.
However, all data must be reported including the excluded test runs.
11.9.7 Analyze the results from the RM test runs using Equations 9-
14 in section 12.6. Calculate the RA between the CEMS results and the
RM.

11.10 Record Keeping and Reporting

11.10.1 For systems that use a liquid evaporative standard generator
to deliver HCl reference gas standards, record supporting data for these
devices, including liquid feed calibrations, liquid standard
concentration(s) and NIST-traceability, feed rate and gas flow
calibrations for all diluent and HCl gas flows. All calibrations must
include a stated uncertainty, and the combined uncertainty of the
delivered HCl reference gas concentration must be calculated and
reported.
11.10.2 Record the results of the CD test, the RT test, the ME test,
the RA test, and for IP-CEMS, the results of the beam intensity,
temperature and pressure verification procedures. Also keep records of
the RM and CEMS field data, calculations, and reference gas
certifications necessary to confirm that the performance of the CEMS met
the performance specifications.
11.10.3 For systems that use Method 205 to prepare HCl reference gas
standards, record results of Method 205 performance test field
evaluation, reference gas certifications, and gas dilution system
calibration.
11.10.4 Record the LOD for the CEMS. For extractive CEMS, record the
LOD in ppmv. For IP-CEMS, record the LOD on a ppm-meter basis along with
a calculation of the installation specific LOD in ppmv. For both CEMS
types, you must also record the field verified SADL.
11.10.5 Record the results of the interference test.
11.10.6 Report the results of all certification tests to the
appropriate regulatory agency (or agencies), in hardcopy and/or
electronic format, as required by the applicable regulation or permit.

12.0 Calculations and Data Analysis

12.1 Nomenclature

Ci = Zero HCl reference gas concentration used for test i
(ppmv);
Ci,eff = Equivalent concentration of the reference gas value,
Ci, at the specified conditions (ppmv);
CC = Confidence coefficient (ppmv);
CDextractive = Calibration drift for extractive CEMS
(percent);
CDIP = Calibration drift for IP-CEMS (percent);
CD0 = Calibration drift at zero HCl concentrations for an IP-
CEMS (percent);
davg = Mean difference between CEMS response and the
reference gas (ppmv);
di = Difference of CEMS response and the RM value (ppmv);
I = Total interference from major matrix stack gases, (percent);
LSF = Line strength factor for IP-CEMS instrument specific correction
for temperature and gas matrix effects derived from the HITRAN and/or
manufacturer specific database (unitless);
FMCavg = Average of the 3 absolute values of the difference
between the measured HCl reference gas concentrations with and without
interference from selected stack gases (ppmv);
MCi = Measured zero or HCl reference gas concentration i
(ppmv);
MCl = Average of the measured zero or HCl reference gas concentration i
(ppmv);
MCint = Measured HCl concentration of the HCl reference gas
plus the individual or combined interference gases (ppmv);
MEextractive = Measurement error for extractive CEMS
(percent);

[[Page 776]]

MEIP = Measurement error for IP-CEMS (percent);
MNavg = Average concentration at all sampling points (ppmv);
MNbi = Measured native concentration bracketing each
calibration check measurement (ppmv);
MNi = Measured native concentration for test or run i (ppmv);
n = Number of measurements in an average value;
PLCell = Path length of IP-CEMS calibration cell (m);
PLStack = Path length of IP-CEMS stack optical path (m);
RA = Relative accuracy of CEMS compared to a RM (percent);
RMi = RM concentration for test run i (ppmv);
RMavg = Mean measured RM value (ppmv);
S = Span of the instrument (ppmv);
Sd = Standard deviation of the differences (ppmv);
Sti = Stratification at traverse point i (percent);
SADL = Standard addition detection level (ppmv);
t0.975 = One-sided t-value at the 97.5th percentile obtained
from Table 5 in section 17.0 for n-1 measurements;
Treference = Temperature of the calibration cell for IP-CEMS
(degrees Kelvin);
Tstack = Temperature of the stack at the monitoring location
for IP-CEM (degrees Kelvin).

12.2 Calculate the Difference Between the Measured HCl Concentration
With and Without Interferents for Each Interference Gas (Or Mixture) for
Your CEMS as:
[GRAPHIC] [TIFF OMITTED] TR07JY15.068

Calculate the total percent interference as:
[GRAPHIC] [TIFF OMITTED] TR07JY15.069

12.3 Calculate the ME or CD at Concentration i for an Extractive CEMS
as:
[GRAPHIC] [TIFF OMITTED] TR07JY15.070

[GRAPHIC] [TIFF OMITTED] TR07JY15.071

12.4 Calculate the ME or CD at Concentration i

for IP-CEMS That Use a Calibration Cell as

Follows:

12.4.1 Calculate the equivalent concentration Ci,eff
using Equation 4:
[GRAPHIC] [TIFF OMITTED] TR07JY15.072

12.4.2 Calculate the average native concentration before and after
each calibration check measurement as:

[[Page 777]]

[GRAPHIC] [TIFF OMITTED] TR07JY15.073

12.4.3 Calculate the ME or CD at concentration i for an IP-CEM as:
[GRAPHIC] [TIFF OMITTED] TR07JY15.074

[GRAPHIC] [TIFF OMITTED] TR07JY15.100

12.4.4 Calculate the zero CD as a percent of span for an IP-CEMS as:
[GRAPHIC] [TIFF OMITTED] TR07JY15.075

12.5 Calculate the Percent Stratification at Each Traverse Point as:
[GRAPHIC] [TIFF OMITTED] TR07JY15.076

12.6 Calculate the RA Using RM and CEMS Data

12.6.1 Determine the CEMS final integrated minute average pollutant
concentration or emission rate for each RM test period. Consider system
RT, if important, and confirm that the results have been corrected to
the same moisture, temperature and diluent concentration basis.
12.6.2 When Method 26A (or if approved for use, Method 26), found in
40 CFR part 60, appendix A-8 of this part, is used as the RM, compare
each CEMS integrated average value against the corresponding RM value
for identical test periods. Make these comparisons on the same basis
(e.g., wet, dry, ppmv, or units of the standard). To convert results
generate by Method 26A or 26 in mg/DSCM to ppmv, use the conversion
factor 0.662 ppm/(mg/DSCM).
12.6.3 If the RM is Method 320 or Method 321, found in 40 CFR part
63, appendix A, or ASTM D6348-12, make a direct comparison of the
average RM results and CEMS average value for identical test periods.
12.6.4 For each test run, calculate the arithmetic difference of the
RM and CEMS results using Equation 9.
[GRAPHIC] [TIFF OMITTED] TR07JY15.077

12.6.5 Calculate the standard deviation of the differences (Sd) of
the CEMS measured and RM results using Equation 10.

[[Page 778]]

[GRAPHIC] [TIFF OMITTED] TR07JY15.078

12.6.6 Calculate the confidence coefficient (CC) for the RATA using
Equation 11.
[GRAPHIC] [TIFF OMITTED] TR07JY15.079

12.6.7 Calculate the mean difference (davg) between the RM and CEMS
values in the units of ppmv or the emission standard using Equation 12.
[GRAPHIC] [TIFF OMITTED] TR07JY15.080

12.6.8 Calculate the average RM value using Equation 13.
[GRAPHIC] [TIFF OMITTED] TR07JY15.081

12.6.9 Calculate RA of the CEMS using Equation 14.
[GRAPHIC] [TIFF OMITTED] TR07JY15.082

13.0 Method Performance

13.1 Level of Detection. You may not use a CEMS whose LOD or SADL is
greater than 20 percent of the applicable regulatory limit or other
action level for the intended use of the data.
13.2 Calibration Drift. The zero- and mid-level calibration drift
for the CEMS must not exceed 5.0 percent of the span value for 7
consecutive operating days.
13.3 Measurement Error. The ME must be less than or equal to 5.0
percent of the span value at the low-, mid-, and high-level reference
gas concentrations.
13.4 Relative Accuracy. Unless otherwise specified in an applicable
regulation or permit, the RA of the CEMS, whether calculated in units of
HCl concentration or in units of the emission standard, must be less
than or equal to 20.0 percent of the RM when RMavg is used in the
denominator of Equation 14.
13.4.1 In cases where the RA is calculated on a concentration (ppmv)
basis, if the average RM emission level for the test is less than 75
percent of the HCl concentration equivalent to the emission standard,
you may substitute the HCl concentration equivalent to the standard in
the denominator of Equation 14 in place of RMavg.
13.4.2 Similarly, if the RA is calculated in units of the emission
standard and the HCl emission level measured by the RMs is less than 75
percent of the emission standard, you may substitute the emission
standard in the denominator of Equation 14 in place of RMavg.

[[Page 779]]

13.4.3 The alternative calculated RA in paragraph 13.4.1 or 13.4.2
must be less than or equal to 15.0 percent.
13.5 Interference Test.
13.5.1 The sum of the interference response(s) from Equation 2 must
not be greater than 2.5 percent of the calibration span or 3.0 percent
of the equivalent HCl concentration used for the interference test,
whichever is less restrictive. The results are also acceptable if the
sum of the interference response(s) does not exceed six times the LOD or
0.5 ppmv for a calibration span of 5 to 10 ppm, or 0.2 ppmv for a
calibration span of less than 5 ppmv.
13.6 IP-CEMS Beam Intensity Test. For IP-CEMS, the percent
difference between the measured concentration with and without
attenuation of the light source must not exceed 3.0 percent.
13.7 IP-CEMS Temperature Measurement Verification. Your temperature
sensor satisfies the accuracy required if the absolute relative
difference between measured value of stack temperature (Mt)
and the temperature value from the calibrated temperature reference
device (Vt) is 1.0 percent or if the absolute
difference between Mt and Vt is 2.8
[deg]C (5.0 [deg]F), whichever is less restrictive.
13.8 IP-CEMS Pressure Sensor Measurement Verification. Your pressure
sensor satisfies the accuracy required if the absolute relative
difference between the measured value of stack pressure (MP)
and the pressure value from the calibrated pressure reference device
(VP) is 5.0 percent or if the absolute difference
between Mp and VP is 0.12 kilopascals
(0.5 inches of water column), whichever is less restrictive.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Bibliography

1. Method 318--Extractive FTIR Method for the Measurement of
Emissions From the Mineral Wool and Wool Fiberglass Industries, 40 CFR,
part 63, subpart HHHHHHH, appendix A.
2. ``EPA Protocol for the Use of Extractive Fourier Transform
Infrared (FTIR) Spectrometry in Analyses of Gaseous Emissions from
Stationary Industrial Sources,'' February, 1995.
3. ``Measurement of Gaseous Organic and Inorganic Emissions by
Extractive FTIR Spectroscopy,'' EPA Contract No. 68-D2-0165, Work
Assignment 3-08.
4. ``Method 301--Field Validation of Pollutant Measurement Methods
from Various Waste Media,'' 40 CFR part 63, appendix A.
5. EPA Traceability Protocol for Assay and Certification of Gaseous
Calibration Standards, U.S. Environmental Protection Agency office of
Research and Development, EPA/600/R-12/531, May 2012.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Table 1--Interference Test Gas Concentrations
------------------------------------------------------------------------
Approximate concentration (balance
Potential interferent gas \1\ N2)
------------------------------------------------------------------------
CO2............................... 15% 1% CO2.\2\
CO................................ 100 20 ppm.
CH2O.............................. 20 5 ppm.
CH4............................... 100 20 ppm.
NH3............................... 10 5 ppm (extractive CEMS only).
NO2............................... 250 50 ppm.
SO2............................... 200 20 ppm.
O2................................ 3% 1% O2.\2\
H2O............................... 10% 1% H2O.\2\
N2................................ Balance.\2\
------------------------------------------------------------------------
\1\ Any of these specific gases can be tested at a lower level if the
manufacturer has provided reliable means for limiting or scrubbing
that gas to a specified level in CEMS field installations.
\2\ Gases for short path IP cell interference tests cannot be added
above 100 percent stack equivalent concentration. Add these gases at
the indicated percentages to make up the remaining cell volume.

[[Page 780]]

[GRAPHIC] [TIFF OMITTED] TR07JY15.083

Table 3--Design Standards for Temperature Sensors
------------------------------------------------------------------------
You can use the following design
If the sensor is a . . . standards as guidance in selecting a
sensor for your IP-CEMS
------------------------------------------------------------------------
1. Thermocouple.............. a. ASTM E235-88 (1996), ``Specification
for Thermocouples, Sheathed, Type K, for
Nuclear or Other High-Reliability
Applications.''
b. ASTM E585/E585M-04, ``Specification
for Compacted Mineral-Insulated, Metal-
Sheathed, Base Metal Thermocouple
Cable.''

[[Page 781]]

c. ASTM E608/E608M-06, ``Specification
for Mineral-Insulated, Metal-Sheathed
Base Metal Thermocouples.''
d. ASTM E696-07, ``Specification for
Tungsten-Rhenium Alloy Thermocouple
Wire.''
e. ASTM E1129/E1129M-98 (2002),
``Standard Specification for
Thermocouple Connectors.''
f. ASTM E1159-98 (2003), ``Specification
for Thermocouple Materials, Platinum-
Rhodium Alloys, and Platinum.''
g. ISA-MC96.1-1982, ``Temperature
Measurement Thermocouples.''
2. Resistance temperature ASTM E1137/E1137M-04, ``Standard
detector. Specification for Industrial Platinum
Resistance Thermometers.''
------------------------------------------------------------------------

Table 4--Performance Specification Test Zero and Reference Gas Ranges
--------------------------------------------------------------------------------------------------------------------------------------------------------
HCl Zero and Reference Gas Concentrations in Terms of Percent of
Span \a\
Test Units ------------------------------------------------------------------- Section
Zero Low Level Mid Level High Level
--------------------------------------------------------------------------------------------------------------------------------------------------------
Calibration Drift........................ % of Span.................... spike) and total flow through
the CEM sampling system (Qprobe).
8.2.4.3 If your CEMS is capable of measuring an independent stable
tracer gas, you may use a spike gas that includes the tracer to
determine the DF using Equation A2 or A3 (sections 11.2.2 and 11.2.3 of
this appendix) depending on whether the tracer gas is also present in
the native source emissions.

[[Page 784]]

8.2.4.4 For extractive CEMS, you must correct the background
measurements of HCl for the dilution caused by the addition of the spike
gas standard. For spiking systems that alternate between addition of HCl
and zero gas at a constant DF, the background measurements between
spikes will not be equal to the native source concentration.
8.2.5 Begin by collecting unspiked sample measurements of HCl. You
must use the average of two unspiked sample measurements as your pre-
spike background.
Note: Measurements should agree within 5.0 percent or three times
the level of detection to avoid biasing the spike results.
8.2.5.1 Introduce the HCl gas spike into the permanent CEMS probe,
upstream of the particulate filter or sample conditioning system and as
close to the sampling inlet as practical.
8.2.5.2 Maintain the HCl gas spike for at least twice the DS
response time of your CEMS or until the consecutive measurements agree
within 5.0 percent. Collect two independent measurements of the native
plus spiked HCl concentration.
8.2.5.3 Stop the flow of spike gas for at least twice the DS
response time of your CEMS or until the consecutive measurements agree
within 5.0 percent. Collect two independent measurements of the native
HCl concentration.
8.2.6 Repeat the collection of sample measurements in section 8.2.5
until you have data for each spike concentration including a final set
of unspiked sample measurements according to section 8.2.5.3.
8.2.7 Verify that the CEMS responded as expected for each spike gas
injection, and that the data quality is not impacted by large shifts in
the native source concentration. Discard and repeat any spike injections
as necessary to generate a complete set of the required replicate spike
measurements.
8.2.8 Calculate the standard addition response (SAR) for extractive
CEMS, using Equation A4 in section 11.2, of this appendix.
8.2.9 If the DS results do not meet the specifications for the
appropriate performance test in PS-18 or Procedure 6 of appendix F of
this part, you must take corrective action and repeat the DS procedure.
8.3 SA Procedure for IP-CEMS (Static Spiking).
8.3.1 For IP-CEMS, you must make measurements of native source gas
HCl concentration and an HCl standard addition using a calibration cell
added to the optical measurement path.
8.3.2 Introduce zero gas into a calibration cell located in the
optical measurement path of the instrument. Continue to flush the zero
gas into the cell for at least the SA response time of your CEMS or
until two consecutive measurements taken are within 5.0 percent, then
collect two independent measurements. Alternatively you may measure
native concentrations without the calibration cell in the optical path.
8.3.3 Introduce the HCl spike gas into the calibration cell.
Continue to flush the spike gas into the cell for at least the SA
response time of your CEMS or until two consecutive measurements taken
are within 5.0 percent of one another. Then collect two independent
measurements of the SA addition to the native concentration.
Alternatively you may insert a sealed calibration cell, containing HCl
at the appropriate concentration, into the optical path to measure the
SA addition to the native concentration.
8.3.4 Repeat the collection of SA-elevated and native HCl
measurements in sections 8.3.2 and 8.3.3 until you have data for each SA
concentration. Then, make a final native HCl measurement. The measured
concentrations must be corrected for calibration cell and stack
temperature, pressure and stack measurement path length.
8.3.5 Calculate the standard addition response (SAR) for an IP-CEMS,
using Equation A8 in section 11.3 of this appendix.
8.3.6 If the SA results do not meet the specifications for the
appropriate performance test in PS-18 or Procedure 6 of appendix F of
this part, you must take corrective action and repeat the SA procedure.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Calculations and Data Analysis. Calculate the SA response for
each measurement and its associated native HCl measurement(s), using
equations in this section. (Note: For cases where the emission standard
is expressed in units of lb/MMBtu or corrected to a specified
O2 or CO2 concentration, an absolute accuracy
specification based on a span at stack conditions may be calculated
using the average concentration and applicable conversion factors. The
appropriate procedures for use in cases where a percent removal standard
is more restrictive than the emission standard are the same as in 40 CFR
part 60, PS-2, sections 12 and 13.)
11.1 Nomenclature.

Cspike = Actual HCl reference gas concentration spiked (e.g.,
bottle or reference gas concentration) ppmv;
Ctracer spiked = Tracer gas concentration injected with spike
gas (``reference concentration'') ppmv;
DF = Spiked gas dilution factor;
DSCD = Calibration drift determined using DS procedure (percent);
DSE = Dynamic spike error (ppmv);
ESA = Effective spike addition (ppmv);
MCSA = Measured SA-elevated source gas concentration (ppmv);
MCspiked = Measured HCl reference gas concentration i (ppmv);

[[Page 785]]

MCnative = Average measured concentration of the native HCl
(ppmv);
Mnative tracer = Measured tracer gas concentration present in
native effluent gas (ppmv);
Mspiked tracer = Measured diluted tracer gas concentration in
a spiked sample (ppmv);
Qspike = Flow rate of the dynamic spike gas (Lpm);
Qprobe = Average total stack sample flow through the system
(Lpm);
S = Span (ppmv);
SAR = Standard addition response (ppmv)

11.2 Calculating Dynamic Spike Response and Error for Extractive
CEMS.
11.2.1 If you determine your spike DF using spike gas and stack
sample flow measurements, calculate the DF using equation A1:
[GRAPHIC] [TIFF OMITTED] TR07JY15.087

11.2.2 If you determine your spike DF using an independent stable
tracer gas that is not present in the native source emissions, calculate
the DF for DS using equation A2:
[GRAPHIC] [TIFF OMITTED] TR07JY15.088

11.2.3 If you determine your spike dilution factor using an
independent stable tracer that is present in the native source
emissions, calculate the dilution factor for dynamic spiking using
equation A3:
[GRAPHIC] [TIFF OMITTED] TR07JY15.089

11.2.4 Calculate the SA response using Equation A4:
[GRAPHIC] [TIFF OMITTED] TR07JY15.090

11.2.5 Calculate the DS error using Equation A5.
[GRAPHIC] [TIFF OMITTED] TR07JY15.091

11.2.6 Calculating CD using DS. When using the DS option for
determining mid-level CD, calculate the CD as a percent of span using
equation A6:
[GRAPHIC] [TIFF OMITTED] TR07JY15.092

[[Page 786]]

11.2.7 The effective spike addition (ESA) is the expected increase
in the measured concentration as a result of injecting a spike.
Calculate ESA using Equation A7:
[GRAPHIC] [TIFF OMITTED] TR07JY15.093

11.3 Standard Addition Response for IP-CEMS. If you use an IP-CEMS
and a calibration cell, calculate the SA response using Equation A8.
[GRAPHIC] [TIFF OMITTED] TR07JY15.094

13. Tables and Figures.

[[Page 787]]

[GRAPHIC] [TIFF OMITTED] TR07JY15.095

[48 FR 13327, Mar. 30, 1983 and 48 FR 23611, May 25, 1983, as amended at
48 FR 32986, July 20, 1983; 51 FR 31701, Aug. 5, 1985; 52 FR 17556, May
11, 1987; 52 FR 30675, Aug. 18, 1987; 52 FR 34650, Sept. 14, 1987; 53 FR
7515, Mar. 9, 1988; 53 FR 41335, Oct. 21, 1988; 55 FR 18876, May 7,
1990; 55 FR 40178, Oct. 2, 1990; 55 FR 47474, Nov. 14, 1990; 56 FR 5526,
Feb. 11, 1991; 59 FR 64593, Dec. 15, 1994; 64 FR 53032, Sept. 30, 1999;
65 FR 62130, 62144, Oct. 17, 2000; 65 FR 48920, Aug. 10, 2000; 69 FR
1802, Jan. 12, 2004; 70 FR 28673, May 18, 2005; 71 FR 55127, Sept. 21,
2006; 72 FR 32767, June 13, 2007; 72 FR 51527, Sept. 7, 2007; 72 FR
55278, Sept. 28, 2007; 74 FR 12580, 12585, Mar. 25, 2009; 74 FR 18474,
Apr. 23, 2009; 75 FR 55037, Sept. 9, 2010; 79 FR 11271, Feb. 27, 2014;
80 FR 38633, July 7, 2015; 80 FR 42397, July 17, 2015]

Effective Date Note: At 81 FR 31518, May 19, 2016, appendix B to
part 60 was amended by: a. revising Sections 3.1 through 3.23, 11.5.6.5,
11.8.6.2, 12.1, 12.2 and 12.4.4; b. adding Sections 3.24, 3.25, and
12.2.1; and c. revising Section 11.2.3 in appendix A of Performance
Specification 18, effective Aug. 17, 2016. For the convenience of the
user, the added and revised text is set forth as follows:

Sec. Appendix B to Part 60--Performance Specifications

* * * * *

PERFORMANCE SPECIFICATION 18-PERFORMANCE SPECIFICATIONS AND TEST
PROCEDURES FOR GASEOUS HYDROGEN CHLORIDE (HCl) CONTINUOUS EMISSION
MONITORING SYSTEMS AT STATIONARY SOURCES

* * * * *

3.0 Definitions

3.1 Beam attenuation is the reduction in electromagnetic radiation
(light) throughput from the maximum beam intensity experienced during
site specific CEMS operation.
3.2 Beam intensity is the electromagnetic radiation (light)
throughput for an IP-CEMS

[[Page 788]]

instrument measured following manufacturers specifications.
3.3 Calibration cell means a gas containment cell used with cross
stack or integrated path (IP) CEMS for calibration and to perform many
of the test procedures required by this performance specification. The
cell may be a removable sealed cell or an evacuated and/or purged cell
capable of exchanging reference and other calibration gases as well as
zero gas standards. When charged, it contains a known concentration of
HCl and/or interference gases. The calibration cell is filled with zero
gas or removed from the optical path during stack gas measurement.
3.4 Calibration drift (CD) means the absolute value of the
difference between the CEMS output response and an upscale reference gas
or a zero-level gas, expressed as a percentage of the span value, when
the CEMS is challenged after a stated period of operation during which
no unscheduled adjustments, maintenance or repairs took place.
3.5 Centroidal area means a central area that is geometrically
similar to the stack or duct cross section and is no greater than 10
percent of the stack or duct cross-sectional area.
3.6 Continuous Emission Monitoring System (CEMS) means the total
equipment required to measure the pollutant concentration or emission
rate continuously. The system generally consists of the following three
major subsystems:
3.6.1 Sample interface means that portion of the CEMS used for one
or more of the following: Sample acquisition, sample transport, sample
conditioning, defining the optical measurement path, and protection of
the monitor from the effects of the stack effluent.
3.6.2 HCl analyzer means that portion of the HCl CEMS that measures
the total vapor phase HCl concentration and generates a proportional
output.
3.6.3 Data recorder means that portion of the CEMS that provides a
permanent electronic record of the analyzer output. The data recorder
may record other pertinent data such as effluent flow rates, various
instrument temperatures or abnormal CEMS operation. The data recorder
may also include automatic data reduction capabilities and CEMS control
capabilities.
3.7 Diluent gas means a major gaseous constituent in a gaseous
pollutant mixture. For combustion sources, either carbon dioxide
(CO2) or oxygen (O2) or a combination of these two
gases are the major gaseous diluents of interest.
3.8 Dynamic spiking (DS) means the procedure where a known
concentration of HCl gas is injected into the probe sample gas stream
for extractive CEMS at a known flow rate to assess the performance of
the measurement system in the presence of potential interference from
the flue gas sample matrix.
3.9 Independent measurement(s) means the series of CEMS data values
taken during sample gas analysis separated by two times the procedure
specific response time (RT) of the CEMS.
3.10 Integrated path CEMS (IP-CEMS) means an in-situ CEMS that
measures the gas concentration along an optical path in the stack or
duct cross section.
3.11 Interference means a compound or material in the sample matrix
other than HCl whose characteristics may bias the CEMS measurement
(positively or negatively). The interference may not prevent the sample
measurement, but could increase the analytical uncertainty in the
measured HCl concentration through reaction with HCl or by changing the
electronic signal generated during HCl measurement.
3.12 Interference test means the test to detect CEMS responses to
interferences that are not adequately accounted for in the calibration
procedure and may cause measurement bias.
3.13 Level of detection (LOD) means the lowest level of pollutant
that the CEMS can detect in the presence of the source gas matrix
interferents with 99 percent confidence.
3.14 Liquid evaporative standard means a reference gas produced by
vaporizing National Institute of Standards and Technology (NIST)
traceable liquid standards of known HCl concentration and quantitatively
diluting the resultant vapor with a carrier gas.
3.15 Measurement error (ME) is the mean difference between the
concentration measured by the CEMS and the known concentration of a
reference gas standard, divided by the span, when the entire CEMS,
including the sampling interface, is challenged.
3.16 Optical path means the route light travels from the light
source to the receiver used to make sample measurements.
3.17 Path length means, for an extractive optical CEMS, the distance
in meters of the optical path within a gas measurement cell. For an IP-
CEMS, path length means the distance in meters of the optical path that
passes through the source gas in the stack or duct.
3.18 Point CEMS means a CEMS that measures the source gas
concentration, either at a single point at the sampling probe tip or
over a path length for IP-CEMS less than 10 percent of the equivalent
diameter of the stack or duct cross section.
3.19 Stack pressure measurement device means a NIST-traceable gauge
or monitor that measures absolute pressure and conforms to the design
requirements of ASME B40.100-2010, ``Pressure Gauges and Gauge
Attachments'' (incorporated by reference--see Sec. 60.17).
3.20 Reference gas standard means a NIST-traceable gas standard
containing a known

[[Page 789]]

concentration of HCl certified in accordance with an EPA traceability
protocol in section 7.1 of this PS.
3.21 Relative accuracy (RA) means the absolute mean difference
between the gas concentration or the emission rate determined by the
CEMS and the value determined by the RM, plus the confidence coefficient
of a series of nine test runs, divided by the average of the RM or the
applicable emission standard.
3.22 Response time (RT) means the time it takes for the measurement
system, while operating normally at its target sample flow rate,
dilution ratio, or data collection rate to respond to a known step
change in gas concentration, either from a low- or zero-level to a high-
level gas concentration or from a high-level to a low or zero-level gas
concentration, and to read 95 percent of the change to the stable
instrument response. There may be several RTs for an instrument related
to different functions or procedures (e.g., DS, LOD, and ME).
3.23 Span value means an HCl concentration approximately equal to
two times the concentration equivalent to the emission standard unless
otherwise specified in the applicable regulation, permit or other
requirement. Unless otherwise specified, the span may be rounded up to
the nearest multiple of 5.
3.24 Standard addition means the addition of known amounts of HCl
gas (either statically or dynamically) to the actual measurement path or
measured sample gas stream.
3.25 Zero gas means a gas or liquid with an HCl concentration that
is below the LOD of the measurement system.

* * * * *

11.0 Performance Specification Test Procedure

* * * * *

11.5.6.5 If your system LOD field verification does not demonstrate
a SAR greater than or equal to your initial controlled environment LOD,
you must increase the SA concentration incrementally and repeat the
field verification procedure until the SAR is equal to or greater than
LOD. The site-specific standard addition detection level (SADL) is equal
to the standard addition needed to achieve the acceptable SAR, and SADL
replaces the controlled environment LOD. For extractive CEMS, the SADL
is calculated as the ESA using Equation A7 in appendix A of this PS. For
IP-CEMS, the SADL is the SA calculated using Equation A8 in appendix A
of this PS. As described in section 13.1 of this PS, the LOD or the SADL
that replaces an LOD must be less than 20 percent of the applicable
emission limit.

* * * * *

11.8.6.2 For IP-CEMS, you must include the source measurement
optical path while performing the upscale CD measurement; you may
exclude the source measurement optical path when determining the zero
gas concentration. Calculate the CD for IP CEMS using equations 4, 5,
6B, and 7 in section 12.4.

