[Federal Register Volume 65, Number 201 (Tuesday, October 17, 2000)]
[Rules and Regulations]
[Pages 61744-62273]
From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[FR Doc No: 00-19099]



[[Page 61743]]

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Part II





Environmental Protection Agency





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40 CFR Part 60, 61, and 63



Amendments for Testing and Monitoring Provisions; Final Rule

  Federal Register / Vol. 65, No. 201 / Tuesday, October 17, 2000 / 
Rules and Regulations  

[[Page 61744]]


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ENVIRONMENTAL PROTECTION AGENCY

40 CFR Parts 60, 61, and 63

[FRL-6523-6]
RIN 2060-AG21


Amendments for Testing and Monitoring Provisions

AGENCY: Environmental Protection Agency (EPA).

ACTION: Final rule: amendments.

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SUMMARY: In this rule, we, the Environmental Protection Agency (EPA) 
are making final minor amendments to our stationary source testing and 
monitoring rules. These amendments include miscellaneous editorial 
changes and technical corrections that are needed. We are also 
promulgating Performance Specification 15, which contains the criteria 
for certifying continuous emission monitoring systems (CEMS) that use 
fourier transform infrared spectroscopy (FTIR). In addition, we are 
changing the outline of the test methods and CEMS performance 
specifications already listed in Parts 60, 61, and 63 to fit a new 
format recommended by the Environmental Monitoring Management Council 
(EMMC). The editorial changes and technical corrections update the 
rules and help maintain their original intent. Performance 
Specification 15 will provide the needed acceptance criteria for FTIR 
CEMS as they emerge as a new technology. We are reformatting the test 
methods and performance specifications to make them more uniform in 
content and interchangeable with other Agency methods. The amendments 
apply to a large number of industries that are already subject to the 
current provisions of Parts 60, 61, and 63. Therefore, we have not 
listed specific affected industries or their Standard Industrial 
Classification codes here.

DATES: Effective Date. This regulation is effective October 17, 2000. 
The incorporation by reference of certain publications listed in the 
rule is approved by the Director of the Federal Register as of October 
17, 2000.

ADDRESSES: Docket. Docket No. A-97-12, contains information relevant to 
this rule. You can read and copy it between 8 a.m. and 5:30 p.m., 
Monday through Friday, (except for Federal holidays), at our Air and 
Radiation Docket and Information Center, U.S. Environmental Protection 
Agency, 401 M Street, SW., Washington, DC 20460; telephone (202) 260-
7548. Go to Room M-1500, Waterside Mall (ground floor). The docket 
office may charge a reasonable fee for copying.
    Summary of Comments and Responses Document. You may obtain the 
Summary of Comments and Responses Document over the Internet at http://www.epa.gov/ttn/emc; choose the ``Methods'' menu, then choose the 
``Summary of Comments and Responses'' hypertext under Category A.

FOR FURTHER INFORMATION CONTACT: Mr. Foston Curtis, Emission 
Measurement Center (MD-19), Emissions, Monitoring, and Analysis 
Division, U.S. Environmental Protection Agency, Research Triangle Park, 
North Carolina 27711; telephone (919) 541-1063; facsimile number (919) 
541-1039; electronic mail address ``[email protected]''.

SUPPLEMENTARY INFORMATION: Outline. The information presented in this 
preamble is organized as follows:

I. Why were these amendments made?
II. What does the new EMMC Format for methods look like?
III. What were the significant public comments and what resulting 
changes were made since proposal?
    A. Updates to the ASTM Methods
    B. Performance requirements for continuous instrumental methods 
of Part 60--Methods 3A, 6C, 7E, 10, and 20
    C. Method 18 (Part 60)
    D. Method 25 (Part 60)
    E. Performance Specification 15 (Part 60)
IV. What revisions were made that were not in the proposed rule?
V. What are the administrative requirements for this rule?
    A. Docket
    B. Office of Management and Budget Review
    C. Regulatory Flexibility Act Compliance
    D. Paperwork Reduction Act
    E. Unfunded Mandates Reform Act
    F. E.O. 13132--Federalism
    G. E.O. 13084--Consultation and Coordination with Indian Tribal 
Governments
    H. Executive Order 13084--Protection of Children from 
Environmental Health Risks and Safety Risks
    I. Submission to Congress and the General Accounting Office
    J. National Technology Transfer and Advancement Act
    K. Plain Language in Government Writing

I. Why Were These Amendments Made?

    We have compiled miscellaneous errors and editions that are needed 
for the test methods, performance specifications, and associated 
regulations in 40 CFR Parts 60, 61, and 63. The corrections and 
revisions consist primarily of typographical errors, technical errors 
in equations and diagrams, and narrative that is no longer applicable 
or is obsolete. Some of the revisions were brought to our attention by 
the public. The major changes to the rule proposed on August 27, 1997 
that resulted from public comments are discussed in Section III. Please 
note that, although numerous technical corrections were made to Parts 
60, 61, and 63 rules, none affected a compliance standard or reporting 
or recordkeeping requirement. Revisions were only made to sections that 
pertain to source testing or monitoring of emissions and operations.

II. What Does the New EMMC Format for Methods Look Like?

    The new EMMC format we have adopted for analytical methods was 
developed by consensus and will help integrate make consistent the test 
methods written by different EPA programs. The test methods and 
performance specifications being restructured in the new format are 
shown in Table 1.

  Table 1.--Test Methods and Performance Specifications Restructured in
                             the EMMC Format
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 40 CFR 60 App. A   40 CFR 60 App. B      40 CFR 61         40 CFR 63
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 1, 1A             PS-2               101, 101A         303, 303A
 2, 2A, 2B, 2C,    PS-3               102               304A, 304B
 2D, 2E
 3, 3A, 3B         PS-4, PS-4A        103               305
 4                 PS-5               104               306, 306A, 306B
 5, 5A, 5B, 5D,    PS-6               105
 5E, 5F, 5G, 5H
 6, 6A, 6B, 6C     .................  106
 7, 7A 7B, 7C,     .................  107, 107A
 7D, 7E
 8                 .................  108, 108A, 108B,
                                       108C
 10, 10A, 10B      .................  111
 11
 12

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 13A, 13B
 14
 15, 15A
 16, 16A, 16B
 17
 18
 19
 20
 21
 22
 23
 24, 24A
 25, 25A, 25B,
 25C, 25D, 25E
 26, 26A
 27
 28, 28A
 29
------------------------------------------------------------------------

    The methods and specifications listed in Table 1 were restructured 
in the format shown in Table 2. Only in a few instances were there 
deviations from this recommended format.

                          Table 2.--EMMC Format
------------------------------------------------------------------------
               Section No.                        Section heading
------------------------------------------------------------------------
1.0....................................  Scope and Application.
2.0....................................  Summary of the Method.
3.0....................................  Definitions.
4.0....................................  Interferences.
5.0....................................  Safety.
6.0....................................  Equipment and Supplies.
7.0....................................  Reagents and Standards.
8.0....................................  Sample Collection,
                                          Preservation, Storage and
                                          Transport.
9.0....................................  Quality Control.
10.0...................................  Calibration and
                                          Standardization.
11.0...................................  Analytical Procedure.
12.0...................................  Calculations and Data Analysis.
13.0...................................  Method Performance.
14.0...................................  Pollution Prevention.
15.0...................................  Waste Management.
16.0...................................  References.
17.0...................................  Tables, Diagrams, Flowcharts,
                                          and Validation Data.
------------------------------------------------------------------------

III. What Were the Significant Public Comments and What Resulting 
Changes Were Made Since Proposal?

    We asked that public comments on the August 27, 1997 proposal (62 
FR 45369) be submitted by October 27, 1997. On November 18, 1997, we 
reopened (62 FR 61483) the comment period to allow additional time for 
review and comment. We received comments from facility owners and 
operators, trade associations, State and Local air pollution control 
agencies, environmental consultants, and private citizens. Their 
comments were considered in developing this final action. A detailed 
discussion of all comments are contained in the Summary of Comments and 
Responses Document (see ADDRESSES section of this preamble). The major 
public comments and the Agency's responses are summarized below.

