[Federal Register Volume 59, Number 78 (Friday, April 22, 1994)]
[Unknown Section]
[Page 0]
From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[FR Doc No: 94-9574]
[[Page Unknown]]
[Federal Register: April 22, 1994]
_______________________________________________________________________
Part IV
Environmental Protection Agency
_______________________________________________________________________
40 CFR Part 60
Standards of Performance for New Stationary Sources; Final Rule
ENVIRONMENTAL PROTECTION AGENCY
40 CFR Part 60
[AD-FRL-4846-9]
Standards of Performance for New Stationary Sources; Appendix A--
Test Methods; Revisions to Methods 18 and 26 and Addition of Methods
25D and 26A to Appendix A
AGENCY: Environmental Protection Agency (EPA).
ACTION: Final rule.
-----------------------------------------------------------------------
SUMMARY: The purpose of this action is to make revisions to Method 18,
``Measurement of Gaseous Organic Compound Emissions by Gas
Chromatography'' and to Method 26, ``Determination of Hydrogen Halide
and Halogen Emissions from Stationary Sources--Midget Impinger
Method,'' and to add Method 25D, ``Determination of the Volatile
Organic Concentration of Waste Samples'' and Method 26A,
``Determination of Hydrogen Halide and Halogen Emissions from
Stationary Sources--Isokinetic Method,'' to appendix A of 40 CFR part
60. Method 18 is being revised to clarify the phrase ``engineering
judgment'' as it relates to choosing a sampling methodology. Method 26
for an isokinetic determination of hydrogen chloride emissions is being
revised to add provisions for determining emissions of other hydrogen
halides and halogens. Method 25D is being added as the applicable test
method for the determination of the volatile organic concentration of
wastes. Method 26A is being added as an isokinetic version of Method
26.
A result of this action is that these standard methods will be
available to support compliance determinations with regulations being
promulgated in other rulemaking.
DATES: Effective Date: April 22, 1994.
The incorporation by reference of certain publications listed in
this rule is approved by the Director of the Office of the Federal
Register as of April 22, 1994.
See SUPPLEMENTARY INFORMATION section concerning judicial review.
ADDRESSES: Docket. Docket No. A-90-19, containing material relevant to
this rulemaking for Methods 18, 26, and 26A, and Docket No. A-90-23,
containing material relevant to Method 25D, are available for public
inspection and copying between 8 a.m. and 4 p.m., Monday through
Friday, at EPA's Air Docket, room M-1500, 1st Floor, Waterside Mall,
401 M Street, SW., Washington, DC 20460. A reasonable fee may be
charged for copying.
Two additional dockets pertain to development of the method and the
rulemaking for reference method 25D: (1) Docket No. F-91-CESP-FFFFF,
which contains copies of all BID references and other information
related to the development of the reference method 25D proposal; (2)
Docket No. F-92-CESF-FFFFF, which contains copies of all BID references
and other information related to development of the final reference
method 25D following proposal. The public may review all materials in
these dockets at the EPA RCRA Docket Office.
The EPA RCRA Docket Office is located in room 2427 of the U.S.
Environmental Protection Agency, 401 M Street SW., Washington, DC
20460. The Docket Office is open from 9 a.m. to 4 p.m., Monday through
Friday, except for Federal holidays. The public must have an
appointment to review docket materials. Appointments can be scheduled
by calling the Docket Office at (202) 260-9327.
FOR FURTHER INFORMATION CONTACT: For information concerning Method 26
or Method 26A contact Terry Harrison, Emission Measurement Branch,
([919] 541-5233) or Robin R. Segall, Emission Measurement Branch ([919]
541-0893). For information concerning Method 18 or 25D contact Rima
Dishakjian, Emission Measurement Branch, ([919] 541-0443). The address
for each of these contacts is Emission Measurement Branch (MD-19),
Technical Support Division, U. S. Environmental Protection Agency,
Research Triangle Park, North Carolina 27711.
SUPPLEMENTARY INFORMATION:
Judicial Review
Under section 307(b)(1) of the Clean Air Act (CAA), judicial review
of the actions taken by this notice is available only on the filing of
a petition for review in the U.S. Court of Appeals for the District of
Columbia Circuit within 60 days of today's publication of this rule.
Under section 307(b)(2) of the CAA, the requirements that are subject
to today's notice may not be challenged later in civil or criminal
proceedings brought by EPA to enforce these requirements.