* * * * *

12.0 Calculations and Data Analysis
12.1 Nomenclature
Ci = Zero or HCl reference gas concentration used for test i
(ppmv);
Ci,eff = Equivalent concentration of the reference gas value,
Ci, at the specified conditions (ppmv);
CC = Confidence coefficient (ppmv);
CDextractive = Calibration drift for extractive CEMS
(percent);
CDIP = Calibration drift for IP-CEMS (percent);
CD0 = Calibration drift at zero HCl concentrations for an IP-
CEMS (percent);
davg = Mean difference between CEMS response and the
reference gas (ppmv);
di = Difference of CEMS response and the RM value (ppmv);
I = Total interference from major matrix stack gases, (percent);
LSF = Line strength factor for IP-CEMS instrument specific correction
for temperature and gas matrix effects derived from the HITRAN and/or
manufacturer specific database (unitless);
FMCavg = Average of the 3 absolute values of the difference
between the measured HCl calibration gas concentrations with and without
interference from selected stack gases (ppmv);
MCi = Measured HCl reference gas concentration i (ppmv);
MCi = Average of the measured HCl reference gas concentration
i (ppmv);
MCint = Measured HCl concentration of the HCl reference gas
plus the individual or combined interference gases (ppmv);
MEextractive = Measurement error for extractive CEMS
(percent);
MEIP = Measurement error for IP-CEMS (percent);
MNavg = Average concentration at all sampling points (ppmv);
MNbi = Measured native concentration bracketing each
calibration check measurement (ppmv);
MNi = Measured native concentration for test or run I (ppmv);
n = Number of measurements in an average value;
Pstack = Absolute stack pressure (mm Hg)

[[Page 790]]

Preference = Absolute pressure of the calibration cell for
IP-CEMS (mm Hg)
PLCell = Path length of IP-CEMS calibration cell (m);
PLStack = Path length of IP-CEMS stack optical path (m);
RA = Relative accuracy of CEMS compared to a RM (percent);
RMi = RM concentration for test run i (ppmv);
RMavg = Mean measured RM value (ppmv);
S = Span value (ppmv);
Sd = Standard deviation of the differences (ppmv);
Sti = Stratification at traverse point i (percent);
SADL = Standard addition detection level (ppmv);
t0.975 = One-sided t-value at the 97.5th percentile obtained
from Table 5 in section 17.0 for n-1 measurements;
Treference = Temperature of the calibration cell for IP-CEMS
(degrees Kelvin);
Tstack = Temperature of the stack at the monitoring location
for IP-CEM (degrees Kelvin).

12.2 Calculate the difference between the measured HCl concentration
with and without interferents for each interference gas (or mixture) for
your CEMS as:
[GRAPHIC] [TIFF OMITTED] TR19MY16.024

Calculate the total percent interference as:
[GRAPHIC] [TIFF OMITTED] TR19MY16.025

12.2.1 Calculate the equivalent concentration Ci,eff
using Equation 4:
[GRAPHIC] [TIFF OMITTED] TR19MY16.026

* * * * *

12.4.4 Calculate the zero CD as a percent of span for an IP-CEMS as:
[GRAPHIC] [TIFF OMITTED] TR19MY16.027

* * * * *

PS-18 Appendix A Standard Addition Procedures

* * * * *

11.0 Calculations and Data Analysis. * * *

* * * * *

Sec. Appendix C to Part 60--Determination of Emission Rate Change

1. Introduction

1.1 The following method shall be used to determine whether a
physical or operational

[[Page 791]]

change to an existing facility resulted in an increase in the emission
rate to the atmosphere. The method used is the Student's t test,
commonly used to make inferences from small samples.

2. Data

2.1 Each emission test shall consist of n runs (usually three) which
produce n emission rates. Thus two sets of emission rates are generated,
one before and one after the change, the two sets being of equal size.
2.2 When using manual emission tests, except as provided in Sec.
60.8(b) of this part, the reference methods of appendix A to this part
shall be used in accordance with the procedures specified in the
applicable subpart both before and after the change to obtain the data.
2.3 When using continuous monitors, the facility shall be operated
as if a manual emission test were being performed. Valid data using the
averaging time which would be required if a manual emission test were
being conducted shall be used.

3. Procedure

3.1 Subscripts a and b denote prechange and postchange respectively.
3.2 Calculate the arithmetic mean emission rate, E, for each set of
data using Equation 1.
[GRAPHIC] [TIFF OMITTED] TC01JN92.292

Where:

Ei = Emission rate for the i th run.
n = number of runs.

3.3 Calculate the sample variance, S2, for each set of data using
Equation 2.
[GRAPHIC] [TIFF OMITTED] TC01JN92.293

3.4 Calculate the pooled estimate, Sp, using Equation 3.
[GRAPHIC] [TIFF OMITTED] TC01JN92.294

3.5 Calculate the test statistic, t, using Equation 4.
[GRAPHIC] [TIFF OMITTED] TC01JN92.295

4. Results

4.1 If Eb>,Ea and t>t', where t' is the critical value of t obtained
from Table 1, then with 95% confidence the difference between Eb and Ea
is significant, and an increase in emission rate to the atmosphere has
occurred.

Table 1
------------------------------------------------------------------------
t' (95
percent
Degrees of freedom (na=nb-2) confidence
level)
------------------------------------------------------------------------
2.......................................................... 2.920
3.......................................................... 2.353
4.......................................................... 2.132
5.......................................................... 2.015
6.......................................................... 1.943
7.......................................................... 1.895
8.......................................................... 1.860
------------------------------------------------------------------------

For greater than 8 degrees of freedom, see any standard statistical
handbook or text.
5.1 Assume the two performance tests produced the following set of
data:

------------------------------------------------------------------------
Test a Test b
------------------------------------------------------------------------
Run 1. 100.................................................. 115
Run 2. 95................................................... 120
Run 3. 110.................................................. 125
------------------------------------------------------------------------

5.2 Using Equation 1--
Ea = 100 + 95 + 110/3 = 102
Eb = 115 + 120 + 125/3 = 120
5.3 Using Equation 2--
Sa2 = (100^-102) \2\ + (95^-102) \2\ +
(110^-102) \2\/3^-1 = 58.5
Sb2 = (115^-120) \2\ + (120^-120) \2\ +
(125^-120) \2\/3^-1 = 25
5.4 Using Equation 3--
Sp = [(3 - 1)(58.5) + (3 + 1)(25) / 3 + 3 - 2]\1/2\ = 6.46
5.5 Using Equation 4--
[GRAPHIC] [TIFF OMITTED] TC01JN92.296

5.6 Since (n\1\ + n\2\ - 2) = 4, t' = 2.132 (from Table 1). Thus
since t>t' the difference in the values of Ea and Eb is significant, and
there has been an increase in emission rate to the atmosphere.

6. Continuous Monitoring Data

6.1 Hourly averages from continuous monitoring devices, where
available, should be used as data points and the above procedure
followed.

[40 FR 58420, Dec. 16, 1975]

[[Page 792]]

Sec. Appendix D to Part 60--Required Emission Inventory Information

(a) Completed NEDS point source form(s) for the entire plant
containing the designated facility, including information on the
applicable criteria pollutants. If data concerning the plant are already
in NEDS, only that information must be submitted which is necessary to
update the existing NEDS record for that plant. Plant and point
identification codes for NEDS records shall correspond to those
previously assigned in NEDS; for plants not in NEDS, these codes shall
be obtained from the appropriate Regional Office.
(b) Accompanying the basic NEDS information shall be the following
information on each designated facility:
(1) The state and county identification codes, as well as the
complete plant and point identification codes of the designated facility
in NEDS. (The codes are needed to match these data with the NEDS data.)
(2) A description of the designated facility including, where
appropriate:
(i) Process name.
(ii) Description and quantity of each product (maximum per hour and
average per year).
(iii) Description and quantity of raw materials handled for each
product (maximum per hour and average per year).
(iv) Types of fuels burned, quantities and characteristics (maximum
and average quantities per hour, average per year).
(v) Description and quantity of solid wastes generated (per year)
and method of disposal.
(3) A description of the air pollution control equipment in use or
proposed to control the designated pollutant, including:
(i) Verbal description of equipment.
(ii) Optimum control efficiency, in percent. This shall be a
combined efficiency when more than one device operates in series. The
method of control efficiency determination shall be indicated (e.g.,
design efficiency, measured efficiency, estimated efficiency).
(iii) Annual average control efficiency, in percent, taking into
account control equipment down time. This shall be a combined efficiency
when more than one device operates in series.
(4) An estimate of the designated pollutant emissions from the
designated facility (maximum per hour and average per year). The method
of emission determination shall also be specified (e.g., stack test,
material balance, emission factor).

[40 FR 53349, Nov. 17, 1975]

Sec. Appendix E to Part 60 [Reserved]

Sec. Appendix F to Part 60--Quality Assurance Procedures

Procedure 1. Quality Assurance Requirements for Gas Continuous Emission
Monitoring Systems Used for Compliance Determination

1. Applicability and Principle

1.1 Applicability. Procedure 1 is used to evaluate the effectiveness
of quality control (QC) and quality assurance (QA) procedures and the
quality of data produced by any continuous emission monitoring system
(CEMS) that is used for determining compliance with the emission
standards on a continuous basis as specified in the applicable
regulation. The CEMS may include pollutant (e.g., S02 and
N0x) and diluent (e.g., 02 or C02)
monitors.
This procedure specifies the minimum QA requirements necessary for
the control and assessment of the quality of CEMS data submitted to the
Environmental Protection Agency (EPA). Source owners and operators
responsible for one or more CEMS's used for compliance monitoring must
meet these minimum requirements and are encouraged to develop and
implement a more extensive QA program or to continue such programs where
they already exist.
Data collected as a result of QA and QC measures required in this
procedure are to be submitted to the Agency. These data are to be used
by both the Agency and the CEMS operator in assessing the effectiveness
of the CEMS QC and QA procedures in the maintenance of acceptable CEMS
operation and valid emission data.
Appendix F, Procedure 1 is applicable December 4, 1987. The first
CEMS accuracy assessment shall be a relative accuracy test audit (RATA)
(see section 5) and shall be completed by March 4, 1988 or the date of
the initial performance test required by the applicable regulation,
whichever is later.
1.2 Principle. The QA procedures consist of two distinct and equally
important functions. One function is the assessment of the quality of
the CEMS data by estimating accuracy. The other function is the control
and improvement of the quality of the CEMS data by implementing QC
policies and corrective actions. These two functions form a control
loop: When the assessment function indicates that the data quality is
inadequate, the control effort must be increased until the data quality
is acceptable. In order to provide uniformity in the assessment and
reporting of data quality, this procedure explicitly specifies the
assessment methods for response drift and accuracy. The methods are
based on procedures included in the applicable performance
specifications (PS's) in appendix B of 40 CFR part 60. Procedure 1 also
requires the analysis of the EPA audit

[[Page 793]]

samples concurrent with certain reference method (RM) analyses as
specified in the applicable RM's.
Because the control and corrective action function encompasses a
variety of policies, specifications, standards, and corrective measures,
this procedure treats QC requirements in general terms to allow each
source owner or operator to develop a QC system that is most effective
and efficient for the circumstances.

2. Definitions

2.1 Continuous Emission Monitoring System. The total equipment
required for the determination of a gas concentration or emission rate.
2.2 Diluent Gas. A major gaseous constituent in a gaseous pollutant
mixture. For combustion sources, CO2 and O2 are
the major gaseous constituents of interest.
2.3 Span Value. The upper limit of a gas concentration measurement
range that is specified for affected source categories in the applicable
subpart of the regulation.
2.4 Zero, Low-Level, and High-Level Values. The CEMS response values
related to the source specific span value. Determination of zero, low-
level, and high-level values is defined in the appropriate PS in
appendix B of this part.
2.5 Calibration Drift (CD). The difference in the CEMS output
reading from a reference value after a period of operation during which
no unscheduled maintenance, repair or adjustment took place. The
reference value may be supplied by a cylinder gas, gas cell, or optical
filter and need not be certified.
2.6 Relative Accuracy (RA). The absolute mean difference between the
gas concentration or emission rate determined by the CEMS and the value
determined by the RM's plus the 2.5 percent error confidence coefficient
of a series of tests divided by the mean of the RM tests or the
applicable emission limit.

3. QC Requirements

Each source owner or operator must develop and implement a QC
program. As a minimum, each QC program must include written procedures
which should describe in detail, complete, step-by-step procedures and
operations for each of the following activities:
1. Calibration of CEMS.
2. CD determination and adjustment of CEMS.
3. Preventive maintenance of CEMS (including spare parts inventory).
4. Data recording, calculations, and reporting.
5. Accuracy audit procedures including sampling and analysis
methods.
6. Program of corrective action for malfunctioning CEMS.
As described in section 5.2, whenever excessive inaccuracies occur
for two consecutive quarters, the source owner or operator must revise
the current written procedures or modify or replace the CEMS to correct
the deficiency causing the excessive inaccuracies.
These written procedures must be kept on record and available for
inspection by the enforcement agency.

4. CD Assessment

4.1 CD Requirement. As described in 40 CFR 60.13(d), source owners
and operators of CEMS must check, record, and quantify the CD at two
concentration values at least once daily (approximately 24 hours) in
accordance with the method prescribed by the manufacturer. The CEMS
calibration must, as minimum, be adjusted whenever the daily zero (or
low-level) CD or the daily high-level CD exceeds two times the limits of
the applicable PS's in appendix B of this regulation.
4.2 Recording Requirement for Automatic CD Adjusting Monitors.
Monitors that automatically adjust the data to the corrected calibration
values (e.g., microprocessor control) must be programmed to record the
unadjusted concentration measured in the CD prior to resetting the
calibration, if performed, or record the amount of adjustment.
4.3 Criteria for Excessive CD. If either the zero (or low-level) or
high-level CD result exceeds twice the applicable drift specification in
appendix B for five, consecutive, daily periods, the CEMS is out-of-
control. If either the zero (or low-level) or high-level CD result
exceeds four times the applicable drift specification in appendix B
during any CD check, the CEMS is out-of-control. If the CEMS is out-of-
control, take necessary corrective action. Following corrective action,
repeat the CD checks.
4.3.1 Out-Of-Control Period Definition. The beginning of the out-of-
control period is the time corresponding to the completion of the fifth,
consecutive, daily CD check with a CD in excess of two times the
allowable limit, or the time corresponding to the completion of the
daily CD check preceding the daily CD check that results in a CD in
excess of four times the allowable limit. The end of the out-of-control
period is the time corresponding to the completion of the CD check
following corrective action that results in the CD's at both the zero
(or low-level) and high-level measurement points being within the
corresponding allowable CD limit (i.e., either two times or four times
the allowable limit in appendix B).
4.3.2 CEMS Data Status During Out-of-Control Period. During the
period the CEMS is out-of-control, the CEMS data may not be used in
calculating emission compliance nor be counted towards meeting minimum
data availability as required and described in the applicable subpart
[e.g., Sec. 60.47a(f)].

[[Page 794]]

4.4 Data Recording and Reporting. As required in Sec. 60.7(d) of
this regulation (40 CFR part 60), all measurements from the CEMS must be
retained on file by the source owner for at least 2 years. However,
emission data obtained on each successive day while the CEMS is out-of-
control may not be included as part of the minimum daily data
requirement of the applicable subpart [e.g., Sec. 60.47a(f)] nor be
used in the calculation of reported emissions for that period.

5. Data Accuracy Assessment

5.1 Auditing Requirements. Each CEMS must be audited at least once
each calendar quarter. Successive quarterly audits shall occur no closer
than 2 months. The audits shall be conducted as follows:
5.1.1 Relative Accuracy Test Audit (RATA). The RATA must be
conducted at least once every four calendar quarters, except as
otherwise noted in section 5.1.4 of this appendix. Conduct the RATA as
described for the RA test procedure in the applicable PS in appendix B
(e.g., PS 2 for SO2 and NOX). In addition, analyze
the appropriate performance audit samples received from EPA as described
in the applicable sampling methods (e.g., Methods 6 and 7).
5.1.2 Cylinder Gas Audit (CGA). If applicable, a CGA may be
conducted in three of four calendar quarters, but in no more than three
quarters in succession.
To conduct a CGA: (1) Challenge the CEMS (both pollutant and diluent
portions of the CEMS, if applicable) with an audit gas of known
concentration at two points within the following ranges:

------------------------------------------------------------------------
Audit range
-------------------------------------------------------------
Audit Diluent monitors for--
point Pollutant monitors ----------------------------------------
CO2 O2
------------------------------------------------------------------------
1......... 20 to 30% of span 5 to 8% by volume.. 4 to 6% by volume.
value.
2......... 50 to 60% of span 10 to 14% by volume 8 to 12% by
value. volume.
------------------------------------------------------------------------

Challenge the CEMS three times at each audit point, and use the
average of the three responses in determining accuracy.
Use of separate audit gas cylinder for audit points 1 and 2. Do not
dilute gas from audit cylinder when challenging the CEMS.
The monitor should be challenged at each audit point for a
sufficient period of time to assure adsorption-desorption of the CEMS
sample transport surfaces has stabilized.
(2) Operate each monitor in its normal sampling mode, i.e., pass the
audit gas through all filters, scrubbers, conditioners, and other
monitor components used during normal sampling, and as much of the
sampling probe as is practical. At a minimum, the audit gas should be
introduced at the connection between the probe and the sample line.
(3) Use Certified Reference Materials (CRM's) (See Citation 1) audit
gases that have been certified by comparison to National Institute of
Standards and Technology (NIST) or EPA Traceability Protocol Materials
(ETPM's) following the most recent edition of EPA's Traceability
Protocol No. 1 (See Citation 2). Procedures for preparation of CRM's are
described in Citation 1. Procedures for preparation of ETPM's are
described in Citation 2. As an alternative to CRM's or ETPM gases,
Method 205 (See Citation 3) may be used. The difference between the
actual concentration of the audit gas and the concentration indicated by
the monitor is used to assess the accuracy of the CEMS.
5.1.3 Relative Accuracy Audit (RAA). The RAA may be conducted three
of four calendar quarters, but in no more than three quarters in
succession. To conduct a RAA, follow the procedure described in the
applicable PS in appendix B for the relative accuracy test, except that
only three sets of measurement data are required. Analyses of EPA
performance audit samples are also required.
The relative difference between the mean of the RM values and the
mean of the CEMS responses will be used to assess the accuracy of the
CEMS.
5.1.4 Other Alternative Audits. Other alternative audit procedures
may be used as approved by the Administrator for three of four calendar
quarters. One RATA is required at least every four calendar quarters,
except in the case where the affected facility is off-line (does not
operate) in the fourth calendar quarter since the quarter of the
previous RATA. In that case, the RATA shall be performed in the quarter
in which the unit recommences operation. Also, cylinder gas audits are
not be required for calendar quarters in which the affected facility
does not operate.
5.2 Excessive Audit Inaccuracy. If the RA, using the RATA, CGA, or
RAA exceeds the criteria in section 5.2.3, the CEMS is out-of-control.
If the CEMS is out-of-control, take necessary corrective action to
eliminate the problem. Following corrective action, the source owner or
operator must audit the CEMS with a RATA, CGA, or RAA to determine if
the CEMS is operating within the specifications. A RATA must always be
used following an out-of-control period resulting from a RATA. The audit
following corrective action does not require analysis of EPA performance
audit samples. If audit results show the CEMS to be out-of-control, the
CEMS operator shall report both the audit showing the CEMS to be out-of-
control and the results of the audit following corrective action showing
the CEMS to be operating within specifications.

[[Page 795]]

5.2.1 Out-Of-Control Period Definition. The beginning of the out-of-
control period is the time corresponding to the completion of the
sampling for the RATA, RAA, or CGA. The end of the out-of-control period
is the time corresponding to the completion of the sampling of the
subsequent successful audit.
5.2.2 CEMS Data Status During Out-Of-Control Period. During the
period the monitor is out-of-control, the CEMS data may not be used in
calculating emission compliance nor be counted towards meeting minimum
data availabilty as required and described in the applicable subpart
[e.g., Sec. 60.47a(f)].
5.2.3 Criteria for Excessive Audit Inaccuracy. Unless specified
otherwise in the applicable subpart, the criteria for excessive
inaccuracy are:
(1) For the RATA, the allowable RA in the applicable PS in appendix
B.
(2) For the CGA, 15 percent of the average audit value or 5 ppm,
whichever is greater.
(3) For the RAA, 15 percent of the three run average or 7.5
percent of the applicable standard, whichever is greater.
5.3 Criteria for Acceptable QC Procedure. Repeated excessive
inaccuracies (i.e., out-of-control conditions resulting from the
quarterly audits) indicates the QC procedures are inadequate or that the
CEMS is incapable of providing quality data. Therefore, whenever
excessive inaccuracies occur for two consective quarters, the source
owner or operator must revise the QC procedures (see section 3) or
modify or replace the CEMS.

6. Calculations for CEMS Data Accuracy

6.1 RATA RA Calculation. Follow the equations described in section 8
of appendix B, PS 2 to calculate the RA for the RATA. The RATA must be
calculated in units of the applicable emission standard (e.g., ng/J).
6.2 RAA Accuracy Calculation. Use the calculation procedure in the
relevant performance specification to calculate the accuracy for the
RAA. The RAA must be calculated in the units of the applicable emission
standard.
6.3 CGA Accuracy Calculation. Use Equation 1-1 to calculate the
accuracy for the CGA, which is calculated in units of the appropriate
concentration (e.g., ppm SO2 or percent O2). Each
component of the CEMS must meet the acceptable accuracy requirement.
[GRAPHIC] [TIFF OMITTED] TC16NO91.240

where:

A = Accuracy of the CEMS, percent.
Cm = Average CEMS response during audit in units of
applicable standard or appropriate concentration.
Ca = Average audit value (CGA certified value or three-
run average for RAA) in units of applicable standard or appropriate
concentration.

6.4 Example Accuracy Calculations. Example calculations for the
RATA, RAA, and CGA are available in Citation 3.

7. Reporting Requirements

At the reporting interval specified in the applicable regulation,
report for each CEMS the accuracy results from section 6 and the CD
assessment results from section 4. Report the drift and accuracy
information as a Data Assessment Report (DAR), and include one copy of
this DAR for each quarterly audit with the report of emissions required
under the applicable subparts of this part.
As a minimum, the DAR must contain the following information:
1. Source owner or operator name and address.
2. Identification and location of monitors in the CEMS.
3. Manufacturer and model number of each monitor in the CEMS.
4. Assessment of CEMS data accuracy and date of assessment as
determined by a RATA, RAA, or CGA described in section 5 including the
RA for the RATA, the A for the RAA or CGA, the RM results, the cylinder
gases certified values, the CEMS responses, and the calculations results
as defined in section 6. If the accuracy audit results show the CEMS to
be out-of-control, the CEMS operator shall report both the audit results
showing the CEMS to be out-of-control and the results of the audit
following corrective action showing the CEMS to be operating within
specifications.
5. Results from EPA performance audit samples described in section 5
and the applicable RM's.
6. Summary of all corrective actions taken when CEMS was determined
out-of-control, as described in sections 4 and 5.
An example of a DAR format is shown in Figure 1.

8. Bibliography

1. ``A Procedure for Establishing Traceability of Gas Mixtures to
Certain National Bureau of Standards Standard Reference Materials.''
Joint publication by NBS and EPA-600/7-81-010, Revised 1989. Available
from the U.S. Environmental Protection Agency. Quality Assurance
Division (MD-77). Research Triangle Park, NC 27711.
2. ``EPA Traceability Protocol For Assay And Certification Of
Gaseous Calibration Standards.'' EPA-600/R-97/121, September 1997.
Available from EPA's Emission Measurement Center at http://www.epa.gov/
ttn/emc.
3. Method 205, ``Verification of Gas Dilution Systems for Field
Instrument Calibrations,'' 40 CFR 51, appendix M.

[[Page 796]]

Figure 1--Example Format for Data Assessment Report

Period ending date______________________________________________________
Year____________________________________________________________________
Company name____________________________________________________________
Plant name______________________________________________________________
Source unit no._________________________________________________________
CEMS manufacturer_______________________________________________________
Model no._______________________________________________________________
CEMS serial no._________________________________________________________
CEMS type (e.g., in situ)_______________________________________________
CEMS sampling location (e.g., control device outlet)____________________
CEMS span values as per the applicable regulation: ------------ (e.g.,
SO2 -------- ppm, NOX -------- ppm). ------------
----
I. Accuracy assessment results (Complete A, B, or C below for each
CEMS or for each pollutant and diluent analyzer, as applicable.) If the
quarterly audit results show the CEMS to be out-of-control, report the
results of both the quarterly audit and the audit following corrective
action showing the CEMS to be operating properly.

A. Relative accuracy test audit (RATA) for -------- (e.g.,
SO2 in ng/J).

1. Date of audit --------.
2. Reference methods (RM's) used -------- (e.g., Methods 3 and 6).
3. Average RM value -------- (e.g., ng/J, mg/dsm\3\, or percent
volume).
4. Average CEMS value --------.
5. Absolute value of mean difference [d] --------.
6. Confidence coefficient [CC] --------.
7. Percent relative accuracy (RA) -------- percent.
8. EPA performance audit results:
a. Audit lot number (1) -------- (2) --------
b. Audit sample number (1) -------- (2) --------
c. Results (mg/dsm\3\) (1) -------- (2) --------
d. Actual value (mg/dsm\3\)* (1) -------- (2) --------
e. Relative error* (1) -------- (2) --------

B. Cylinder gas audit (CGA) for -------- (e.g., SO2 in
ppm).

------------------------------------------------------------------------
Audit Audit
point point
1 2
------------------------------------------------------------------------
1. Date of audit...................
2. Cylinder ID number..............
3. Date of certification...........
4. Type of certification........... ...... ...... (e.g., EPA Protocol
1 or CRM).
5. Certified audit value........... ...... ...... (e.g., ppm).
6. CEMS response value............. ...... ...... (e.g., ppm).
7. Accuracy........................ ...... ...... percent.
------------------------------------------------------------------------

C. Relative accuracy audit (RAA) for -------- (e.g., SO2
in ng/J).

1. Date of audit --------.
2. Reference methods (RM's) used -------- (e.g., Methods 3 and 6).
3. Average RM value -------- (e.g., ng/J).
4. Average CEMS value --------.
5. Accuracy -------- percent.
6. EPA performance audit results:
a. Audit lot number (1) -------- (2) --------
b. Audit sample number (1) -------- (2) --------
c. Results (mg/dsm\3\) (1) -------- (2) --------
d. Actual value (mg/dsm\3\) *(1) -------- (2)
e. Relative error* (1) -------- (2) --------
---------------------------------------------------------------------------

* To be completed by the Agency.
---------------------------------------------------------------------------

D. Corrective action for excessive inaccuracy.

1. Out-of-control periods.
a. Date(s) --------.
b. Number of days --------.
2. Corrective action taken_____________________________________________
3. Results of audit following corrective action. (Use format of A,
B, or C above, as applicable.)

II. Calibration drift assessment.

A. Out-of-control periods.
1. Date(s) --------.
2. Number of days --------.

B. Corrective action taken_____________________________________________
________________________________________________________________________

Procedure 2--Quality Assurance Requirements for Particulate Matter
Continuous Emission Monitoring Systems at Stationary Sources

1.0 What Are the Purpose and Applicability of Procedure 2?

The purpose of Procedure 2 is to establish the minimum requirements
for evaluating the effectiveness of quality control (QC) and quality
assurance (QA) procedures and the quality of data produced by your
particulate matter (PM) continuous emission monitoring system (CEMS).
Procedure 2 applies to PM CEMS used for continuously determining
compliance with emission standards or operating permit limits as
specified in an applicable regulation or permit. Other QC procedures may
apply to diluent (e.g., O2) monitors and other auxiliary
monitoring equipment included with your CEMS to facilitate PM
measurement or determination of PM concentration in units specified in
an applicable regulation.
1.1 What measurement parameter does Procedure 2 address? Procedure 2
covers the instrumental measurement of PM as defined by your source's
applicable reference method (no Chemical Abstract Service number
assigned).
1.2 For what types of devices must I comply with Procedure 2? You
must comply with Procedure 2 for the total equipment that:
(1) We require you to install and operate on a continuous basis
under the applicable regulation, and

[[Page 797]]

(2) You use to monitor the PM mass concentration associated with the
operation of a process or emission control device.
1.3 What are the data quality objectives (DQOs) of Procedure 2? The
overall DQO of Procedure 2 is the generation of valid, representative
data that can be transferred into useful information for determining PM
CEMS concentrations averaged over a prescribed interval. Procedure 2 is
also closely associated with Performance Specification 11 (PS-11).
(1) Procedure 2 specifies the minimum requirements for controlling
and assessing the quality of PM CEMS data submitted to us or the
delegated permitting authority.
(2) You must meet these minimum requirements if you are responsible
for one or more PM CEMS used for compliance monitoring. We encourage you
to develop and implement a more extensive QA program or to continue such
programs where they already exist.
1.4 What is the intent of the QA/QC procedures specified in
Procedure 2? Procedure 2 is intended to establish the minimum QA/QC
requirements for PM CEMS and is presented in general terms to allow you
to develop a program that is most effective for your circumstances. You
may adopt QA/QC procedures that go beyond these minimum requirements to
ensure compliance with applicable regulations.
1.5 When must I comply with Procedure 2? You must comply with the
basic requirements of Procedure 2 immediately following successful
completion of the initial correlation test of PS-11.

2.0 What Are the Basic Requirements of Procedure 2?

Procedure 2 requires you to perform periodic evaluations of PM CEMS
performance and to develop and implement QA/QC programs to ensure that
PM CEMS data quality is maintained.
2.1 What are the basic functions of Procedure 2?
(1) Assessment of the quality of your PM CEMS data by estimating
measurement accuracy;
(2) Control and improvement of the quality of your PM CEMS data by
implementing QC requirements and corrective actions until the data
quality is acceptable; and
(3) Specification of requirements for daily instrument zero and
upscale drift checks and daily sample volume checks, as well as routine
response correlation audits, absolute correlation audits, sample volume
audits, and relative response audits.

3.0 What Special Definitions Apply to Procedure 2?

The definitions in Procedure 2 include those provided in PS-11 of
Appendix B, with the following additions:
3.1 ``Absolute Correlation Audit (ACA)'' means an evaluation of your
PM CEMS response to a series of reference standards covering the full
measurement range of the instrument (e.g., 4 mA to 20 mA).
3.2 ``Correlation Range'' means the range of PM CEMS responses used
in the complete set of correlation test data.
3.3 ``PM CEMS Correlation'' means the site-specific relationship
(i.e., a regression equation) between the output from your PM CEMS
(e.g., mA) and the particulate concentration, as determined by the
reference method. The PM CEMS correlation is expressed in the same units
as the PM concentration measured by your PM CEMS (e.g., mg/acm). You
must derive this relation from PM CEMS response data and manual
reference method data that were gathered simultaneously. These data must
be representative of the full range of source and control device
operating conditions that you expect to occur. You must develop the
correlation by performing the steps presented in sections 12.2 and 12.3
of PS-11.
3.4 ``Reference Method Sampling Location'' means the location in
your source's exhaust duct from which you collect manual reference
method data for developing your PM CEMS correlation and for performing
relative response audits (RRAs) and response correlation audits (RCAs).
3.5 ``Response Correlation Audit (RCA)'' means the series of tests
specified in section 10.3(8) of this procedure that you conduct to
ensure the continued validity of your PM CEMS correlation.
3.6 ``Relative Response Audit (RRA)'' means the brief series of
tests specified in section 10.3(6) of this procedure that you conduct
between consecutive RCAs to ensure the continued validity of your PM
CEMS correlation.
3.7 ``Sample Volume Audit (SVA)'' means an evaluation of your PM
CEMS measurement of sample volume if your PM CEMS determines PM
concentration based on a measure of PM mass in an extracted sample
volume and an independent determination of sample volume.