A. Update to ASTM Methods

    Several commenters supported our updating the references to ASTM 
Standards to include the dates of the most recent versions. However, 
some were concerned that updated standards not supplant the versions 
previously allowed and those promulgated with the original regulation. 
The ASTM recommended we follow the tradition of other governmental 
agencies and list only the latest version of each standard. This would 
present the latest, most improved standard. They felt that previously 
approved versions would still be acceptable for future use, and this 
could be noted in the preamble to the final rule.
    On January 14, 1998, we published a supplementary Federal Register 
notice to solicit public comments on this idea. We received three 
comment letters. All commenters objected to the idea of listing only 
the latest version of the ASTM standard. The commenters noted problems 
that would be encountered with State Implementation Plans (SIP) wherein 
only the specific ASTM standards listed in the subparts would be 
allowed. They feared that listing only the latest version of the 
standard would change the current allowance to use earlier versions. 
This could potentially change the intent of the original emission 
standard. Most commenters didn't think a preamble explanation was 
sufficient assurance for continued allowance of earlier versions since 
preambles are not published in the Code of Federal Regulations. There 
were additional concerns for laboratories using currently acceptable 
versions who would need to upgrade their practice to reflect the latest 
version of a standard. The commenters were not amenable to only listing 
the latest standard unless

[[Page 61746]]

language were added to the General Provisions of each part stating that 
previously allowed versions of the standards were still allowed at the 
discretion of the source. We feel the commenters have valid concerns 
and have decided to continue the convention of listing all acceptable 
versions of the ASTM standards including the new updates. The intent of 
this action is to allow any of the yearly-designated versions of a 
specific standard to be used in the applications where cited.

B. Performance Requirements for Continuous Instrumental Methods of Part 
60--Methods 3A, 6C, 7E, 10, and 20

    Several commenters thought the preamble language for this proposal 
gave inadequate notice of the changes being made. Commenters stated 
that, in the proposal, we did not provide an adequate basis and purpose 
statement and misled the readers into thinking that the proposal 
contained no substantive changes to these test methods. Based on the 
number of substantive changes in this proposal, and in light of the 
Section 307(d) requirements, the commenters felt that we must address 
these issues in a new proposal before the revisions can go final with 
the rest of the package. We agree with the commenters that the preamble 
to the proposed rule may not have given adequate public notice for some 
of the revisions. The revisions to the continuous instrumental methods 
(Methods 3A, 6C, 7E, 10, and 20) may be considered substantive, but 
were not enumerated in the preamble nor was a supporting rationale 
given. Therefore, the revisions to Methods 3A, 6C, 7E, 10, and 20 will 
be reproposed as a separate rule. The comments already received on the 
proposal of these methods will be held for consideration with any 
future comments that result from the reproposal.

C. Method 18 (Part 60, Appendix A)

    One commenter thought Method 18 was difficult to follow. The 
commenter suggested that, to simplify organization of the method, we 
should divide the method into five categories. Each title would begin 
with ``Measurement of Gaseous Organic Compounds by Gas Chromatography'' 
but have the following subtitles:

18A--Evacuated container sampling procedure.
18B--Bag sampling procedure.
18C--Direct interface procedure.
18D--Dilution interface procedure.
18E--Adsorption tube sampling procedure.

    Another commenter suggested dividing the method into two different 
methods, one for the direct extractive technique, and the other for 
sample collection into bags, flasks, or adsorbents.
    The method is currently divided according to the various sampling 
procedures; for example, Section 8.2.2 is the Direct Interface Sampling 
and Analysis Procedures, Section 8.2.3 is Dilution Interface Sampling 
and Analysis Procedures, and so on. We do not believe that multiple 
sampling procedures warrant dividing Method 18 into separate methods. 
We feel a single method allowing different procedures offers the source 
greater flexibility than citing specific procedures for particular 
situations. One commenter noted that the proposed method requires 
triplicate injections for analysis of the calibration standards used 
for preparing the pre-test calibration curve, triplicate injections of 
the test samples, and triplicate injections for construction of the 
post-test calibration curve. The commenter questioned the additional 
accuracy expected for the extra hours spent in sample analysis and 
calibration while in the field conducting a source test compared to the 
current method which requires two consecutive analyses for pre- and 
post-test calibration and sample analyses meeting the same criteria for 
acceptance. We are increasing the calibration requirement to triple 
injections to tighten the method's quality assurance procedures. 
Triplicate calibration injections is the normal procedure prevalent in 
the analytical community, as well as in other Agency methodologies. It 
is difficult to establish precision and accuracy with duplicate 
injections. However, triplicate injections provide a reasonable measure 
of analytical precision without being overly burdensome. We do not feel 
the increase in time and costs associated with the third injection will 
significantly affect a typical test, considering the added benefits to 
data quality that are gained.
    Several commenters asked us to revise and clarify various aspects 
of Section 10. We have made these modifications to address their 
concerns.
    Regarding Section 13.1, one commenter noted that Method 18 is not a 
method in the general sense, but is more of a guideline on how to 
develop and document a test method. The commenter therefore felt that 
any prospective method should be written up and submitted to us along 
with the proper documentation that includes recovery study results. We 
disagree with this commenter. Method 18, which has been cited and used 
for many years, is a specific gas chromatography method with specific 
sampling, analytical, and data quality requirements. The method was 
written to accomodate many test sites having many possible target 
compounds and gas matrices. The tester has been given numerous 
sampling, separation, and analytical system options to make the method 
adaptable to the needs of various compliance demonstrations.
    Several commenters asked us to clarify the 5 to 10 percent relative 
standard deviation (RSD) requirement for calibration standards in 
Section 13.1.
    We have added clarity to Section 13.1. The 5 to 10 percent RSD is 
not a precision criterion for calibration standards but a typical 
precision range for analyzing field samples. Five percent RSD is 
required for triplicate injections of calibration standards.

D. Method 25 (Part 60, Appendix A)

    One commenter noted that Method 25 has limitations due to 
conditions that may exist in stack gas. If such conditions exist, the 
commenter recommends interfacing a nonmethane analyzer directly to the 
source or use Method 25A or 25B to measure the emissions. The commenter 
recommended modifying Method 25 to allow instruments that are able to 
determine the methane and nonmethane portions using components 
different from those described by Method 25 when the analyzer is 
directly interfaced to the source. The commenter feels that Method 25 
would be more practical for determining methane/nonmethane emissions at 
the field site if the method could be modified to allow these other 
analyzers. The commenter feels that it will also be necessary that 
fixed performance specifications be defined in the method, such as 
those for Method 6C. We believe these comments address method changes 
that are beyond those covered in the proposal and are, therefore, 
beyond the scope of this action. The commenter is encouraged to pursue 
these method changes through other appropriate channels such as 
submitting a request to use them as an alternative method.

E. Performance Specification 15 (Part 60, Appendix B)

    One commenter noted that the statement of applicability for the 
demonstration is limited to the criteria we gave. The commenter stated 
that, with performance based measurement systems, the focus is on data 
quality objectives (DQO) where the performance specifications are 
coupled with the DQO. We believe the purpose of reference methods and, 
in this case

[[Page 61747]]

performance specifications, is to provide standard procedures for 
sources to follow in order to provide quality emission data. However, 
we do provide latitude to sources by publishing performance-based 
methods and PS whenever possible. This performance specification is one 
such procedure; as long as an FTIR sampling system meets the 
requirements of the performance specifications, it can be used for any 
regulated pollutant.
    Based on public comments and upon further deliberation, we have 
removed the system calibration requirement from Section 10.3 of PS-15. 
Since both a system calibration and the calibration transfer standard 
measurement basically test instrument function, having both of these 
requirements in the performance specifications is redundant.
    One commenter felt that the number of runs should be given as 
``guidance'' rather than made a requirement. We set the requirement for 
nine runs (when comparing the FTIR to a reference method) and 10 runs 
(when comparing the FTIR to a reference monitor) because these are 
standard prodedures for performance specifications. We note that this 
performance specification also allows analyte spiking as an option; 
therefore, a revision on this point is not necessary.
    One commenter noted that Section 11.1.1.4.3 states ``if the RM is a 
CEM, synchronize the sampling flow rates of the RM and the FTIR CEM.'' 
The commenter noted that instrumental analyzers are currently used for 
reference methods. EPA Methods 6C, 7E, 3A, and 10 measure 
SO2, NOX, O2, CO2, and CO 
on a continuous basis for a short period of time and are referred to as 
instrumental analyzers and not CEMs. The commenter felt the statement 
should read ``if the reference method is an instrumental analyzer, 
synchronize the sampling flow rates of the RM and the FTIR.'' We agree 
with the commenter and have made the noted change.

IV. What Revisions Were Made That Were Not in the Proposed Rule?

    A revision was made to Section 6.6 of Method 21 of Part 60 to 
clarify the VOC monitoring instrument specifications. The requirement 
for the instrument to be intrinsically safe for Classes 1 and 2, 
Division 1 conditions has been amended to require them to be 
intrinsically safe for Class 1 and/or Class 2, Division 1 conditions, 
as appropriate. The performance test provisions of Sec. 60.754(d) for 
determining control device efficiency when combusting landfill gas were 
amended to allow the use of Method 25 as an alternative to Methods 18 
and 25C. The tester has the option of using either Method 18, 25, or 
25C in this case. These amendments were not published in the proposed 
rule.

V. Administrative Requirements

A. Docket

    Docket A-97-12 is an organized and complete file of all information 
submitted to us or otherwise considered in the development of this 
final 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) [Clean Air Act Section 307(d)(7)(A), 42 U.S.C. 
7607(d)(7)(A)].

