[Federal Register Volume 59, Number 78 (Friday, April 22, 1994)]
[Unknown Section]
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From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[FR Doc No: 94-9574]


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[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.

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    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.

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    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.

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    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.

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    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.

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    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.

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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  10-2.
    5.7.3  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 5.7). 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.

6. Calculations

    6.1  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.
Chh=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.
mco=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.

    6.2  Concentration of Carbon, as Methane, in the Calibration 
Gas.

Cc=(19.681  x  Pp) + (13.121  x  Pvc)    Eq. 1

    6.3  Concentration of Chloride in the Calibration Gas.

Ch=28.998  x  Pvc    Eq. 2

    6.4  Mass of Carbon, as Methane, in a Calibration Run.

mco=Cc  x  Qc  x  tc    Eq. 3

    6.5  Mass of Chloride in a Calibration Run.

mch=Cch  x  Qc  x  tc    Eq. 4

    6.6  FID Response Factor, mg/counts.

Rt=mco/Ac    Eq. 5

    6.7  ELCD Response Factor, mg/counts.

Rth=mch/Ac    Eq. 6

    6.8  Mass of Carbon in the Sample.

msc=DRt (As-Ab)    Eq. 7

    6.9  Mass of Chloride in the Sample.

msh=DRth (As-Ab)    Eq. 8

    6.10  Mass of Volatile Organics in the Sample.

mvo=msc + msh    Eq. 9

    6.11  Relative Standard Deviation.

TR22AP94.019

    6.12  Mass of Sample.

ms=msf-mst    Eq. 11

    6.13  Concentration of Volatile Organics in Waste.

C=(mvo x 1000)/ms    Eq. 12

    6.14  Weighted Average VO Concentration of Multi-phase Waste.

TR22AP94.020

    6. 40 CFR Part 60 is amended by adding Method 26A to Appendix A 
as follows:
Appendix A--Test Methods
* * * * *

Method 26A--Determination of Hydrogen Halide and Halogen Emissions from 
Stationary Sources--Isokinetic Method

1. Applicability, Principle, Interferences, Precision, Bias, and 
Stability

    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. 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). [Note: Mention of trade names or specific products does 
not constitute endorsement by the Environmental Protection Agency.]
    1.2  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 moisture present. 
The filter collects other particulate matter including halide salts. 
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-), 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 TeflonR probe liner, cyclone, and filter holder 
should not be used. The TeflonR filter support must be used. 
The tester must also meet the probe and filter temperature 
requirements of both sampling trains.]
    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 an 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. The 
simultaneous presence of both HBr and C12 may cause a positive 
bias in the HCl result with a corresponding negative bias in the 
C12 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.
    1.4  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.
    1.5  Sample Stability. The collected Cl- samples can be 
stored for up to 4 weeks for analysis for HCl and C12.
    1.6  Detection Limit. The in-stack detection limit for HCl is 
approximately 0.02g per liter of stack gas; the analytical 
detection limit for HCl is 0.1 1g/ml. Detection limits for 
the other analyses should be similar.

2. Apparatus

    2.1  Sampling. The sampling train is shown in Figure 26A-1; the 
apparatus is similar to the Method 5 train where noted as follows:

BILLING CODE 6560-50-P

TR22AP94.018


BILLING CODE 6560-50-C

    2.1.1  Probe Nozzle. Borosilicate or quartz glass; constructed 
and calibrated according to Method 5, Sections 2.1.1 and 5.1, 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.
    2.1.2  Probe Liner. Same as Method 5, Section 2.1.2, except 
metal liners shall not be used. Water-cooling of the stainless steel 
sheath is recommended at temperatures exceeding 500  deg.C. 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).
    2.1.3  Pitot Tube, Differential Pressure Gauge, Filter Heating 
System, Metering System, Barometer, Gas Density Determination 
Equipment. Same as Method 5, Sections 2.1.3, 2.1.4, 2.1.6, 2.1.8, 
2.1.9, and 2.1.10.
    2.1.4  Cyclone (Optional). Glass or PTeflon . 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 moisture droplets present.
    2.1.5  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 holder shall be attached 
immediately to the outlet of the cyclone.
    2.1.6  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 2.1.7). 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 2.1.7). 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.
    2.1.7  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.
    2.2  Sample Recovery. The following items are needed:
    2.2.1  Probe-Liner and Probe-Nozzle Brushes, Wash Bottles,
    Glass Sample Storage Containers, Petri Dishes, Graduated 
Cylinder or Balance, and Rubber Policeman. Same as Method 5, 
Sections 2.2.1, 2.2.2, 2.2.3, 2.2.4, 2.2.5, and 2.2.7.
    2.2.2  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.
    2.2.3  Funnels. Glass or high-density polyethylene, to aid in 
sample recovery.
    2.3  Analysis. For analysis, the following equipment is needed:
    2.3.1  Volumetric Flasks. Class A, various sizes.
    2.3.2  Volumetric Pipettes. Class A, assortment, to dilute 
samples to calibration range of the ion chromatograph (IC).
    2.3.3  Ion Chromatograph. 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.