4.0 Interferences [Reserved]

5.0 What Do I Need To Know To Ensure the Safety of Persons Using
Procedure 2?

People using Procedure 2 may be exposed to hazardous materials,
operations, and equipment. Procedure 2 does not purport to address all
of the safety issues associated with its use. It is your responsibility
to establish appropriate safety and health practices and determine the
applicable regulatory limitations before performing this procedure. You
must consult your CEMS user's manual for specific precautions to be
taken with regard to your PM CEMS procedures.

[[Page 798]]

6.0 What Equipment and Supplies Do I Need? [Reserved]

7.0 What Reagents and Standards Do I Need?

8.0 What Sample Collection, Preservation, Storage, and Transport Are
Relevant to This Procedure? [Reserved]

9.0 What Quality Control Measures Are Required by This Procedure for My
PM CEMS?

You must develop and implement a QC program for your PM CEMS. Your
QC program must, at a minimum, include written procedures that describe,
in detail, complete step-by-step procedures and operations for the
activities in paragraphs (1) through (8) of this section.
(1) Procedures for performing drift checks, including both zero
drift and upscale drift and the sample volume check (see sections
10.2(1), (2), and (5)).
(2) Methods for adjustment of PM CEMS based on the results of drift
checks, sample volume checks (if applicable), and the periodic audits
specified in this procedure.
(3) Preventative maintenance of PM CEMS (including spare parts
inventory and sampling probe integrity).
(4) Data recording, calculations, and reporting.
(5) RCA and RRA procedures, including sampling and analysis methods,
sampling strategy, and structuring test conditions over the prescribed
range of PM concentrations.
(6) Procedures for performing ACAs and SVAs and methods for
adjusting your PM CEMS response based on ACA and SVA results.
(7) Program of corrective action for malfunctioning PM CEMS,
including flagged data periods.
(8) For extractive PM CEMS, procedures for checking extractive
system ducts for material accumulation.
9.1 What QA/QC documentation must I have? You are required to keep
the written QA/QC procedures on record and available for inspection by
us, the State, and/or local enforcement agency for the life of your CEMS
or until you are no longer subject to the requirements of this
procedure.
9.2 How do I know if I have acceptable QC procedures for my PM CEMS?
Your QC procedures are inadequate or your PM CEMS is incapable of
providing quality data if you fail two consecutive QC audits (i.e., out-
of-control conditions resulting from the annual audits, quarterly
audits, or daily checks). Therefore, if you fail the same two
consecutive audits, you must revise your QC procedures or modify or
replace your PM CEMS to correct the deficiencies causing the excessive
inaccuracies (see section 10.4 for limits for excessive audit
inaccuracy).

10.0 What Calibration/Correlation and Standardization Procedures Must I
Perform for My PM CEMS?

You must generate a site-specific correlation for each of your PM
CEMS installation(s) relating response from your PM CEMS to results from
simultaneous PM reference method testing. The PS-11 defines procedures
for developing the correlation and defines a series of statistical
parameters for assessing acceptability of the correlation. However, a
critical component of your PM CEMS correlation process is ensuring the
accuracy and precision of reference method data. The activities listed
in sections 10.1 through 10.10 assure the quality of the correlation.
10.1 When should I use paired trains for reference method testing?
Although not required, we recommend that you should use paired-train
reference method testing to generate data used to develop your PM CEMS
correlation and for RCA testing. Guidance on the use of paired sampling
trains can be found in the PM CEMS Knowledge Document (see section 16.5
of PS-11).
10.2 What routine system checks must I perform on my PM CEMS? You
must perform routine checks to ensure proper operation of system
electronics and optics, light and radiation sources and detectors, and
electric or electro-mechanical systems. Necessary components of the
routine system checks will depend on design details of your PM CEMS. As
a minimum, you must verify the system operating parameters listed in
paragraphs (1) through (5) of this section on a daily basis. Some PM
CEMS may perform one or more of

[[Page 799]]

these functions automatically or as an integral portion of unit
operations; for other PM CEMS, you must initiate or perform one or more
of these functions manually.
(1) You must check the zero drift to ensure stability of your PM
CEMS response to the zero check value. You must determine system output
on the most sensitive measurement range when the PM CEMS is challenged
with a zero reference standard or procedure. You must, at a minimum,
adjust your PM CEMS whenever the daily zero drift exceeds 4 percent.
(2) You must check the upscale drift to ensure stability of your PM
CEMS response to the upscale check value. You must determine system
output when the PM CEMS is challenged with a reference standard or
procedure corresponding to the upscale check value. You must, at a
minimum, adjust your PM CEMS whenever the daily upscale drift check
exceeds 4 percent.
(3) For light-scattering and extinction-type PM CEMS, you must check
the system optics to ensure that system response has not been altered by
the condition of optical components, such as fogging of lens and
performance of light monitoring devices.
(4) You must record data from your automatic drift-adjusting PM CEMS
before any adjustment is made. If your PM CEMS automatically adjusts its
response to the corrected calibration values (e.g., microprocessor
control), you must program your PM CEMS to record the unadjusted
concentration measured in the drift check before resetting the
calibration. Alternately, you may program your PM CEMS to record the
amount of adjustment.
(5) For extractive PM CEMS that measure the sample volume and use
the measured sample volume as part of calculating the output value, you
must check the sample volume on a daily basis to verify the accuracy of
the sample volume measuring equipment. This sample volume check must be
done at the normal sampling rate of your PM CEMS. You must adjust your
PM CEMS sample volume measurement whenever the daily sample volume check
error exceeds 10 percent.
10.3 What are the auditing requirements for my PM CEMS? You must
subject your PM CEMS to an ACA and an SVA, as applicable, at least once
each calendar quarter. Successive quarterly audits must occur no closer
than 2 months apart. You must conduct an RCA and an RRA at the
frequencies specified in the applicable regulation or facility operating
permit. An RRA or RCA conducted during any calendar quarter can take the
place of the ACA required for that calendar quarter. An RCA conducted
during the period in which an RRA is required can take the place of the
RRA for that period.
(1) When must I perform an ACA? You must perform an ACA each quarter
unless you conduct an RRA or RCA during that same quarter.
(2) How do I perform an ACA? You perform an ACA according to the
procedure specified in paragraphs (2)(i) through (v) of this section.
(i) You must challenge your PM CEMS with an audit standard or an
equivalent audit reference to reproduce the PM CEMS's measurement at
three points within the following ranges:

------------------------------------------------------------------------
Audit point Audit range
------------------------------------------------------------------------
1...................................... 0 to 20 percent of measurement
range
2...................................... 40 to 60 percent of measurement
range
3...................................... 70 to 100 percent of
measurement range
------------------------------------------------------------------------

(ii) You must then challenge your PM CEMS three times at each audit
point and use the average of the three responses in determining accuracy
at each audit point. Use a separate audit standard for audit points 1,
2, and 3. Challenge the PM CEMS at each audit point for a sufficient
period of time to ensure that your PM CEMS response has stabilized.
(iii) Operate your PM CEMS in the mode, manner, and range specified
by the manufacturer.
(iv) Store, maintain, and use audit standards as recommended by the
manufacturer.
(v) Use the difference between the actual known value of the audit
standard and the response of your PM CEMS to assess the accuracy of your
PM CEMS.
(3) When must I perform an SVA? You must perform an audit of the
measured sample volume (e.g., the sampling flow rate for a known time)
once per quarter for applicable PM CEMS with an extractive sampling
system. Also, you must perform and pass an SVA prior to initiation of
any of the reference method data collection runs for an RCA or RRA.
(4) How do I perform an SVA? You perform an SVA according to the
procedure specified in paragraphs (4)(i) through (iii) of this section.
(i) You perform an SVA by independently measuring the volume of
sample gas extracted from the stack or duct over each batch cycle or
time period with a calibrated device. You may make this measurement
either at the inlet or outlet of your PM CEMS, so long as it measures
the sample gas volume without including any dilution or recycle air.
Compare the measured volume with the volume reported by your PM CEMS for
the same cycle or time period to calculate sample volume accuracy.
(ii) You must make measurements during three sampling cycles for
batch extractive monitors (e.g., Beta-gauge) or during three periods of
at least 20 minutes for continuous extractive PM CEMS.

[[Page 800]]

(iii) You may need to condense, collect, and measure moisture from
the sample gas prior to the calibrated measurement device (e.g., dry gas
meter) and correct the results for moisture content. In any case, the
volumes measured by the calibrated device and your PM CEMS must be on a
consistent temperature, pressure, and moisture basis.
(5) How often must I perform an RRA? You must perform an RRA at the
frequency specified in the applicable regulation or facility operating
permit. You may conduct an RCA instead of an RRA during the period when
the RRA is required.
(6) How do I perform an RRA? You must perform the RRA according to
the procedure specified in paragraphs (6)(i) and (ii) of this section.
(i) You perform an RRA by collecting three simultaneous reference
method PM concentration measurements and PM CEMS measurements at the as-
found source operating conditions and PM concentration.
(ii) We recommend that you use paired trains for reference method
sampling. Guidance on the use of paired sampling trains can be found in
the PM CEMS Knowledge Document (see section 16.5 of PS-11).
(7) How often must I perform an RCA? You must perform an RCA at the
frequency specified in the applicable regulation or facility operating
permit.
(8) How do I perform an RCA? You must perform the RCA according to
the procedures for the PM CEMS correlation test described in PS-11,
section 8.6, except that the minimum number of runs required is 12 in
the RCA instead of 15 as specified in PS-11.
(9) What other alternative audits can I use? You can use other
alternative audit procedures as approved by us, the State, or local
agency for the quarters when you would conduct ACAs.
10.4 What are my limits for excessive audit inaccuracy? Unless
specified otherwise in the applicable subpart, the criteria for
excessive audit inaccuracy are listed in paragraphs (1) through (6) of
this section.
(1) What are the criteria for excessive zero or upscale drift? Your
PM CEMS is out of control if the zero drift check or upscale drift check
either exceeds 4 percent for five consecutive daily periods or exceeds 8
percent for any one day.
(2) What are the criteria for excessive sample volume measurement
error? Your PM CEMS is out of control if sample volume check error
exceeds 10 percent for five consecutive daily periods or exceeds 20
percent for any one day.
(3) What are the criteria for excessive ACA error? Your PM CEMS is
out of control if the results of any ACA exceed 10 percent of the
average audit value, as calculated using Equation 2-1a, or 7.5 percent
of the applicable standard, as calculated using Equation 2-1b, whichever
is greater.
(4) What is the criterion for excessive SVA error? Your PM CEMS is
out of control if results exceed 5 percent of the average sample volume
audit value.
(5) What are the criteria for passing an RCA? To pass an RCA, you
must meet the criteria specified in paragraphs (5)(i) through (iii) of
this section. If your PM CEMS fails to meet these RCA criteria, it is
out of control.
(i) For all 12 data points, the PM CEMS response value can be no
greater than the greatest PM CEMS response value used to develop your
correlation curve.
(ii) For 9 of the 12 data points, the PM CEMS response value must
lie within the PM CEMS output range used to develop your correlation
curve.
(iii) At least 75 percent of a minimum number of 12 sets of PM CEMS
and reference method measurements must fall within a specified area on a
graph of the correlation regression line. The specified area on the
graph of the correlation regression line is defined by two lines
parallel to the correlation regression line, offset at a distance of 25
percent of the numerical emission limit value from the correlation
regression line.
(6) What are the criteria to pass an RRA? To pass an RRA, you must
meet the criteria specified in paragraphs (6)(i) and (ii) of this
section. If your PM CEMS fails to meet these RRA criteria, it is out of
control.
(i) For all three data points, the PM CEMS response value can be no
greater than the greatest PM CEMS response value used to develop your
correlation curve.
(ii) For two of the three data points, the PM CEMS response value
must lie within the PM CEMS output range used to develop your
correlation curve.
(iii) At least two of the three sets of PM CEMS and reference method
measurements must fall within the same specified area on a graph of the
correlation regression line as required for the RCA and described in
paragraph (5)(iii) of this section.
10.5 What do I do if my PM CEMS is out of control? If your PM CEMS
is out of control, you must take the actions listed in paragraphs (1)
and (2) of this section.
(1) You must take necessary corrective action to eliminate the
problem and perform tests, as appropriate, to ensure that the corrective
action was successful.
(i) Following corrective action, you must repeat the previously
failed audit to confirm that your PM CEMS is operating within the
specifications.
(ii) If your PM CEMS failed an RRA, you must take corrective action
until your PM CEMS passes the RRA criteria. If the RRA criteria cannot
be achieved, you must perform an RCA.
(iii) If your PM CEMS failed an RCA, you must follow procedures
specified in section 10.6 of this procedure.

[[Page 801]]

(2) You must report both the audit showing your PM CEMS to be out of
control and the results of the audit following corrective action showing
your PM CEMS to be operating within specifications.
10.6 What do I do if my PM CEMS fails an RCA? After an RCA failure,
you must take all applicable actions listed in paragraphs (1) through
(3) of this section.
(1) Combine RCA data with data from the active PM CEMS correlation
and perform the mathematical evaluations defined in PS-11 for
development of a PM CEMS correlation, including examination of alternate
correlation models (i.e., linear, polynomial, logarithmic, exponential,
and power). If the expanded data base and revised correlation meet PS-11
statistical criteria, use the revised correlation.
(2) If the criteria specified in paragraph (1) of this section are
not achieved, you must develop a new PM CEMS correlation based on
revised data. The revised data set must consist of the test results from
only the RCA. The new data must meet all requirements of PS-11 to
develop a revised PM CEMS correlation, except that the minimum number of
sets of PM CEMS and reference method measurements is 12 instead of the
minimum of 15 sets required by PS-11. Your PM CEMS is considered to be
back in controlled status when the revised correlation meets all of the
performance criteria specified in section 13.2 of PS-11.
(3) If the actions in paragraphs (1) and (2) of this section do not
result in an acceptable correlation, you must evaluate the cause(s) and
comply with the actions listed in paragraphs (3)(i) through (iv) of this
section within 90 days after the completion of the failed RCA.
(i) Completely inspect your PM CEMS for mechanical or operational
problems. If you find a mechanical or operational problem, repair your
PM CEMS and repeat the RCA.
(ii) You may need to relocate your PM CEMS to a more appropriate
measurement location. If you relocate your PM CEMS, you must perform a
new correlation test according to the procedures specified in PS-11.
(iii) The characteristics of the PM or gas in your source's flue gas
stream may have changed such that your PM CEMS measurement technology is
no longer appropriate. If this is the case, you must install a PM CEMS
with measurement technology that is appropriate for your source's flue
gas characteristics. You must perform a new correlation test according
to the procedures specified in PS-11.
(iv) If the corrective actions in paragraphs (3)(i) through (iii) of
this section were not successful, you must petition us, the State, or
local agency for approval of alternative criteria or an alternative for
continuous PM monitoring.
10.7 When does the out-of-control period begin and end? The out-of-
control period begins immediately after the last test run or check of an
unsuccessful RCA, RRA, ACA, SVA, drift check, or sample volume check.
The out-of-control period ends immediately after the last test run or
check of the subsequent successful audit or drift check.
10.8 Can I use the data recorded by my PM CEMS during out-of-control
periods? During any period when your PM CEMS is out of control, you may
not use your PM CEMS data to calculate emission compliance or to meet
minimum data availability requirements described in the applicable
regulation.
10.9 What are the QA/QC reporting requirements for my PM CEMS? You
must report the accuracy results for your PM CEMS, specified in section
10.4 of this procedure, at the interval specified in the applicable
regulation. Report the drift and accuracy information as a Data
Assessment Report (DAR), and include one copy of this DAR for each
quarterly audit with the report of emissions required under the
applicable regulation. An example DAR is provided in Procedure 1,
Appendix F of this part.
10.10 What minimum information must I include in my DAR? As a
minimum, you must include the information listed in paragraphs (1)
through (5) of this section in the DAR:
(1) Your name and address.
(2) Identification and location of monitors in your CEMS.
(3) Manufacturer and model number of each monitor in your CEMS.
(4) Assessment of PM CEMS data accuracy/acceptability, and date of
assessment, as determined by an RCA, RRA, ACA, or SVA described in
section 10, including the acceptability determination for the RCA or
RRA, the accuracy for the ACA or SVA, the reference method results, the
audit standards, your PM CEMS responses, and the calculation results as
defined in section 12. If the accuracy audit results show your PM CEMS
to be out of control, you must report both the audit results showing
your PM CEMS to be out of control and the results of the audit following
corrective action showing your PM CEMS to be operating within
specifications.
(5) Summary of all corrective actions you took when you determined
your PM CEMS to be out of control, as described in section 10.5, or
after failing on RCA, as described in section 10.6.
10.7 Where and how long must I retain the QA data that this
procedure requires me to record for my PM CEMS? You must keep the
records required by this procedure for your PM CEMS onsite and available
for inspection by us, the State, and/or local enforcement agency for a
period of 5 years.

[[Page 802]]

11.0 What Analytical Procedures Apply to This Procedure?

Sample collection and analysis are concurrent for this procedure.
You must refer to the appropriate reference method for the specific
analytical procedures.

12.0 What Calculations and Data Analysis Must I Perform for my PM CEMS?

(1) How do I determine RCA and RRA acceptability? You must plot each
of your PM CEMS and reference method data sets from an RCA or RRA on a
graph based on your PM CEMS correlation line to determine if the
criteria in paragraphs 10.4(5) or (6), respectively, are met.
(2) How do I calculate ACA accuracy? You must use either Equation 2-
1a or 2-1b to calculate ACA accuracy for each of the three audit points.
However, when calculating ACA accuracy for the first audit point (0 to
20 percent of measurement range), you must use Equation 2-1b to
calculate ACA accuracy if the reference standard value (Rv)
equals zero.
[GRAPHIC] [TIFF OMITTED] TR25MR09.104

Where:

ACA Accuracy = The ACA accuracy at each audit point, in percent,
RCEM = Your PM CEMS response to the reference standard, and
RV = The reference standard value.

[GRAPHIC] [TIFF OMITTED] TR25MR09.105

Where:

ACA Accuracy = The ACA accuracy at each audit point, in percent,
CCEM = The PM concentration that corresponds to your PM CEMS
response to the reference standard, as calculated using the
correlation equation for your PM CEMS,
CRV = The PM concentration that corresponds to the reference
standard value in units consistent with CCEM, and
Cs = The PM concentration that corresponds to the applicable
emission limit in units consistent with CCEM.

(3) How do I calculate daily upscale and zero drift? You must
calculate the upscale drift using Equation 2-2 and the zero drift using
Equation 2-3:
[GRAPHIC] [TIFF OMITTED] TR27FE14.021

Where:

UD = The upscale drift of your PM CEMS, in percent,
RCEM = Your PM CEMS response to the upscale check value, and
RU = The upscale check value.
FS = Full-scale value.
[GRAPHIC] [TIFF OMITTED] TR27FE14.022

[[Page 803]]

Where:

ZD = The zero (low-level) drift of your PM CEMS, in percent,
RCEM = Your PM CEMS response of the zero check value,
RL = The zero check value.
(4) How do I calculate SVA accuracy? You must use Equation 2-4 to
calculate the accuracy, in percent, for each of the three SVA tests or
the daily sample volume check:
[GRAPHIC] [TIFF OMITTED] TR27FE14.023

Where:

VM = Sample gas volume determined/reported by your PM CEMS
(e.g., dscm),
VR = Sample gas volume measured by the independent calibrated
reference device (e.g., dscm) for the SVA or the reference
value for the daily sample volume check.
Note: Before calculating SVA accuracy, you must correct the sample
gas volumes measured by your PM CEMS and the independent calibrated
reference device to the same basis of temperature, pressure, and
moisture content. You must document all data and calculations.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Which References are Relevant to This Method? [Reserved]

17.0 What Tables, Diagrams, Flowcharts, and Validation Data Are Relevant
to This Method? [Reserved]

Procedure 3--Quality Assurance Requirements for Continuous Opacity
Monitoring Systems at Stationary Sources

1.0 What are the purpose and applicability of Procedure 3?

The purpose of Procedure 3 is to establish quality assurance and
quality control (QA/QC) procedures for continuous opacity monitoring
systems (COMS). Procedure 3 applies to COMS used to demonstrate
continuous compliance with opacity standards specified in new source
performance standards (NSPS) promulgated by EPA pursuant to section
111(b) of the Clean Air Act, 42 U.S.C. 7411(b)--Standards of Performance
for New Stationary Sources.
1.1 What are the data quality objectives of Procedure 3? The overall
data quality objective (DQO) of Procedure 3 is the generation of valid
and representative opacity data. Procedure 3 specifies the minimum
requirements for controlling and assessing the quality of COMS data
submitted to us or the delegated regulatory agency. Procedure 3 requires
you to perform periodic evaluations of a COMS performance and to develop
and implement QA/QC programs to ensure that COMS data quality is
maintained.
1.2 What is the intent of the QA/QC procedures specified in
Procedure 3? Procedure 3 is intended to establish the minimum QA/QC
requirements to verify and maintain an acceptable level of quality of
the data produced by COMS. It is presented in general terms to allow you
to develop a program that is most effective for your circumstances.
1.3 When must I comply with Procedure 3? You must comply with
Procedure 3 no later than November 12, 2014.

2.0 What are the basic functions of Procedure 3?

The basic functions of Procedure 3 are assessment of the quality of
your COMS data and control and improvement of the quality of the data by
implementing QC requirements and corrective actions. Procedure 3
provides requirements for:
(1) Daily instrument zero and upscale drift checks and status
indicators checks;
(2) Quarterly performance audits which include the following
assessments:
(i) Optical alignment,
(ii) Calibration error, and
(iii) Zero compensation.

Sources that achieve quality assured data for four consecutive quarters
may reduce their auditing frequency to semi-annual. If a performance
audit is failed, the source must resume quarterly testing for that audit
requirement until it again demonstrates successful performance over four
consecutive quarters.
(3) Annual zero alignment.

3.0 What special definitions apply to Procedure 3?

The definitions in Procedure 3 include those provided in Performance
Specification 1 (PS-1) of Appendix B of this part and ASTM D6216-12 and
the following additional definitions.

[[Page 804]]

3.1 Out-of-control periods. Out-of-control periods mean that one or
more COMS parameters falls outside of the acceptable limits established
by this rule.
(1) Daily Assessments. Whenever the calibration drift (CD) exceeds
twice the specification of PS-1, the COMS is out-of-control. The
beginning of the out-of-control period is the time corresponding to the
completion of the daily calibration drift check. The end of the out-of-
control period is the time corresponding to the completion of
appropriate adjustment and subsequent successful CD assessment.
(2) Quarterly and Annual Assessments. Whenever an annual zero
alignment or quarterly performance audit fails to meet the criteria
established in paragraphs (2) and (3) of section 10.4, the COMS is out-
of-control. The beginning of the out-of-control period is the time
corresponding to the completion of the performance audit indicating the
failure to meet these established criteria. The end of the out-of-
control period is the time corresponding to the completion of
appropriate corrective actions and the subsequent successful audit (or,
if applicable, partial audit).

4.0 What interferences must I avoid?

Opacity cannot be measured accurately in the presence of condensed
water vapor. Thus, COMS opacity compliance determinations cannot be made
when condensed water vapor is present, such as downstream of a wet
scrubber without a reheater or at other saturated flue gas locations.
Therefore, COMS must be located where condensed water vapor is not
present.

5.0 What do I need to know to ensure the safety of persons using
Procedure 3?

Those implementing Procedure 3 may be exposed to hazardous
materials, operations and equipment. Procedure 3 does not purport to
address all of the safety issues associated with its use. It is your
responsibility to establish appropriate health and safety practices and
determine the applicable regulatory limitations before performing this
procedure. You should consult the COMS user's manual for specific
precautions to take.

6.0 What equipment and supplies do I need?

The equipment and supplies that you need are specified in PS-1. You
are not required to purchase a new COMS if your existing COMS meets the
requirements specified in Procedure 3.

7.0 What reagents and standards do I need?

The reagents and standards that you need are specified in PS-1. You
are not required to purchase a new COMS if your existing COMS meets the
requirements specified in Procedure 3.

8.0 What sample collection, preservation, storage, and transport are
relevant to this procedure? [Reserved]

9.0 What quality control measures are required by this procedure for my
COMS?

You must develop and implement a QC program for your COMS. Your QC
program must, at a minimum, include written procedures which describe in
detail complete step-by-step procedures and operations for the
activities in paragraphs (1) through (4):
(1) Procedures for performing drift checks, including both zero and
upscale drift and the status indicators check,
(2) Procedures for performing quarterly performance audits,
(3) A means of checking the zero alignment of the COMS, and
(4) A program of corrective action for a malfunctioning COMS. The
corrective action must include, at a minimum, the requirements specified
in section 10.5.
9.1 What QA/QC documentation must I have? You are required to keep
the QA/QC written procedures required in section 9.0 on site and
available for inspection by us, the state, and/or local enforcement
agencies.
9.2 What actions must I take if I fail QC audits? If you fail two
consecutive annual audits, two consecutive quarterly audits, or five
consecutive daily checks, you must either revise your QC procedures or
determine if your COMS is malfunctioning. If you determine that your
COMS is malfunctioning, you must take the necessary corrective action as
specified in section 10.5. If you determine that your COMS requires
extensive repairs, you may use a substitute COMS provided the substitute
meets the requirements in section 10.6.

10.0 What calibration and standardization procedures must I perform for
my COMS?

(1) You must perform daily system checks to ensure proper operation
of system electronics and optics, light and radiation sources and
detectors, electric or electro-mechanical systems, and general stability
of the system calibration. Daily is defined as any portion of a calendar
day in which a unit operates.
(2) You must subject your COMS to a performance audit to include
checks of the individual COMS components and factors affecting the
accuracy of the monitoring data at least once per QA operating quarter.
A QA operating quarter is a calendar quarter in which a unit operates at
least 168 hours.
(3) At least annually, you must perform a zero alignment by
comparing the COMS simulated zero to the actual clear path zero.
Annually is defined as a period wherein the unit is operating at least
28 days in a calendar year. The simulated zero device produces a
simulated clear path condition or low-level

[[Page 805]]

opacity condition, where the energy reaching the detector is between 90
and 110 percent of the energy reaching the detector under actual clear
path conditions.
10.1 What daily system checks must I perform on my COMS? The
specific components required to undergo daily system checks will depend
on the design details of your COMS. At a minimum, you must verify the
system operating parameters listed in paragraphs (1) through (3) of this
section. Some COMS may perform one or more of these functions
automatically or as an integral portion of unit operations; other COMS
may perform one or more of these functions manually.
(1) You must check the zero drift to ensure stability of your COMS
response to the simulated zero device. The simulated zero device, an
automated mechanism within the transmissometer that produces a simulated
clear path condition or low-level opacity condition, is used to check
the zero drift. You must, at a minimum, take corrective action on your
COMS whenever the daily zero drift exceeds twice the applicable drift
specification in section 13.3(6) of PS-1.
(2) You must check the upscale drift to ensure stability of your
COMS response to the upscale drift value. The upscale calibration
device, an automated mechanism (employing an attenuator or reduced
reflectance device) within the transmissometer that produces an upscale
opacity value is used to check the upscale drift. You must, at a
minimum, take corrective action on your COMS whenever the daily upscale
drift check exceeds twice the applicable drift specification in section
13.3(6) of PS-1.
(3) You must, at a minimum, check the status indicators, data
acquisition system error messages, and other system self-diagnostic
indicators. You must take appropriate corrective action based on the
manufacturer's recommendations when the COMS is operating outside preset
limits.
10.2 What are the quarterly auditing requirements for my COMS? At a
minimum, the parameters listed in paragraphs (1) through (3) of this
section must be included in the performance audit conducted on a
quarterly basis as defined in section 10.0(2).
(1) For units with automatic zero compensation, you must determine
the zero compensation for the COMS. The value of the zero compensation
applied at the time of the audit must be calculated as equivalent
opacity and corrected to stack exit conditions according to the
procedures specified by the manufacturer. The compensation applied to
the effluent by the monitor system must be recorded.
(2) You must conduct a three-point calibration error test of the
COMS. Three calibration attenuators, either primary or secondary must
meet the requirements of PS-1, with one exception. Instead of
recalibrating the attenuators semi-annually, they must be recalibrated
annually. If two annual calibrations agree within 0.5 percent opacity,
the attenuators may then be calibrated once every five years. The three
attenuators must be placed in the COMS light beam path for at least
three nonconsecutive readings. All monitor responses must then be
independently recorded from the COMS permanent data recorder. Additional
guidance for conducting this test is included in section 8.1(3)(ii) of
PS-1. The low-, mid-, and high-range calibration error results must be
computed as the mean difference and 95 percent confidence interval for
the difference between the expected and actual responses of the monitor
as corrected to stack exit conditions. The equations necessary to
perform the calculations are found in section 12.0 of PS-1. For the
calibration error test method, you must use the external audit device.
When the external audit device is installed, with no calibration
attenuator inserted, the COMS measurement reading must be less than or
equal to one percent opacity. You must also document procedures for
properly handling and storing the external audit device and calibration
attenuators within your written QC program.
(3) You must check the optical alignment of the COMS in accordance
with the instrument manufacturer's recommendations. If the optical
alignment varies with stack temperature, perform the optical alignment
test when the unit is operating.
10.3 What are the annual auditing requirements for my COMS?
(1) You must perform the primary zero alignment method under clear
path conditions. The COMS must be removed from its installation and set
up under clear path conditions. There must be no adjustments to the
monitor other than the establishment of the proper monitor path length
and correct optical alignment of the COMS components. You must record
the COMS response to a clear condition and to the COMS's simulated zero
condition as percent opacity corrected to stack exit conditions. For a
COMS with automatic zero compensation, you must disconnect or disable
the zero compensation mechanism or record the amount of correction
applied to the COMS's simulated zero condition. The response difference
in percent opacity to the clear path and simulated zero conditions must
be recorded as the zero alignment error. You must adjust the COMS's
simulated zero device to provide the same response as the clear path
condition as specified in paragraph (3) of section 10.0.
(2) As an alternative, monitors capable of allowing the installation
of an external zero device may use the device for the zero alignment
provided that: (1) The external zero device setting has been established
for the monitor path length and recorded for the specific COMS by
comparison of the COMS

[[Page 806]]

responses to the installed external zero device and to the clear path
condition, and (2) the external zero device is demonstrated to be
capable of producing a consistent zero response when it is repeatedly
(i.e., three consecutive installations and removals prior to conducting
the final zero alignment check) installed on the COMS. This can be
demonstrated by either the manufacturer's certificate of conformance
(MCOC) or actual on-site performance. The external zero device setting
must be permanently set at the time of initial zeroing to the clear path
zero value and protected when not in use to ensure that the setting
equivalent to zero opacity does not change. The external zero device
response must be checked and recorded prior to initiating the zero
alignment. If the external zero device setting has changed, you must
remove the COMS from the stack in order to reset the external zero
device. If you employ an external zero device, you must perform the zero
alignment audits with the COMS off the stack at least every three years.
If the external zero device is adjusted within the three-year period,
you must perform the zero alignment with the COMS off the stack no later
than three years from the date of adjustment.
(3) The procedure in section 6.8 of ASTM D6216-12 is allowed.
10.4 What are my limits for excessive audit inaccuracy? Unless
specified otherwise in the applicable subpart, the criteria for
excessive inaccuracy are listed in paragraphs (1) through (4).
(1) What is the criterion for excessive zero or upscale drift? Your
COMS is out-of-control if either the zero drift check or upscale drift
check exceeds twice the applicable drift specification in PS-1 for any
one day.
(2) What is the criterion for excessive zero alignment? Your COMS is
out-of-control if the zero alignment error exceeds 2 percent opacity.
(3) What is the criterion to pass the quarterly performance audit?
Your COMS is out-of-control if the results of a quarterly performance
audit indicate noncompliance with the following criteria:
(i) The optical alignment indicator does not show proper alignment
(i.e., does not fall within a specific reference mark or condition).
(ii) The zero compensation exceeds 4 percent opacity, or
(iii) The calibration error exceeds 3 percent opacity.
(4) What is the criterion for data capture? You must adhere to the
data capture criterion specified in the applicable subpart.
10.5 What corrective action must I take if my COMS is
malfunctioning? You must have a corrective action program in place to
address the repair and/or maintenance of your COMS. The corrective
action program must address routine/preventative maintenance and various
types of analyzer repairs. The corrective action program must establish
what diagnostic testing must be performed after each type of activity to
ensure that the COMS is collecting valid, quality-assured data.
Recommended maintenance and repair procedures and diagnostic testing
after repairs may be found in an associated guidance document.
10.6 What requirements must I meet if I use a temporary opacity
monitor?
(1) In the event that your certified opacity monitor has to be
removed for extended service, you may install a temporary replacement
monitor to obtain required opacity emissions data provided that:
(i) The temporary monitor has been certified according to ASTM
D6216-12 for which a MCOC has been provided;
(ii) The use of the temporary monitor does not exceed 1080 hours (45
days) of operation per year as a replacement for a fully certified
opacity monitor. After that time, the analyzer must complete a full
certification according to PS-1 prior to further use as a temporary
replacement monitor. Once a temporary replacement monitor has been
installed and required testing and adjustments have been successfully
completed, it cannot be replaced by another temporary replacement
monitor to avoid the full PS-1 certification testing required after 1080
hours (45 days) of use;
(iii) The temporary monitor has been installed and successfully
completed an optical alignment assessment and status indicator
assessment;
(iv) The temporary monitor has successfully completed an off-stack
clear path zero assessment and zero calibration value adjustment
procedure;
(v) The temporary monitor has successfully completed an abbreviated
zero and upscale drift check consisting of seven zero and upscale
calibration value drift checks which may be conducted within a 24-hour
period with not more than one calibration drift check every three hours
and not less than one calibration drift check every 25 hours. Calculated
zero and upscale drift requirements are the same as specified for the
normal PS-1 certification;
(vi) The temporary monitor has successfully completed a three-point
calibration error test;
(vii) The upscale reference calibration check value of the new
monitor has been updated in the associated data recording equipment;
(viii) The overall calibration of the monitor and data recording
equipment has been verified; and
(ix) The user has documented all of the above in the maintenance
log.
(2) Data generated by the temporary monitor is considered valid when
paragraphs (i) through (ix) in this section have been met.