B. Office of Management and Budget Review

    Under Executive Order 12866 (58 FR 51735 October 4, 1993), we must 
determine whether the regulatory action is ``significant'' and 
therefore subject to Office of Management and Budget (OMB) review and 
the requirements of this 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.
    We have determined that this rule is not a ``significant regulatory 
action'' under the terms of Executive Order 12866 and is therefore not 
subject to OMB review. We have determined that this regulation would 
result in none of the economic effects set forth in Section 1 of the 
Order because it does not impose emission measurement requirements 
beyond those specified in the current regulations, nor does it change 
any emission standard.

C. Regulatory Flexibility Act Compliance

    We have determined that it is not necessary to prepare a regulatory 
flexibility analysis in connection with this final rule. We have also 
determined that this rule will not have a significant economic impact 
on a substantial number of small businesses. This rulemaking does not 
impose emission measurement requirements beyond those specified in the 
current regulations, nor does it change any emission standard.

D. Paperwork Reduction Act

    This rule does not impose or change any information collection 
requirements. The Paperwork Reduction Act of 1980, 44 U.S.C. 3501, et 
seq., is not required.

E. Unfunded Mandates Reform Act

    Title II of the unfunded Mandates Reform Act of 1995 (UMRA), Pub. 
L. 104-4, establishes requirements for Federal agencies to assess the 
effects of their regulatory action on State, local, and tribal 
governments and the private sector. Under section 202 of the UMRA, we 
generally must prepare a written statement, including a cost-benefit 
analysis, for proposed and final rules with ``Federal mandates'' that 
may result in expenditures by State, local, and tribal governments, in 
the aggregate, or by the private sector, of $100 million or more in any 
one year. Before promulgating an EPA rule for which a written statement 
is needed, Section 205 of the UMRA generally requires us to identify 
and consider a reasonable number of regulatory alternatives and adopt 
the least costly, most cost-effective or least burdensome alternative 
that achieves the objectives of the rule. The provisions of Section 205 
do not apply when they are inconsistent with applicable law. Moreover, 
Section 205 allows EPA to adopt an alternative other than the least 
costly, most cost-effective or least burdensome alternative if the 
Administrator publishes with the final rule an explanation why that 
alternative was not adopted. Before we establish any regulatory 
requirement that may significantly or uniquely affect small 
governments, including tribal governments, we must develop a small 
government agency plan as required under Section 203 of the UMRA. The 
plan must provide for notifying potentially affected small governments, 
enabling officials of affected small governments to have meaningful and 
timely input in the development of our regulatory proposals with 
significant Federal intergovernmental mandates, and informing, 
educating, and advising small governments on compliance with the 
regulatory requirements.
    Today's rule contains no Federal mandates (under the regulatory

[[Page 61748]]

provisions of Title II of the UMRA) for State, local, or tribal 
governments or the private sector. We have determined that today's rule 
does not include a Federal mandate because it imposes no enforceable 
duty on any State, local, and tribal governments, or the private 
sector. Today's rule simply makes corrections and minor revisions to 
current testing requirements and promulgates a monitoring specification 
that can be used to support future monitoring rules. For the same 
reason we have also determined that this rule contains no regulatory 
requirements that might significantly or uniquely affect small 
governments.

F. Executive Order 13132 (Federalism)

    Executive Order 13132, entitled ``Federalism'' (64 FR 43255, August 
10, 1999), requires EPA to develop an accountable process to ensure 
``meaningful and timely input by State and local officials in the 
development of regulatory policies that have federalism implications.'' 
``Policies that have federalism implications'' is defined in the 
Executive Order to include regulations that have ``substantial direct 
effects on the States, on the relationship between the national 
government and the States, or on the distribution of power and 
responsibilities among the various levels of government.'' Under 
Executive Order 13132, EPA may not issue a regulation that has 
federalism implications, that imposes substantial direct compliance 
costs, and that is not required by statute, unless the Federal 
government provides the funds necessary to pay the direct compliance 
costs incurred by State and local governments, or EPA consults with 
State and local officials early in the process of developing the 
proposed regulation. EPA also may not issue a regulation that has 
federalism implications and that preempts State law unless the Agency 
consults with State and local officials early in the process of 
developing the proposed regulation.
    If EPA complies by consulting, Executive Order 13132 requires EPA 
to provide to the Office of Management and Budget (OMB), in a 
separately identified section of the preamble to the rule, a federalism 
summary impact statement (FSIS). The FSIS must include a description of 
the extent of EPA's prior consultation with State and local officials, 
a summary of the nature of their concerns and the agency's position 
supporting the need to issue the regulation, and a statement of the 
extent to which the concerns of State and local officials have been 
met. Also, when EPA transmits a draft final rule with federalism 
implications to OMB for review pursuant to Executive Order 12866, EPA 
must include a certification from the agency's Federalism Official 
stating that EPA has met the requirements of Executive Order 13132 in a 
meaningful and timely manner.
    This final rule will not have substantial direct effects on the 
States, on the relationship between the national government and the 
States, or on the distribution of power and responsibilities among the 
various levels of government, as specified in Executive Order 13132. 
This final rule simply makes corrections and minor revisions to current 
testing requirements and promulgates a monitoring specification that 
can be used to support future monitoring rules. Thus, the requirements 
of section 6 of the Executive Order do not apply to this rule.

G. Executive Order 13084: Consultation and Coordination With Indian 
Tribal Governments

    Under Executive Order 13084, we may not issue a regulation that is 
not required by statute, that significantly or uniquely affects the 
communities of Indian tribal governments, and that imposes substantial 
direct compliance costs on those communities, unless the Federal 
government provides the funds necessary to pay the direct compliance 
costs incurred by the tribal governments, or we consult with those 
governments. If we comply by consulting, Executive Order 13094 requires 
us to provide to the Office of Management and Budget, in a separately 
identified section of the preamble to the rule, a description of the 
extent of our prior consultation with representatives of affected 
tribal governments, a summary of the nature of their concerns, and a 
statement supporting the need to issue the regulation. In addition, 
Executive Order 13084 requires us to develop an effective process 
permitting elected and other representatives of Indian tribal 
governments ``to provide meaningful and timely input in the development 
of regulatory policies on matters that significantly or uniquely affect 
their communities.'' Today's rule does not significantly or uniquely 
affect the communities of Indian tribal governments. This rule only 
amends regulatory requirements that are already in effect and adds no 
additional requirements. Accordingly, the requirements of Section 3(b) 
of Executive Order 13084 do not apply to this rule.

H. Executive Order 13045: Protection of Children From Environmental 
Health Risks and Safety Risks

    Executive Order 13045: ``Protection of Children from Environmental 
Health Risks and Safety Risks'' (62 FR 19885, April 23, 1997) applies 
to any rule that: (1) Is determined to be ``economically significant'' 
as defined under E.O. 12866, and (2) concerns an environmental health 
or safety risk that we have reason to believe may have a 
disproportionate effect on children. If the regulatory action meets 
both criteria, we must evaluate the environmental health or safety 
effects of the planned rule on children, and explain why the planned 
regulation is preferable to other potentially effective and reasonably 
feasible alternatives we considered.
    We interpret E.O. 13045 as applying only to those regulatory 
actions that are based on health or safety risks, such that the 
analysis required under section 5-501 of the Order has the potential to 
influence the regulation. This rule is not subject to E.O. 13045 
because it does not establish an environmental standard intended to 
mitigate health or safety risks.

I. Submission to Congress and the General Accounting Office

    The Congressional Review Act, 5 U.S.C. 801, et seq., as added by 
the Small Business Regulatory Enforcement Fairness Act of 1996, 
generally provides that before a rule may take effect, the agency 
promulgating the rule must submit a rule report, which includes a copy 
of the rule, to each House of the Congress and to the Comptroller 
General of the United States. We will submit a report containing this 
rule and other required information to the U.S. Senate, the U.S. House 
of Representatives, and the Comptroller General of the United States 
before it is published in the Federal Register. This action is not a 
``major rule'' as defined by 5 U.S.C. 804(2). This rule will be 
effective October 17, 2000.

J. National Technology Transfer and Advancement Act

    Section 12(d) of the National Technology Transfer and Advancement 
Act of 1995 (NTTAA), P.L. 104-113 (15 U.S.C. 272), directs us to use 
voluntary consensus standards (VCSs) in our regulatory activities 
unless to do so would be inconsistent with applicable law or otherwise 
impractical. Voluntary consensus standards are technical standards 
(e.g., materials specifications, test methods, sampling procedures, 
business practices, etc.) that are developed or adopted by VCS bodies.