Background Information Document
A background information document (BID) summarizing and responding
to legal comments and technical comments pertaining to this rulemaking
may be obtained from either: (1) The National Technical Information
Service (NTIS), 5285 Port Royal Road, Springfield, VA 22161, telephone
(703) 487-4650, or (2) the EPA Technology Transfer Network (TTN). The
TTN is an electronic bulletin board system which is free, except for
the normal long distance charges. To access the HON BID: (1) Set
software to data bits: 8, N, stop bits: 1; (2) Use access number (919)
541-5742 for 1200, 2400, or 9600 bps modems [access problems should be
directed to the system operator at (919) 541-5384]; (3) Specify TTN
Bulletin Board: Clean Air Act Amendments; and (4) Select menu item:
Recently Signed Rules. Please refer to ``Hazardous Air Pollutant
Emissions from Process Units in the Synthetic Organic Chemical
Manufacturing Industry--Background Information for Promulgated
Standards'', and specify volume number(s).
Volume 2E: Comments on Recordkeeping, Reporting, Compliance, and Test
Methods (EPA-453/R-94-003e)
Volume 2F: Commenter Identification List (EPA-453/R-94-003f)
I. The Rulemaking
Method 18 was developed for and is currently applicable to the
speciation of total gaseous organics in a sample to determine emissions
of individual organic compounds. In response to questions from industry
representatives seeking to use the method for compliance
demonstrations, the EPA is clarifying the phrase ``engineering
judgment'' as it relates to choosing a sampling and analytical
methodology. In the revision, an owner or operator will perform an on-
site field and laboratory evaluation of the methodology chosen to
sample and analyze the compounds of interest. This evaluation is used
to characterize the effectiveness of the methodology and correct for
any inefficiency in the chosen technique.
Method 25D is the applicable test method for the determination of
the volatile organic concentration of wastes. The sampling requirements
in the version of Method 25D promulgated today in 40 CFR part 60,
appendix A, have been changed since proposal. The final version of
Method 25D requires that samples of waste be collected from a source
following specific procedures for sampling a single-phase or well-mixed
waste, a multiple-phase waste, and solid materials. Each sample is
suspended in an organic/aqueous matrix, then heated and purged with
nitrogen for 30 minutes to separate certain organic compounds. A
portion of the sample is analyzed for carbon concentration, as methane,
with a flame ionization detector. The other portion of the sample is
analyzed for chlorine concentration, as chloride, with an electrolytic
conductivity detector. The volatile organic concentration of the waste
is then computed as the sum of the measured carbon and chlorine
contents. Responses to comments on the proposed Method 25D are included
in docket A-90-23.
Under subpart G of part 63, EPA is issuing standards to limit
emissions of halides and halogens from incineration or control of
halogenated organic vent streams at SOCMI facilities. Method 26
currently prescribes only measurement of hydrogen chloride emissions
with sampling at a constant rate. The revisions being made in this
action will expand the method's applicability to other hydrogen halides
and halogens. The addition of Method 26A will provide an alternative to
the revised Method 26 and will allow for isokinetic sampling of gas
streams that are saturated with moisture.
Method 26 was developed for and is currently applicable to
determining hydrogen chloride emissions from municipal waste
combustors. Methods similar to Method 26 and Method 26A were developed
for the measurement of hydrogen chloride (HCl) and chlorine (Cl2)
in emissions from hazardous waste incinerators and boilers and
industrial furnaces burning hazardous waste (56 FR 32728).
The revisions to Method 26 as well as Method 26A also extend the
applicability to measurement of hydrogen bromide (HBr), hydrogen
fluoride (HF), and bromine (Br2).
The Agency assessed the methods further, prior to promulgation,
through laboratory and field evaluations. A study concerning the
potential negative bias in Method 26A at HCl levels below 20 ppm was
performed; specifically, the study was to determine the need to replace
certain glass components in the sampling train with Teflon to
reduce surface adsorption effects. Another study to address sample
stability was performed, particularly in regard to the species created
by hydrolysis of the halogens in the alkaline solution in the sampling
train. Finally, a laboratory evaluation of Method 26A was conducted to
assess the bias and precision of the method for the target analyses. To
assist in its assessment, the Agency also solicited comments on
available information on the proposed methodology. Specifically, the
Agency solicited comments with supporting data to better define the
compounds present in the gas matrices which may, for the hydrogen
halides and halogens specified in the methods: (1) Be analytical
interferences, (2) interfere with their quantitative collection in the
impinger solutions, or (3) affect sample stability.
II. Public Participation
The opportunity to hold a public hearing specifically on these
methods was provided, but no one requested a hearing.
III. Significant Comments and Changes to the Proposed Rulemaking
A. Revisions to Methods 18 and 26 and Addition of Method 26A
Several comment letters were received on the proposed test method
changes and additions. These comments have been carefully considered
and, when deemed appropriate by the Administrator, changes have been
made to proposed Method 26A and the proposed revisions to Methods 18
and 26. A detailed discussion of these comments is contained in the
background document which is referred to in the ADDRESSES section of
this preamble.