[[Page 807]]

10.7 When do out-of-control periods begin and end? The out-of-
control periods are as specified in section 3.1.
10.8 What are the limitations on the use of my COMS data collected
during out-of-control periods? During the period your COMS is out-of-
control, you may not use your COMS data to calculate emission compliance
or to meet minimum data capture requirements in this procedure or the
applicable regulation.
10.9 What are the QA/QC reporting requirements for my COMS? You must
report in a Data Assessment Report (DAR) the information required by
sections 10.0, 10.1, 10.2, and 10.3 for your COMS at the interval
specified in the applicable regulation.
10.10 What minimum information must I include in my DAR? At a
minimum, you must include the information listed in paragraphs (1)
through (5) of this section in the DAR.
(1) Name of person completing the report and facility address,
(2) Identification and location of your COMS(s),
(3) Manufacturer, model, and serial number of your COMS(s),
(4) Assessment of COMS data accuracy/acceptability and date of
assessment as determined by a performance audit described in section
10.0. If the accuracy audit results show your COMS to be out-of-control,
you must report both the audit results showing your COMS to be out-of-
control and the results of the audit following corrective action showing
your COMS to be operating within specifications, and
(5) Summary of all corrective actions you took when you determined
your COMS was out-of-control.
10.11 Where and how long must I retain the QA data that this
procedure requires me to record for my COMS? You must keep the records
required by this procedure for your COMS on site and available for
inspection by us, the state, and/or the local enforcement agency for the
period specified in the regulations requiring the use of COMS.

11.0 What analytical procedures apply to this procedure? [Reserved]

12.0 What calculations and data analysis must I perform for my COMS?The
calculations required for the quarterly performance audit are in section
12.0 of PS-1.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

16.1 Performance Specification 1-Specifications and Test Procedures
for Continuous Opacity Monitoring Systems in Stationary Sources, 40 CFR
part 60, Appendix B.
16.2 ASTM D6216-12-Standard Practice for Opacity Monitor
Manufacturers to Certify Conformance with Design and Performance
Specifications, American Society for Testing and Materials (ASTM).

17.0 What tables, diagrams, flowcharts, and validation data are relevant
to this procedure? [Reserved]

Procedure 4. [Reserved]

Procedure 5. Quality Assurance Requirements for Vapor Phase Mercury
Continuous Emissions Monitoring Systems and Sorbent Trap Monitoring
Systems Used for Compliance Determination at Stationary Sources

1.0 Applicability and Principle

1.1 Applicability. The purpose of Procedure 5 is to establish the
minimum requirements for evaluating the effectiveness of quality control
(QC) and quality assurance (QA) procedures as well as the quality of
data produced by vapor phase mercury (Hg) continuous emissions
monitoring systems (CEMS) and sorbent trap monitoring systems. Procedure
5 applies to Hg CEMS and sorbent trap monitoring systems used for
continuously determining compliance with emission standards or operating
permit limits as specified in an applicable regulation or permit. Other
QA/QC procedures may apply to other auxiliary monitoring equipment that
may be needed to determine Hg emissions in the units of measure
specified in an applicable permit or regulation.
Procedure 5 covers the measurement of Hg emissions as defined in
Performance Specification 12A (PS 12A) and Performance Specification 12B
(PS 12B) in appendix B to this part, i.e., total vapor phase Hg
representing the sum of the elemental (Hg[deg], CAS Number 7439-97-6)
and oxidized (Hg⁺²) forms of gaseous Hg.
Procedure 5 specifies the minimum requirements for controlling and
assessing the quality of Hg CEMS and sorbent trap monitoring system data
submitted to EPA or a delegated permitting authority. You must meet
these minimum requirements if you are responsible for one or more Hg
CEMS or sorbent trap monitoring systems used for compliance monitoring.
We encourage you to develop and implement a more extensive QA program or
to continue such programs where they already exist.
You must comply with the basic requirements of Procedure 5
immediately following successful completion of the initial performance
test described in PS 12A or PS 12B in appendix B to this part (as
applicable).
1.2 Principle. The QA procedures consist of two distinct and equally
important functions. One function is the assessment of the

[[Page 808]]

quality of the Hg CEMS or sorbent trap monitoring system data by
estimating accuracy. The other function is the control and improvement
of the quality of the CEMS or sorbent trap monitoring system data by
implementing QC policies and corrective actions. These two functions
form a control loop: When the assessment function indicates that the
data quality is inadequate, the quality control effort must be increased
until the data quality is acceptable. In order to provide uniformity in
the assessment and reporting of data quality, this procedure explicitly
specifies assessment methods for calibration drift, system integrity,
and accuracy. Several of the procedures are based on those of PS 12A and
PS 12B in appendix B to this part. Because the control and corrective
action function encompasses a variety of policies, specifications,
standards, and corrective measures, this procedure treats QC
requirements in general terms to allow each source owner or operator to
develop a QC system that is most effective and efficient for the
circumstances.

2.0 Definitions

2.1 Mercury Continuous Emission Monitoring System (Hg CEMS) means
the equipment required for the determination of the total vapor phase Hg
concentration in the stack effluent. The Hg CEMS consists of the
following major subsystems:
2.1.1 Sample Interface means that portion of the CEMS used for one
or more of the following: sample acquisition, sample transport, sample
conditioning, and protection of the monitor from the effects of the
stack effluent.
2.1.2 Hg Analyzer means that portion of the Hg CEMS that measures
the total vapor phase Hg concentration and generates a proportional
output.
2.1.3 Data Recorder means that portion of the CEMS that provides a
permanent electronic record of the analyzer output. The data recorder
may provide automatic data reduction and CEMS control capabilities.
2.2 Sorbent Trap Monitoring System means the total equipment
required for the collection of gaseous Hg samples using paired three-
partition sorbent traps as described in PS 12B in appendix B to this
part.
2.3 Span Value means the measurement range as specified for the
affected source category in the applicable regulation and/or monitoring
performance specification.
2.4 Zero, Mid-Level, and High Level Values means the reference gas
concentrations used for calibration drift assessments and system
integrity checks on a Hg CEMS, expressed as percentages of the span
value (see section 7.1 of PS 12A in appendix B to this part).
2.5 Calibration Drift (CD) means the absolute value of the
difference between the CEMS output response and either the upscale Hg
reference gas or the zero-level Hg reference gas, expressed as a
percentage of the span value, when the entire CEMS, including the
sampling interface, is challenged after a stated period of operation
during which no unscheduled maintenance, repair, or adjustment took
place.
2.6 System Integrity (SI) Check means a test procedure assessing
transport and measurement of oxidized Hg by a Hg CEMS. In particular,
system integrity is expressed as the absolute value of the difference
between the CEMS output response and the reference value of either a
mid- or high-level mercuric chloride (HgCl2) reference gas,
as a percentage of span, when the entire CEMS, including the sampling
interface, is challenged.
2.7 Relative Accuracy (RA) means the absolute mean difference
between the pollutant concentrations determined by a continuous
monitoring system (e.g., Hg CEMS or sorbent trap monitoring system) and
the values determined by a reference method (RM) plus the 2.5 percent
error confidence coefficient of a series of tests divided by the mean of
the RM tests. Alternatively, for sources with an average RM
concentration less than 5.0 micrograms per standard cubic meter
(g/scm), the RA may be expressed as the absolute value of the
difference between the mean CEMS and RM values.
2.8 Relative Accuracy Test Audit (RATA) means an audit test
procedure consisting of at least nine runs, in which the accuracy of the
total vapor phase Hg concentrations measured by a CEMS or sorbent trap
monitoring system is evaluated by comparison against concurrent
measurements made with a reference test method.
2.9 Quarterly Gas Audit (QGA) means an audit procedure in which the
accuracy of the total vapor phase Hg concentrations measured by a CEMS
is evaluated by challenging the CEMS with a zero and two upscale
reference gases.

3.0 QC Requirements

3.1 Each source owner or operator must develop and implement a QC
program. At a minimum, each QC program must include written procedures
which should describe in detail, complete, step-by-step procedures and
operations for each of the following activities (as applicable):
(a) Calibration drift (CD) checks of Hg CEMS.
(b) CD determination and adjustment of Hg CEMS.
(c) Weekly system integrity check procedures for Hg CEMS.
(d) Routine operation, maintenance, and QA/QC procedures for sorbent
trap monitoring systems.
(e) Routine and preventive maintenance procedures for Hg CEMS
(including spare parts inventory).
(f) Data recording, calculations, and reporting.

[[Page 809]]

(g) Accuracy audit procedures for Hg CEMS and sorbent trap
monitoring systems including sampling and analysis methods.
(h) Program of corrective action for malfunctioning Hg CEMS and
sorbent trap monitoring systems.
These written procedures must be kept on record and available for
inspection by the responsible enforcement agency. Also, as noted in
section 5.2.4, below, whenever excessive inaccuracies of a Hg CEMS occur
for two consecutive quarters, the source owner or operator must revise
the current written procedures or modify or replace the CEMS or sorbent
trap monitoring system to correct the deficiency causing the excessive
inaccuracies.

4.0 Calibration Drift (CD) Assessment

4.1 CD Requirement. As described in 40 CFR 60.13(d) and 63.8(c),
source owners and operators of Hg CEMS must check, record, and quantify
the CD at two concentration values at least once daily (approximately 24
hours) in accordance with the method prescribed by the manufacturer. The
Hg CEMS calibration must, as minimum, be adjusted whenever the daily
zero (or low-level) CD or the daily high-level CD exceeds two times the
limits of the applicable PS in appendix B of this part.
4.2 Recording Requirement for Automatic CD Adjusting CEMS. CEMS that
automatically adjust the data to the corrected calibration values (e.g.,
microprocessor control) must either be programmed to record the
unadjusted concentration measured in the CD prior to resetting the
calibration, if performed, or to record the amount of adjustment.
4.3 Criteria for Excessive CD. If either the zero (or low-level) or
high-level CD result exceeds twice the applicable drift specification in
section 13.2 of PS 12A in appendix B to this part for five, consecutive,
daily periods, the CEMS is out-of-control. If either the zero (or low-
level) or high-level CD result exceeds four times the applicable drift
specification in PS 12A during any CD check, the CEMS is out-of-control.
If the CEMS is out-of-control, take necessary corrective action.
Following corrective action, repeat the CD checks.
4.3.1 Out-Of-Control Period Definition. The beginning of the out-of-
control period is the time corresponding to the completion of the fifth,
consecutive, daily CD check with a CD in excess of two times the
allowable limit, or the time corresponding to the completion of the
daily CD check preceding the daily CD check that results in a CD in
excess of four times the allowable limit. The end of the out-of-control
period is the time corresponding to the completion of the CD check
following corrective action that results in the CD's at both the zero
(or low-level) and high-level measurement points being within the
corresponding allowable CD limit (i.e., either two times or four times
the allowable limit in the applicable PS in appendix B).
4.3.2 CEMS Data Status During Out-of-Control Period. During the
period the CEMS is out-of-control, the CEMS data may not be used either
to determine compliance with an emission limit or to meet a minimum data
availability requirement specified in an applicable regulation or
permit.

5.0 Data Accuracy Assessment

5.1 Hg CEMS Audit Requirements. For each Hg CEMS, an accuracy audit
must be performed at least once each calendar quarter. Successive
quarterly audits must, to the extent practicable, be performed no less
than 2 months apart. The audits must be conducted as follows:
5.1.1 Relative Accuracy Test Audit (RATA). A RATA of the Hg CEMS
must be conducted at least once every four calendar quarters, except as
otherwise noted in section 5.1.4 of this appendix. Perform the RATA as
described in section 8.5 of PS 12A in appendix B to this part. Calculate
the results according to section 12.4 of PS 12A.
5.1.2 Quarterly Gas Audit. A quarterly gas audit (QGA) may be
conducted in three of four calendar quarters, but in no more than three
quarters in succession. To perform a QGA, challenge the CEMS with a
zero-level and two upscale level audit gases of known concentrations,
first of elemental Hg and then of oxidized Hg, within the following
ranges:

------------------------------------------------------------------------
Audit point Audit range
------------------------------------------------------------------------
1................................... 20 to 30% of span value.
2................................... 50 to 60% of span value.
------------------------------------------------------------------------

Sequentially inject each of the three audit gases (zero and two
upscale), three times each for a total of nine injections. Inject the
gases in such a manner that the entire CEMS is challenged. Do not inject
the same gas concentration twice in succession.
Use elemental Hg and oxidized Hg (mercuric chloride,
HgCl2) audit gases that are National Institute of Standards
and Technology (NIST)-certified or NIST-traceable following an EPA
Traceability Protocol. If audit gas cylinders are used, do not dilute
gas when challenging the Hg CEMS. For each reference gas concentration,
determine the average of the three CEMS responses and subtract the
average response from the reference gas value. Calculate the measurement
error at each gas level using Equation 12A-1 in section 8.2 of PS 12A.
5.1.3 Relative Accuracy Audit (RAA). As an alternative to the QGA, a
RAA may be conducted in three of four calendar quarters, but in no more
than three quarters in succession. To conduct a RAA, follow the RATA
test

[[Page 810]]

procedures in section 8.5 of PS 12A in appendix B to this part, except
that only three test runs are required.
5.1.4 Alternative Quarterly Audits. Alternative quarterly audit
procedures may be used as approved by the Administrator for three of
four calendar quarters. One RATA is required at least every four
calendar quarters, except in the case where the affected facility is
off-line (does not operate) in the fourth calendar quarter since the
quarter of the previous RATA. In that case, the RATA must be performed
in the quarter in which the unit recommences operation. Also, quarterly
gas audits (or RAAs, if applicable) are not required for calendar
quarters in which the affected facility does not operate.
5.2 Sorbent Trap Monitoring System Audit Requirements. For each
sorbent trap monitoring system, a RATA must be conducted at least once
every four calendar quarters, except as otherwise noted in section 5.1.4
of this appendix. Perform the RATA as described in section 8.3 of PS 12B
in appendix B to this part. Calculate the results according to section
12.4 of PS 12A.
5.3 Excessive Audit Inaccuracy. If the results of a RATA, QGA, or
RAA exceed the applicable criteria in section 5.3.3, the Hg CEMS or
sorbent trap monitoring system is out-of-control. If the Hg CEMS or
sorbent trap monitoring system is out-of-control, take necessary
corrective action to eliminate the problem. Following corrective action,
the source owner or operator must audit the CEMS or sorbent trap
monitoring system using the same type of test that failed to meet the
accuracy criterion. For instance, a RATA must always be performed
following an out-of-control period resulting from a failed RATA.
Whenever audit results show the Hg CEMS or sorbent trap monitoring
system to be out-of-control, the owner or operator must report both the
results of the failed test and the results of the retest following
corrective action showing the CEMS to be operating within
specifications.
5.3.1 Out-Of-Control Period Definition. The beginning of the out-of-
control period is the hour immediately following the completion of a
RATA, RAA, QGA or system integrity check that fails to meet the
applicable performance criteria in section 5.3.3, below. The end of the
out-of-control period is the time corresponding to the completion of a
subsequent successful test of the same type.
5.3.2 Monitoring Data Status During Out-Of-Control Period. During
the period the monitor is out-of-control, the monitoring data may not be
used to determine compliance with an applicable emission limit or to
meet a minimum data availability requirement in an applicable regulation
or permit.
5.3.3 Criteria for Excessive Audit Inaccuracy. Unless specified
otherwise in an applicable regulation or permit, the criteria for
excessive inaccuracy are:
(a) For the RATA, the allowable RA in the applicable PS in appendix
B (e.g., PS 12A or PS 12B).
(b) For the QGA, 15 percent of the average audit value or 0.5
g/m\3\, whichever is greater.
(c) For the RAA, 20 percent of the three run average or 10 percent
of the applicable standard, whichever is greater.
5.3.4 Criteria for Acceptable QC Procedures. Repeated excessive
inaccuracies (i.e., out-of-control conditions resulting from the
quarterly audits) indicates the QC procedures are inadequate or that the
CEMS or sorbent trap monitoring system is incapable of providing quality
data. Therefore, whenever excessive inaccuracies occur for two
consecutive quarters, the source owner or operator must revise the QC
procedures (see section 3) or modify, repair, or replace the CEMS or
sorbent trap monitoring system.

6.0 Reporting Requirements

6.1 Data Assessment Report. At the reporting interval specified in
the applicable regulation or permit, report for each Hg CEMS and/or
sorbent trap monitoring system the accuracy assessment results from
section 5, above. For Hg CEMS, also report the CD assessment results
from section 4, above. Report this information as a Data Assessment
Report (DAR), and include the appropriate DAR(s) with the emissions
report required under the applicable regulation or permit.
6.2 Contents of the DAR. At a minimum, the DAR must contain the
following information:
6.2.1 Facility name and address including identification of source
owner/operator.
6.2.2 Identification and location of each Hg CEMS and/or sorbent
trap monitoring system.
6.2.3 Manufacturer, model, and serial number of each Hg CEMS and/or
sorbent trap monitoring system.
6.2.4 CD Assessment for each Hg CEMS, including the identification
of out-of-control periods.
6.2.5 System integrity check data for each Hg CEMS.
6.2.6 Accuracy assessment for each Hg CEMS and/or sorbent trap
monitoring system, including the identification of out-of-control
periods. The results of all required RATAs, QGAs, RAAs, and audits of
auxiliary equipment must be reported. If an accuracy audit shows a CEMS
or sorbent trap monitoring system to be out-of-control, report both the
audit results that caused the out-of-control period and the results of
the retest following corrective action, showing the monitoring system to
be operating within specifications.
6.2.7 Summary of all corrective actions taken when the Hg CEMS and/
or sorbent trap monitoring system was determined to be out-of-control.

[[Page 811]]

6.3 Data Retention. As required in 40 CFR 60.7(d) and 63.10(b), all
measurements from CEMS and sorbent trap monitoring systems, including
the quality assurance data required by this procedure, must be retained
by the source owner for at least 5 years.

7.0 Bibliography

7.1 Calculation and Interpretation of Accuracy for Continuous
Emission Monitoring Systems (CEMS). section 3.0.7 of the Quality
Assurance Handbook for Air Pollution Measurement Systems, Volume III,
Stationary Source Specific Methods. EPA-600/4-77-027b. August 1977. U.S.
Environmental Protection Agency. Office of Research and Development
Publications, 26 West St. Clair Street, Cincinnati, OH 45268.

Procedure 6. Quality Assurance Requirements for Gaseous Hydrogen
Chloride (HCl) Continuous Emission Monitoring Systems Used for
Compliance Determination at Stationary Sources

1.0 Applicability and Principle

1.1 Applicability. Procedure 6 is used to evaluate the effectiveness
of quality control (QC) and quality assurance (QA) procedures and
evaluate the quality of data produced by any hydrogen chloride (HCl)
gas, CAS: 7647-01-0, continuous emission monitoring system (CEMS) that
is used for determining compliance with emission standards for HCl on a
continuous basis as specified in an applicable permit or regulation.
1.1.1 This procedure specifies the minimum QA requirements necessary
for the control and assessment of the quality of CEMS data submitted to
the Environmental Protection Agency (EPA) or a delegated authority. If
you are responsible for one or more CEMS used for HCl compliance
monitoring you must meet these minimum requirements and you are
encouraged to develop and implement a more extensive QA program or to
continue such programs where they already exist.
1.1.2 Data collected as a result of QA and QC measures required in
this procedure are to be submitted to the EPA or the delegated authority
in accordance with the applicable regulation or permit. These data are
to be used by both the delegated authority and you, as the CEMS
operator, in assessing the effectiveness of the CEMS QC and QA
procedures in the maintenance of acceptable CEMS operation and valid
emission data.

1.2 Principle

1.2.1 The QA procedures consist of two distinct and equally
important functions. One function is the assessment of the quality of
the CEMS data by estimating accuracy. The other function is the control
and improvement of the quality of the CEMS data by implementing QC
policies and corrective actions. These two functions form an iterative
control loop. When the assessment function indicates that the data
quality is inadequate, the control effort must be increased until the
data quality is acceptable. In order to provide uniformity in the
assessment and reporting of data quality, this procedure specifies the
assessment procedures to evaluate response drift and accuracy. The
procedures specified are based on Performance Specification 18 (PS-18)
in appendix B to this part.
(Note: Because the control and corrective action function
encompasses a variety of policies, specifications, standards and
corrective measures, this procedure treats QC requirements in general
terms to allow you, as source owner or operator to develop the most
effective and efficient QC system for your circumstances.)

2.0 Definitions

See PS-18 of this subpart for the primary definitions used in this
Procedure.

3.0 QC Requirements

3.1 You, as a source owner or operator, must develop and implement a
QC program. At a minimum, each QC program must include written
procedures and/or manufacturer's information which should describe in
detail, complete, step-by-step procedures and operations for each of the
following activities:
(a) Calibration Drift (CD) checks of CEMS;
(b) CD determination and adjustment of CEMS;
(c) Integrated Path (IP) CEMS temperature and pressure sensor
accuracy checks;
(d) IP CEMS beam intensity checks;
(e) Routine and preventative maintenance of CEMS (including spare
parts inventory);
(f) Data recording, calculations, and reporting;
(g) Accuracy audit procedures for CEMS including reference
method(s); and
(h) Program of corrective action for malfunctioning CEMS.
3.2 These written procedures must be kept on site and available for
inspection by the delegated authority. As described in section 5.4,
whenever excessive inaccuracies occur for two consecutive quarters, you
must revise the current written procedures, or modify or replace the
CEMS to correct the deficiency causing the excessive inaccuracies.

4.0 Daily Data Quality Requirements and Measurement Standardization
Procedures

4.1 CD Assessment. An upscale gas, used to meet a requirement in
this section must be either a NIST-traceable reference gas or a gas
certified by the gas vendor to 5.0 percent accuracy.

[[Page 812]]

4.1.1 CD Requirement. Consistent with 40 CFR 60.13(d) and 63.8(c),
you, as source owners or operators of CEMS must check, record, and
quantify the CD at two levels, using a zero gas and mid-level gas at
least once daily (approximately every 24 hours). Perform the CD check in
accordance with the procedure in applicable performance specification
(e.g., section 11.8 of PS-18 in appendix B of this part). The daily
zero- and mid-level CD must not exceed two times the drift limits
specified in the applicable performance specification (e.g., section
13.2 of PS-18 in appendix B to this part.)
4.1.2 Recording Requirement for CD Corrective action. Corrective
actions taken to bring a CEMS back in control after exceeding a CD limit
must be recorded and reported with the associated CEMS data. Reporting
corrective action must include the unadjusted concentration measured
prior to resetting the calibration and the adjusted value after
resetting the calibration to bring the CEMS back into control.
4.1.3 Dynamic Spiking Option for Mid-level CD. For extractive CEMS,
you have the option to conduct a daily dynamic spiking procedure found
in section 11.8.8 of PS-18 of appendix B of this part in lieu of the
daily mid-level CD check. If this option is selected, the daily zero CD
check is still required.
4.1.4 Out of Control Criteria for Excessive CD. As specified in
Sec. 63.8(c)(7)(i)(A), a CEMS is out of control if the zero or mid-
level CD exceeds two times the applicable CD specification in the
applicable PS or in the relevant standard. When a CEMS is out of
control, you as owner or operator of the affected source must take the
necessary corrective actions and repeat the tests that caused the system
to go out of control (in this case, the failed CD check) until the
applicable performance requirements are met.
4.1.5 Additional Quality Assurance for Data above Span. This
procedure must be used when required by an applicable regulation and may
be used when significant data above span is being collected.
4.1.5.1 Any time the average measured concentration of HCl exceeds
150 percent of the span value for greater than two hours, conduct the
following `above span' CEMS response check.
4.1.5.1.1 Within a period of 24 hours (before or after) of the
`above span' period, introduce a higher, `above span' HCl reference gas
standard to the CEMS. Use `above span' reference gas that meets the
requirements of section 7.0 of PS-18 and target a concentration level
between 75 and 125 percent of the highest hourly concentration measured
during the period of measurements above span.
4.1.5.1.2 Introduce the reference gas at the probe for extractive
CEMS or for IP-CEMS as an equivalent path length corrected concentration
in the instrument calibration cell.
4.1.5.1.3 At no time may the `above span' concentration exceed the
analyzer full-scale range.
4.1.5.2 Record and report the results of this procedure as you would
for a daily calibration. The `above span' response check is successful
if the value measured by the CEMS is within 20 percent of the certified
value of the reference gas.
4.1.5.3 If the `above span' response check is conducted during the
period when measured emissions are above span and there is a failure to
collect at least one data point in an hour due to the response check
duration, then determine the emissions average for that missed hour as
the average of hourly averages for the hour preceding the missed hour
and the hour following the missed hour.
4.1.5.4 In the event that the `above span' response check is not
successful (i.e., the CEMS measured value is not within 20 percent of
the certified value of the reference gas), then you must normalize the
one-hour average stack gas values measured above the span during the 24-
hour period preceding or following the `above span' response check for
reporting based on the CEMS response to the reference gas as shown in
Eq. 6-1:
[GRAPHIC] [TIFF OMITTED] TR07JY15.096

4.2 Beam Intensity Requirement for HCl IP-CEMS.

4.2.1 Beam Intensity Measurement. If you use a HCl IP-CEMS, you must
quantify and record the beam intensity of the IP-CEMS in appropriate
units at least once daily (approximately 24 hours apart) according to
manufacturer's specifications and procedures.
4.2.2 Out of Control Criteria for Excessive Beam Intensity Loss. If
the beam intensity falls below the level established for the operation
range determined following the procedures in section 11.2 of PS-18 of
this part,

[[Page 813]]

then your CEMS is out-of-control. This quality check is independent of
whether the CEMS daily CD is acceptable. If your CEMS is out-of-control,
take necessary corrective action. You have the option to repeat the beam
intensity test procedures in section 11.2 of PS-18 to expand the
acceptable range of acceptable beam intensity. Following corrective
action, repeat the beam intensity check.
4.3 Out Of Control Period Duration for Daily Assessments. The
beginning of the out-of-control period is the hour in which the owner or
operator conducts a daily performance check (e.g., calibration drift or
beam intensity check) that indicates an exceedance of the performance
requirements established under this procedure. The end of the out-of-
control period is the completion of daily assessment of the same type
following corrective actions, which shows that the applicable
performance requirements have been met.
4.4 CEMS Data Status During Out-of-Control Period. During the period
the CEMS is out-of-control, the CEMS data may not be used in calculating
compliance with an emissions limit nor be counted towards meeting
minimum data availability as required and described in the applicable
regulation or permit.