3. Reagents

    Unless otherwise indicated, all reagents must conform to the 
specifications of 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.
    3.1  Sampling.
    3.1.1  Water. Deionized, distilled water that conforms to 
American Society of Testing and Materials (ASTM) Specification D 
1193-77, Type 3 (incorporated by reference as specified in 
Sec. 60.17).
    3.1.2  Acidic Absorbing Solution, 0.1 N Sulfuric Acid 
(H2SO4). To prepare 1 L, slowly add 2.80 ml of 
concentrated 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.
    3.1.3  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.
    3.1.4  Filter. Teflon mat (e.g., Pallflex 
TX40H145) filter. When the stack gas temperature exceeds 210  deg.C 
(410  deg.F) a quartz fiber filter may be used.
    3.1.5  Silica Gel, Crushed Ice, and Stopcock Grease. Same as 
Method 5, Sections 3.1.2, 3.1.4, and 3.1.5, respectively.
    3.1.6  Sodium Thiosulfate, (Na2S2O33.5 H2O).

3.2  Sample Recovery

    3.2.1  Water. Same as Section 3.1.1.
    3.2.2  Acetone. Same as Method 5, Section 3.2.
    3.3  Sample Analysis.
    3.3.1  Water. Same as Section 3.1.1.
    3.3.2  Reagent 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.
    3.3.3  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 2 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 26A-1.
g Cl-/ml=g of NaCl x 103 x 35.453/58.44      Eq. 
26A-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 26A-2 and 26A-3 to calculate the Br- and F- 
concentrations.

g Br-/ml=g of NaBr x 103 x 79.904/102.90      Eq. 
26A-2
g F-/ml=g of NaF x 103 x 18.998/41.99      Eq. 
26A-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 1 month.
    3.3.4  Chromatographic Eluent. Same as Method 26, Section 3.2.4.

4. Procedure

    Because of the complexity of this method, testers and analysts 
should be trained and experienced with the procedures to ensure 
reliable results.
    4.1  Sampling.
    4.1.1  Pretest Preparation. Follow the general procedure given 
in Method 5, Section 4.1.1, except the filter need only be 
desiccated and weighed if a particulate determination will be 
conducted.
    4.1.2  Preliminary Determinations. Same as Method 5, Section 
4.1.2.
    4.1.3  Preparation of Sampling Train. Follow the general 
procedure given in Method 5, Section 4.1.3, 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.
    4.1.4  Leak-Check Procedures. Follow the leak-check procedures 
given in Method 5, Sections 4.4.1 (Pretest Leak-Check), 4.1.4.2 
(Leak-Checks During the Sample Run), and 4.1.4.3 (Post-Test Leak-
Check).
    4.1.5  Train Operation. Follow the general procedure given in 
Method 5, Section 4.1.5. Maintain a temperature around the filter 
and (cyclone, if used) of greater than 120  deg.C (248  deg.F).
    For each run, record the data required on a data sheet such as 
the one shown in Method 5, Figure 5-2. 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. After the impinger is reinstalled in the 
train, conduct a leak-check as described in Method 5, Section 
4.1.4.2.
    4.1.6  Post-Test Moisture Removal (Optional). When the optional 
cyclone is included in the sampling train or when moisture 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 at least 
120  deg.C (248  deg.F) at a low flow rate (e.g., H=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 moisture. If 
moisture 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.]
    4.2  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. 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, 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 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:
    4.2.1  Container No. 1 (Optional; Filter Catch for Particulate 
Determination). Same as Method 5, Section 4.2, Container No. 1.
    4.2.2  Container No. 2 (Optional; Front-Half Rinse for 
Particulate Determination). Same as Method 5, Section 4.2, Container 
No. 2.
    4.2.3  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 and analyze with the samples.
    4.2.4  Container No. 4 (Alkaline Impinger Catch for Halogen and 
Moisture Determination). Measure and record the liquid in the 
alkaline impingers as described in Section 4.2.3. 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-dscm of 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.] Seal the container, shake to mix, and 
label; mark the fluid level. Retain alkaline absorbing solution 
blank and analyze with the samples.
    4.2.5  Container No. 5 (Silica Gel for Moisture Determination). 
Same as Method 5, Section 4.2, Container No. 3.
    4.2.6  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.
    4.2.7  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.
    4.3  Sample Preparation and Analysis. 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.
    4.3.1  Container Nos. 1 and 2 and Acetone Blank (Optional; 
Particulate Determination). Same as Method 5, Section 4.3.
    4.3.2  Container No. 5. Same as Method 5, Section 4.3 for silica 
gel.
    4.3.3  Container Nos. 3 and 4 and Absorbing Solution and Water 
Blanks. Quantitatively transfer each sample to a volumetric flask or 
graduated cylinder and dilute with water to a final volume within 50 
ml of the largest sample.
    4.3.3.1  The IC conditions will depend upon analytical column 
type and whether suppressed or nonsuppressed IC is used. Prior to 
calibration and 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.
    4.3.3.2  Between injections of the appropriate series of 
calibration standards, inject in duplicate the reagent blanks and 
the field samples. Measure the areas or heights of the Cl-, 
Br-, and F- peaks. Use the average response to determine 
the concentrations of the field samples and reagent blanks using the 
linear calibration curve. If the values from duplicate injections 
are not within 5 percent of their mean, the duplicate injection 
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.
    4.4  Audit Sample Analysis. Audit samples must be analyzed 
subject to availability.