[[Page 61749]]

The NTTAA requires us to provide Congress, through OMB, explanations 
when we decide not to use available and applicable VCSs.
    This rulemaking involves technical standards. Specifically, this 
rule makes technical corrections to portions of the subparts in Parts 
60, 61, and 63 pertaining to source testing or monitoring of emissions 
and operations. The rule does not, however, change the nature of any of 
the technical standards currently in use. Moreover, many of the 
technical standards currently in use are VCSs developed by the American 
Society for Testing and Materials (ASTM). In fact, we have taken the 
opportunity presented by this rulemaking to update the references to 
the ASTM standards to include the dates of the most recent versions of 
these standards (see Section III.A. of the preamble for a full 
discussion). A complete list of the ASTM standards updated by this rule 
can be found in Part 60.17. Thus, today's action is consistent with our 
obligation to use VCSs in our regulatory activities whenever 
practicable.
    Finally, we are promulgating PS-15, which identifies certification 
criteria for continuous emission monitoring systems (CEMS) using 
fourier transform infrared spectroscopy (FTIR). PS-15 is a performance 
specification that is being issued as an example procedure for use by 
industry and regulatory agencies as appropriate. While there are no 
underlying national EPA standards that will require the use of this 
procedure at this time, we conducted a search for VCS FTIR performance 
specifications and found none. We plan to periodically conduct 
rulemaking to make minor updates to test methods and performance 
specifications. In these rulemakings, we will review updates to VCS 
incorporated by reference and consider VCSs that may be used in lieu of 
EPA reference methods. We plan to provide the opportunity for public 
comment during these update rulemakings in part to allow VCS 
organizations to suggest where VCSs may be available for our use.

K. Plain Language in Government Writing

    This rule is not written in the plain language format. In most 
cases, the rule corrects errors and makes updates to small portions of 
existing regulations that are not in plain language. The new plain 
language format was not used to keep the language of the amended 
sections consistent with that of the unamended rules. Also, the test 
methods were reformatted and proposed before the plain language 
provisions were mandated. Due to their volume, the time and costs 
associated with the magnitude of effort required to rewrite the final 
methods in plain language is prohibitive. However, this preamble is 
written in plain language, and we believe the amendments and 
reformatted test methods have been written clearly.

List of Subjects

40 CFR Part 60

    Environmental protection, Administrative practice and procedure, 
Air pollution control, Continuous emission monitors, Incorporation by 
reference.

40 CFR Part 61

    Environmental protection, Air pollution control, Incorporation by 
reference.

40 CFR Part 63

    Environmental protection, Administrative practice and procedure, 
Air pollution control, Hazardous substances, Intergovernmental 
relations, Incorporation by reference, Reporting and recordkeeping 
requirements.

    Dated: January 10, 2000.
Carol M. Browner,
Administrator.

    For the reasons stated in the preamble, The Environmental 
Protection Agency amends title 40, chapter I of the Code of Federal 
Regulations as follows:

PART 60--STANDARDS OF PERFORMANCE FOR NEW STATIONARY SOURCES

    1. The authority citation for part 60 continues to read as follows:

    Authority: 42 U.S.C. 7401, 7411, 7413, 7414, 7416, 7601, and 
7602.


Sec. 60.11  [Amended]

    2. Amend Sec. 60.11 by:
    a. In paragraphs (b) and (e)(1), by revising the words ``Reference 
Method 9'' to read ``Method 9'' wherever they occur;
    b. In paragraph (e)(5), revise the words ``to determine opacity 
compliance'' in the last sentence to read ``to determine compliance 
with the opacity standard.''


Sec. 60.13  [Amended]

    3. Amend Sec. 60.13 by:
    a. Revising the last two sentences in paragraph (d)(1), revising 
paragraph (g), and revising the first sentence in paragraph (j)(2).
    b. Revising the words ``ng/J of pollutant'' to read ``ng of 
pollutant per J of heat input'' in the sixth sentence of paragraph (h).
    c. Revising the words ``with the effluent gases'' to read ``in the 
effluent gases'' in paragraph (i)(1).
    d. Revising the words ``effluent from two or more affected 
facilities are released'' to read ``effluent from two or more affected 
facilities is released'' in paragraph (i)(9).
    e. Revising the words ``relative accuracy test'' to read ``relative 
accuracy (RA) test'' in the paragraph (j) introductory text.
    f. Revising the words ``relative accuracy'' to read ``RA'' in 
paragraphs (j)(1) and (2).
    g. Revising the section references ``section 7'' and ``section 10'' 
to read ``Section 8.4'' and ``Section 16.0,'' respectively, in 
paragraphs (j)(1) and (2).
    The revisions read as follows:


Sec. 60.13  Monitoring requirements.

* * * * *
    (d) * * *
    (1) * * * For continuous monitoring systems measuring opacity of 
emissions not using automatic zero adjustments, the optical surfaces 
exposed to the effluent gases shall be cleaned prior to performing the 
zero and span drift adjustments. For systems using automatic zero 
adjustments, the optical surfaces shall be cleaned when the cumulative 
automatic zero compensation exceeds 4 percent opacity.
* * * * *
    (g)(1) When more than one continuous monitoring system is used to 
measure the emissions from only one affected facility (e.g., multiple 
breechings, multiple outlets), the owner or operator shall report the 
results as required from each continuous monitoring system. When the 
effluent from one affected facility is released to the atmosphere 
through more than one point, the owner or operator shall install an 
applicable continuous monitoring system on each separate effluent 
unless installation of fewer systems is approved by the Administrator.
    (2) When the effluents from two or more affected facilities subject 
to the same opacity standard are combined before being released to the 
atmosphere, the owner or operator may either install a continuous 
opacity monitoring system at a location monitoring the combined 
effluent or install an opacity combiner system comprised of opacity and 
flow monitoring systems on each stream, and shall report as per 
Sec. 60.7(c) on the combined effluent. When the affected facilities are 
not subject to the same opacity standard, the owner or operator shall 
report the results as per Sec. 60.7(c) on the combined effluent against 
the most stringent opacity standard

[[Page 61750]]

applicable, except for documented periods of shutdown of the affected 
facility, subject to the most stringent opacity standard. During such 
times, the next most stringent opacity standard shall apply.
    (3) When the effluents from two or more affected facilities subject 
to the same emissions standard, other than opacity, are combined before 
being released to the atmosphere, the owner or operator may install 
applicable continuous emission monitoring systems on each effluent or 
on the combined effluent. The owner or operator may report the results 
as required for each affected facility or for the combined effluent. 
When the affected facilities are not subject to the same emissions 
standard, separate continuous emission monitoring systems shall be 
installed on each effluent and the owner or operator shall report as 
required for each affected facility.
* * * * *
    (j) * * *
    (2) The waiver of a CEMS RA test will be reviewed and may be 
rescinded at such time, following successful completion of the 
alternative RA procedure, that the CEMS data indicate that the source 
emissions are approaching the level. * * *
* * * * *


Sec. 60.14  [Amended]

    4. In Sec. 60.14, paragraph (b)(1) is amended by revising the words 
``utilization of emission factors demonstrate'' to read ``utilization 
of emission factors demonstrates.''


Sec. 60.17  [Amended]

    5. Amend Sec. 60.17 by:
    a. Revising paragraphs (a), (i), and (j).
    b. In paragraph (b)(1), revise the words ``Secs. 60.204(d)(2), 
60.214(d)(2), 60.224(d)(2), 60.234(d)(2)'' to read 
``Secs. 60.204(b)(3), 60.214(b)(3), 60.224(b)(3), 60.234(b)(3).''
    c. In paragraph (d), by revising the words ``IBR approved January 
27, 1983 for Sec. 60.285(d)(4)'' to read ``IBR approved January 27, 
1983 for Sec. 60.285(d)(3).''
    The revisions read as follows:


Sec. 60.17  Incorporation by reference.