5.0 Data Accuracy Assessment

You must audit your CEMS for the accuracy of HCl measurement on a
regular basis at the frequency described in this section, unless
otherwise specified in an applicable regulation or permit. Quarterly
audits are performed at least once each calendar quarter. Successive
quarterly audits, to the extent practicable, shall occur no closer than
2 months apart. Annual audits are performed at least once every four
consecutive calendar quarters.

5.1 Temperature and Pressure Accuracy Assessment for IP CEMS.

5.1.1 Stack or source gas temperature measurement audits for HCl IP-
CEMS must be conducted and recorded at least annually in accordance with
the procedure described in section 11.3 of PS-18 in appendix B to this
part. As an alternative, temperature measurement devices may be replaced
with certified instruments on an annual basis. Units removed from
service may be bench tested against an NIST traceable sensor and reused
during subsequent years. Any measurement instrument or device that is
used to conduct ongoing verification of temperature measurement must
have an accuracy that is traceable to NIST.
5.1.2 Stack or source gas pressure measurement audits for HCl IP-
CEMS must be conducted and recorded at least annually in accordance with
the procedure described in section 11.4 of PS-18 in appendix B of this
part. As an alternative, pressure measurement devices may be replaced
with certified instruments on an annual basis. Units removed from
service may be bench tested against an NIST traceable sensor and reused
during subsequent years. Any measurement instrument or device that is
used to conduct ongoing verification of pressure measurement must have
an accuracy that is traceable to NIST.
5.1.3 Out of Control Criteria for Excessive Parameter Verification
Inaccuracy. If the temperature or pressure verification audit exceeds
the criteria in sections 5.3.4.5 and 5.3.4.6, respectively, the CEMS is
out-of-control. If the CEMS is out-of-control, take necessary corrective
action to eliminate the problem. Following corrective action, you must
repeat the failed verification audit until the temperature or pressure
measurement device is operating within the applicable specifications, at
which point the out-of-control period ends.
5.2 Concentration Accuracy Auditing Requirements. Unless otherwise
specified in an applicable rule or permit, you must audit the HCl
measurement accuracy of each CEMS at least once each calendar quarter,
except in the case where the affected facility is off-line (does not
operate). In that case, the audit must be performed as soon as is
practicable in the quarter in which the unit recommences operation.
Successive quarterly audits must, to the extent practicable, be
performed no less than 2 months apart. The accuracy audits shall be
conducted as follows:
5.2.1 Relative Accuracy Test Audit. A RATA must be conducted at
least once every four calendar quarters, except as otherwise noted in
sections 5.2.5 or 5.5 of this procedure. Perform the RATA as described
in section 11.9 of PS-18 in appendix B to this part. If the HCl
concentration measured by the RM during a RATA (in ppmv) is less than or
equal to 20 percent of the concentration equivalent to the applicable
emission standard, you must perform a Cylinder Gas Audit (CGA) or a
Dynamic Spike Audit (DSA) for at least one subsequent (one of the
following three) quarterly accuracy audits.
5.2.2 Quarterly Relative Accuracy Audit (RAA). A quarterly RAA may
be conducted as an option to conducting a RATA in three of four calendar
quarters, but in no more than three quarters in succession. To conduct
an RAA, follow the test procedures in section 11.9 of PS-18 in appendix
B to this part, except that only three test runs are required. The
difference between the mean of the RM values and the mean of the CEMS
responses relative to the mean of the RM values (or alternatively the
emission standard) is used to assess the accuracy of the CEMS. Calculate
the RAA results as described in section 6.2. As an alternative to an
RAA, a cylinder gas audit or a dynamic spiking audit may be conducted.

[[Page 814]]

5.2.3 Cylinder Gas Audit. A quarterly CGA may be conducted as an
option to conducting a RATA in three of four calendar quarters, but in
no more than three consecutive quarters. To perform a CGA, challenge the
CEMS with a zero-level and two upscale level audit gases of known
concentrations within the following ranges:

------------------------------------------------------------------------
Audit point Audit range
------------------------------------------------------------------------
1 (Mid-Level)......................... 50 to 60% of span value.
2 (High-Level)........................ 80 to 100% of span value.
------------------------------------------------------------------------

5.2.3.1 Inject each of the three audit gases (zero and two upscale)
three times each for a total of nine injections. Inject the gases in
such a manner that the entire CEMS is challenged. Do not inject the same
gas concentration twice in succession.
5.2.3.2 Use HCl audit gases that meet the requirements of section 7
of PS-18 in appendix B to this part.
5.2.3.3 Calculate results as described in section 6.3.
5.2.4 Dynamic Spiking Audit. For extractive CEMS, a quarterly DSA
may be conducted as an option to conducting a RATA in three of four
calendar quarters, but in no more than three quarters in succession.
5.2.4.1 To conduct a DSA, you must challenge the entire HCl CEMS
with a zero gas in accordance with the procedure in section 11.8 of PS-
18 in appendix B of this part. You must also conduct the DS procedure as
described in appendix A to PS-18 of appendix B to this part. You must
conduct three spike injections with each of two upscale level audit
gases. The upscale level gases must meet the requirements of section 7
of PS-18 in appendix B to this part and must be chosen to yield
concentrations at the analyzer of 50 to 60 percent of span and 80 to 100
percent of span. Do not inject the same gas concentration twice in
succession.
5.2.4.2 Calculate results as described in section 6.4. You must
calculate the dynamic spiking error (DSE) for each of the two upscale
audit gases using the combination of Equation A5 and A6 in appendix A to
PS-18 in appendix B to this part to determine CEMS accuracy.
5.2.5 Other Alternative Quarterly Audits. Other alternative audit
procedures, as approved by the Administrator, may be used for three of
four calendar quarters.
5.3 Out of Control Criteria for Excessive Audit Inaccuracy. If the
results of the RATA, RAA, CGA, or DSA do not meet the applicable
performance criteria in section 5.3.4, the CEMS is out-of-control. If
the CEMS is out-of-control, take necessary corrective action to
eliminate the problem. Following corrective action, the CEMS must pass a
test of the same type that resulted in the out-of-control period to
determine if the CEMS is operating within the specifications (e.g., a
RATA must always follow an out-of-control period resulting from a RATA).
5.3.1 If the audit results show the CEMS to be out-of-control, you
must report both the results of the audit showing the CEMS to be out-of-
control and the results of the audit following corrective action showing
the CEMS to be operating within specifications.
5.3.2 Out-Of-Control Period Duration for Excessive Audit Inaccuracy.
The beginning of the out-of-control period is the time corresponding to
the completion of the sampling for the failed RATA, RAA, CGA or DSA. The
end of the out-of-control period is the time corresponding to the
completion of the sampling of the subsequent successful audit.
5.3.3 CEMS Data Status During Out-Of-Control Period. During the
period the CEMS is out-of-control, the CEMS data may not be used in
calculating emission compliance nor be counted towards meeting minimum
data availability as required and described in the applicable regulation
or permit.
5.3.4 Criteria for Excessive Quarterly and Yearly Audit Inaccuracy.
Unless specified otherwise in the applicable regulation or permit, the
criteria for excessive inaccuracy are:
5.3.4.1 For the RATA, the CEMS must meet the RA specifications in
section 13.4 of PS-18 in appendix B to this part.
5.3.4.2 For the CGA, the accuracy must not exceed 5.0 percent of the
span value at the zero gas and the mid- and high-level reference gas
concentrations.
5.3.4.3 For the RAA, the RA must not exceed 20.0 percent of the
RMavg as calculated using Equation 6-2 in section 6.2 of this
procedure whether calculated in units of HCl concentration or in units
of the emission standard. In cases where the RA is calculated on a
concentration (ppmv) basis, if the average HCl concentration measured by
the RM during the test is less than 75 percent of the HCl concentration
equivalent to the applicable standard, you may substitute the equivalent
emission standard value (in ppmvw) in the denominator of Equation 6-2 in
the place of RMavg and the result of this alternative
calculation of RA must not exceed 15.0 percent.
5.3.4.4 For DSA, the accuracy must not exceed 5.0 percent of the
span value at the zero gas and the mid- and high-level reference gas
concentrations or 20.0 percent of the applicable emission standard,
whichever is greater.
5.3.4.5 For the gas temperature measurement audit, the CEMS must
satisfy the requirements in section 13.7 in PS-18 of appendix B to this
part.
5.3.4.6 For the gas pressure measurement audit, the CEMS must
satisfy the requirements in section 13.8 in PS-18 of appendix B to this
part.

[[Page 815]]

5.4 Criteria for Acceptable QC Procedures. Repeated excessive
inaccuracies (i.e., out-of-control conditions resulting from the
quarterly or yearly audits) indicate that the QC procedures are
inadequate or that the CEMS is incapable of providing quality data.
Therefore, whenever excessive inaccuracies occur for two consecutive
quarters, you must revise the QC procedures (see section 3.0) or modify
or replace the CEMS.
5.5 Criteria for Optional QA Test Frequency. If all the quality
criteria are met in sections 4 and 5 of this procedure, the CEMS is in-
control.
5.5.1 Unless otherwise specified in an applicable rule or permit, if
the CEMS is in-control and if your source emits 75 percent of
the HCl emission limit for each averaging period as specified in the
relevant standard for eight consecutive quarters that include a minimum
of two RATAs, you may revise your auditing procedures to use CGA, RAA or
DSA each quarter for seven subsequent quarters following a RATA.
5.5.2 You must perform at least one RATA that meets the acceptance
criteria every 2 years.
5.5.3 If you fail a RATA, RAA, CGA, or DSA, then the audit schedule
in section 5.2 must be followed until the audit results meet the
criteria in section 5.3.4 to start requalifying for the optional QA test
frequency in section 5.5.

6.0 Calculations for CEMS Data Accuracy

6.1 RATA RA Calculation. Follow Equations 9 through 14 in section 12
of PS-18 in appendix B to this part to calculate the RA for the RATA.
The RATA must be calculated either in units of the applicable emission
standard or in concentration units (ppmv).
6.2 RAA Accuracy Calculation. Use Equation 6-2 to calculate the
accuracy for the RAA. The RA may be calculated in concentration units
(ppmv) or in the units of the applicable emission standard.
[GRAPHIC] [TIFF OMITTED] TR07JY15.097

Where:

RA = Accuracy of the CEMS (percent)
MNavg = Average measured CEMS response during the audit in
units of applicable standard or appropriate concentration.
RMavg = Average reference method value in units of applicable
standard or appropriate concentration.
6.3 CGA Accuracy Calculation. For each gas concentration, determine
the average of the three CEMS responses and subtract the average
response from the audit gas value. For extractive CEMS, calculate the ME
at each gas level using Equation 3A in section 12.3 of PS-18 in appendix
B to this part. For IP-CEMS, calculate the ME at each gas level using
Equation 6A in section 12.4.3 of PS-18 in appendix B to this part.
6.4 DSA Accuracy Calculation. DSA accuracy is calculated as a
percent of span. To calculate the DSA accuracy for each upscale spike
concentration, first calculate the DSE using Equation A5 in appendix A
of PS-18 in appendix B to this part. Then use Equation 6-3 to calculate
the average DSA accuracy for each upscale spike concentration. To
calculate DSA accuracy at the zero level, use equation 3A in section
12.3 of PS-18 in appendix B to this part.
[GRAPHIC] [TIFF OMITTED] TR07JY15.098

7.0 Reporting Requirements

At the reporting interval specified in the applicable regulation or
permit, report for each CEMS the quarterly and annual accuracy audit
results from section 6 and the daily assessment results from section 4.
Unless otherwise specified in the applicable regulation or permit,
include all data sheets, calculations, CEMS data records (i.e., charts,
records of CEMS responses), reference gas certifications and reference
method results necessary to confirm that the performance of the CEMS met
the performance specifications.
7.1 Unless otherwise specified in the applicable regulations or
permit, report the daily assessments (CD and beam intensity) and
accuracy audit information at the interval for emissions reporting
required under the applicable regulations or permits.

[[Page 816]]

7.1.1 At a minimum, the daily assessments and accuracy audit
information reporting must contain the following information:
a. Company name and address.
b. Identification and location of monitors in the CEMS.
c. Manufacturer and model number of each monitor in the CEMS.
d. Assessment of CEMS data accuracy and date of assessment as
determined by a RATA, RAA, CGA or DSA described in section 5 including:
i. The RA for the RATA;
ii. The accuracy for the CGA, RAA, or DSA;
iiii. Temperature and pressure sensor audit results for IP-CEMS;
iv. The RM results, the reference gas certified values;
v. The CEMS responses;
vi. The calculation results as defined in section 6; and
vii. Results from the performance audit samples described in section
5 and the applicable RMs.
e. Summary of all out-of-control periods including corrective
actions taken when CEMS was determined out-of-control, as described in
sections 4 and 5.
7.1.2 If the accuracy audit results show the CEMS to be out-of-
control, you must report both the audit results showing the CEMS to be
out-of-control and the results of the audit following corrective action
showing the CEMS to be operating within specifications.

8.0 Bibliography

1. EPA Traceability Protocol for Assay and Certification of Gaseous
Calibration Standards, U.S. Environmental Protection Agency office of
Research and Development, EPA/600/R-12/531, May 2012.
2. Method 205, ``Verification of Gas Dilution Systems for Field
Instrument Calibrations,'' 40 CFR part 51, appendix M.

9.0 Tables, Diagrams, Flowcharts--[Reserved]

[52 FR 21008, June 4, 1987; 52 FR 27612, July 22, 1987, as amended at 56
FR 5527, Feb. 11, 1991; 69 FR 1816, Jan. 12, 2004; 72 FR 32768, June 13,
2007; 74 FR 12590, Mar. 25, 2009; 75 FR 55040, Sept. 9, 2010; 79 FR
11274, Feb. 27, 2014; 79 FR 28441, May 16, 2014; 80 FR 38649, July 7,
2015]

Effective Date Note: At 81 FR 31520, May 19, 2016, appendix F to
part 60 was amended by revising Sections 4.1.5, 4.1.5.1, 4.1.5.3, and
5.2.4.2 in Procedure 6, effective Aug. 17, 2016. For the convenience of
the user, the revised text is set forth as follows:

Sec. Appendix F to Part 60--Quality Assurance Procedures

* * * * *

Procedure 6. Quality Assurance Requirements for Gaseous Hydrogen
Chloride (HCl) Continuous Emission Monitoring Systems Used for
Compliance Determination at Stationary Sources

* * * * *

4.0 Daily Data Quality Requirements and Measurement Standardization
Procedures

* * * * *

4.1.5 Additional Quality Assurance for Data above Span. Unless
otherwise specified in an applicable rule or permit, this procedure must
be used to assure data quality and may be used when significant data
above span is being collected.
4.1.5.1 Any time the average measured concentration of HCl exceeds
150 percent of the span value for two consecutive 1-hour averages,
conduct the following `above span' CEMS response check.

* * * * *

4.1.5.3 Unless otherwise specified in an applicable rule or permit,
if the `above span' response check is conducted during the period when
measured emissions are above span and there is a failure to collect at
least one data point in an hour due to the response check duration, then
determine the emissions average for that missed hour as the average of
hourly averages for the hour preceding the missed hour and the hour
following the missed hour

* * * * *

5.0 Data Accuracy Assessment

* * * * *

5.2.4.2 Calculate results as described in section 6.4. To determine
CEMS accuracy you must calculate the dynamic spiking error (DSE) for
each of the two upscale audit gases using equation A5 in appendix A to
PS-18 and Equation 6-3 in section 6.4 of Procedure 6 in appendix B to
this part.

* * * * *

[[Page 817]]

Sec. Appendix G to Part 60--Provisions for an Alternative Method of
Demonstrating Compliance With 40 CFR 60.43 for the Newton Power Station
of Central Illinois Public Service Company

1. Designation of Affected Facilities
1.1 The affected facilities to which this alternative compliance
method applies are the Unit 1 and 2 coal-fired steam generating units
located at the Central Illinois Public Service Company's (CIPS) Newton
Power Station in Jasper County, Illinois. Each of these units is subject
to the Standards of Performance for Fossil-Fuel-Fired Steam Generators
for Which Construction Commenced After August 17, 1971 (subpart D).
2. Definitions
2.1 All definitions in subparts D and Da of part 60 apply to this
provision except that:
24-hour period means the period of time between 12:00 midnight and
the following midnight.
Boiler operating day means a 24-hour period during which any fossil
is combusted in either the Unit 1 or Unit 2 steam generating unit and
during which the provisions of Sec. 60.43(e) are applicable.
CEMs means continuous emission monitoring system.
Coal bunker means a single or group of coal trailers, hoppers, silos
or other containers that:
(1) are physically attached to the affected facility; and
(2) provide coal to the coal pulverizers.
DAFGDS means the dual alkali flue gas desulfurization system for the
Newton Unit 1 steam generating unit.
3. Compliance Provisions
3.1 If the owner or operator of the affected facility elects to
comply with the 470 ng/J (1.1 lbs/MMBTU) of combined heat input emission
limit under Sec. 60.43(e), he shall notify the Regional Administrator,
of the United States Environmental Protection Agency (USEPA), Region 5
and the Director, of the Illinois Environmental Protection Agency (IEPA)
at least 30 days in advance of the date such election is to take effect,
stating the date such operation is to commence. When the owner or
operator elects to comply with this limit after one or more periods of
reverting to the 520 ng/J heat input (1.2 lbs/MMBTU) limit of Sec.
60.43(a)(2), as provided under 3.4, he shall notify the Regional
Administrator of the USEPA, Region 5 and the Director of the (IEPA) in
writing at least ten (10) days in advance of the date such election is
to take effect.
3.2 Compliance with the sulfur dioxide emission limit under Sec.
60.43(e) is determined on a continuous basis by performance testing
using CEMs. Within 60 days after the initial operation of Units 1 and 2
subject to the combined emission limit in Sec. 60.43(e), the owner or
operator shall conduct an initial performance test, as required by Sec.
60.8, to determine compliance with the combined emission limit. This
initial performance test is to be scheduled so that the thirtieth boiler
operating day of the 30 successive boiler operating days is completed
within 60 days after initial operation subject to the 470 ng/J (1.1 lbs/
MMBTU) combined emission limit. Following the initial performance test,
a separate performance test is completed at the end of each boiler
operating day Unit 1 and Unit 2 are subject to Sec. 60.43(e), and a new
30 day average emission rate calculated.
3.2.1 Following the initial performance test, a new 30 day average
emission rate is calculated for each boiler operating day the affected
facility is subject to Sec. 60.43(e). If the owner or operator of the
affected facility elects to comply with Sec. 60.43(e) after one or more
periods of reverting to the 520 ng/J heat input (1.2 lbs/MMBTU) limit
under Sec. 60.43(a)(2), as provided under 3.4, the 30 day average
emission rate under Sec. 60.43(e) is calculated using emissions data of
the current boiler operating day and data for the previous 29 boiler
operating days when the affected facility was subject to Sec. 60.43(e).
Periods of operation of the affected facility under Sec. 60.43(a)(2)
are not considered boiler operating days. Emissions data collected
during operation under Sec. 60.43(a)(2) are not considered relative to
4.6 and emissions data are not included in calculations of emission
under Sec. 60.43(e).
3.2.2 When the affected facility is operated under the provisions of
Sec. 60.43(e), the Unit 1 DAFGDS bypass damper must be fully closed.
The DAFGDS bypass may be opened only during periods of DAFGDS startup,
shutdown, malfunction or testing as described under sections 3.5.1,
3.5.2, 3.5.3, 3.5.4, and 4.8.2.
3.3 Compliance with the sulfur dioxide emission limit set forth in
Sec. 60.43(e) is based on the average combined hourly emission rate
from Units 1 and 2 for 30 successive boiler operating days determined as
follows:
[GRAPHIC] [TIFF OMITTED] TC15NO91.206

where:

n = the number of available hourly combined emission rate values in the
30 successive boiler operating day period where Unit 1 and
Unit 2 are subject to Sec. 60.43(e).
E30 = average emission rate for 30 successive boiler operating days
where Unit 1 and Unit 2 are subject to Sec. 60.43(e).
EC = the hourly combined emission rate from Units 1 and 2, in ng/J or
lbs/MMBTU.

[[Page 818]]

3.3.1 The average hourly combined emission rate for Units 1 and 2for
each hour of operation of either Unit 1 or 2, or both, is determined as
follows:

EC=[(E1) + (E2)]/[H1 + H2]

where:

EC = the hourly combined SO2 emission rate, lbs/MMBTU, from
Units 1 and 2 when Units 1 and 2 are subject to Sec.
60.43(e).
E1 = the hourly SO2 mass emission, lb/hr, from Unit 1 as
determined from CEMs data using the calculation procedures in
section 4 of this appendix.
E2 = the hourly SO2 mass emission, lb/hr, from Unit 2 as
determined from CEMs data using the calculation procedures in
section 4 of this appendix.
H1 = the hourly heat input, MMBTU/HR to Unit 1 as determined in section
4 of this appendix.
H2 = the hourly heat input, MMBTU/HR, to Unit 2 as determined by section
4 of this appendix.

3.3.2 If data for any of the four hourly parameters (E1, E2, H1and
H2, under 3.3.1 are unavailable during an hourly period, the combined
emission rate (EC) is not calculated and the period is counted as
missing data under 4.6.1., except as provided under 3.5. and 4.4.2.
3.4 After the date of initial operation subject to the combined
emission limit, Units 1 and 2 shall remain subject to the combined
emission limit and the owner or operator shall remain subject to the
requirements of this Appendix until the initial performance test as
required by 3.2 is completed and the owner or operator of the affected
facility elects and provides notice to revert on a certain date to the
520 ng/J heat input (1.2 lbs/MMBTU) limit of Sec. 60.43(a)(2)
applicable separately at each unit. The Regional Administrator of the
USEPA, Region 5 and the Director, of the IEPA shall be given written
notification from CIPS as soon as possible of CIPs' decision to revert
to the 520 ng/J heat input (1.2 lbs/MMBTU) limit of Sec. 60.43(a)(2)
separately at each unit, but no later than 10 days in advance of the
date such election is to take effect.
3.5 Emission monitoring data for Unit 1 may be excluded from
calculations of the 30 day rolling average only during the following
times:
3.5.1 Periods of DAFGDS startup.
3.5.2 Periods of DAFGDS shutdown.
3.5.3 Periods of DAFGDS malfunction during system emergencies as
defined in Sec. 60.41a.
3.5.4 The first 250 hours per calendar year of DAFGDS malfunctions
of Unit 1 DAFGDS provided that efforts are made to minimize emissions
from Unit 1 in accordance with Sec. 60.11(d), and if, after 16 hours
but not more than 24 hours of DAFGDS malfunction, the owner or operator
of the affected facility begins (following the customary loading
procedures) loading into the Unit 1 coal bunker, coal with a potential
SO2 emission rate equal to or less than the emission rate of
Unit 2 recorded at the beginning of the DAFGDS malfunction. Malfunction
periods under 3.5.3 are not counted toward the 250 hour/yr limit under
this section.
3.5.4.1 The malfunction exemption in 3.5.4 is limited to the first
250 hours per calendar year of DAFGDS malfunction.
3.5.4.2 For malfunctions of the DAFGDS after the 250 hours per
calendar year limit (cumulative), other than those defined in 3.5.3, the
owner or operator of the affected facility shall combust lower sulfur
coal or use any other method to comply with the 470 ng/J (1.1 lbs/MMBTU)
combined emission limit.
3.5.4.3 During the first 250 hours of DAFGDS malfunction per year or
during periods of DAFGDS startup, or DAFGDS shutdown, CEMs emissions
data from Unit 2 shall continue to be included in the daily calculation
of the combined 30 day rolling average emission rate; that is, the load
on Unit 1 is assumed to be zero (H1 and E1 = O; EC = E2/H2).
3.5.5-3.5.7 [Reserved]
3.6 The provision for excluding CEMs data from Unit 1 during the
first 250 hours of DAFGDS malfunctions from combined hourly emissions
calculations supersedes the provisions of Sec. 60.11(d). However, the
general purpose contained in Sec. 60.11(d) (i.e., following good
control practices to minimize air pollution emission during
malfunctions) has not been superseded.

4. Continuous Emission Monitoring

4.1 The CEMs required under section 3.2 are operated and data are
recorded for all periods of operation of the affected facility including
periods of the DAFGDS startup, shutdown and malfunction except for CEMs
breakdowns, repairs, calibration checks, and zero and span adjustment.
All provisions of Sec. 60.45 apply except as follows:
4.2 The owner or operator shall install, calibrate, maintain, and
operate CEMs and monitoring devices for measuring the following:
4.2.1 For Unit 1:
4.2.1.1 Sulfur dioxide, oxygen or carbon dioxide, and volumetric
flow rate for the Unit 1 DAFGDS stack.
4.2.1.2 Sulfur dioxide, oxygen or carbon dioxide, and volumetric
flow rate for the Unit 1 DAFGDS bypass stack.
4.2.1.3 Moisture content of the flue gas must be determined
continuously for the Unit 1 DAFGDS stack and the Unit 1 DAFGDS bypass
stack, if the sulfur dioxide concentration in each stack is measured on
a dry basis.
4.2.2 For Unit 2, sulfur dioxide, oxygen or carbon dioxide, and
volumetric flow rate.

[[Page 819]]

4.2.2.1 Moisture content of the flue gas must be determined
continuously for the Unit 2 stack, if the sulfur dioxide concentration
in the stack is measured on a dry basis.
4.2.3 For Units 1 and 2, the hourly heat input, the hourly steam
production rate, or the hourly gross electrical power output from each
unit.
4.3 For the Unit 1 bypass stack and the Unit 2 stack, the span value
of the sulfur dioxide analyzer shall be equivalent to 200 percent of the
maximum estimated hourly potential sulfur dioxide emissions of the fuel
fired in parts per million sulfur dioxide. For the Unit 1 DAFGDS stack,
the span value of the sulfur dioxide analyzer shall be equivalent to 100
percent of the maximum estimated hourly potential emissions of the fuel
fired in parts per million sulfur dioxide. The span value for volumetric
flow monitors shall be equivalent to 125 percent of the maximum
estimated hourly flow in standard cubic meters/minute (standard cubic
feet per minute). The span value of the continuous moisture monitors, if
required by 4.2.1.3 and 4.2.2.1, shall be equivalent to 100 percent by
volume. The span value of the oxygen or carbon dioxide analyzers shall
be equivalent to 25 percent by volume.
4.3.1-4.3.2 [Reserved]
4.4 The monitoring devices required in 4.2 shall be installed,
calibrated, and maintained as follows:
4.4.1 Each volumetric flow rate monitoring device specified in 4.2
shall be installed at approximately the same location as the sulfur
dioxide emission monitoring sample location.
4.4.2 Hourly steam production rate and hourly electrical power
output monitoring devices for Unit 1 and Unit 2 shall be calibrated and
maintained according to manufacturer's specifications. The data from
either of these devices may be used in the calculation of the combined
emission rate in section 3.3.1, only when the hourly heat input for Unit
1 (H1) or the hourly heat input for Unit 2 (H2) cannot be determined
from CEM data, and the hourly heat input to steam production or hourly
heat input to electrical power output efficiency over a given segment of
each boiler or generator operating range, respectively, varies by less
than 5 percent within the specified operating range, or the efficiencies
of the boiler/generator units differ by less than 5 percent. The hourly
heat input for Unit 1 (H1) or the hourly heat input for Unit 2 (H2) in
section 3.3.1 may also be calculated based on the fuel firing rates and
fuel analysis.
4.4.3-4.4.5 [Reserved]
4.5 The hourly mass emissions from Unit 1 (E1) and Unit 2 (E2) and
the hourly heat inputs from Unit 1 (H1) and Unit 2 (H2) used to
determine the hourly combined emission rate for Units 1 and 2 (EC) in
section 3.3.1 are calculated using CEM data for each respective stack as
follows:
4.5.1 The hourly SO2 mass emission from each respective
stack is determined as follows:

E = (C) (F) (D) (K)

Where:

E = SO2 mass emission from the respective stack in lb per
hour
C = SO2 concentration from the respective stack ppm
F = flue gas flow rate from the respective stack in scfm
D = density of SO2 in lb per standard cubic feet
K = time conversion, 60 mins./hr

4.5.2 The hourly heat input from each respective stack is determined
as follows:

H=[(F) (C) (K)/(Fc)

where:

H = heat input from the respective stack in MMBTU per hour
C = CO2 or O2 concentration from the respective
stack as a decimal
F = flue gas flow rate from the respective stack in scfm
K = time conversion, 60 mins./hr
Fc = fuel constant for the appropriate diluent in scf/MMBTU
as per Sec. Sec. 60.45(f) (4) and (5)

4.5.3 The hourly SO2 mass emission for Unit 1 in pounds
per hour (E1) is calculated as follows, when leakage or diversion of any
DAFGDS inlet gas to the bypass stack occurs:

E1 = (EF) + (EB)

Where:

EF = Hourly SO2 mass emission measured in DAFGDS stack, lb/
hr, using the calculation in section 4.5.1.
EB = Hourly SO2 mass emission measured in bypass stack, lb/
hr, using the calculation in section 4.5.1.
Other than during conditions under 3.5.1, 3.5.2, 3.5.3, 3.5.4, or 4.8.2,
the DAFGDS bypass damper must be fully closed and any leakage
will be indicated by the bypass stack volumetric flow and
SO2 measurements, and when no leakage through the
bypass damper is indicated:

E1 = EF

4.5.4 The hourly heat input for Unit 1 in MMBTU per hour (H1) is
calculated as follows, when leakage or diversion of any DAFGDS inlet gas
to the bypass stack occurs:

H1 = (HF) + (HB)

where:

HF = Hourly heat input as determined from the DAFGDS stack CEMs, in
MMBTU per hour, using the calculation in section 4.5.2
HB = Hourly heat input as determined from the DAFGDS bypass stack CEMs,
in

[[Page 820]]

MMBTU per hour, using the calculation in section 4.5.2

4.6 For the CEMs required for Unit 1 and Unit 2, the owner or
operator of the affected facility shall maintain and operate the CEMs
and obtain combined emission data values (EC) for at least 75 percent of
the boiler operting hours per day for at least 26 out of each 30
successive boiler operating days.
4.6.1 When hourly SO2 emission data are not obtained by
the CEMs because of CEMs breakdowns, repairs, calibration checks and
zero and span adjustment, hourly emission data required by 4.6 are
obtained by using Methods 6 or 6C and 3 or 3A, 6A, or 8 and 3, or by
other alternative methods approved by the Regional Administrator of the
USEPA, Region 5 and the Director, of the IEPA. Failure to obtain the
minimum data requirements of 4.6 by CEMs, or by CEMs supplemented with
alternative methods of this section, is a violation of performance
testing requirements.
4.6.2 Independent of complying with the minimum data requirements of
4.6, all valid emissions data collected are used to calculate combined
hourly emission rates (EC) and 30-day rolling average emission rates
(E30) are calculated and used to judge compliance with 60.43(e).
4.7 For each continuous emission monitoring system, a quality
control plan shall be prepared by CIPS and submitted to the Regional
Administrator of the USEPA, Region 5 and the Director, of the IEPA. The
plan is to be submitted to the Regional Administrator of the USEPA,
Region 5 and the Director, of the IEPA 45 days before initiation of the
initial performance test. At a minimum, the plan shall contain the
following quality control elements:
4.7.1 Calibration of continuous emission monitoring systems (CEMs)
and volumetric flow measurement devices.
4.7.2 Calibration drift determination and adjustment of CEMs and
volumetric flow measurement devices.
4.7.3 Periodic CEMs, volumetric flow measurement devices and
relative accuracy determinations.
4.7.4 Preventive maintenance of CEMs and volumetric flow measurement
devices (including spare parts inventory).
4.7.5 Data recording and reporting.
4.7.6 Program of corrective action for malfunctioning CEMs and
volumetric flow measurement devices.
4.7.7 Criteria for determining when the CEMs and volumetric flow
measurement devices are not producing valid data.
4.7.8 Calibration and periodic checks of monitoring devices
identified in 4.4.2.
4.8 For the purpose of conducting the continuous emission monitoring
system performance specification tests as required by Sec. 60.13 and
appendix B, the following conditions apply:
4.8.1 The calibration drift specification of Performance
Specification 2, appendix B shall be determined separately for each of
the Unit 1 SO2 CEMs and the Unit 2 SO2 CEMs. The
calibration drift specification of Performance Specification 3, appendix
B shall be determined separately for each of the Unit 1 diluent CEMs and
Unit 2 diluent CEMs.
4.8.2 The relative accuracy of the combined SO2 emission
rate for Unit 1 and Unit 2, as calculated from CEMs and volumetric flow
data using the procedures in 3.3.1, 4.5.1, 4.5.2 and 4.5.3 shall be no
greater than 20 percent of the mean value of the combined emission rate,
as determined from testing conducted simultaneously on the DAFGDS stack,
the DAFGDS bypass stack and the Unit 2 stack using reference methods 2,
3, or 3A and 6 or 6C, or shall be no greater than 10 percent of the
emission limit in Sec. 60.43(e), whichever criteria is less stringent.
The relative accuracy shall be computed from at least nine comparisons
of the combined emission rate values using the procedures in section 7
and the equations in section 8, Performance Specification 2, appendix B.
Throughout, but only during, the relative accuracy test period the
DAFGDS bypass damper shall be partially opened such that there is a
detectable flow.
4.8.3-4.8.3.4 [Reserved]
4.9 The total monitoring system required by 4.2 shall be subject
only to an annual relative accuracy test audit (RATA) in accordance with
the quality assurance requirements of section 5.1.1 of 40 CFR part 60,
appendix F. Each SO2 and diluent CEMs shall be subject to
cylinder gas audits (OGA) in accordance with the quality assurance
requirements of section 5.1.2 of appendix F with the exception that any
SO2 or diluent CEMs without any type of probe or sample line
shall be exempt from the OGA requirements.