The following changes were made to Method 18 as a result of public
comments received: Several commenters expressed concern that the
recovery study in the proposal did not take matrix interferences into
account, since it called for studies in the laboratories. In response
to these comments, the recovery study will be carried out on site, on
actual test samples. For bag and adsorbent sampling, spiked and
unspiked samples will be analyzed in order to quantify the fraction of
sample spike recovered. A correction factor will be required, as in the
proposed version of the method. For direct interface sampling, a
calibration gas will be introduced at the probe in order to check for
leaks in the sampling system. In response to a commenter, the
calibration gas can be introduced anywhere on the probe, but before the
filter. The commenter had expressed concern that on tall stacks, it
would be difficult to introduce a gaseous standard at the tip of the
probe.
Five minor changes were made to Method 26 and Method 26A between
proposal and promulgation as a result of the laboratory and field
studies cited earlier.
The use of Teflon probes and filter holders were
optionally allowed as well as quartz and borosilicate glass. This gives
the affected sources more options and does not affect the Agency's
ability to determine compliance. The data gathered was not sufficient
to show that use of Teflon probes and filter holders should
be required however.
The probe and filter temperature requirement was changed for Method
26A from 120 deg.C14 deg.C to require that the
temperature never be less than 120 deg.C during the sampling run.
Again this approach was taken to allow more flexibility. The Agency
determined that a minimum temperature requirement would minimize the
potential for condensation of acid gases in the probe and on the
filter; with these methods the filter is used to separate halide
particulate matter from the acid gases and is not recovered or analyzed
as part of the method. Therefore allowing the option of collection at
higher temperatures would be acceptable from an Agency perspective. The
source owner should be aware, however, that in some cases, operation at
a higher temperature could result in a positive bias by allowing of
certain compounds such as NH4Cl to pass through the filter.
Following a similar logic, the temperature requirement for the post
test sample train purge (required when the optional use of a cyclone is
used in high moisture environments) was changed to a minimum
temperature of 120 deg.C. The Agency concluded from the field and
laboratory studies that it is imperative that all of the moisture
collected in the cyclone be evaporated and captured during this purge
to assure quantitative recovery of the acid gases. Allowing higher
temperatures will allow this to be accomplished in a shorter time than
at 120 deg.C and potentially reduce the economic burden on the source.
There are, however, practical limitations which the tester will need to
consider in establishing an upper limit for that source to avoid
compromising the filter material or vaporizing halide particulate
matter captured on the filter.
A requirement was added that sodium thiosulfate be added, in excess
of theoretical amounts needed, to the alkaline impinger contents and
wash after sample collection to assure that the hypohalous acid formed
would be reacted to form a second Cl- ion. This then lead to the
equation in Section 8.8 being changed by deleting the factor of 2 since
now 2 halide (Cl- and Br-) ions are formed for each molecule
of halogen captured and measured instead of only one.
Maximum allowable absorbing solution blank correction values were
added to assure that large uncertainties in the compliance status of a
source will not result from laboratories employing poor laboratory
practices. The maximum values reflect attainable goals of current
technology.
Similar changes were made in Method 26 since both methods are
intended to measure the same compounds.
One commenter suggested that Method 13 and Method 13A might, in
some cases, be a better alternative to Method 26A for fluoride
emissions. The cited methods are for total fluoride emissions while
Method 26 and Method 26A are intended specifically for the gaseous
hydrogen fluoride (as well as other halogens and halides); some
modification of Method 13A and Method 13B would be needed to accomplish
this and would likely be source specific. Testers always have the
option of requesting alternative methods; requests should be submitted
in writing and should be accompanied by supporting data.
B. Addition of Method 25D
On July 22, 1991, the EPA proposed a new test method (refer to 56
FR 33491) to be added to appendix A of 40 CFR part 60 for determining
the volatile organic concentration of a waste (Method 25D). Based on
public comments on this proposed test method and EPA's evaluation of
additional technical analyses performed after proposal, certain
requirements of the test method were changed by the EPA from those
proposed. The substantive changes since proposal to Method 25D are
summarized below.
Changes since proposal were made to the sampling requirements for
Method 25D, being promulgated today in appendix A to 40 CFR part 60.
The sampling requirements for Method 25D have been revised to include
procedures for single-phase or well-mixed waste, multiple-phase waste,
and solid waste in addition to an alternative to sampling tap
installation. The final test method still provides a provision for
alternative sampling techniques subject to the approval of the EPA
Administrator.