* * * * *
    (a) The following materials are available for purchase from at 
least one of the following addresses: American Society for Testing and 
Materials (ASTM), 1916 Race Street, Philadelphia, PA 19103; or 
University Microfilms International, 300 North Zeeb Road, Ann Arbor, MI 
48106.
    (1) ASTM A99-76, 82 (Reapproved 1987), Standard Specification for 
Ferromanganese, incorporation by reference (IBR) approved January 27, 
1983 for Sec. 60.261.
    (2) ASTM A100-69, 74, 93, Standard Specification for Ferrosilicon, 
IBR approved January 27, 1983 for Sec. 60.261.
    (3) ASTM A101-73, 93, Standard Specification for Ferrochromium, IBR 
approved January 27, 1983 for Sec. 60.261.
    (4) ASTM A482-76, 93, Standard Specification for 
Ferrochromesilicon, IBR approved January 27, 1983 for Sec. 60.261.
    (5) ASTM A483-64, 74 (Reapproved 1988), Standard Specification for 
Silicomanganese, IBR approved January 27, 1983 for Sec. 60.261.
    (6) ASTM A495-76, 94, Standard Specification for Calcium-Silicon 
and Calcium Manganese-Silicon, IBR approved January 27, 1983 for 
Sec. 60.261.
    (7) ASTM D86-78, 82, 90, 93, 95, 96, Distillation of Petroleum 
Products, IBR approved for Secs. 60.562-2(d), 60.593(d), and 60.633(h).
    (8) ASTM D129-64, 78, 95, Standard Test Method for Sulfur in 
Petroleum Products (General Bomb Method), IBR approved for Appendix A: 
Method 19, Section 12.5.2.2.3; and Sec. 60.106(j)(2).
    (9) ASTM D240-76, 92, Standard Test Method for Heat of Combustion 
of Liquid Hydrocarbon Fuels by Bomb Calorimeter, IBR approved January 
27, 1983 for Secs. 60.46(c), 60.296(b), and Appendix A: Method 19, 
Section 12.5.2.2.3.
    (10) ASTM D270-65, 75, Standard Method of Sampling Petroleum and 
Petroleum Products, IBR approved January 27, 1983 for Appendix A: 
Method 19, Section 12.5.2.2.1.
    (11) ASTM D323-82, 94, Test Method for Vapor Pressure of Petroleum 
Products (Reid Method), IBR approved April 8, 1987 for Secs. 60.111(l), 
60.111a(g), 60.111b(g), and 60.116b(f)(2)(ii).
    (12) ASTM D388-77, 90, 91, 95, 98, 98a, Standard Specification for 
Classification of Coals by Rank, IBR approved for Secs. 60.41(f), 
60.45(f)(4)(i), 60.45(f)(4)(ii), 60.45(f)(4)(vi), 60.41a, 60.41b, and 
60.251(b) and (c).
    (13) ASTM D396-78, 89, 90, 92, 95, 96, 97, 98, Standard 
Specification for Fuel Oils, IBR approved for Secs. 60.41b, 60.41c, 
60.111(b), and 60.111a(b).
    (14) ASTM D975-78, 96, 98, 98a, Standard Specification for Diesel 
Fuel Oils, IBR approved January 27, 1983 for Secs. 60.111(b) and 
60.111a(b).
    (15) ASTM D1072-80, 90 (Reapproved 1994), Standard Method for Total 
Sulfur in Fuel Gases, IBR approved July 31, 1984 for Sec. 60.335(d).
    (16) ASTM D1137-53, 75, Standard Method for Analysis of Natural 
Gases and Related Types of Gaseous Mixtures by the Mass Spectrometer, 
IBR approved January 27, 1983 for Sec. 60.45(f)(5)(i).
    (17) ASTM D1193-77, 91, Standard Specification for Reagent Water, 
IBR approved for Appendix A: Method 5, Section 7.1.3; Method 5E, 
Section 7.2.1; Method 5F, Section 7.2.1; Method 6, Section 7.1.1; 
Method 7, Section 7.1.1; Method 7C, Section 7.1.1; Method 7D, Section 
7.1.1; Method 10A, Section 7.1.1; Method 11, Section 7.1.3; Method 12, 
Section 7.1.3; Method 13A, Section 7.1.2; Method 26, Section 7.1.2; 
Method 26A, Section 7.1.2; and Method 29, Section 7.2.2.
    (18) ASTM D1266-87, 91, 98, Standard Test Method for Sulfur in 
Petroleum Products (Lamp Method), IBR approved August 17, 1989 for 
Sec. 60.106(j)(2).
    (19) ASTM D1475-60, 80, 90, Standard Test Method for Density of 
Paint, Varnish Lacquer, and Related Products, IBR approved January 27, 
1983 for Sec. 60.435(d)(1), Appendix A: Method 24, Section 6.1; and 
Method 24A, Sections 6.5 and 7.1.
    (20) ASTM D1552-83, 95, Standard Test Method for Sulfur in 
Petroleum Products (High Temperature Method), IBR approved for Appendix 
A: Method 19, Section 12.5.2.2.3; and Sec. 60.106(j)(2).
    (21) ASTM D1826-77, 94, Standard Test Method for Calorific Value of 
Gases in Natural Gas Range by Continuous Recording Calorimeter, IBR 
approved January 27, 1983 for Secs. 60.45(f)(5)(ii), 60.46(c)(2), 
60.296(b)(3), and Appendix A: Method 19, Section 12.3.2.4.
    (22) ASTM D1835-82, 86, 87, 91, 97, Standard Specification for 
Liquefied Petroleum (LP) Gases, approved for Secs. 60.41b and 60.41c.
    (23) ASTM D1945-64, 76, 91, 96, Standard Method for Analysis of 
Natural Gas by Gas Chromatography, IBR approved January 27, 1983 for 
Sec. 60.45(f)(5)(i).
    (24) ASTM D1946-77, 90 (Reapproved 1994), Standard Method for 
Analysis of Reformed Gas by Gas Chromatography, IBR approved for 
Secs. 60.45(f)(5)(i), 60.18(f)(3), 60.614(e)(2)(ii), 60.614(e)(4), 
60.664(e)(2)(ii), 60.664(e)(4), 60.564(f)(1), 60.704(d)(2)(ii), and 
60.704(d)(4).
    (25) ASTM D2013-72, 86, Standard Method of Preparing Coal Samples 
for Analysis, IBR approved January 27, 1983, for Appendix A: Method 19, 
Section 12.5.2.1.3.
    (26) ASTM D2015-77 (Reapproved 1978), 96, Standard Test Method for 
Gross Calorific Value of Solid Fuel by the Adiabatic Bomb Calorimeter, 
IBR

[[Page 61751]]