5. Recordkeeping Requirements

5.1 The plant owner or operator shall keep a record of each hourly
emission rate, each hourly SO2 CEMs value and hourly flow
rate value, and each hourly Btu heat input rate, hourly steam rate, or
hourly electrical power output, and a record of each hourly weighted
average emission rate. These records shall be kept for all periods of
operation of Unit 1 or 2 under provisions of Sec. 60.43(e), including
operations of Unit 1 (E1) during periods of DAFGDS startup, shutdown,
and malfunction when H1 and E1 are assumed to be zero (0) (see 4.5).
5.2 The plant owner or operator shall keep a record of each hourly
gas flow rate through the DAFGDS stack, each hourly stack gas flow rate
through the bypass stack during any periods that the DAFGDS bypass
damper is opened or flow is indicated, and reason for bypass operation.

[[Page 821]]

6. Reporting Requirements

6.1 The owner or operator of any affected facility shall submit the
written reports required under 6.2 of this section and subpart A to the
Regional Administrator of the USEPA, Region 5 and the Director, of the
IEPA for every calendar quarter. All quarterly reports shall be
submitted by the 30th day following the end of each calendar quarter.
6.2 For sulfur dioxide, the following data resubmitted to the
Regional Administrator of the USEPA, Region 5 and the Director, of the
IEPA for each 24-hour period:
6.2.1 Calendar date
6.2.2 The combined average sulfur dioxide emission rate (ng/J or lb/
million Btu) for the past 30 successive boiler operating days (ending
with the last 30-day period in the quarter); and, for any noncompliance
periods, reasons for noncompliance with the emission standards and
description of corrective action taken.
6.2.3 Identification of the boiler operating days for which valid
sulfur dioxide emissions data required by 4.6 have not been obtained for
75 percent of the boiler operating hours; reasons for not obtaining
sufficient data; and description of corrective actions taken to prevent
recurrence.
6.2.4 Identification of the time periods (hours) when Unit 1 or Unit
2 were operated but combined hourly emission rates (EC) were not
calculated because of the unavailability of parameters E1, E2, H1, or H2
as described in 3.2.
6.2.5 Identification of the time periods (hours) when Unit 1 and
Unit 2 were operated and where the combined hourly emission rate (EC)
equalled Unit 2 (E2/H2) emissions because of the Unit 1 malfunction
provisions under 3.5.3, and 3.5.4.
6.2.6 Identification of the time periods (hours) when emissions from
the Unit 1 DAFGDS have been excluded from the calculation of average
sulfur dioxide emission rates because of Unit 1 DAFGDS startup,
shutdown, malfunction, or other reasons; and justification for excluding
data for reasons other than startup or shutdown. Reporting of hourly
emission rate of Unit 1 (E1/H2) during each hour of the DAFGDS startup,
malfunction under 3.5.1, 3.5.2, 3.5.3, and 3.5.4 (see 4.5).
6.2.7 Identification of the number of days in the calendar quarter
that the affected facility was operated (any fuel fired).
6.2.8 Identify any periods where Unit 1 DAFGDS malfunctions occurred
and the cumulative hours of Unit 1 DAFGDS malfunction for the quarter.
6.2.9 Identify any periods of time that any exhaust gases were
discharged to the DAFGDS bypass stack and the hourly gas flow rate
through the DAFGDS stack and through the DAFGDS bypass stack during such
periods and reason for bypass operation.
6.2.10 [Reserved]

[52 FR 28955, Aug. 4, 1987, as amended at 58 FR 28785, May 17, 1993; 59
FR 8135, Feb. 18, 1994]

Sec. Appendix H to Part 60 [Reserved]

Sec. Appendix I to Part 60--Owner's Manuals and Temporary Labels for
Wood Heaters Subject to Subparts AAA and QQQQ of Part 60

1. Introduction

The purpose of this appendix is to provide specific instructions and
examples to manufacturers for compliance with the owner's manual
provisions of subparts AAA and QQQQ of this part.

2. Instructions for Preparation of Wood Heater Owner's Manuals

2.1 Introduction
Although the owner's manuals do not require premarket approval, EPA
will monitor the contents to ensure that sufficient information is
included to provide heater proper operation and maintenance information
affecting emissions to consumers. The manufacturer must make current and
historical owner's manuals available on the company Web site and upon
request to the EPA. The purpose of this section is to provide
instructions to manufacturers for compliance with the owner's manual
provisions of Sec. 60.536(g) of subpart AAA that applies to wood
heaters and Sec. 60.5478(f) of subpart QQQQ that applies to hydronic
heaters and forced-air furnaces. A checklist of topics and illustrative
language is provided as instructions. Owner's manuals should be tailored
to specific wood heater models, as appropriate.

2.2 Topics Required To Be Addressed in Owner's Manual

(a) Wood heater description and compliance status;
(b) Tamper warnings;
(c) Overall heater warranty information and catalyst information and
warranty (if catalyst-equipped);
(d) Fuel selection;
(e) Achieving and maintaining catalyst light-off (if catalyst-
equipped);
(f) Catalyst monitoring (if catalyst-equipped);
(g) Troubleshooting catalytic-equipped heaters (if catalyst-
equipped);
(h) Catalyst replacement (if catalyst-equipped);
(i) Wood heater proper operation and maintenance, including
minimizing visible emissions;

[[Page 822]]

(j) Wood heater proper installation, including location, stack
height and achieving proper draft;
(k) Use of smoke detectors and carbon monoxide monitors; and
(l) Efficiency.

2.3 Sample Text/Descriptions

(a) The following are example texts and/or further descriptions
illustrating the topics identified above. Although the regulation
requires manufacturers to address (where applicable) the 10 topics
identified above, the exact language is not specified. Manuals should be
written specific to the model and design of the wood heater. The
following instructions are composed of generic descriptions and texts.
(b) If manufacturers choose to use the language provided in the
example, the portion in italics should be revised as appropriate. Any
manufacturer electing to use the EPA example language will be considered
to be in compliance with owner's manual requirements provided that the
particular language is printed in full with only such changes as are
necessary to ensure accuracy.
Example language is not provided for certain topics, since these
areas are generally heater specific. For these topics, manufacturers
should develop text that is specific to the proper operation and
maintenance of their particular products.

2.3.1 Wood Heater Description and Compliance Status

Owner's manuals must include:
(a) Manufacturer and model;
(b) Compliance status (2015 standard, 2016 standard, 2017 standard,
2020 standard, crib wood standard or cord wood alternative standard,
last allowable sell date, etc.); and
(c) Heat output range.
Exhibit 1--Example Text covering 2.3.1(a), (b), and (c) of this
appendix:
``This manual describes the installation and operation of the Brand
X, Model 0 catalytic equipped wood heater. This heater meets the 2015
U.S. Environmental Protection Agency's crib wood emission limits for
wood heaters sold after May 15, 2015. Under specific test conditions
this heater has been shown to deliver heat at rates ranging from 8,000
to 35,000 Btu/hr.''

2.3.2 Tamper Warnings

(a) The following statement must be included in the owner's manual
for all units:
``This wood heater has a manufacturer-set minimum low burn rate that
must not be altered. It is against federal regulations to alter this
setting or otherwise operate this wood heater in a manner inconsistent
with operating instructions in this manual.''
(b) The following statement must be included in the owner's manual
for catalyst-equipped units:
``This wood heater contains a catalytic combustor, which needs
periodic inspection and replacement for proper operation. It is against
federal regulations to operate this wood heater in a manner inconsistent
with operating instructions in this manual, or if the catalytic element
is deactivated or removed.''

2.3.3 Overall Heater Warranty Information and Catalyst Information and
Warranty (if catalyst-equipped)

The following information must be included with or supplied in the
owner's and warranty manuals:
(a) Manufacturer and model, including catalyst if catalyst-equipped;
(b) Warranty details, including catalyst if catalyst-equipped; and
(c) Instructions for warranty claims.
Exhibit 2--Example Text covering 2.3.3(a), (b), and (c) of this
appendix for catalysts:
``The combustor supplied with this heater is a Brand Z, Long Life
Combustor. Consult the catalytic combustor warranty also supplied with
this wood heater. Warranty claims should be addressed to:

Stove or Catalyst Manufacturer__________________________________________

Address_________________________________________________________________
Phone #----------------------------''

2.3.3.1 This section should also provide clear instructions on how
to exercise the warranty (how to package parts for return shipment,
etc.).
2.3.4 Fuel Selection
Owner's manuals must include:
(a) Instructions on acceptable fuels;
(b) Warning against inappropriate fuels; and
(c) How to determine seasoned wood compared to unseasoned wood, how
to use moisture meters and other techniques and the importance of
seasoned wood.
Exhibit 3--Example Text covering 2.3.4(a) and (b) of this appendix:
``This heater is designed to burn natural wood only. Higher
efficiencies and lower emissions generally result when burning air dried
seasoned hardwoods, as compared to softwoods or to green or freshly cut
hardwoods. DO NOT BURN:
(1) Garbage;
(2) Lawn clippings or yard waste;
(3) Materials containing rubber, including tires;
(4) Materials containing plastic;
(5) Waste petroleum products, paints or paint thinners, or asphalt
products;
(6) Materials containing asbestos;
(7) Construction or demolition debris;
(8) Railroad ties or pressure-treated wood;

[[Page 823]]

(9) Manure or animal remains;
(10) Salt water driftwood or other previously salt water saturated
materials;
(11) Unseasoned wood; or
(12) Paper products, cardboard, plywood, or particleboard. The
prohibition against burning these materials does not prohibit the use of
fire starters made from paper, cardboard, saw dust, wax and similar
substances for the purpose of starting a fire in an affected wood
heater.
Burning these materials may result in release of toxic fumes or
render the heater ineffective and cause smoke.''

2.3.5 Achieving and Maintaining Catalyst Light-Off

Owner's manuals must describe in detail proper procedures for:
(a) Operation of catalyst bypass (stove specific);
(b) Achieving catalyst light-off from a cold start; and
(c) Achieving catalyst light-off when refueling.
2.3.5.1 No example text is supplied for describing operation of
catalyst bypass mechanisms (Item 2.3.5(a) of this appendix) since these
are typically stove-specific. Manufacturers must provide instructions
specific to their model describing:
(1) Bypass position during startup;
(2) Bypass position during normal operation; and
(3) Bypass position during reloading.
Exhibit 4--Example Text for Item 2.3.5(b) of this appendix:
``The temperature in the stove and the gases entering the combustor
must be raised to between 500[deg] to 700 [deg]F for catalytic activity
to be initiated. During the startup of a cold stove, a medium to high
firing rate must be maintained for about 20 minutes. This ensures that
the stove, catalyst, and fuel are all stabilized at proper operating
temperatures. Even though it is possible to have gas temperatures reach
600 [deg]F within 2 to 3 minutes after a fire is started, if the fire is
allowed to die down immediately, it may go out or the combustor may stop
working. Once the combustor starts working, heat generated in it by
burning the smoke will keep it working.''
Exhibit 5--Example Text for Item 2.3.5(c) of this appendix:
``REFUELING: During the refueling and rekindling of a cool fire, or
a fire that has burned down to the charcoal phase, operate the stove at
a medium to high firing rate for about 10 minutes to ensure that the
catalyst reaches approximately 600 [deg]F.''

2.3.6 Catalyst Monitoring

Owner's manuals must include:
(a) Recommendation to visually inspect combustor at least three
times during the heating season;
(b) Discussion on expected combustor temperatures for monitor-
equipped units; and
(c) Suggested monitoring and inspection techniques and importance of
ensuring catalyst is operating properly.
Exhibit 6--Example Text covering 2.3.6(a), (b) and (c) of this
appendix:
``It is important to periodically monitor the operation of the
catalytic combustor to ensure that it is functioning properly and to
determine when it needs to be replaced. A non-functioning combustor will
result in a loss of heating efficiency, and an increase in creosote and
emissions. Following is a list of items that should be checked on a
periodic basis:
Combustors should be visually inspected at least three
times during the heating season to determine if physical degradation has
occurred. Actual removal of the combustor is not recommended unless more
detailed inspection is warranted because of decreased performance. If
any of these conditions exists, refer to Catalyst Troubleshooting
section of this owner's manual.
This catalytic (or hybrid) heater is equipped with a
temperature probe to monitor catalyst operation. Properly functioning
combustors typically maintain temperatures in excess of 500 [deg]F, and
often reach temperatures in excess of 1,000 [deg]F. If catalyst
temperatures are not in excess of 500 [deg]F, refer to Catalyst
Troubleshooting section of this owner's manual.
You can get an indication of whether the catalyst is
working by comparing the amount of smoke leaving the chimney when the
smoke is going through the combustor and catalyst light-off has been
achieved, to the amount of smoke leaving the chimney when the smoke is
not routed through the combustor (bypass mode).
Step 1--Light stove in accordance with instructions in section
3.3.5.
Step 2--With smoke routed through the catalyst, go outside and
observe the emissions leaving the chimney.
Step 3--Engage the bypass mechanism and again observe the emissions
leaving the chimney.
Significantly more smoke will be seen when the exhaust is not routed
through the combustor (bypass mode).''

2.3.7 Catalyst Troubleshooting

The owner's manual must provide clear descriptions of symptoms and
remedies to common combustor problems and importance. It is recommended
that photographs of catalyst peeling, plugging, thermal cracking,
mechanical cracking, and masking be included in the manual to aid the
consumer in identifying problems and to provide direction for corrective
action.

[[Page 824]]

2.3.8 Catalyst Replacement

The owner's manual must provide clear step-by-step instructions on
how to remove and replace the catalytic combustor. The section should
include diagrams and/or photographs.

2.3.9 Wood Heater Proper Operation and Maintenance

The owner's manual must provide clear descriptions of symptoms and
remedies to common heater problems and importance. The owner's manual
information must be adequate to enable consumers to achieve optimal
emissions performance. Such information must be consistent with the
operating instructions provided by the manufacturer to the approved test
laboratory for operating the wood heater during certification testing,
except for details of the certification test that would not be relevant
to the user.
Owner's manual must include:
(a) Recommendations about building and maintaining a fire,
especially for cold starts and the effectiveness of the top-down
approach for starting fires;
(b) Instruction on proper use of air controls, including how to
establish good combustion and how to ensure good combustion at the
lowest burn rate for which the heater is warranted;
(c) Ash removal and disposal;
(d) Instruction replacement of gaskets, air tubes and other parts
that are critical to the emissions performance of the unit, and other
maintenance and repair instructions;
(e) Warning against overfiring; and
(f) Suggested monitoring and inspection techniques and importance of
ensuring heater is operating properly, including ensuring visible
emissions are minimized.
2.3.9.1 No example text is supplied for 2.3.9(a), (b), (d) and (f)
of this appendix since these items are model specific. Manufacturers
should provide detailed instructions on building and maintaining a fire
including selection of fuel pieces, fuel quantity and stacking
arrangement. Manufacturers should also provide instruction on proper air
settings (both primary and secondary) for attaining minimum and maximum
heat outputs and any special instructions for operating thermostatic
controls. Step-by-step instructions on inspection and replacement of
gaskets should also be included. Manufacturers should provide diagrams
and/or photographs to assist the consumer. Gasket type and size should
be specified.
Exhibit 7--Example Text for Item 2.3.9(c) of this appendix:
``Whenever ashes get 3 to 4 inches deep in your firebox or ash pan,
and when the fire has burned down and cooled, remove excess ashes. Leave
an ash bed approximately 1 inch deep on the firebox bottom to help
maintain a hot charcoal bed.''
``Ashes should be placed in a metal container with a tight-fitting
lid. The closed container of ashes should be placed on a noncombustible
floor or on the ground, away from all combustible materials, pending
final disposal. The ashes should be retained in the closed container
until all cinders have thoroughly cooled.''
Exhibit 8--Example Text covering Item 2.3.9(e) of this appendix:

``DO NOT OVERFIRE THIS HEATER''

``Attempts to achieve heat output rates that exceed heater design
specifications can result in permanent damage to the heater and to the
catalytic combustor if so equipped.''

2.3.10 Wood Heater Installation, Including Stack Height, Heater
Locations and Achieving Proper Draft

Owner's manual must include:
(a) Importance of proper draft;
(b) Conditions indicating inadequate draft;
(c) Conditions indicating excessive draft; and
(d) Guidance on proper stack height and proper heater locations,
i.e., not too close to neighbors or in valleys that would cause
unhealthy air quality or nuisance conditions.
2.3.10.1 No example text is supplied for (d) because state, local
and tribal requirements are model and location specific.
Exhibit 9--Example Text for Item (a):
``Draft is the force which moves air from the appliance up through
the chimney. The amount of draft in your chimney depends on the length
of the chimney, local geography, nearby obstructions and other factors.
Too much draft may cause excessive temperatures in the appliance and may
damage the catalytic combustor. Inadequate draft may cause backpuffing
into the room and `plugging' of the chimney or the catalyst.''
Exhibit 10--Example Text for Item (b):
``Inadequate draft will cause the appliance to leak smoke into the
room through appliance and chimney connector joints.''
Exhibit 11--Example Text for Item (c):
``An uncontrollable burn or excessive temperature indicates
excessive draft.''

2.3.11 Efficiency

Owner's manual must include:
(a) Description of how the efficiency was determined, e.g., use
higher heating value of the fuel instead of lower heating value of the
fuel, discuss sweet spot versus annual average versus annual fuel usage
efficiency (AFUE);
(b) How operation and fuels affect efficiency, e.g., seasoned wood
versus high moisture fuel; operation at sweet spot versus low-burn
rates; and

[[Page 825]]

(c) How location affects the efficiency, e.g., in main living area
versus basement versus outdoors in sub-freezing temperatures.

2.3.12 Smoke and Carbon Monoxide Emissions and Monitors

Owner's manual must include:
(a) Discussion of smoke and carbon monoxide (CO) emissions,
including the CO data submitted in the certification application and
expected variations for different operating conditions;
(b) Recommendation to have smoke monitors; and
(c) Recommendation to have monitors for areas that are expected to
generate CO, e.g., heater fueling areas, pellet fuel bulk storage areas,
sheds containing hydronic heaters.

3. Instructions for Preparation of Wood Heater Temporary Labels

3.1 Temporary labels that show the values for emissions, efficiency,
recommended heating area and the compliance status may (voluntarily) be
affixed by the manufacturer to wood heaters that meet the 2020
particulate matter emission standards early or that meet the cord wood
alternative compliance options in subparts AAA and QQQQ of this part.
3.2 The seller of each heater covered by section 3.1 may ensure that
the temporary label remains affixed until each heater is purchased by
the end user.
3.3 The temporary label option for the 2020 particulate matter
emission standards end as of May 15, 2020.
3.4 The template for the temporary labels will be supplied by the
Administrator upon request.

[80 FR 13751, Mar. 16, 2015]

[[Page 827]]

FINDING AIDS

--------------------------------------------------------------------

A list of CFR titles, subtitles, chapters, subchapters and parts and
an alphabetical list of agencies publishing in the CFR are included in
the CFR Index and Finding Aids volume to the Code of Federal Regulations
which is published separately and revised annually.

Table of CFR Titles and Chapters
Alphabetical List of Agencies Appearing in the CFR
List of CFR sections Affected

[[Page 829]]

Table of CFR Titles and Chapters

(Revised as of July 1, 2016)

Title 1--General Provisions

I Administrative Committee of the Federal Register
(Parts 1--49)
II Office of the Federal Register (Parts 50--299)
III Administrative Conference of the United States (Parts
300--399)
IV Miscellaneous Agencies (Parts 400--500)

Title 2--Grants and Agreements

Subtitle A--Office of Management and Budget Guidance
for Grants and Agreements
I Office of Management and Budget Governmentwide
Guidance for Grants and Agreements (Parts 2--199)
II Office of Management and Budget Guidance (Parts 200--
299)
Subtitle B--Federal Agency Regulations for Grants and
Agreements
III Department of Health and Human Services (Parts 300--
399)
IV Department of Agriculture (Parts 400--499)
VI Department of State (Parts 600--699)
VII Agency for International Development (Parts 700--799)
VIII Department of Veterans Affairs (Parts 800--899)
IX Department of Energy (Parts 900--999)
X Department of the Treasury (Parts 1000--1099)
XI Department of Defense (Parts 1100--1199)
XII Department of Transportation (Parts 1200--1299)
XIII Department of Commerce (Parts 1300--1399)
XIV Department of the Interior (Parts 1400--1499)
XV Environmental Protection Agency (Parts 1500--1599)
XVIII National Aeronautics and Space Administration (Parts
1800--1899)
XX United States Nuclear Regulatory Commission (Parts
2000--2099)
XXII Corporation for National and Community Service (Parts
2200--2299)
XXIII Social Security Administration (Parts 2300--2399)
XXIV Housing and Urban Development (Parts 2400--2499)
XXV National Science Foundation (Parts 2500--2599)
XXVI National Archives and Records Administration (Parts
2600--2699)
XXVII Small Business Administration (Parts 2700--2799)

[[Page 830]]

XXVIII Department of Justice (Parts 2800--2899)
XXIX Department of Labor (Parts 2900--2999)
XXX Department of Homeland Security (Parts 3000--3099)
XXXI Institute of Museum and Library Services (Parts 3100--
3199)
XXXII National Endowment for the Arts (Parts 3200--3299)
XXXIII National Endowment for the Humanities (Parts 3300--
3399)
XXXIV Department of Education (Parts 3400--3499)
XXXV Export-Import Bank of the United States (Parts 3500--
3599)
XXXVI Office of National Drug Control Policy, Executive
Office of the President (Parts 3600--3699)
XXXVII Peace Corps (Parts 3700--3799)
LVIII Election Assistance Commission (Parts 5800--5899)
LIX Gulf Coast Ecosystem Restoration Council (Parts 5900--
5999)

Title 3--The President

I Executive Office of the President (Parts 100--199)

Title 4--Accounts

I Government Accountability Office (Parts 1--199)

Title 5--Administrative Personnel

I Office of Personnel Management (Parts 1--1199)
II Merit Systems Protection Board (Parts 1200--1299)
III Office of Management and Budget (Parts 1300--1399)
IV Office of Personnel Management and Office of the
Director of National Intelligence (Parts 1400--
1499)
V The International Organizations Employees Loyalty
Board (Parts 1500--1599)
VI Federal Retirement Thrift Investment Board (Parts
1600--1699)
VIII Office of Special Counsel (Parts 1800--1899)
IX Appalachian Regional Commission (Parts 1900--1999)
XI Armed Forces Retirement Home (Parts 2100--2199)
XIV Federal Labor Relations Authority, General Counsel of
the Federal Labor Relations Authority and Federal
Service Impasses Panel (Parts 2400--2499)
XVI Office of Government Ethics (Parts 2600--2699)
XXI Department of the Treasury (Parts 3100--3199)
XXII Federal Deposit Insurance Corporation (Parts 3200--
3299)
XXIII Department of Energy (Parts 3300--3399)
XXIV Federal Energy Regulatory Commission (Parts 3400--
3499)
XXV Department of the Interior (Parts 3500--3599)
XXVI Department of Defense (Parts 3600--3699)
XXVIII Department of Justice (Parts 3800--3899)

[[Page 831]]

XXIX Federal Communications Commission (Parts 3900--3999)
XXX Farm Credit System Insurance Corporation (Parts 4000--
4099)
XXXI Farm Credit Administration (Parts 4100--4199)
XXXIII Overseas Private Investment Corporation (Parts 4300--
4399)
XXXIV Securities and Exchange Commission (Parts 4400--4499)
XXXV Office of Personnel Management (Parts 4500--4599)
XXXVI Department of Homeland Security (Parts 4600--4699)
XXXVII Federal Election Commission (Parts 4700--4799)
XL Interstate Commerce Commission (Parts 5000--5099)
XLI Commodity Futures Trading Commission (Parts 5100--
5199)
XLII Department of Labor (Parts 5200--5299)
XLIII National Science Foundation (Parts 5300--5399)
XLV Department of Health and Human Services (Parts 5500--
5599)
XLVI Postal Rate Commission (Parts 5600--5699)
XLVII Federal Trade Commission (Parts 5700--5799)
XLVIII Nuclear Regulatory Commission (Parts 5800--5899)
XLIX Federal Labor Relations Authority (Parts 5900--5999)
L Department of Transportation (Parts 6000--6099)
LII Export-Import Bank of the United States (Parts 6200--
6299)
LIII Department of Education (Parts 6300--6399)
LIV Environmental Protection Agency (Parts 6400--6499)
LV National Endowment for the Arts (Parts 6500--6599)
LVI National Endowment for the Humanities (Parts 6600--
6699)
LVII General Services Administration (Parts 6700--6799)
LVIII Board of Governors of the Federal Reserve System
(Parts 6800--6899)
LIX National Aeronautics and Space Administration (Parts
6900--6999)
LX United States Postal Service (Parts 7000--7099)
LXI National Labor Relations Board (Parts 7100--7199)
LXII Equal Employment Opportunity Commission (Parts 7200--
7299)
LXIII Inter-American Foundation (Parts 7300--7399)
LXIV Merit Systems Protection Board (Parts 7400--7499)
LXV Department of Housing and Urban Development (Parts
7500--7599)
LXVI National Archives and Records Administration (Parts
7600--7699)
LXVII Institute of Museum and Library Services (Parts 7700--
7799)
LXVIII Commission on Civil Rights (Parts 7800--7899)
LXIX Tennessee Valley Authority (Parts 7900--7999)
LXX Court Services and Offender Supervision Agency for the
District of Columbia (Parts 8000--8099)
LXXI Consumer Product Safety Commission (Parts 8100--8199)
LXXIII Department of Agriculture (Parts 8300--8399)
LXXIV Federal Mine Safety and Health Review Commission
(Parts 8400--8499)

[[Page 832]]

LXXVI Federal Retirement Thrift Investment Board (Parts
8600--8699)
LXXVII Office of Management and Budget (Parts 8700--8799)
LXXX Federal Housing Finance Agency (Parts 9000--9099)
LXXXIII Special Inspector General for Afghanistan
Reconstruction (Parts 9300--9399)
LXXXIV Bureau of Consumer Financial Protection (Parts 9400--
9499)
LXXXVI National Credit Union Administration (Parts 9600--
9699)
XCVII Department of Homeland Security Human Resources
Management System (Department of Homeland
Security--Office of Personnel Management) (Parts
9700--9799)
XCVII Council of the Inspectors General on Integrity and
Efficiency (Parts 9800--9899)
XCIX Military Compensation and Retirement Modernization
Commission (Parts 9900--9999)
C National Council on Disability (Partys 10000--10049)

Title 6--Domestic Security

I Department of Homeland Security, Office of the
Secretary (Parts 1--199)
X Privacy and Civil Liberties Oversight Board (Parts
1000--1099)