IV. Administrative Requirements
A. Docket
The docket is an organized and complete file of all the information
submitted to or otherwise considered by EPA in the development of this
rulemaking. The principal purposes of the docket are: (1) To allow
interested parties to identify and locate documents so that they can
effectively participate in the rulemaking process and (2) to serve as
the record in case of judicial review (except for interagency review
materials) [Section 307(d)(7)(A)].
B. Paperwork Reduction Act
This rule does not contain any information collection requirements
subject to OMB review under the Paperwork Reduction Act of 1980, 44
U.S.C. 3501 et seq.
C. Executive Order 12866
Under Executive Order 12866 (58 FR 51736), the Agency must
determine whether the regulatory action is ``significant'' and
therefore subject to Office of Management and Budget (OMB) review and
the requirements of the Executive Order. The Order defines
``significant regulatory action'' as one that is likely to result in a
rule that may:
(1) Have an annual effect on the economy of $100 million or more or
adversely affect in a material way the economy, a sector of the
economy, productivity, competition, jobs, the environment, public
health or safety, or State, local, or tribal governments or
communities,
(2) Create a serious inconsistency or otherwise interfere with an
action taken or planned by another agency,
(3) Materially alter the budgetary impact of entitlements, grants,
user fees, or loan programs or the rights and obligations of recipients
thereof; or
(4) Raise novel legal or policy issues arising out of legal
mandates, the President's priorities, or the principles set forth in
the Executive Order.
Because the methods are not used until required in relevant
standards, there are no environmental, economic, or energy impacts
associated with the promulgated methods. Thus, this action is not
considered a ``significant'' regulatory action within the meaning of
Executive Order 12866.
D. Regulatory Flexibility Act Compliance
The Regulatory Flexibility Act (5 U.S.C. 601 et seq.) requires the
EPA to consider potential impacts of Federal regulations on small
business entities. Because these test methods impose no impacts, a
Regulatory Flexibility analysis has not been conducted.
Pursuant to the provisions of 5 U.S.C. 605(b), I hereby certify
that this rule will not have an economic impact on small entities
because no additional costs will be incurred.
List of Subjects in 40 CFR Part 60
Environmental Protection, Air pollution control, Incorporation by
reference, Intergovernmental relations, Reporting and recordkeeping
requirements, Synthetic organic chemical manufacturing, Test method,
Vapor-phase organic concentration, Volatile organic concentration,
Waste, Waste testing.
Dated: February 28, 1994.
Carol M. Browner,
The Administrator.
For the reasons set out in the preamble, title 40, chapter I, part
60 of the Code of Federal Regulations is amended as follows:
PART 60--[AMENDED]
1. The authority of citation for part 60 continues to read as
follows:
Authority: 42 U.S.C. 7401, 7411, 7414, 7416, 7601.
2. Section 60.17 is amended by revising paragraph (a)(22) to read
as follows:
Sec. 60.17 Incorporation by reference.
* * * * *
(a) * * *
(22) ASTM D 1193-77, Standard Specification for Reagent Water, for
appendix A to part 60, Method 6, par. 3.1.1; Method 7, par. 3.2.2;
Method 7C, par. 3.1.1; Method 7D, par. 3.1.1; Method 8, par. 3.1.3;
Method 12, par. 4.1.3; Method 25D, par. 3.2.2.4; Method 26A, par.
3.1.1.
* * * * *
Appendix A--Test Methods [Amended]
3. In appendix A, Method 18 is amended by revising section 2.1; by
adding paragraph (c) to section 3; by revising sections 7.4.4.1 and
7.4.4.5; and adding section 7.6 to read as follows:
Method 18--Measurement of Gaseous Organic Compound Emissions by Gas
Chromatography
* * * * *
2.1 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.
* * * * *
3. Precision and Accuracy
* * * * *
(c) Recovery. After developing an appropriate sampling and
analytical system for the pollutants of interest, conduct the
procedure in Section 7.6. Conduct the appropriate recovery study in
Section 7.6 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 7.5.
* * * * *
7. Final Sampling and Analysis Procedure
* * * * *
7.4.4 Quality Assurance.
7.4.4.1 Determine the recovery efficiency of the pollutants of
interest according to Section 7.6.
7.4.4.2 * * *
7.4.4.3 * * *
7.4.4.4 * * *
7.4.4.5 Calculations. All calculations can be performed
according to the respective NIOSH method. 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 7.6. Report
results as ppm by volume, dry basis.
* * * * *
7.6 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.
7.6.1 Recovery Study for Direct Interface or Dilution Interface
Sampling. If the procedures in Section 7.2 or 7.3 are to be used to
analyze the stack gas, conduct the calibration procedure as stated
in Section 7.2.2 or 7.3.2, 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 until two consecutive samples are within 5
percent of their mean value. The mean of the calibration gas
response directly to the analyzer and the mean of the calibration
gas response sampled through the probe shall be within 10 percent of
each other. 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.