5. Calibration

    Maintain a laboratory log of all calibrations.
    5.1  Probe Nozzle, Pitot Tube, Dry Gas Metering System, Probe 
Heater, Temperature Gauges, Leak-Check of Metering System, and 
Barometer. Same as Method 5, Sections 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 
and 5.7, respectively.
    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 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. 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 height, of 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.

6. Quality Control

    Same as Method 5, Section 4.4.

7. Quality Assurance

    7.1  Applicability. When the method is used to demonstrate 
compliance with a regulation, a set of two audit samples shall be 
analyzed.
    7.2  Audit Procedure. The currently available audit samples are 
chloride solutions. Concurrently analyze the two audit samples 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 Environmental Protection Agency 
(EPA) audit samples.
    7.3  Audit Sample Availability. Audit samples will be supplied 
only to enforcement agencies for compliance tests. Audit samples may 
be obtained by writing the Source Test Audit Coordinator (MD-77B), 
Quality Assurance Division, Atmospheric Research and Exposure 
Assessment Laboratory, U.S. Environmental Protection Laboratory, 
Research Triangle Park, NC 27711 or by calling the Source Test Audit 
Coordinator (STAC) at (919) 541-7834. The request for the audit 
samples should be made at least 30 days prior to the scheduled 
compliance sample analysis.
    7.4  Audit Results. Calculate the concentrations in mg/dscm 
using the specified sample volume in the audit instructions. Include 
the results of both audit samples, their identification numbers, and 
the analyst's name with the results of the compliance determination 
samples in appropriate reports to the EPA regional office or the 
appropriate enforcement agency. (NOTE: Acceptability of results may 
be obtained immediately by reporting the audit results in mg/dscm 
and compliance results in total g HCl/sample to the 
responsible enforcement agency.) The concentrations of the audit 
samples obtained by the analyst shall agree within 10 percent of the 
actual concentrations. If the 10 percent specification is not met, 
reanalyze the compliance samples and audit samples, and include 
initial and reanalysis values in the test report. Failure to meet 
the 10 percent specification may require retests until the audit 
problems are resolved.

8. Calculations

    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.
    8.1  Nomenclature. Same as Method 5, Section 6.1. In addition:

1 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.
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.
VS=Volume of filtered and diluted sample, ml.

    8.2  Average Dry Gas Meter Temperature and Average Orifice 
Pressure Drop. See data sheet (Figure 5-2 of Method 5).
    8.3  Dry Gas Volume. Calculate Vm(std) and adjust for 
leakage, if necessary, using the equation in Section 6.3 of Method 
5.
    8.4  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 5-2 of Method 5); use 
Equations 5-2 and 5-3 of Method 5.
    8.5  Isokinetic Variation and Acceptable Results. Use Method 5, 
Sections 6.11 and 6.12.
    8.6  Acetone Blank Concentration, Acetone Wash Blank Residue 
Weight, Particulate Weight, and Particulate Concentration. For 
particulate determination.
    8.7  Total g HCl, HBr, or HF Per Sample.

    mHX=K Vs (SX--BX-)    Eq. 26A-4
where:
    KHC1 = 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).

    8.8  Total g Cl2 or Br2 Per Sample.

mX2= Vs (SX--BX-)    Eq. 26A-5
    8.9  Concentration of Hydrogen Halide or Halogen in Flue Gas.

C=K mHX,X2/Vm(std)    Eq. 26A-6
where: K=1010- mg/g

    8.10  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 5.2 
and 5.3 of Method 2.

9. Bibliography

    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.
[FR Doc. 94-9574 Filed 4-21-94; 8:45 am]
BILLING CODE 6560-50-P