Title 7--Agriculture

Subtitle A--Office of the Secretary of Agriculture
(Parts 0--26)
Subtitle B--Regulations of the Department of
Agriculture
I Agricultural Marketing Service (Standards,
Inspections, Marketing Practices), Department of
Agriculture (Parts 27--209)
II Food and Nutrition Service, Department of Agriculture
(Parts 210--299)
III Animal and Plant Health Inspection Service, Department
of Agriculture (Parts 300--399)
IV Federal Crop Insurance Corporation, Department of
Agriculture (Parts 400--499)
V Agricultural Research Service, Department of
Agriculture (Parts 500--599)
VI Natural Resources Conservation Service, Department of
Agriculture (Parts 600--699)
VII Farm Service Agency, Department of Agriculture (Parts
700--799)
VIII Grain Inspection, Packers and Stockyards
Administration (Federal Grain Inspection Service),
Department of Agriculture (Parts 800--899)
IX Agricultural Marketing Service (Marketing Agreements
and Orders; Fruits, Vegetables, Nuts), Department
of Agriculture (Parts 900--999)
X Agricultural Marketing Service (Marketing Agreements
and Orders; Milk), Department of Agriculture
(Parts 1000--1199)

[[Page 833]]

XI Agricultural Marketing Service (Marketing Agreements
and Orders; Miscellaneous Commodities), Department
of Agriculture (Parts 1200--1299)
XIV Commodity Credit Corporation, Department of
Agriculture (Parts 1400--1499)
XV Foreign Agricultural Service, Department of
Agriculture (Parts 1500--1599)
XVI Rural Telephone Bank, Department of Agriculture (Parts
1600--1699)
XVII Rural Utilities Service, Department of Agriculture
(Parts 1700--1799)
XVIII Rural Housing Service, Rural Business-Cooperative
Service, Rural Utilities Service, and Farm Service
Agency, Department of Agriculture (Parts 1800--
2099)
XX Local Television Loan Guarantee Board (Parts 2200--
2299)
XXV Office of Advocacy and Outreach, Department of
Agriculture (Parts 2500--2599)
XXVI Office of Inspector General, Department of Agriculture
(Parts 2600--2699)
XXVII Office of Information Resources Management, Department
of Agriculture (Parts 2700--2799)
XXVIII Office of Operations, Department of Agriculture (Parts
2800--2899)
XXIX Office of Energy Policy and New Uses, Department of
Agriculture (Parts 2900--2999)
XXX Office of the Chief Financial Officer, Department of
Agriculture (Parts 3000--3099)
XXXI Office of Environmental Quality, Department of
Agriculture (Parts 3100--3199)
XXXII Office of Procurement and Property Management,
Department of Agriculture (Parts 3200--3299)
XXXIII Office of Transportation, Department of Agriculture
(Parts 3300--3399)
XXXIV National Institute of Food and Agriculture (Parts
3400--3499)
XXXV Rural Housing Service, Department of Agriculture
(Parts 3500--3599)
XXXVI National Agricultural Statistics Service, Department
of Agriculture (Parts 3600--3699)
XXXVII Economic Research Service, Department of Agriculture
(Parts 3700--3799)
XXXVIII World Agricultural Outlook Board, Department of
Agriculture (Parts 3800--3899)
XLI [Reserved]
XLII Rural Business-Cooperative Service and Rural Utilities
Service, Department of Agriculture (Parts 4200--
4299)

Title 8--Aliens and Nationality

I Department of Homeland Security (Immigration and
Naturalization) (Parts 1--499)

[[Page 834]]

V Executive Office for Immigration Review, Department of
Justice (Parts 1000--1399)

Title 9--Animals and Animal Products

I Animal and Plant Health Inspection Service, Department
of Agriculture (Parts 1--199)
II Grain Inspection, Packers and Stockyards
Administration (Packers and Stockyards Programs),
Department of Agriculture (Parts 200--299)
III Food Safety and Inspection Service, Department of
Agriculture (Parts 300--599)

Title 10--Energy

I Nuclear Regulatory Commission (Parts 0--199)
II Department of Energy (Parts 200--699)
III Department of Energy (Parts 700--999)
X Department of Energy (General Provisions) (Parts
1000--1099)
XIII Nuclear Waste Technical Review Board (Parts 1300--
1399)
XVII Defense Nuclear Facilities Safety Board (Parts 1700--
1799)
XVIII Northeast Interstate Low-Level Radioactive Waste
Commission (Parts 1800--1899)

Title 11--Federal Elections

I Federal Election Commission (Parts 1--9099)
II Election Assistance Commission (Parts 9400--9499)

Title 12--Banks and Banking

I Comptroller of the Currency, Department of the
Treasury (Parts 1--199)
II Federal Reserve System (Parts 200--299)
III Federal Deposit Insurance Corporation (Parts 300--399)
IV Export-Import Bank of the United States (Parts 400--
499)
V Office of Thrift Supervision, Department of the
Treasury (Parts 500--599)
VI Farm Credit Administration (Parts 600--699)
VII National Credit Union Administration (Parts 700--799)
VIII Federal Financing Bank (Parts 800--899)
IX Federal Housing Finance Board (Parts 900--999)
X Bureau of Consumer Financial Protection (Parts 1000--
1099)
XI Federal Financial Institutions Examination Council
(Parts 1100--1199)
XII Federal Housing Finance Agency (Parts 1200--1299)
XIII Financial Stability Oversight Council (Parts 1300--
1399)
XIV Farm Credit System Insurance Corporation (Parts 1400--
1499)

[[Page 835]]

XV Department of the Treasury (Parts 1500--1599)
XVI Office of Financial Research (Parts 1600--1699)
XVII Office of Federal Housing Enterprise Oversight,
Department of Housing and Urban Development (Parts
1700--1799)
XVIII Community Development Financial Institutions Fund,
Department of the Treasury (Parts 1800--1899)

Title 13--Business Credit and Assistance

I Small Business Administration (Parts 1--199)
III Economic Development Administration, Department of
Commerce (Parts 300--399)
IV Emergency Steel Guarantee Loan Board (Parts 400--499)
V Emergency Oil and Gas Guaranteed Loan Board (Parts
500--599)

Title 14--Aeronautics and Space

I Federal Aviation Administration, Department of
Transportation (Parts 1--199)
II Office of the Secretary, Department of Transportation
(Aviation Proceedings) (Parts 200--399)
III Commercial Space Transportation, Federal Aviation
Administration, Department of Transportation
(Parts 400--1199)
V National Aeronautics and Space Administration (Parts
1200--1299)
VI Air Transportation System Stabilization (Parts 1300--
1399)

Title 15--Commerce and Foreign Trade

Subtitle A--Office of the Secretary of Commerce (Parts
0--29)
Subtitle B--Regulations Relating to Commerce and
Foreign Trade
I Bureau of the Census, Department of Commerce (Parts
30--199)
II National Institute of Standards and Technology,
Department of Commerce (Parts 200--299)
III International Trade Administration, Department of
Commerce (Parts 300--399)
IV Foreign-Trade Zones Board, Department of Commerce
(Parts 400--499)
VII Bureau of Industry and Security, Department of
Commerce (Parts 700--799)
VIII Bureau of Economic Analysis, Department of Commerce
(Parts 800--899)
IX National Oceanic and Atmospheric Administration,
Department of Commerce (Parts 900--999)
XI Technology Administration, Department of Commerce
(Parts 1100--1199)
XIII East-West Foreign Trade Board (Parts 1300--1399)

[[Page 836]]

XIV Minority Business Development Agency (Parts 1400--
1499)
Subtitle C--Regulations Relating to Foreign Trade
Agreements
XX Office of the United States Trade Representative
(Parts 2000--2099)
Subtitle D--Regulations Relating to Telecommunications
and Information
XXIII National Telecommunications and Information
Administration, Department of Commerce (Parts
2300--2399)

Title 16--Commercial Practices

I Federal Trade Commission (Parts 0--999)
II Consumer Product Safety Commission (Parts 1000--1799)

Title 17--Commodity and Securities Exchanges

I Commodity Futures Trading Commission (Parts 1--199)
II Securities and Exchange Commission (Parts 200--399)
IV Department of the Treasury (Parts 400--499)

Title 18--Conservation of Power and Water Resources

I Federal Energy Regulatory Commission, Department of
Energy (Parts 1--399)
III Delaware River Basin Commission (Parts 400--499)
VI Water Resources Council (Parts 700--799)
VIII Susquehanna River Basin Commission (Parts 800--899)
XIII Tennessee Valley Authority (Parts 1300--1399)

Title 19--Customs Duties

I U.S. Customs and Border Protection, Department of
Homeland Security; Department of the Treasury
(Parts 0--199)
II United States International Trade Commission (Parts
200--299)
III International Trade Administration, Department of
Commerce (Parts 300--399)
IV U.S. Immigration and Customs Enforcement, Department
of Homeland Security (Parts 400--599)

Title 20--Employees' Benefits

I Office of Workers' Compensation Programs, Department
of Labor (Parts 1--199)
II Railroad Retirement Board (Parts 200--399)
III Social Security Administration (Parts 400--499)
IV Employees' Compensation Appeals Board, Department of
Labor (Parts 500--599)

[[Page 837]]

V Employment and Training Administration, Department of
Labor (Parts 600--699)
VI Office of Workers' Compensation Programs, Department
of Labor (Parts 700--799)
VII Benefits Review Board, Department of Labor (Parts
800--899)
VIII Joint Board for the Enrollment of Actuaries (Parts
900--999)
IX Office of the Assistant Secretary for Veterans'
Employment and Training Service, Department of
Labor (Parts 1000--1099)

Title 21--Food and Drugs

I Food and Drug Administration, Department of Health and
Human Services (Parts 1--1299)
II Drug Enforcement Administration, Department of Justice
(Parts 1300--1399)
III Office of National Drug Control Policy (Parts 1400--
1499)

Title 22--Foreign Relations

I Department of State (Parts 1--199)
II Agency for International Development (Parts 200--299)
III Peace Corps (Parts 300--399)
IV International Joint Commission, United States and
Canada (Parts 400--499)
V Broadcasting Board of Governors (Parts 500--599)
VII Overseas Private Investment Corporation (Parts 700--
799)
IX Foreign Service Grievance Board (Parts 900--999)
X Inter-American Foundation (Parts 1000--1099)
XI International Boundary and Water Commission, United
States and Mexico, United States Section (Parts
1100--1199)
XII United States International Development Cooperation
Agency (Parts 1200--1299)
XIII Millennium Challenge Corporation (Parts 1300--1399)
XIV Foreign Service Labor Relations Board; Federal Labor
Relations Authority; General Counsel of the
Federal Labor Relations Authority; and the Foreign
Service Impasse Disputes Panel (Parts 1400--1499)
XV African Development Foundation (Parts 1500--1599)
XVI Japan-United States Friendship Commission (Parts
1600--1699)
XVII United States Institute of Peace (Parts 1700--1799)

Title 23--Highways

I Federal Highway Administration, Department of
Transportation (Parts 1--999)
II National Highway Traffic Safety Administration and
Federal Highway Administration, Department of
Transportation (Parts 1200--1299)

[[Page 838]]

III National Highway Traffic Safety Administration,
Department of Transportation (Parts 1300--1399)

Title 24--Housing and Urban Development

Subtitle A--Office of the Secretary, Department of
Housing and Urban Development (Parts 0--99)
Subtitle B--Regulations Relating to Housing and Urban
Development
I Office of Assistant Secretary for Equal Opportunity,
Department of Housing and Urban Development (Parts
100--199)
II Office of Assistant Secretary for Housing-Federal
Housing Commissioner, Department of Housing and
Urban Development (Parts 200--299)
III Government National Mortgage Association, Department
of Housing and Urban Development (Parts 300--399)
IV Office of Housing and Office of Multifamily Housing
Assistance Restructuring, Department of Housing
and Urban Development (Parts 400--499)
V Office of Assistant Secretary for Community Planning
and Development, Department of Housing and Urban
Development (Parts 500--599)
VI Office of Assistant Secretary for Community Planning
and Development, Department of Housing and Urban
Development (Parts 600--699) [Reserved]
VII Office of the Secretary, Department of Housing and
Urban Development (Housing Assistance Programs and
Public and Indian Housing Programs) (Parts 700--
799)
VIII Office of the Assistant Secretary for Housing--Federal
Housing Commissioner, Department of Housing and
Urban Development (Section 8 Housing Assistance
Programs, Section 202 Direct Loan Program, Section
202 Supportive Housing for the Elderly Program and
Section 811 Supportive Housing for Persons With
Disabilities Program) (Parts 800--899)
IX Office of Assistant Secretary for Public and Indian
Housing, Department of Housing and Urban
Development (Parts 900--1699)
X Office of Assistant Secretary for Housing--Federal
Housing Commissioner, Department of Housing and
Urban Development (Interstate Land Sales
Registration Program) (Parts 1700--1799)
XII Office of Inspector General, Department of Housing and
Urban Development (Parts 2000--2099)
XV Emergency Mortgage Insurance and Loan Programs,
Department of Housing and Urban Development (Parts
2700--2799) [Reserved]
XX Office of Assistant Secretary for Housing--Federal
Housing Commissioner, Department of Housing and
Urban Development (Parts 3200--3899)
XXIV Board of Directors of the HOPE for Homeowners Program
(Parts 4000--4099) [Reserved]
XXV Neighborhood Reinvestment Corporation (Parts 4100--
4199)

[[Page 839]]

Title 25--Indians

I Bureau of Indian Affairs, Department of the Interior
(Parts 1--299)
II Indian Arts and Crafts Board, Department of the
Interior (Parts 300--399)
III National Indian Gaming Commission, Department of the
Interior (Parts 500--599)
IV Office of Navajo and Hopi Indian Relocation (Parts
700--799)
V Bureau of Indian Affairs, Department of the Interior,
and Indian Health Service, Department of Health
and Human Services (Part 900)
VI Office of the Assistant Secretary-Indian Affairs,
Department of the Interior (Parts 1000--1199)
VII Office of the Special Trustee for American Indians,
Department of the Interior (Parts 1200--1299)

Title 26--Internal Revenue

I Internal Revenue Service, Department of the Treasury
(Parts 1--End)

Title 27--Alcohol, Tobacco Products and Firearms

I Alcohol and Tobacco Tax and Trade Bureau, Department
of the Treasury (Parts 1--399)
II Bureau of Alcohol, Tobacco, Firearms, and Explosives,
Department of Justice (Parts 400--699)

Title 28--Judicial Administration

I Department of Justice (Parts 0--299)
III Federal Prison Industries, Inc., Department of Justice
(Parts 300--399)
V Bureau of Prisons, Department of Justice (Parts 500--
599)
VI Offices of Independent Counsel, Department of Justice
(Parts 600--699)
VII Office of Independent Counsel (Parts 700--799)
VIII Court Services and Offender Supervision Agency for the
District of Columbia (Parts 800--899)
IX National Crime Prevention and Privacy Compact Council
(Parts 900--999)
XI Department of Justice and Department of State (Parts
1100--1199)

Title 29--Labor

Subtitle A--Office of the Secretary of Labor (Parts
0--99)
Subtitle B--Regulations Relating to Labor
I National Labor Relations Board (Parts 100--199)

[[Page 840]]

II Office of Labor-Management Standards, Department of
Labor (Parts 200--299)
III National Railroad Adjustment Board (Parts 300--399)
IV Office of Labor-Management Standards, Department of
Labor (Parts 400--499)
V Wage and Hour Division, Department of Labor (Parts
500--899)
IX Construction Industry Collective Bargaining Commission
(Parts 900--999)
X National Mediation Board (Parts 1200--1299)
XII Federal Mediation and Conciliation Service (Parts
1400--1499)
XIV Equal Employment Opportunity Commission (Parts 1600--
1699)
XVII Occupational Safety and Health Administration,
Department of Labor (Parts 1900--1999)
XX Occupational Safety and Health Review Commission
(Parts 2200--2499)
XXV Employee Benefits Security Administration, Department
of Labor (Parts 2500--2599)
XXVII Federal Mine Safety and Health Review Commission
(Parts 2700--2799)
XL Pension Benefit Guaranty Corporation (Parts 4000--
4999)

Title 30--Mineral Resources

I Mine Safety and Health Administration, Department of
Labor (Parts 1--199)
II Bureau of Safety and Environmental Enforcement,
Department of the Interior (Parts 200--299)
IV Geological Survey, Department of the Interior (Parts
400--499)
V Bureau of Ocean Energy Management, Department of the
Interior (Parts 500--599)
VII Office of Surface Mining Reclamation and Enforcement,
Department of the Interior (Parts 700--999)
XII Office of Natural Resources Revenue, Department of the
Interior (Parts 1200--1299)

Title 31--Money and Finance: Treasury

Subtitle A--Office of the Secretary of the Treasury
(Parts 0--50)
Subtitle B--Regulations Relating to Money and Finance
I Monetary Offices, Department of the Treasury (Parts
51--199)
II Fiscal Service, Department of the Treasury (Parts
200--399)
IV Secret Service, Department of the Treasury (Parts
400--499)
V Office of Foreign Assets Control, Department of the
Treasury (Parts 500--599)
VI Bureau of Engraving and Printing, Department of the
Treasury (Parts 600--699)
VII Federal Law Enforcement Training Center, Department of
the Treasury (Parts 700--799)

[[Page 841]]

VIII Office of International Investment, Department of the
Treasury (Parts 800--899)
IX Federal Claims Collection Standards (Department of the
Treasury--Department of Justice) (Parts 900--999)
X Financial Crimes Enforcement Network, Department of
the Treasury (Parts 1000--1099)

Title 32--National Defense

Subtitle A--Department of Defense
I Office of the Secretary of Defense (Parts 1--399)
V Department of the Army (Parts 400--699)
VI Department of the Navy (Parts 700--799)
VII Department of the Air Force (Parts 800--1099)
Subtitle B--Other Regulations Relating to National
Defense
XII Defense Logistics Agency (Parts 1200--1299)
XVI Selective Service System (Parts 1600--1699)
XVII Office of the Director of National Intelligence (Parts
1700--1799)
XVIII National Counterintelligence Center (Parts 1800--1899)
XIX Central Intelligence Agency (Parts 1900--1999)
XX Information Security Oversight Office, National
Archives and Records Administration (Parts 2000--
2099)
XXI National Security Council (Parts 2100--2199)
XXIV Office of Science and Technology Policy (Parts 2400--
2499)
XXVII Office for Micronesian Status Negotiations (Parts
2700--2799)
XXVIII Office of the Vice President of the United States
(Parts 2800--2899)

Title 33--Navigation and Navigable Waters

I Coast Guard, Department of Homeland Security (Parts
1--199)
II Corps of Engineers, Department of the Army (Parts
200--399)
IV Saint Lawrence Seaway Development Corporation,
Department of Transportation (Parts 400--499)

Title 34--Education

Subtitle A--Office of the Secretary, Department of
Education (Parts 1--99)
Subtitle B--Regulations of the Offices of the
Department of Education
I Office for Civil Rights, Department of Education
(Parts 100--199)
II Office of Elementary and Secondary Education,
Department of Education (Parts 200--299)
III Office of Special Education and Rehabilitative
Services, Department of Education (Parts 300--399)

[[Page 842]]

IV Office of Career, Technical and Adult Education,
Department of Education (Parts 400--499)
V Office of Bilingual Education and Minority Languages
Affairs, Department of Education (Parts 500--599)
[Reserved]
VI Office of Postsecondary Education, Department of
Education (Parts 600--699)
VII Office of Educational Research and Improvement,
Department of Education (Parts 700--799)
[Reserved]
Subtitle C--Regulations Relating to Education
XI [Reserved]
XII National Council on Disability (Parts 1200--1299)

Title 35 [Reserved]

Title 36--Parks, Forests, and Public Property

I National Park Service, Department of the Interior
(Parts 1--199)
II Forest Service, Department of Agriculture (Parts 200--
299)
III Corps of Engineers, Department of the Army (Parts
300--399)
IV American Battle Monuments Commission (Parts 400--499)
V Smithsonian Institution (Parts 500--599)
VI [Reserved]
VII Library of Congress (Parts 700--799)
VIII Advisory Council on Historic Preservation (Parts 800--
899)
IX Pennsylvania Avenue Development Corporation (Parts
900--999)
X Presidio Trust (Parts 1000--1099)
XI Architectural and Transportation Barriers Compliance
Board (Parts 1100--1199)
XII National Archives and Records Administration (Parts
1200--1299)
XV Oklahoma City National Memorial Trust (Parts 1500--
1599)
XVI Morris K. Udall Scholarship and Excellence in National
Environmental Policy Foundation (Parts 1600--1699)

Title 37--Patents, Trademarks, and Copyrights

I United States Patent and Trademark Office, Department
of Commerce (Parts 1--199)
II U.S. Copyright Office, Library of Congress (Parts
200--299)
III Copyright Royalty Board, Library of Congress (Parts
300--399)
IV Assistant Secretary for Technology Policy, Department
of Commerce (Parts 400--599)

Title 38--Pensions, Bonuses, and Veterans' Relief

I Department of Veterans Affairs (Parts 0--199)
II Armed Forces Retirement Home (Parts 200--299)

[[Page 843]]

Title 39--Postal Service

I United States Postal Service (Parts 1--999)
III Postal Regulatory Commission (Parts 3000--3099)

Title 40--Protection of Environment

I Environmental Protection Agency (Parts 1--1099)
IV Environmental Protection Agency and Department of
Justice (Parts 1400--1499)
V Council on Environmental Quality (Parts 1500--1599)
VI Chemical Safety and Hazard Investigation Board (Parts
1600--1699)
VII Environmental Protection Agency and Department of
Defense; Uniform National Discharge Standards for
Vessels of the Armed Forces (Parts 1700--1799)
VIII Gulf Coast Ecosystem Restoration Council (Parts 1800--
1899)

Title 41--Public Contracts and Property Management

Subtitle A--Federal Procurement Regulations System
[Note]
Subtitle B--Other Provisions Relating to Public
Contracts
50 Public Contracts, Department of Labor (Parts 50-1--50-
999)
51 Committee for Purchase From People Who Are Blind or
Severely Disabled (Parts 51-1--51-99)
60 Office of Federal Contract Compliance Programs, Equal
Employment Opportunity, Department of Labor (Parts
60-1--60-999)
61 Office of the Assistant Secretary for Veterans'
Employment and Training Service, Department of
Labor (Parts 61-1--61-999)
62--100 [Reserved]
Subtitle C--Federal Property Management Regulations
System
101 Federal Property Management Regulations (Parts 101-1--
101-99)
102 Federal Management Regulation (Parts 102-1--102-299)
103--104 [Reserved]
105 General Services Administration (Parts 105-1--105-999)
109 Department of Energy Property Management Regulations
(Parts 109-1--109-99)
114 Department of the Interior (Parts 114-1--114-99)
115 Environmental Protection Agency (Parts 115-1--115-99)
128 Department of Justice (Parts 128-1--128-99)
129--200 [Reserved]
Subtitle D--Other Provisions Relating to Property
Management [Reserved]
Subtitle E--Federal Information Resources Management
Regulations System [Reserved]
Subtitle F--Federal Travel Regulation System
300 General (Parts 300-1--300-99)
301 Temporary Duty (TDY) Travel Allowances (Parts 301-1--
301-99)

[[Page 844]]

302 Relocation Allowances (Parts 302-1--302-99)
303 Payment of Expenses Connected with the Death of
Certain Employees (Part 303-1--303-99)
304 Payment of Travel Expenses from a Non-Federal Source
(Parts 304-1--304-99)

Title 42--Public Health

I Public Health Service, Department of Health and Human
Services (Parts 1--199)
IV Centers for Medicare & Medicaid Services, Department
of Health and Human Services (Parts 400--599)
V Office of Inspector General-Health Care, Department of
Health and Human Services (Parts 1000--1999)

Title 43--Public Lands: Interior

Subtitle A--Office of the Secretary of the Interior
(Parts 1--199)
Subtitle B--Regulations Relating to Public Lands
I Bureau of Reclamation, Department of the Interior
(Parts 400--999)
II Bureau of Land Management, Department of the Interior
(Parts 1000--9999)
III Utah Reclamation Mitigation and Conservation
Commission (Parts 10000--10099)

Title 44--Emergency Management and Assistance

I Federal Emergency Management Agency, Department of
Homeland Security (Parts 0--399)
IV Department of Commerce and Department of
Transportation (Parts 400--499)

Title 45--Public Welfare

Subtitle A--Department of Health and Human Services
(Parts 1--199)
Subtitle B--Regulations Relating to Public Welfare
II Office of Family Assistance (Assistance Programs),
Administration for Children and Families,
Department of Health and Human Services (Parts
200--299)
III Office of Child Support Enforcement (Child Support
Enforcement Program), Administration for Children
and Families, Department of Health and Human
Services (Parts 300--399)
IV Office of Refugee Resettlement, Administration for
Children and Families, Department of Health and
Human Services (Parts 400--499)
V Foreign Claims Settlement Commission of the United
States, Department of Justice (Parts 500--599)

[[Page 845]]

VI National Science Foundation (Parts 600--699)
VII Commission on Civil Rights (Parts 700--799)
VIII Office of Personnel Management (Parts 800--899)
X Office of Community Services, Administration for
Children and Families, Department of Health and
Human Services (Parts 1000--1099)
XI National Foundation on the Arts and the Humanities
(Parts 1100--1199)
XII Corporation for National and Community Service (Parts
1200--1299)
XIII Office of Human Development Services, Department of
Health and Human Services (Parts 1300--1399)
XVI Legal Services Corporation (Parts 1600--1699)
XVII National Commission on Libraries and Information
Science (Parts 1700--1799)
XVIII Harry S. Truman Scholarship Foundation (Parts 1800--
1899)
XXI Commission on Fine Arts (Parts 2100--2199)
XXIII Arctic Research Commission (Part 2301)
XXIV James Madison Memorial Fellowship Foundation (Parts
2400--2499)
XXV Corporation for National and Community Service (Parts
2500--2599)

Title 46--Shipping

I Coast Guard, Department of Homeland Security (Parts
1--199)
II Maritime Administration, Department of Transportation
(Parts 200--399)
III Coast Guard (Great Lakes Pilotage), Department of
Homeland Security (Parts 400--499)
IV Federal Maritime Commission (Parts 500--599)

Title 47--Telecommunication

I Federal Communications Commission (Parts 0--199)
II Office of Science and Technology Policy and National
Security Council (Parts 200--299)
III National Telecommunications and Information
Administration, Department of Commerce (Parts
300--399)
IV National Telecommunications and Information
Administration, Department of Commerce, and
National Highway Traffic Safety Administration,
Department of Transportation (Parts 400--499)

Title 48--Federal Acquisition Regulations System

1 Federal Acquisition Regulation (Parts 1--99)
2 Defense Acquisition Regulations System, Department of
Defense (Parts 200--299)

[[Page 846]]

3 Health and Human Services (Parts 300--399)
4 Department of Agriculture (Parts 400--499)
5 General Services Administration (Parts 500--599)
6 Department of State (Parts 600--699)
7 Agency for International Development (Parts 700--799)
8 Department of Veterans Affairs (Parts 800--899)
9 Department of Energy (Parts 900--999)
10 Department of the Treasury (Parts 1000--1099)
12 Department of Transportation (Parts 1200--1299)
13 Department of Commerce (Parts 1300--1399)
14 Department of the Interior (Parts 1400--1499)
15 Environmental Protection Agency (Parts 1500--1599)
16 Office of Personnel Management, Federal Employees
Health Benefits Acquisition Regulation (Parts
1600--1699)
17 Office of Personnel Management (Parts 1700--1799)
18 National Aeronautics and Space Administration (Parts
1800--1899)
19 Broadcasting Board of Governors (Parts 1900--1999)
20 Nuclear Regulatory Commission (Parts 2000--2099)
21 Office of Personnel Management, Federal Employees
Group Life Insurance Federal Acquisition
Regulation (Parts 2100--2199)
23 Social Security Administration (Parts 2300--2399)
24 Department of Housing and Urban Development (Parts
2400--2499)
25 National Science Foundation (Parts 2500--2599)
28 Department of Justice (Parts 2800--2899)
29 Department of Labor (Parts 2900--2999)
30 Department of Homeland Security, Homeland Security
Acquisition Regulation (HSAR) (Parts 3000--3099)
34 Department of Education Acquisition Regulation (Parts
3400--3499)
51 Department of the Army Acquisition Regulations (Parts
5100--5199)
52 Department of the Navy Acquisition Regulations (Parts
5200--5299)
53 Department of the Air Force Federal Acquisition
Regulation Supplement (Parts 5300--5399)
[Reserved]
54 Defense Logistics Agency, Department of Defense (Parts
5400--5499)
57 African Development Foundation (Parts 5700--5799)
61 Civilian Board of Contract Appeals, General Services
Administration (Parts 6100--6199)
63 Department of Transportation Board of Contract Appeals
(Parts 6300--6399)
99 Cost Accounting Standards Board, Office of Federal
Procurement Policy, Office of Management and
Budget (Parts 9900--9999)

[[Page 847]]

Title 49--Transportation

Subtitle A--Office of the Secretary of Transportation
(Parts 1--99)
Subtitle B--Other Regulations Relating to
Transportation
I Pipeline and Hazardous Materials Safety
Administration, Department of Transportation
(Parts 100--199)
II Federal Railroad Administration, Department of
Transportation (Parts 200--299)
III Federal Motor Carrier Safety Administration,
Department of Transportation (Parts 300--399)
IV Coast Guard, Department of Homeland Security (Parts
400--499)
V National Highway Traffic Safety Administration,
Department of Transportation (Parts 500--599)
VI Federal Transit Administration, Department of
Transportation (Parts 600--699)
VII National Railroad Passenger Corporation (AMTRAK)
(Parts 700--799)
VIII National Transportation Safety Board (Parts 800--999)
X Surface Transportation Board (Parts 1000--1399)
XI Research and Innovative Technology Administration,
Department of Transportation (Parts 1400--1499)
[Reserved]
XII Transportation Security Administration, Department of
Homeland Security (Parts 1500--1699)