approved January 27, 1983 for Sec. 60.45(f)(5)(ii), 60.46(c)(2), and 
Appendix A: Method 19, Section 12.5.2.1.3.
    (27) ASTM D2016-74, 83, Standard Test Methods for Moisture Content 
of Wood, IBR approved for Appendix A: Method 28, Section 16.1.1.
    (28) ASTM D2234-76, 96, 97a, 97b, 98, Standard Methods for 
Collection of a Gross Sample of Coal, IBR approved January 27, 1983 for 
Appendix A: Method 19, Section 12.5.2.1.1.
    (29) ASTM D2369-81, 87, 90, 92, 93, 95, Standard Test Method for 
Volatile Content of Coatings, IBR approved January 27, 1983 for 
Appendix A: Method 24, Section 6.2.
    (30) ASTM D2382-76, 88, Heat of Combustion of Hydrocarbon Fuels by 
Bomb Calorimeter (High-Precision Method), IBR approved for 
Secs. 60.18(f)(3), 60.485(g)(6), 60.614(e)(4), 60.664(e)(4), 
60.564(f)(3), and 60.704(d)(4).
    (31) ASTM D2504-67, 77, 88 (Reapproved 1993), Noncondensable Gases 
in C3 and Lighter Hydrocarbon Products by Gas 
Chromatography, IBR approved for Sec. 60.485(g)(5).
    (32) ASTM D2584-68 (Reapproved 1985), 94, Standard Test Method for 
Ignition Loss of Cured Reinforced Resins, IBR approved February 25, 
1985 for Sec. 60.685(c)(3)(i).
    (33) ASTM D2622-87, 94, 98, Standard Test Method for Sulfur in 
Petroleum Products by X-Ray Spectrometry, IBR approved August 17, 1989 
for Sec. 60.106(j)(2).
    (34) ASTM D2879-83, 96, 97, Test Method for Vapor Pressure-
Temperature Relationship and Initial Decomposition Temperature of 
Liquids by Isoteniscope, IBR approved April 8, 1987 for 
Secs. 60.485(e)(1), 60.111b(f)(3), 60.116b(e)(3)(ii), and 
60.116b(f)(2)(i).
    (35) ASTM D2880-78, 96, Standard Specification for Gas Turbine Fuel 
Oils, IBR approved January 27, 1983 for Secs. 60.111(b), 60.111a(b), 
and 60.335(d).
    (36) ASTM D2908-74, 91, Standard Practice for Measuring Volatile 
Organic Matter in Water by Aqueous-Injection Gas Chromatography, IBR 
approved for Sec. 60.564(j).
    (37) ASTM D2986-71, 78, 95a, Standard Method for Evaluation of Air, 
Assay Media by the Monodisperse DOP (Dioctyl Phthalate) Smoke Test, IBR 
approved January 27, 1983 for Appendix A: Method 5, Section 7.1.1; 
Method 12, Section 7.1.1; and Method 13A, Section 7.1.1.2.
    (38) ASTM D3031-81, Standard Test Method for Total Sulfur in 
Natural Gas by Hydrogenation, IBR approved July 31, 1984 for 
Sec. 60.335(d).
    (39) ASTM D3173-73, 87, Standard Test Method for Moisture in the 
Analysis Sample of Coal and Coke, IBR approved January 27, 1983 for 
Appendix A: Method 19, Section 12.5.2.1.3.
    (40) ASTM D3176-74, 89, Standard Method for Ultimate Analysis of 
Coal and Coke, IBR approved January 27, 1983 for Sec. 60.45(f)(5)(i) 
and Appendix A: Method 19, Section 12.3.2.3.
    (41) ASTM D3177-75, 89, Standard Test Method for Total Sulfur in 
the Analysis Sample of Coal and Coke, IBR approved January 27, 1983 for 
Appendix A: Method 19, Section 12.5.2.1.3.
    (42) ASTM D3178-73 (Reapproved 1979), 89, Standard Test Methods for 
Carbon and Hydrogen in the Analysis Sample of Coal and Coke, IBR 
approved January 27, 1983 for Sec. 60.45(f)(5)(i).
    (43) ASTM D3246-81, 92, 96, Standard Method for Sulfur in Petroleum 
Gas by Oxidative Microcoulometry, IBR approved July 31, 1984 for 
Sec. 60.335(d).
    (44) ASTM D3270-73T, 80, 91, 95, Standard Test Methods for Analysis 
for Fluoride Content of the Atmosphere and Plant Tissues (Semiautomated 
Method), IBR approved for Appendix A: Method 13A, Section 16.1.
    (45) ASTM D3286-85, 96, Standard Test Method for Gross Calorific 
Value of Coal and Coke by the Isoperibol Bomb Calorimeter, IBR approved 
for Appendix A: Method 19, Section 12.5.2.1.3.
    (46) ASTM D3370-76, 95a, Standard Practices for Sampling Water, IBR 
approved for Sec. 60.564(j).
    (47) ASTM D3792-79, 91, Standard Method for Water Content of Water-
Reducible Paints by Direct Injection into a Gas Chromatograph, IBR 
approved January 27, 1983 for Appendix A: Method 24, Section 6.3.
    (48) ASTM D4017-81, 90, 96a, Standard Test Method for Water in 
Paints and Paint Materials by the Karl Fischer Titration Method, IBR 
approved January 27, 1983 for Appendix A: Method 24, Section 6.4.
    (49) ASTM D4057-81, 95, Standard Practice for Manual Sampling of 
Petroleum and Petroleum Products, IBR approved for Appendix A: Method 
19, Section 12.5.2.2.3.
    (50) ASTM D4084-82, 94, Standard Method for Analysis of Hydrogen 
Sulfide in Gaseous Fuels (Lead Acetate Reaction Rate Method), IBR 
approved July 31, 1984 for Sec. 60.335(d).
    (51) ASTM D4177-95, Standard Practice for Automatic Sampling of 
Petroleum and Petroleum Products, IBR approved for Appendix A: Method 
19, 12.5.2.2.1.
    (52) ASTM D4239-85, 94, 97, Standard Test Methods for Sulfur in the 
Analysis Sample of Coal and Coke Using High Temperature Tube Furnace 
Combustion Methods, IBR approved for Appendix A: Method 19, Section 
12.5.2.1.3.
    (53) ASTM D4442-84, 92, Standard Test Methods for Direct Moisture 
Content Measurement in Wood and Wood-base Materials, IBR approved for 
Appendix A: Method 28, Section 16.1.1.
    (54) ASTM D4444-92, Standard Test Methods for Use and Calibration 
of Hand-Held Moisture Meters, IBR approved for Appendix A: Method 28, 
Section 16.1.1.
    (55) ASTM D4457-85 (Reapproved 1991), Test Method for Determination 
of Dichloromethane and 1, 1, 1-Trichloroethane in Paints and Coatings 
by Direct Injection into a Gas Chromatograph, IBR approved for Appendix 
A: Method 24, Section 6.5.
    (56) ASTM D4809-95, Standard Test Method for Heat of Combustion of 
Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision Method), IBR 
approved for Secs. 60.18(f)(3), 60.485(g)(6), 60.564(f)(3), 
60.614(d)(4), 60.664(e)(4), and 60.704(d)(4).
    (57) ASTM D5403-93, Standard Test Methods for Volatile Content of 
Radiation Curable Materials. IBR approved September 11, 1995 for 
Appendix A: Method 24, Section 6.6.
    (58) ASTM D5865-98, Standard Test Method for Gross Calorific Value 
of Coal and Coke. IBR approved for Sec. 60.45(f)(5)(ii), 60.46(c)(2), 
and Appendix A: Method 19, Section 12.5.2.1.3.
    (59) ASTM E168-67, 77, 92, General Techniques of Infrared 
Quantitative Analysis, IBR approved for Secs. 60.593(b)(2) and 
60.632(f).
    (60) ASTM E169-63, 77, 93, General Techniques of Ultraviolet 
Quantitative Analysis, IBR approved for Secs. 60.593(b)(2) and 
60.632(f).
    (61) ASTM E260-73, 91, 96, General Gas Chromatography Procedures, 
IBR approved for Secs. 60.593(b)(2) and 60.632(f).
* * * * *
    (i) Test Methods for Evaluating Solid Waste, Physical/Chemical 
Methods,'' EPA Publication SW-846 Third Edition (November 1986), as 
amended by Updates I (July 1992), II (September 1994), IIA (August, 
1993), IIB (January 1995), and III (December 1996). This document may 
be obtained from the U.S. EPA, Office of Solid Waste and Emergency 
Response, Waste Characterization Branch, Washington, DC 20460, and is 
incorporated by reference for Appendix A to Part 60,

[[Page 61752]]

Method 29, Sections 7.5.34; 9.2.1; 9.2.3; 10.2; 10.3; 11.1.1; 11.1.3; 
13.2.1; 13.2.2; 13.3.1; and Table 29-3.
    (j) ``Standard Methods for the Examination of Water and 
Wastewater,'' 16th edition, 1985. Method 303F: ``Determination of 
Mercury by the Cold Vapor Technique.'' This document may be obtained 
from the American Public Health Association, 1015 18th Street, NW., 
Washington, DC 20036, and is incorporated by reference for Appendix A 
to Part 60, Method 29, Sections 9.2.3; 10.3; and 11.1.3.
* * * * *


Sec. 60.18  [Amended]

    6. Amend Sec. 60.18 as follows:
    a. In paragraph (f)(1), the first sentence is amended by revising 
``Reference Method 22'' to read ``Method 22 of Appendix A to this 
part.''
    b. In paragraph (f)(3), the definition of ``Ci'' is 
amended by revising ``ASTM D1946-77'' to read ``ASTM D1946-77 or 90 
(Reapproved 1994).''
    c. In paragraph (f)(3), the definition of ``Hi'' is 
amended by revising ``ASTM D2382-76'' to read ``ASTM D2382-76 or 88 or 
D4809-95.''


Sec. 60.41  [Amended]

    7. In Sec. 60.41, paragraph (f) is amended by revising the words 
``the American Society and Testing and Materials, Designation D388-77'' 
to read ``ASTM D388-77, 90, 91, 95, or 98a.''


Sec. 60.42  [Amended]

    8. In Sec. 60.42, paragraphs (b)(1) and (b)(2), are amended by 
removing the symbol ``%'' wherever it appears, and adding ``percent'' 
in its place.


Sec. 60.45  [Amended]

    9. Amend Sec. 60.45 as follows:
    a. In paragraph (b)(2) by removing the words ``under paragraph (d) 
of this section.''
    b. In paragraphs (f)(4)(i), (f)(4)(ii), and (f)(4)(vi) by revising 
the words ``ASTM D388-77'' to read ``ASTM D388-77, 90, 91, 95, or 
98a.''
    c. In paragraph (f)(5)(i) by revising the words ``ASTM method 
D1137-53, (75), D1945-64(76), or D1946-77'' to read ``ASTM D1137-53 or 
75, D1945-64, 76, 91, or 96 or D1946-77 or 90 (Reapproved 1994).''
    d. In paragraph (f)(5)(i) by revising the words ``ASTM method 
D3178-74 or D3176'' to read ``ASTM D3178-73 (Reapproved 1979), 89, or 
D3176-74 or 89.''
    e. In paragraph (f)(5)(ii) by revising the words ``ASTM D1826-77'' 
to read ``ASTM D1826-77 or 94.''
    f. In paragraph (f)(5)(ii) by revising the words ``ASTM D2015-77'' 
to read ``ASTM D2015-77 (Reapproved 1978), 96, or D5865-98.''


Sec. 60.46  [Amended]

    10. Amend Sec. 60.46 as follows:
    a. In paragraph (b)(2)(i), the second sentence is amended by 
revising the words ``in the sampling train may be set to provide a gas 
temperature no greater than'' to read ``in the sampling train shall be 
set to provide an average gas temperature of.''
    b. In paragraph (b)(2)(ii), the third sentence is amended by 
revising the words ``the arithmetic mean of all the individual 
O2 sample concentrations at each traverse point'' to read 
``the arithmetic mean of the sample O2 concentrations at all 
traverse points.''
    c. Paragraph (c)(2) is amended by revising the words ``D2015-77'' 
to read ``D2015-77 (Reapproved 1978), 96, or D5865-98''.
    d. Paragraph (c)(2) is further amended by revising the words 
``D240-76'' to read ``D240-76 or 92.''
    e. In paragraph (c)(2) is further amended by revising the words 
``D1826-77'' to read ``D1826-77 or 94.''