7.6.2 Recovery Study for Bag Sampling. Follow the procedures
for bag sampling and analysis in Section 7.1. After analyzing all
three bag samples, choose one of the bag samples and analyze twice
more (this bag will become the spiked bag). Spike the chosen bag
sample with a known mixture (gaseous or liquid) of all of the target
pollutants. Follow a procedure similar to the calibration standard
preparation procedure listed in Section 6.2, as appropriate. 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. Analyze
the bag three times after spiking. Calculate the average fraction
recovered (R) of each spiked target compound with the following
equation:
TR22AP94.006
where
t = measured average concentration (ppm) of target compound and
source sample (analysis results subsequent to bag spiking)
u = source sample average concentration (ppm) of target compound
in the bag (analysis results before bag spiking)
s = theoretical concentration (ppm) of spiked target compound in
the bag
For the bag sampling technique to be considered valid for a
compound, 0.70R1.30. 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 following
equation:
TR22AP94.007
7.6.3 Recovery Study for Adsorption Tube Sampling. If following
the adsorption tube procedure in Section 7.4, 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 and with a pitot tube on the outside of each probe. 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 the same
analytical procedure and instrumentation. Determine the fraction of
spiked compound recovered (R) using the following equations.
TR22AP94.008
where
mv = mass per volume of spiked compound measured
(g/L).
ms = total mass of compound measured on adsorbent with
spiked train (g).
vs = volume of stack gas sampled with spiked train (L).
mu = total mass of compound measured on adsorbent with
unspiked train (g).
vu = volume of stack gas sampled with unspiked train (L).
TR22AP94.009
where S = theoretical mass of compound spiked onto adsorbent in
spiked train (g).
7.6.3.1 Repeat the procedure in Section 7.6.3 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 following equation:
TR22AP94.010
* * * * *
4. Method 26 of appendix A is amended by revising Sections 1.1,
1.2, 1.3, 1.5, 1.6, 2.1.5, 2.2.2, 3.2.2, 3.2.3, 4.1.1, 4.2, 4.3, 4.4.2,
4.4.3, 5.2, and 7.2; in Section 2.1, revising Figure 26A-1; in Section
3.1.2, by revising the words ``Absorbing solution'' in the first
sentence to read, ``Acidic Absorbing Solution''; in Section 3.1.3, by
revising the words ``Chlorine Scrubber Solution'' in the first sentence
to read, ``Alkaline Absorbing Solution''; adding new Sections 3.1.4,
7.3, and 7.4; and adding Citations 4 and 5 to Section 8. Bibliography;
to read as follows:
Appendix A--Test Methods
* * * * *
Method 26--Determination of Hydrogen Halide and Halogen Emissions from
Stationary Sources - Midget Impinger Method
* * * * *
1. * * *
1.1 Applicability. This method is applicable for determining
emissions of hydrogen halides (HX) [hydrogen chloride (HCl),
hydrogen bromide (HBr), and hydrogen fluoride (HF)] and halogens
(X2) [chlorine (Cl2) and bromine (Br2)] from
stationary sources. Sources, such as those controlled by wet
scrubbers, that emit acid particulate matter must be sampled using
Method 26A.
[Note: Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.]
1.2 Principle. 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 other particulate matter including halide salts. 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).
1.3 Interferences. 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. 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.
High concentrations of nitrogen oxides (NOX) may produce
sufficient nitrate (NO3-) to interfere with measurements
of very low Br- levels.
* * * * *
1.5 Sample Stability. The collected Cl- samples can be
stored for up to 4 weeks.
1.6 Detection Limit. The analytical detection limit for
Cl- is 0.1 g/ml. Detection limits for the other
analyses should be similar.
* * * * *
2. * * *
2.1 * * *
BILLING CODE 6560-50-P
TR22AP94.011
BILLING CODE 6560-50-C
2.1.5 * * *
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.
* * * * *
2.2 * * *
2.2.2 Storage Bottles. 100- or 250-ml, high-density
polyethylene bottles with Teflon screw cap liners to store
impinger samples.
* * * * *
3. * * *
3.1.2 Acidic Absorbing Solution * * *
3.1.3 Alkaline Absorbing Solution * * *
3.1.4 Sodium Thiosulfate (Na2S2O3.5
H2O)
3.2 * * *
3.2.2 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.
3.2.3 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 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.
g Cl-/ml = g of NaCl x 103 x 35.453/58.44
Eq. 26-1
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 to calculate the Br- and F-
concentrations.
g Br-/ml=g of NaBr x 10\3\ x 79.904/102.90 Eq. 26-2
g F-/ml=g of NaF x 10\3\ x 18.998/41.99
Eq. 26-3
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.