Title 50--Wildlife and Fisheries

I United States Fish and Wildlife Service, Department of
the Interior (Parts 1--199)
II National Marine Fisheries Service, National Oceanic
and Atmospheric Administration, Department of
Commerce (Parts 200--299)
III International Fishing and Related Activities (Parts
300--399)
IV Joint Regulations (United States Fish and Wildlife
Service, Department of the Interior and National
Marine Fisheries Service, National Oceanic and
Atmospheric Administration, Department of
Commerce); Endangered Species Committee
Regulations (Parts 400--499)
V Marine Mammal Commission (Parts 500--599)
VI Fishery Conservation and Management, National Oceanic
and Atmospheric Administration, Department of
Commerce (Parts 600--699)

[[Page 849]]

Alphabetical List of Agencies Appearing in the CFR

(Revised as of July 1, 2016)

CFR Title, Subtitle or
Agency Chapter

Administrative Committee of the Federal Register 1, I
Administrative Conference of the United States 1, III
Advisory Council on Historic Preservation 36, VIII
Advocacy and Outreach, Office of 7, XXV
Afghanistan Reconstruction, Special Inspector 5, LXXXIII
General for
African Development Foundation 22, XV
Federal Acquisition Regulation 48, 57
Agency for International Development 2, VII; 22, II
Federal Acquisition Regulation 48, 7
Agricultural Marketing Service 7, I, IX, X, XI
Agricultural Research Service 7, V
Agriculture Department 2, IV; 5, LXXIII
Advocacy and Outreach, Office of 7, XXV
Agricultural Marketing Service 7, I, IX, X, XI
Agricultural Research Service 7, V
Animal and Plant Health Inspection Service 7, III; 9, I
Chief Financial Officer, Office of 7, XXX
Commodity Credit Corporation 7, XIV
Economic Research Service 7, XXXVII
Energy Policy and New Uses, Office of 2, IX; 7, XXIX
Environmental Quality, Office of 7, XXXI
Farm Service Agency 7, VII, XVIII
Federal Acquisition Regulation 48, 4
Federal Crop Insurance Corporation 7, IV
Food and Nutrition Service 7, II
Food Safety and Inspection Service 9, III
Foreign Agricultural Service 7, XV
Forest Service 36, II
Grain Inspection, Packers and Stockyards 7, VIII; 9, II
Administration
Information Resources Management, Office of 7, XXVII
Inspector General, Office of 7, XXVI
National Agricultural Library 7, XLI
National Agricultural Statistics Service 7, XXXVI
National Institute of Food and Agriculture 7, XXXIV
Natural Resources Conservation Service 7, VI
Operations, Office of 7, XXVIII
Procurement and Property Management, Office of 7, XXXII
Rural Business-Cooperative Service 7, XVIII, XLII
Rural Development Administration 7, XLII
Rural Housing Service 7, XVIII, XXXV
Rural Telephone Bank 7, XVI
Rural Utilities Service 7, XVII, XVIII, XLII
Secretary of Agriculture, Office of 7, Subtitle A
Transportation, Office of 7, XXXIII
World Agricultural Outlook Board 7, XXXVIII
Air Force Department 32, VII
Federal Acquisition Regulation Supplement 48, 53
Air Transportation Stabilization Board 14, VI
Alcohol and Tobacco Tax and Trade Bureau 27, I
Alcohol, Tobacco, Firearms, and Explosives, 27, II
Bureau of
AMTRAK 49, VII
American Battle Monuments Commission 36, IV
American Indians, Office of the Special Trustee 25, VII

[[Page 850]]

Animal and Plant Health Inspection Service 7, III; 9, I
Appalachian Regional Commission 5, IX
Architectural and Transportation Barriers 36, XI
Compliance Board
Arctic Research Commission 45, XXIII
Armed Forces Retirement Home 5, XI
Army Department 32, V
Engineers, Corps of 33, II; 36, III
Federal Acquisition Regulation 48, 51
Bilingual Education and Minority Languages 34, V
Affairs, Office of
Blind or Severely Disabled, Committee for 41, 51
Purchase from People Who Are
Broadcasting Board of Governors 22, V
Federal Acquisition Regulation 48, 19
Career, Technical and Adult Education, Office of 34, IV
Census Bureau 15, I
Centers for Medicare & Medicaid Services 42, IV
Central Intelligence Agency 32, XIX
Chemical Safety and Hazardous Investigation 40, VI
Board
Chief Financial Officer, Office of 7, XXX
Child Support Enforcement, Office of 45, III
Children and Families, Administration for 45, II, III, IV, X
Civil Rights, Commission on 5, LXVIII; 45, VII
Civil Rights, Office for 34, I
Council of the Inspectors General on Integrity 5, XCVIII
and Efficiency
Court Services and Offender Supervision Agency 5, LXX
for the District of Columbia
Coast Guard 33, I; 46, I; 49, IV
Coast Guard (Great Lakes Pilotage) 46, III
Commerce Department 2, XIII; 44, IV; 50, VI
Census Bureau 15, I
Economic Analysis, Bureau of 15, VIII
Economic Development Administration 13, III
Emergency Management and Assistance 44, IV
Federal Acquisition Regulation 48, 13
Foreign-Trade Zones Board 15, IV
Industry and Security, Bureau of 15, VII
International Trade Administration 15, III; 19, III
National Institute of Standards and Technology 15, II
National Marine Fisheries Service 50, II, IV
National Oceanic and Atmospheric 15, IX; 50, II, III, IV,
Administration VI
National Telecommunications and Information 15, XXIII; 47, III, IV
Administration
National Weather Service 15, IX
Patent and Trademark Office, United States 37, I
Productivity, Technology and Innovation, 37, IV
Assistant Secretary for
Secretary of Commerce, Office of 15, Subtitle A
Technology Administration 15, XI
Technology Policy, Assistant Secretary for 37, IV
Commercial Space Transportation 14, III
Commodity Credit Corporation 7, XIV
Commodity Futures Trading Commission 5, XLI; 17, I
Community Planning and Development, Office of 24, V, VI
Assistant Secretary for
Community Services, Office of 45, X
Comptroller of the Currency 12, I
Construction Industry Collective Bargaining 29, IX
Commission
Consumer Financial Protection Bureau 5, LXXXIV; 12, X
Consumer Product Safety Commission 5, LXXI; 16, II
Copyright Royalty Board 37, III
Corporation for National and Community Service 2, XXII; 45, XII, XXV
Cost Accounting Standards Board 48, 99
Council on Environmental Quality 40, V
Court Services and Offender Supervision Agency 5, LXX; 28, VIII
for the District of Columbia
Customs and Border Protection 19, I
Defense Contract Audit Agency 32, I

[[Page 851]]

Defense Department 2, XI; 5, XXVI; 32,
Subtitle A; 40, VII
Advanced Research Projects Agency 32, I
Air Force Department 32, VII
Army Department 32, V; 33, II; 36, III;
48, 51
Defense Acquisition Regulations System 48, 2
Defense Intelligence Agency 32, I
Defense Logistics Agency 32, I, XII; 48, 54
Engineers, Corps of 33, II; 36, III
National Imagery and Mapping Agency 32, I
Navy Department 32, VI; 48, 52
Secretary of Defense, Office of 2, XI; 32, I
Defense Contract Audit Agency 32, I
Defense Intelligence Agency 32, I
Defense Logistics Agency 32, XII; 48, 54
Defense Nuclear Facilities Safety Board 10, XVII
Delaware River Basin Commission 18, III
District of Columbia, Court Services and 5, LXX; 28, VIII
Offender Supervision Agency for the
Drug Enforcement Administration 21, II
East-West Foreign Trade Board 15, XIII
Economic Analysis, Bureau of 15, VIII
Economic Development Administration 13, III
Economic Research Service 7, XXXVII
Education, Department of 2, XXXIV; 5, LIII
Bilingual Education and Minority Languages 34, V
Affairs, Office of
Career, Technical and Adult Education, Office 34, IV
of
Civil Rights, Office for 34, I
Educational Research and Improvement, Office 34, VII
of
Elementary and Secondary Education, Office of 34, II
Federal Acquisition Regulation 48, 34
Postsecondary Education, Office of 34, VI
Secretary of Education, Office of 34, Subtitle A
Special Education and Rehabilitative Services, 34, III
Office of
Career, Technical, and Adult Education, Office 34, IV
of
Educational Research and Improvement, Office of 34, VII
Election Assistance Commission 2, LVIII; 11, II
Elementary and Secondary Education, Office of 34, II
Emergency Oil and Gas Guaranteed Loan Board 13, V
Emergency Steel Guarantee Loan Board 13, IV
Employee Benefits Security Administration 29, XXV
Employees' Compensation Appeals Board 20, IV
Employees Loyalty Board 5, V
Employment and Training Administration 20, V
Employment Standards Administration 20, VI
Endangered Species Committee 50, IV
Energy, Department of 2, IX; 5, XXIII; 10, II,
III, X
Federal Acquisition Regulation 48, 9
Federal Energy Regulatory Commission 5, XXIV; 18, I
Property Management Regulations 41, 109
Energy, Office of 7, XXIX
Engineers, Corps of 33, II; 36, III
Engraving and Printing, Bureau of 31, VI
Environmental Protection Agency 2, XV; 5, LIV; 40, I, IV,
VII
Federal Acquisition Regulation 48, 15
Property Management Regulations 41, 115
Environmental Quality, Office of 7, XXXI
Equal Employment Opportunity Commission 5, LXII; 29, XIV
Equal Opportunity, Office of Assistant Secretary 24, I
for
Executive Office of the President 3, I
Environmental Quality, Council on 40, V
Management and Budget, Office of 2, Subtitle A; 5, III,
LXXVII; 14, VI; 48, 99

[[Page 852]]

National Drug Control Policy, Office of 2, XXXVI; 21, III
National Security Council 32, XXI; 47, 2
Presidential Documents 3
Science and Technology Policy, Office of 32, XXIV; 47, II
Trade Representative, Office of the United 15, XX
States
Export-Import Bank of the United States 2, XXXV; 5, LII; 12, IV
Family Assistance, Office of 45, II
Farm Credit Administration 5, XXXI; 12, VI
Farm Credit System Insurance Corporation 5, XXX; 12, XIV
Farm Service Agency 7, VII, XVIII
Federal Acquisition Regulation 48, 1
Federal Aviation Administration 14, I
Commercial Space Transportation 14, III
Federal Claims Collection Standards 31, IX
Federal Communications Commission 5, XXIX; 47, I
Federal Contract Compliance Programs, Office of 41, 60
Federal Crop Insurance Corporation 7, IV
Federal Deposit Insurance Corporation 5, XXII; 12, III
Federal Election Commission 5, XXXVII; 11, I
Federal Emergency Management Agency 44, I
Federal Employees Group Life Insurance Federal 48, 21
Acquisition Regulation
Federal Employees Health Benefits Acquisition 48, 16
Regulation
Federal Energy Regulatory Commission 5, XXIV; 18, I
Federal Financial Institutions Examination 12, XI
Council
Federal Financing Bank 12, VIII
Federal Highway Administration 23, I, II
Federal Home Loan Mortgage Corporation 1, IV
Federal Housing Enterprise Oversight Office 12, XVII
Federal Housing Finance Agency 5, LXXX; 12, XII
Federal Housing Finance Board 12, IX
Federal Labor Relations Authority 5, XIV, XLIX; 22, XIV
Federal Law Enforcement Training Center 31, VII
Federal Management Regulation 41, 102
Federal Maritime Commission 46, IV
Federal Mediation and Conciliation Service 29, XII
Federal Mine Safety and Health Review Commission 5, LXXIV; 29, XXVII
Federal Motor Carrier Safety Administration 49, III
Federal Prison Industries, Inc. 28, III
Federal Procurement Policy Office 48, 99
Federal Property Management Regulations 41, 101
Federal Railroad Administration 49, II
Federal Register, Administrative Committee of 1, I
Federal Register, Office of 1, II
Federal Reserve System 12, II
Board of Governors 5, LVIII
Federal Retirement Thrift Investment Board 5, VI, LXXVI
Federal Service Impasses Panel 5, XIV
Federal Trade Commission 5, XLVII; 16, I
Federal Transit Administration 49, VI
Federal Travel Regulation System 41, Subtitle F
Financial Crimes Enforcement Network 31, X
Financial Research Office 12, XVI
Financial Stability Oversight Council 12, XIII
Fine Arts, Commission on 45, XXI
Fiscal Service 31, II
Fish and Wildlife Service, United States 50, I, IV
Food and Drug Administration 21, I
Food and Nutrition Service 7, II
Food Safety and Inspection Service 9, III
Foreign Agricultural Service 7, XV
Foreign Assets Control, Office of 31, V
Foreign Claims Settlement Commission of the 45, V
United States
Foreign Service Grievance Board 22, IX
Foreign Service Impasse Disputes Panel 22, XIV
Foreign Service Labor Relations Board 22, XIV
Foreign-Trade Zones Board 15, IV

[[Page 853]]

Forest Service 36, II
General Services Administration 5, LVII; 41, 105
Contract Appeals, Board of 48, 61
Federal Acquisition Regulation 48, 5
Federal Management Regulation 41, 102
Federal Property Management Regulations 41, 101
Federal Travel Regulation System 41, Subtitle F
General 41, 300
Payment From a Non-Federal Source for Travel 41, 304
Expenses
Payment of Expenses Connected With the Death 41, 303
of Certain Employees
Relocation Allowances 41, 302
Temporary Duty (TDY) Travel Allowances 41, 301
Geological Survey 30, IV
Government Accountability Office 4, I
Government Ethics, Office of 5, XVI
Government National Mortgage Association 24, III
Grain Inspection, Packers and Stockyards 7, VIII; 9, II
Administration
Gulf Coast Ecosystem Restoration Council 2, LIX; 40, VIII
Harry S. Truman Scholarship Foundation 45, XVIII
Health and Human Services, Department of 2, III; 5, XLV; 45,
Subtitle A,
Centers for Medicare & Medicaid Services 42, IV
Child Support Enforcement, Office of 45, III
Children and Families, Administration for 45, II, III, IV, X
Community Services, Office of 45, X
Family Assistance, Office of 45, II
Federal Acquisition Regulation 48, 3
Food and Drug Administration 21, I
Human Development Services, Office of 45, XIII
Indian Health Service 25, V
Inspector General (Health Care), Office of 42, V
Public Health Service 42, I
Refugee Resettlement, Office of 45, IV
Homeland Security, Department of 2, XXX; 5, XXXVI; 6, I; 8,
I
Coast Guard 33, I; 46, I; 49, IV
Coast Guard (Great Lakes Pilotage) 46, III
Customs and Border Protection 19, I
Federal Emergency Management Agency 44, I
Human Resources Management and Labor Relations 5, XCVII
Systems
Immigration and Customs Enforcement Bureau 19, IV
Transportation Security Administration 49, XII
HOPE for Homeowners Program, Board of Directors 24, XXIV
of
Housing and Urban Development, Department of 2, XXIV; 5, LXV; 24,
Subtitle B
Community Planning and Development, Office of 24, V, VI
Assistant Secretary for
Equal Opportunity, Office of Assistant 24, I
Secretary for
Federal Acquisition Regulation 48, 24
Federal Housing Enterprise Oversight, Office 12, XVII
of
Government National Mortgage Association 24, III
Housing--Federal Housing Commissioner, Office 24, II, VIII, X, XX
of Assistant Secretary for
Housing, Office of, and Multifamily Housing 24, IV
Assistance Restructuring, Office of
Inspector General, Office of 24, XII
Public and Indian Housing, Office of Assistant 24, IX
Secretary for
Secretary, Office of 24, Subtitle A, VII
Housing--Federal Housing Commissioner, Office of 24, II, VIII, X, XX
Assistant Secretary for
Housing, Office of, and Multifamily Housing 24, IV
Assistance Restructuring, Office of
Human Development Services, Office of 45, XIII
Immigration and Customs Enforcement Bureau 19, IV
Immigration Review, Executive Office for 8, V

[[Page 854]]

Independent Counsel, Office of 28, VII
Independent Counsel, Offices of 28, VI
Indian Affairs, Bureau of 25, I, V
Indian Affairs, Office of the Assistant 25, VI
Secretary
Indian Arts and Crafts Board 25, II
Indian Health Service 25, V
Industry and Security, Bureau of 15, VII
Information Resources Management, Office of 7, XXVII
Information Security Oversight Office, National 32, XX
Archives and Records Administration
Inspector General
Agriculture Department 7, XXVI
Health and Human Services Department 42, V
Housing and Urban Development Department 24, XII, XV
Institute of Peace, United States 22, XVII
Inter-American Foundation 5, LXIII; 22, X
Interior Department 2, XIV
American Indians, Office of the Special 25, VII
Trustee
Endangered Species Committee 50, IV
Federal Acquisition Regulation 48, 14
Federal Property Management Regulations System 41, 114
Fish and Wildlife Service, United States 50, I, IV
Geological Survey 30, IV
Indian Affairs, Bureau of 25, I, V
Indian Affairs, Office of the Assistant 25, VI
Secretary
Indian Arts and Crafts Board 25, II
Land Management, Bureau of 43, II
National Indian Gaming Commission 25, III
National Park Service 36, I
Natural Resource Revenue, Office of 30, XII
Ocean Energy Management, Bureau of 30, V
Reclamation, Bureau of 43, I
Safety and Enforcement Bureau, Bureau of 30, II
Secretary of the Interior, Office of 2, XIV; 43, Subtitle A
Surface Mining Reclamation and Enforcement, 30, VII
Office of
Internal Revenue Service 26, I
International Boundary and Water Commission, 22, XI
United States and Mexico, United States
Section
International Development, United States Agency 22, II
for
Federal Acquisition Regulation 48, 7
International Development Cooperation Agency, 22, XII
United States
International Joint Commission, United States 22, IV
and Canada
International Organizations Employees Loyalty 5, V
Board
International Trade Administration 15, III; 19, III
International Trade Commission, United States 19, II
Interstate Commerce Commission 5, XL
Investment Security, Office of 31, VIII
James Madison Memorial Fellowship Foundation 45, XXIV
Japan-United States Friendship Commission 22, XVI
Joint Board for the Enrollment of Actuaries 20, VIII
Justice Department 2, XXVIII; 5, XXVIII; 28,
I, XI; 40, IV
Alcohol, Tobacco, Firearms, and Explosives, 27, II
Bureau of
Drug Enforcement Administration 21, II
Federal Acquisition Regulation 48, 28
Federal Claims Collection Standards 31, IX
Federal Prison Industries, Inc. 28, III
Foreign Claims Settlement Commission of the 45, V
United States
Immigration Review, Executive Office for 8, V
Independent Counsel, Offices of 28, VI
Prisons, Bureau of 28, V
Property Management Regulations 41, 128
Labor Department 2, XXIX; 5, XLII
Employee Benefits Security Administration 29, XXV
Employees' Compensation Appeals Board 20, IV

[[Page 855]]

Employment and Training Administration 20, V
Employment Standards Administration 20, VI
Federal Acquisition Regulation 48, 29
Federal Contract Compliance Programs, Office 41, 60
of
Federal Procurement Regulations System 41, 50
Labor-Management Standards, Office of 29, II, IV
Mine Safety and Health Administration 30, I
Occupational Safety and Health Administration 29, XVII
Public Contracts 41, 50
Secretary of Labor, Office of 29, Subtitle A
Veterans' Employment and Training Service, 41, 61; 20, IX
Office of the Assistant Secretary for
Wage and Hour Division 29, V
Workers' Compensation Programs, Office of 20, I, VII
Labor-Management Standards, Office of 29, II, IV
Land Management, Bureau of 43, II
Legal Services Corporation 45, XVI
Library of Congress 36, VII
Copyright Royalty Board 37, III
U.S. Copyright Office 37, II
Local Television Loan Guarantee Board 7, XX
Management and Budget, Office of 5, III, LXXVII; 14, VI;
48, 99
Marine Mammal Commission 50, V
Maritime Administration 46, II
Merit Systems Protection Board 5, II, LXIV
Micronesian Status Negotiations, Office for 32, XXVII
Military Compensation and Retirement 5, XCIX
Modernization Commission
Millennium Challenge Corporation 22, XIII
Mine Safety and Health Administration 30, I
Minority Business Development Agency 15, XIV
Miscellaneous Agencies 1, IV
Monetary Offices 31, I
Morris K. Udall Scholarship and Excellence in 36, XVI
National Environmental Policy Foundation
Museum and Library Services, Institute of 2, XXXI
National Aeronautics and Space Administration 2, XVIII; 5, LIX; 14, V
Federal Acquisition Regulation 48, 18
National Agricultural Library 7, XLI
National Agricultural Statistics Service 7, XXXVI
National and Community Service, Corporation for 2, XXII; 45, XII, XXV
National Archives and Records Administration 2, XXVI; 5, LXVI; 36, XII
Information Security Oversight Office 32, XX
National Capital Planning Commission 1, IV
National Commission for Employment Policy 1, IV
National Commission on Libraries and Information 45, XVII
Science
National Council on Disability 5, C; 34, XII
National Counterintelligence Center 32, XVIII
National Credit Union Administration 5, LXXXVI; 12, VII
National Crime Prevention and Privacy Compact 28, IX
Council
National Drug Control Policy, Office of 2, XXXVI; 21, III
National Endowment for the Arts 2, XXXII
National Endowment for the Humanities 2, XXXIII
National Foundation on the Arts and the 45, XI
Humanities
National Geospatial-Intelligence Agency 32, I
National Highway Traffic Safety Administration 23, II, III; 47, VI; 49, V
National Imagery and Mapping Agency 32, I
National Indian Gaming Commission 25, III
National Institute of Food and Agriculture 7, XXXIV
National Institute of Standards and Technology 15, II
National Intelligence, Office of Director of 5, IV; 32, XVII
National Labor Relations Board 5, LXI; 29, I
National Marine Fisheries Service 50, II, IV
National Mediation Board 29, X
National Oceanic and Atmospheric Administration 15, IX; 50, II, III, IV,
VI

[[Page 856]]

National Park Service 36, I
National Railroad Adjustment Board 29, III
National Railroad Passenger Corporation (AMTRAK) 49, VII
National Science Foundation 2, XXV; 5, XLIII; 45, VI
Federal Acquisition Regulation 48, 25
National Security Council 32, XXI
National Security Council and Office of Science 47, II
and Technology Policy
National Telecommunications and Information 15, XXIII; 47, III, IV
Administration
National Transportation Safety Board 49, VIII
Natural Resources Conservation Service 7, VI
Natural Resource Revenue, Office of 30, XII
Navajo and Hopi Indian Relocation, Office of 25, IV
Navy Department 32, VI
Federal Acquisition Regulation 48, 52
Neighborhood Reinvestment Corporation 24, XXV
Northeast Interstate Low-Level Radioactive Waste 10, XVIII
Commission
Nuclear Regulatory Commission 2, XX; 5, XLVIII; 10, I
Federal Acquisition Regulation 48, 20
Occupational Safety and Health Administration 29, XVII
Occupational Safety and Health Review Commission 29, XX
Ocean Energy Management, Bureau of 30, V
Oklahoma City National Memorial Trust 36, XV
Operations Office 7, XXVIII
Overseas Private Investment Corporation 5, XXXIII; 22, VII
Patent and Trademark Office, United States 37, I
Payment From a Non-Federal Source for Travel 41, 304
Expenses
Payment of Expenses Connected With the Death of 41, 303
Certain Employees
Peace Corps 2, XXXVII; 22, III
Pennsylvania Avenue Development Corporation 36, IX
Pension Benefit Guaranty Corporation 29, XL
Personnel Management, Office of 5, I, XXXV; 5, IV; 45,
VIII
Human Resources Management and Labor Relations 5, XCVII
Systems, Department of Homeland Security
Federal Acquisition Regulation 48, 17
Federal Employees Group Life Insurance Federal 48, 21
Acquisition Regulation
Federal Employees Health Benefits Acquisition 48, 16
Regulation
Pipeline and Hazardous Materials Safety 49, I
Administration
Postal Regulatory Commission 5, XLVI; 39, III
Postal Service, United States 5, LX; 39, I
Postsecondary Education, Office of 34, VI
President's Commission on White House 1, IV
Fellowships
Presidential Documents 3
Presidio Trust 36, X
Prisons, Bureau of 28, V
Privacy and Civil Liberties Oversight Board 6, X
Procurement and Property Management, Office of 7, XXXII
Productivity, Technology and Innovation, 37, IV
Assistant Secretary
Public Contracts, Department of Labor 41, 50
Public and Indian Housing, Office of Assistant 24, IX
Secretary for
Public Health Service 42, I
Railroad Retirement Board 20, II
Reclamation, Bureau of 43, I
Refugee Resettlement, Office of 45, IV
Relocation Allowances 41, 302
Research and Innovative Technology 49, XI
Administration
Rural Business-Cooperative Service 7, XVIII, XLII
Rural Development Administration 7, XLII
Rural Housing Service 7, XVIII, XXXV
Rural Telephone Bank 7, XVI
Rural Utilities Service 7, XVII, XVIII, XLII

[[Page 857]]

Safety and Environmental Enforcement, Bureau of 30, II
Saint Lawrence Seaway Development Corporation 33, IV
Science and Technology Policy, Office of 32, XXIV
Science and Technology Policy, Office of, and 47, II
National Security Council
Secret Service 31, IV
Securities and Exchange Commission 5, XXXIV; 17, II
Selective Service System 32, XVI
Small Business Administration 2, XXVII; 13, I
Smithsonian Institution 36, V
Social Security Administration 2, XXIII; 20, III; 48, 23
Soldiers' and Airmen's Home, United States 5, XI
Special Counsel, Office of 5, VIII
Special Education and Rehabilitative Services, 34, III
Office of
State Department 2, VI; 22, I; 28, XI
Federal Acquisition Regulation 48, 6
Surface Mining Reclamation and Enforcement, 30, VII
Office of
Surface Transportation Board 49, X
Susquehanna River Basin Commission 18, VIII
Technology Administration 15, XI
Technology Policy, Assistant Secretary for 37, IV
Tennessee Valley Authority 5, LXIX; 18, XIII
Thrift Supervision Office, Department of the 12, V
Treasury
Trade Representative, United States, Office of 15, XX
Transportation, Department of 2, XII; 5, L
Commercial Space Transportation 14, III
Contract Appeals, Board of 48, 63
Emergency Management and Assistance 44, IV
Federal Acquisition Regulation 48, 12
Federal Aviation Administration 14, I
Federal Highway Administration 23, I, II
Federal Motor Carrier Safety Administration 49, III
Federal Railroad Administration 49, II
Federal Transit Administration 49, VI
Maritime Administration 46, II
National Highway Traffic Safety Administration 23, II, III; 47, IV; 49, V
Pipeline and Hazardous Materials Safety 49, I
Administration
Saint Lawrence Seaway Development Corporation 33, IV
Secretary of Transportation, Office of 14, II; 49, Subtitle A
Transportation Statistics Bureau 49, XI
Transportation, Office of 7, XXXIII
Transportation Security Administration 49, XII
Transportation Statistics Bureau 49, XI
Travel Allowances, Temporary Duty (TDY) 41, 301
Treasury Department 2, X;5, XXI; 12, XV; 17,
IV; 31, IX
Alcohol and Tobacco Tax and Trade Bureau 27, I
Community Development Financial Institutions 12, XVIII
Fund
Comptroller of the Currency 12, I
Customs and Border Protection 19, I
Engraving and Printing, Bureau of 31, VI
Federal Acquisition Regulation 48, 10
Federal Claims Collection Standards 31, IX
Federal Law Enforcement Training Center 31, VII
Financial Crimes Enforcement Network 31, X
Fiscal Service 31, II
Foreign Assets Control, Office of 31, V
Internal Revenue Service 26, I
Investment Security, Office of 31, VIII
Monetary Offices 31, I
Secret Service 31, IV
Secretary of the Treasury, Office of 31, Subtitle A
Thrift Supervision, Office of 12, V
Truman, Harry S. Scholarship Foundation 45, XVIII
United States and Canada, International Joint 22, IV
Commission
United States and Mexico, International Boundary 22, XI
and Water Commission, United States Section
[[Page 858]]

U.S. Copyright Office 37, II
Utah Reclamation Mitigation and Conservation 43, III
Commission
Veterans Affairs Department 2, VIII; 38, I
Federal Acquisition Regulation 48, 8
Veterans' Employment and Training Service, 41, 61; 20, IX
Office of the Assistant Secretary for
Vice President of the United States, Office of 32, XXVIII
Wage and Hour Division 29, V
Water Resources Council 18, VI
Workers' Compensation Programs, Office of 20, I, VII
World Agricultural Outlook Board 7, XXXVIII

[[Page 859]]

List of CFR sections Affected

All changes in this volume of the Code of Federal Regulations (CFR) that
were made by documents published in the Federal Register since January
1, 2011 are enumerated in the following list. Entries indicate the
nature of the changes effected. Page numbers refer to Federal Register
pages. The user should consult the entries for chapters, parts and
subparts as well as sections for revisions.
For changes to this volume of the CFR prior to this listing, consult the
annual edition of the monthly List of CFR sections Affected (LSA). The
LSA is available at www.fdsys.gov. For changes to this volume of the CFR
prior to 2001, see the ``List of CFR sections Affected, 1949-1963, 1964-
1972, 1973-1985, and 1986-2000'' published in 11 separate volumes. The
``List of CFR sections Affected 1986-2000'' is available at
www.fdsys.gov.

2011

(No regulations published)

2012

40 CFR
77 FR
Page
Chapter I
60 Appendix A-6 amended............................................44491
Appendix A-7 amended............................................2460
Appendix F amended..............................................8162
Regulation at 77 FR 8162 comment period extended...............13977
Regulation at 77 FR 8162 withdrawn.............................18709

2013

(No regulations published)

2014

40 CFR
79 FR
Page
Chapter I
60 Appendix A-1 amended............................................11257
Appendix A-2 amended...........................................11260
Appendix A-3 amended...........................................11260
Appendix A-4 amended...........................................11263
Appendix A-5 amended...........................................11266
Appendix A-6 amended...........................................11266
Appendix A-7 amended...........................................11267
Appendix A-8 amended...........................................11268
Appendix B amended.............................................11271
Appendix F amended.............................................11274
Appendix F amended; eff. 11-12-14..............................28441

2015

40 CFR
80 FR
Page
Chapter I
60 Appendix A-8 amended............................................13727
Appendix B amended.............................................38633
Appendix B corrected...........................................42397
Appendix F amended.............................................38649
Appendix I revised.............................................13751

2016

(Regulations published from January 1, 2016, through July 1, 2016)

40 CFR
81 FR
Page
Chapter I
60 Appendix B amended; eff. 8-17-16................................31518
Appendix F amended; eff. 8-17-16...............................31520

[all]