Sec. 60.41a  [Amended]

    11. Amend Sec. 60.41a as follows:
    a. In the definitions for ``subbituminous coal'' and ``lignite,'' 
by revising ``D388-77'' to read ``D388-77, 90, 91, 95, or 98a.''
    b. In paragraph (a)(2) of the definition of ``potential combustion 
concentration'' by revising ``75 ng/J'' to read ``73 ng/J.''


Sec. 60.43a  [Amended]

    12. In Sec. 60.43a, paragraph (d)(2), revising the words ``resource 
recovery facility'' to read ``resource recovery unit.''


Sec. 60.47a  [Amended]

    13. Amend Sec. 60.47a as follows:
    a. In paragraph (b)(3) by removing the words ``(appendix A).''
    b. In the first sentence of paragraph (g) by revising the words 
``lbs/million Btu'' to read ``lb/million Btu.''
    c. In the second sentence of paragraph (h)(3) by revising the words 
``309 minutes in each hour'' to read ``30 minutes in each hour.''
    d. In paragraph (i)(1) by revising the words ``6, 7, and 3B, as 
applicable, shall be used to determine O2, SO2, 
and NOX concentrations'' to read ``3B, 6, and 7 shall be 
used to determine O2, SO2, and NOX 
concentrations, respectively.''


Sec. 60.48a  [Amended]

    14. Amend Sec. 60.48a as follows:
    a. In paragraph (b)(2)(ii), in the fourth sentence by revising the 
words ``the arithmetic mean of all the individual O2 
concentrations at each traverse point.'' to read ``the arithmetic mean 
of the sample O2 concentrations at all traverse points.''
    b. In paragraph (c)(3), in the first sentence by adding a closing 
parenthesis after the abbreviation ``(%Rg'' so that it now 
reads ``(%Rg)''.
    c. In paragraph (f), in the first and second sentences by removing 
the words ``(appendix A).''


Sec. 60.40b  [Amended]

    15. Sec. 60.40b is amended by adding paragraph (j) as follows:


Sec. 60.40b  Applicability and delegation of authority.

* * * * *
    (j) Any affected facility meeting the applicability requirements 
under paragraph (a) of this section and commencing construction, 
modification, or reconstruction after June 19, 1986 is not subject to 
Subpart D (Standards of Performance for Fossil-Fuel-Fired Steam 
Generators, Sec. 60.40).
* * * * *


Sec. 60.41b  [Amended]

    16. Amend Sec. 60.41b as follows:
    a. In the definition for ``coal'' by revising ``ASTM D388-77'' to 
read ``ASTM D388-77, 90, 91, 95, or 98a.''
    b. In the definition for ``distillate oil'' by revising ``ASTM 
D396-78'' to read ``ASTM D396-78, 89, 90, 92, 96, or 98.''
    c. In the definition for ``lignite'' by revising ``ASTM D388-77'' 
to read ``ASTM D388-77, 90, 91, 95, or 98a.''
    d. In the definition for ``natural gas'' by revising ``ASTM D1835-
82'' to read ``ASTM D1835-82, 86, 87, 91, or 97.''


Sec. 60.42b  [Amended]

    17. In Sec. 60.42b, paragraph (d), the second sentence is amended 
by revising the words ``facilities under this paragraph'' to read 
``facilities under paragraphs (d)(1), (2), or (3).''


Sec. 60.43b  [Amended]

    18. In Sec. 60.43b, paragraph (a)(1) is amended by revising the 
words ``22 ng/J (0.05 lb/million Btu)'' to read ``22 ng/J (0.051 lb/
million Btu).''


Sec. 60.46b  [Amended]

    19. Amend Sec. 60.46b as follows:
    a. In paragraph (d)(4) by revising the words ``160  deg.C (320 
deg.F)'' to read ``16014  deg.C (32025 
deg.F).''
    b. In paragraph (d)(6)(iii) by removing the words ``(appendix A).''


Sec. 60.41c  [Amended]

    20. Amend Sec. 60.41c as follows:
    a. In the definition for ``natural gas'' by revising ``D1835-86'' 
to read ``D1835-86, 87, 91, or 97.''

[[Page 61753]]

    b. In the definitions for ``distillate oil'' and ``residual oil'' 
by revising ``D396-78'' to read ``D396-78, 89, 90, 92, 96, or 98.''


Sec. 60.42c  [Amended]

    21. Amend Sec. 60.42c as follows:
    a. In paragraph (a), in the first sentence by revising the words 
``the owner the operator'' to read ``the owner or operator.''
    b. In paragraph (c), in the second sentence by revising the words 
``facilities under this paragraph'' to read ``facilities under 
paragraphs (c)(1), (2), (3), or (4).''


Sec. 60.43c  [Amended]

    22. In Sec. 60.43c, paragraph (a)(1) is amended by revising the 
words ``22 ng/J (0.05 lb/million Btu)'' to read ``22 ng/J (0.051 lb/
million Btu).''


Sec. 60.44c  [Amended]

    23. In Sec. 60.44c, paragraph (i), the third sentence is amended by 
revising the words ``24-hour averaged'' to read ``24-hour average.''


Sec. 60.45c  [Amended]

    24. Amend Sec. 60.45c as follows:
    a. Redesignate paragraphs (a)(5) through (a)(7) as paragraphs 
(a)(6) through (a)(8), respectively.
    b. Revise paragraphs (a)(1) through (a)(4) and add paragraph 
(a)(5).
    The redesignation, revisions and addition read as follows:


Sec. 60.45c  Compliance and performance test methods and procedures for 
particulate matter.

    (a) * * *
    (1) Method 1 shall be used to select the sampling site and the 
number of traverse sampling points.
    (2) Method 3 shall be used for gas analysis when applying Method 5, 
Method 5B, or Method 17.
    (3) Method 5, Method 5B, or Method 17 shall be used to measure the 
concentration of PM as follows:
    (i) Method 5 may be used only at affected facilities without wet 
scrubber systems.
    (ii) Method 17 may be used at affected facilities with or without 
wet scrubber systems provided the stack gas temperature does not exceed 
a temperature of 160  deg.C (320  deg.F). The procedures of Sections 
8.1 and 11.1 of Method 5B may be used in Method 17 only if Method 17 is 
used in conjunction with a wet scrubber system. Method 17 shall not be 
used in conjunction with a wet scrubber system if the effluent is 
saturated or laden with water droplets.
    (iii) Method 5B may be used in conjunction with a wet scrubber 
system.
    (4) The sampling time for each run shall be at least 120 minutes 
and the minimum sampling volume shall be 1.7 dry standard cubic meters 
(dscm) [60 dry standard cubic feet (dscf)] except that smaller sampling 
times or volumes may be approved by the Administrator when necessitated 
by process variables or other factors.
    (5) For Method 5 or Method 5B, the temperature of the sample gas in 
the probe and filter holder shall be monitored and maintained at 
16014  deg.C (32025  deg.F).
* * * * *


Sec. 60.46c  [Amended]

    25. In Sec. 60.46c, paragraphs (b) and (d) are amended by revising 
the abbreviation ``CEM'' to read ``CEMS'' wherever it appears.


Sec. 60.47c  [Amended]

    26. In Sec. 60.47c, paragraphs (a) and (b) are amended by revising 
the abbreviation ``CEMS'' to read ``COMS'' wherever it appears.


Sec. 60.48c  [Amended]

    27. In Sec. 60.48c, paragraph (b) is amended by replacing the 
abbreviation ``CEMS'' with the words ``CEMS and/or COMS.''


Sec. 60.52  [Amended]

    28. In Sec. 60.52, paragraph (a) is amended by revising the words 
``the performance test required to be conducted by Sec. 60.8 is 
completed'' to read ``the initial performance test is completed or 
required to be completed under Sec. 60.8 of this part, whichever date 
comes first.''


Sec. 60.54  [Amended]

    29. Amend Sec. 60.54 as follows:
    a. In paragraph (b)(1) by revising the words ``The emission rate 
(c12)'' to read ``The concentration (c12).''
    b. In paragraph (b)(3)(i), in the third sentence by revising the 
words ``the arithmetic mean of all the individual CO2 sample 
concentrations at each traverse point'' to read ``the arithmetic mean 
of the sample CO2 concentrations at all traverse points.''


Sec. 60.51a  [Amended]

    30. Section 60.51a is amended by adding a new difinition in 
alphabetical order to read as follows:


Sec. 60.51a  Definitions.