* * * * *
4. * * *
4.1 * * *
4.1.1 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.
* * * * *
4.2 Sample Recovery. 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. Repeat this procedure for the alkaline impingers
and connecting glassware using a separate storage bottle. Add 25 mg
sodium thiosulfate per the product of ppm of halogen anticipated to
be in the stack gas times the dscm stack gas sampled. [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.] 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 3.2.2); 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.
4.3 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.
4.4 * * *
4.4.2 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 5.2. Ensure adequate baseline
separation of the analyses.
4.4.3 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. Dilute any
sample and the blank with equal volumes of water if the
concentration exceeds that of the highest standard.
* * * * *
5. * * *
5.2 Ion Chromatograph. 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 H2SO2 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. Using one of the standards in each series, ensure adequate
baseline separation for the peaks of interest. 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.
Determine the peak areas, or heights, for the standards and plot
individual values versus halide ion concentrations in g/ml.
Draw a smooth curve through the points. Use linear regression to
calculate a formula describing the resulting linear curve.
* * * * *
7. * * *
7.2 Total g HCl, HBr, or HF Per Sample.
mHX=K Vs (SX--BX-) Eq. 26-4
where:
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.
mHX=Mass of HCl, HBr, or HF in sample, g.
SX-=Analysis of sample, g halide ion
(Cl-, Br-, F-)/ml.
Vs=Volume of filtered and diluted sample, ml.
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).
7.3 Total g Cl2 or Br2 Per Sample.
mX2=Vs (SX--BX-) Eq. 26-5
where:
mX2=Mass of Cl2 or Br2 in sample, g.
7.4 Concentration of Hydrogen Halide or Halogen in Flue Gas.
C=K mHX,X2/Vm(std) Eq. 26-6
where:
C=Concentration of hydrogen halide (HX) or halogen (X2),
dry basis, mg/dscm.
Vm(std)= Dry gas volume measured by the dry gas meter,
corrected to standard conditions, dscm.
K=10-3 mg/g.
8. * * *
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.
* * * * *
5. Part 60 is amended by adding and reserving Method 25C and adding
Method 25D to Appendix A as follows:
Appendix A--Test Methods
* * * * *
Method 25D--Determination of the Volatile Organic Concentration of
Waste Samples
Introduction
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. Applicability and Principle
1.1 Applicability. This method is applicable for determining
the volatile organic (VO) concentration of a waste sample.
1.2 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.
2. Apparatus
2.1 Sampling. The following equipment is required:
2.1.1 Sampling Tube. Flexible Teflon, 0.25 in. ID.
Note: Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.
2.1.2 Sample Container. Borosilicate glass, 40 mL, and a Teflon
lined screw cap capable of forming an air tight seal.
2.1.3 Cooling Coil. Fabricated from 0.25 in. ID 304 stainless
steel tubing with a thermocouple at the coil outlet.
2.2 Analysis. The following equipment is required:
2.2.1 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.
BILLING CODE 6560-50-P
TR22AP94.012
BILLING CODE 6560-50-C
2.2.1.1 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
cylindrical glass tube. One end of the tube is open while the other
end is sealed. Exact dimensions are shown in Figure 25D-2.
2.2.1.2 Purging Lance. Glass tube, 6-mm OD by 30 cm long. The
purging end of the tube is fitted with a four-arm bubbler with each
tip drawn to an opening 1 mm in diameter.
Details and exact dimensions are shown in Figure 25D-2.
BILLING CODE 6560-50-P
TR22AP94.013
BILLING CODE 6560-50-C
2.2.1.3 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.
BILLING CODE 6560-50-P
TR22AP94.014
BILLING CODE 6560-50-C
2.2.1.4 Constant Temperature Chamber. A forced draft oven
capable of maintaining a uniform temperature around the purging
flask and coalescing filter of 752 deg.C.
2.2.1.5 Three-way Valve. Manually operated, stainless steel. To
introduce calibration gas into system.
2.2.1.6 Flow Controllers. Two, adjustable. One capable of
maintaining a purge gas flow rate of 6.06 L/min. The
other capable of maintaining a calibration gas flow rate of 1-100
mL/min.
2.2.1.7 Rotameter. For monitoring the air flow through the
purging system (0-10 L/min).
2.2.1.8 Sample Splitters. Two heated flow restrictors (placed
inside oven or heated to 12010 deg.C). At a purge rate
of 6 L/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 and to the ELCD will be 15 mL/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\'' OD
stainless steel tubing.
2.2.1.9 Flow Restrictor. Stainless steel tubing, \1/8\'' OD,
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.
2.2.1.10 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.
2.2.1.11 Four-way Valve. Manually operated, stainless steel.
Placed inside oven, used to bypass purging flask.
2.2.1.12 On/Off Valves. Two, stainless steel. One heat
resistant up to 130 deg.C and placed between oven and ELCD. The
other a toggle valve used to control purge gas flow.
2.2.1.13 Pressure Gauge. Range 0-40 psi. To monitor pressure in
purging flask and coalescing filter.
2.2.1.14 Sample Lines. Teflon, 1/4'' OD, 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.
2.2.1.15 Detector Tubing. Stainless steel, \1/8\'' OD, heated
to 12010 deg.C. 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 2.2.1.12) which shall also be
wrapped with heat-tape and insulation.
2.2.2 Volatile Organic Measurement System. Consisting of an FID
to measure the carbon concentration of the sample and an ELCD to
measure the chlorine concentration.
2.2.2.1 FID. A heated FID meeting the following specifications
is required.
2.2.2.1.1 Linearity. A linear response (+ 5 percent) over the
operating range as demonstrated by the procedures established in
Section 5.1.1.
2.2.2.1.2 Range. A full scale range of 50 pg carbon/sec to 50
Kg carbon/sec. Signal attenuators shall be available to
produce a minimum signal response of 10 percent of full scale.
2.2.2.1.3 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).
2.2.2.2 ELCD. An ELCD meeting the following specifications is
required. The ELCD components shall consist of quartz reactor tubing
and 1-propanol as electrolyte. The electrolyte flow through the
conductivity cell shall be 1 to 2 mL/min.
Note: A \1/4\-in. ID quartz reactor tube is recommended to
reduce carbon buildup and the resulting detector maintenance.
2.2.2.2.1 Linearity. A linear response ( 10
)
5.1.2.
2.2.2.2.2 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.
2.2.2.2.3 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.
3. Reagents
3.1 Sampling.
3.1.1 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 and purging it with nitrogen at a flow rate
of 1 to 2 L/min for 2 hours. The cleaned PEG must be stored under a
1 to 2 L/min nitrogen purge until use. The purge apparatus is shown
in Figure 25D-4.
BILLING CODE 6560-50-P
TR22AP94.015
BILLING CODE 6560-50-C
3.2 Analysis.
3.2.1 Sample Separation. The following are required for the
sample purging step.
3.2.1.1 PEG. Same as Section 3.1.1.
3.2.1.2 Purge Gas. Zero grade nitrogen (N2), containing
less than 1 ppm carbon.
3.2.2 Volatile Organics Measurement. The following are required
for measuring the VO concentration.
3.2.2.1 Hydrogen (H2). Zero grade H2, 99.999 percent
pure.
3.2.2.2 Combustion Gas. Zero grade air or oxygen as required by
the FID.
3.2.2.3 Calibration Gas. Pressurized gas cylinder containing 10
percent propane and 1 percent 1,1-dichloroethylene by volume in
nitrogen.
3.2.2.4 Water. Deionized distilled water that conforms to
American Society for Testing and Materials Specification D 1193-77,
Type 3 (incorporated by reference as specified in Sec. 60.17), 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.
3.2.2.5 1-Propanol. ACS grade or better. Electrolyte Solution.
For use in the ELCD.
4. Procedure
4.1 Sampling.
4.1.1 Sampling Plan Design and Development. Use the procedures
in chapter nine of the Office of Solid Waste's publication, Test
Methods for Evaluating Solid Waste, third edition (SW-846), as
guidance in developing a sampling plan.
4.1.2 Single Phase or Well-mixed Waste. 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.
4.1.2.1 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.
BILLING CODE 6560-50-p
TR22AP94.016
BILLING CODE 6560-50-C
4.1.2.2 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 h before sampling (PEG will solidify at ice bath
temperatures; allow the containers to reach room temperature before
sampling).
4.1.2.3 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.
4.1.2.4 After purging, stop the sample flow and direct the
sampling tube to a preweighed sample container, prepared as
described in Section 4.1.2.2. 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. 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.
4.1.3 Multiple-phase Waste. Collect a 10 g sample of each phase
of waste generated using the procedures described in Section 4.1.2
or 4.1.5. Each phase of the waste shall be analyzed as a separate
sample. Calculate the weighted average VO concentration of the waste
using Equation 13 (Section 6.14).
4.1.4 Solid waste. Add approximately 10 g of the solid waste to
a container prepared in the manner described in Section 4.1.2.2,
minimizing headspace. Cap and chill immediately.
4.1.5 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 4.1.2.2 with approximately 10 g of the waste collected in
the large container. Minimize headspace, cap and chill immediately.
4.1.6 Alternative sampling techniques may be used upon the
approval of the Administrator.
4.2 Sample Recovery.
4.2.1 Assemble the purging apparatus as shown in Figures 25D-1
and 25D-2. The oven shall be heated to 75 2 deg.C. The
sampling lines leading from the oven to the detectors shall be
heated to 120 10 deg.C 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.
4.2.2 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.
4.3 Sample Analysis.
4.3.1 Turn on the constant temperature chamber and allow the
temperature to equilibrate at 75 2 deg.C. 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 752 deg.C, 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.
4.3.2 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.
4.3.3 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.
4.4 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 4.2 and 4.3, excluding
Section 4.2.2. 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.
5. Operational Checks and Calibration.
Maintain a record of performance of each item.
5.1 Initial Performance Check of Purging System.
BILLING CODE 6560-50-P
TR22AP94.017
BILLING CODE 6560-50-C
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 5.1.1 and 5.1.2. Install calibration gas at
the three-way calibration gas valve. See Figure 25D-1.
5.1.1 Linearity Check Procedure. Using the calibration standard
described in Section 3.2.2.3 and by varying the injection time, it
is possible to calibrate at multiple concentration levels. Use
Equation 3 to calculate three sets of calibration gas flow rates and
run times needed to introduce a total methane mass (mco) of 1,
5, and 10 mg into the system (low, medium and high FID calibration,
respectively). Use Equation 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.
5.1.2 Linearity Criteria. Calculate the average response factor
(Equations 5 and 6) and the relative standard deviation (RSD)
(Equation 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
5.1.1 and 5.1.2.
5.2 Daily Calibrations.
5.2.1 Daily Linearity Check. Follow the procedures outlined in
Section 5.1.1 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 5.1.2) 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
5.1.2) 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 5.1.1 and 5.1.2.
5.2.2 Calibration Range Check.
5.2.2.1 If the waste concentration for either detector falls
below the range of calibration for that detector, use the procedure
outlined in Section 5.1.1 to choose 2 calibration points that
bracket the new target concentration. Analyze each of these points
in triplicate (as outlined in Section 5.1.1) and use the criteria in
Section 5.1.2 to determine the linearity of the detector in this
``mini-calibration'' range.
5.2.2.2 After the initial linearity check of the
minicalibration 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 5.2.1). The average daily mini-
calibration point should fit the linearity criteria specified in
Section 5.2.1. 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 5.2.2. A mini-calibration curve for waste concentrations
above the calibration curve for either detector is optional.
5.3 Analytical Balance. Calibrate against standard weights.
5.4 Audit Procedure. Concurrently analyze the audit sample and
a set of compliance samples in the same manner to evaluate the
technique of the analyst and the standards preparation. The same
analyst, analytical reagents, and analytical system shall be used
both for compliance samples and the EPA audit sample. If this
condition is met, auditing of subsequent compliance analyses for the
same enforcement agency within 30 days is not required. An audit
sample set may not be used to validate different sets of compliance
samples under the jurisdiction of different enforcement agencies,
unless prior arrangements are made with both enforcement agencies.
5.5 Audit Samples. Audit Sample Availability. Audit samples
will be supplied only to enforcement agencies for compliance tests.
The availability of audit samples may be determined by writing:
Source Test Audit Coordinator (MD-77B), Quality Assurance Division,
Atmospheric Research and Exposure Assessment Laboratory, U.S.
Environmental Protection Agency, Research Triangle Park, NC 27711 or
by calling the Source Test Audit Coordinator (STAC) at (919) 541-
7834. The request for the audit sample must be made at least 30 days
prior to the scheduled compliance sample analysis. If audit samples
are not available, follow the quality control sample procedures in
Section 5.7.
5.6 Audit Results. Calculate the audit sample concentration
according to the calculation procedure described in the audit
instructions included with the audit sample. Fill in the audit
sample concentration and the analyst's name on the audit response
form included with the audit instructions. Send one copy to the EPA
Regional Office or the appropriate enforcement agency and a second
copy to the STAC. The EPA Regional office or the appropriate
enforcement agency will report the results of the audit to the
laboratory being audited. Include this response with the results of
the compliance samples in relevant reports to the EPA Regional
Office or the appropriate enforcement agency.
5.7 Quality Control Samples. If audit samples are not
available, prepare and analyze the two types of quality control
samples (QCS) listed in Sections 5.7.1 and 5.7.2. 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.
5.7.1 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 the QCS according to the procedures described in
Sections 4.2 and 4.3, excluding Section 4.2.2. 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.
5.7.2 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 4.2 and 4.3, excluding Section 4.2.2. 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