* * * * *
    Continuous monitoring system means the total equipment used to 
sample and condition (if applicable), to analyze, and to provide a 
permanent record of emissions or process parameters.
* * * * *


Sec. 60.58a  [Amended]

    31. Amend Sec. 60.58a as follows:
    a. In paragraph (b)(3), in the first sentence by revising the words 
``particulate matter emission standard'' to read ``particulate matter 
emission limit.''
    b. In paragraph (b)(3), in the third sentence by revising the words 
``a gas temperature no greater than'' to read ``a gas temperature of.''
    c. In paragraph (b)(8) by revising the words ``operate a CEMS for 
measuring opacity'' to read ``operate a continuous opacity monitoring 
system (COMS).''
    d. In paragraph (e)(10) by revising the word ``Section'' to read 
``section.''
    e. In paragraph (e)(14) by revising the words ``outlet to'' to read 
``outlet of.''
    f. In paragraph (f)(2) by revising the words ``Method 26'' to read 
``Method 26 or 26A.''


Sec. 60.58b  [Amended]

    32-36. Amend Sec. 60.58b as follows:
    a. In paragraph (b)(1) by revising the words ``(or carbon 
dioxide)'' to read ``(or 20 percent carbon dioxide)'' each place it 
appears.
    b. In paragraph (f)(1), in the second sentence by removing the 
words ``for Method 26.''
    c. In paragraph (f)(2) by removing the words ``Method 26.''


Sec. 60.56c  [Amended]

    37. Amend Sec. 60.56c as follows:
    a. In paragraph (b)(4), in the first and second sentences by 
revising the words ``Method 3 or 3A'' to read ``Method 3, 3A, or 3B.''
    b. In paragraph (b)(10), in the first sentence by revising the 
words ``Method 26'' to read ``Method 26 or 26A.''


Sec. 60.64  [Amended]

    38. Amend Sec. 60.64(b)(1) as follows:
    a. In the definition of the term ``cs'', ``(g/dscf)'' is 
revised to read ``(gr/dscf).''
    b. In the definition of the term ``K'', ``(453.6 g/lb)'' is revised 
to read ``(7000 gr/lb).''


Sec. 60.84  [Amended]

    39. Amend Sec. 60.84 as follows:
    a. In paragraph (d), in the third sentence by revising the words 
``monitoring of'' to read ``monitoring systems for measuring.''
    b. In paragraph (d), in the fourth sentence by revising the words 
``this SO2'' to read ``the SO2.''


Sec. 60.102  [Amended]

    40. In Sec. 60.102, paragraph (a)(1) is amended by revising the 
words ``1.0 kg/

[[Page 61754]]

1000 kg (1.0 lb/1000 lb)'' to read ``1.0 kg/Mg (2.0 lb/ton).


Sec. 60.104  [Amended]

    41. In Sec. 60.104, paragraph (b)(2) is amended by revising the 
words ``9.8 kg/1,000 kg'' to read ``9.8 kg/Mg (20 lb/ton).''


Sec. 60.105  [Amended]

    42. Amend Sec. 60.105 by:
    a. In paragraphs (a)(3)(iii) and (a)(5)(ii), the words ``Methods 6 
and 3'' in the second sentence are revised to read ``Methods 6 or 6C 
and 3 or 3A.''
    b. In paragraph (a)(4)(iii), the words ``Method 11 shall be used 
for conducting the relative accuracy evaluations'' are revised to read 
``Method 11, 15, 15A, or 16 shall be used for conducting the relative 
accuracy evaluations.''
    c. In paragraphs (a)(3)(i), (a)(5)(i), (a)(6)(i), and (a)(7)(i), 
``10'' is revised to read ``25.''
    d. In paragraph (a)(6)(ii), the first sentence and paragraphs 
(a)(8), (a)(9), and (a)(12) are revised.
    e. In paragraph (a)(10), the abbreviation ``vppm'' is revised to 
read ``ppmv''.
    f. In paragraph (c), ``(thousands of kilograms per hour)'' is 
revised to read ``(Mg (tons) per hour).''
    g. In paragraph (d), the words ``(liters/hr or kg/hr)'' are 
removed.
    The revisions read as follows:


Sec. 60.105  Monitoring of emissions and operations.

    (a) * * *
    (6) * * *
    (ii) The performance evaluations for this reduced sulfur (and 
O2) monitor under Sec. 60.13(c) shall use Performance 
Specification 5 of Appendix B of this Part (and Performance 
Specification 3 of Appendix B of this Part for the O2 
analyzer). * * *
* * * * *
    (8) An instrument for continuously monitoring and recording 
concentrations of SO2 in the gases at both the inlet and 
outlet of the SO2 control device from any fluid catalytic 
cracking unit catalyst regenerator for which the owner or operator 
seeks to comply with Sec. 60.104 (b)(1).
    (i) The span value of the inlet monitor shall be set 125 percent of 
the maximum estimated hourly potential SO2 emission 
concentration entering the control device, and the span value of the 
outlet monitor shall be set at 50 percent of the maximum estimated 
hourly potential sulfur dioxide emission concentration entering the 
control device.
    (ii) The performance evaluations for these SO2 monitors 
under Sec. 60.13(c) shall use Performance Specification 2. Methods 6 or 
6C and 3 or 3A shall be used for conducting the relative accuracy 
evaluations.
    (9) An instrument for continuously monitoring and recording 
concentrations of SO2 in the gases discharged into the 
atmosphere from any fluid catalytic cracking unit catalyst regenerator 
for which the owner or operator seeks to comply specifically with the 
50 ppmv emission limit under Sec. 60.104 (b)(1).
    (i) The span value of the monitor shall be set at 50 percent of the 
maximum hourly potential SO2 emission concentration of the 
control device.
    (ii) The performance evaluations for this SO2 monitor 
under Sec. 60.13 (c) shall use Performance Specification 2. Methods 6 
or 6C and 3 or 3A shall be used for conducting the relative accuracy 
evaluations.
* * * * *
    (12) The owner or operator shall use the following procedures to 
evaluate the continuous monitoring systems under paragraphs (a)(8), 
(a)(9), and (a)(10) of this section.
    (i) Method 3 or 3A and Method 6 or 6C for the relative accuracy 
evaluations under the Sec. 60.13(e) performance evaluation.
    (ii) Appendix F, Procedure 1, including quarterly accuracy 
determinations and daily calibration drift tests.
* * * * *


Sec. 60.106  [Amended]

    43. Amend Sec. 60.106 by:

    a. In paragraphs (b)(1), (b)(3), (c)(1), (i)(9) by revising the 
equations and definitions.
    b. In paragraph (b)(3)(ii) by revising the words ``Method 3'' to 
read ``Method 3B.''
    c. Revising paragraph (e).
    d. Revising paragraph (f)(1).
    e. In paragraph (f)(3) by revising the words ``Method 3'' to read 
``Method 3 or 3A'' and by revising ``(h)(3)'' to read ``(h)(6).''
    d. In paragraph (g), in the first sentence by revising the words 
``the applicable test methods and procedures specified in this 
section'' to read ``Method 6 or 6C and Method 3 or 3A.''
    e. In paragraphs (h)(1), (h)(3), and (h)(4) by revising the 
abbreviation ``vppm'' to read ``ppmv'' wherever it occurs.
    f. In paragraph (i)(2)(i) by revising the words ``for the 
concentration of sulfur oxides calculated as sulfur dioxide and 
moisture content'' to read ``for moisture content and for the 
concentration of sulfur oxides calculated as sulfur dioxide.''
    g. Revising paragraph (i)(9) following the introductory text and 
paragraph (i)(10).
    h. In paragraph (i)(11) by revising the words ``per 1,000 kg of 
coke burn-off'' to read ``per Mg (ton) of coke burn-off.''
    i. In paragraph (j)(2) by revising the words ``ASTM D129-64 
(Reapproved 1978)'' to read ``ASTM D129-64, 78, or 95.''
    j. In paragraph (j)(2) by revising the words ``ASTM D1552-83'' to 
read ``ASTM D1552-83 or 95.''
    k. In paragraph (j)(2) by revising the words ``ASTM D2622-87'' to 
read ``ASTM D2622-87, 94, or 98.''
    l. In paragraph (j)(2) by revising the words ``ASTM D1266-87'' to 
read ``ASTM D1266-87, 91, or 98.''
    The revisions read as follows:


Sec. 60.106  Test methods and procedures.

* * * * *
    (b) * * *
    (1) * * *
    [GRAPHIC] [TIFF OMITTED] TR17OC00.000
    

Where:

E = Emission rate of PM, kg/Mg (lb/ton) of coke burn-off.
cs = Concentration of PM, g/dscm (gr/dscf).
Qsd = Volumetric flow rate of effluent gas, dscm/hr (dscf/
hr).
Rc = Coke burn-off rate, Mg/hr (ton/hr) coke.
K=Conversion factor, 1,000 g/kg (7,000 gr/lb).
* * * * *
    (3) * * *

                    
Rc=K1Qr(%CO2+%CO)-
(K2Qa-K3Qr)((%CO/
2)+(%CO2+%O2))

Where:

Rc = Coke burn-off rate, Mg/hr (ton/hr).
Qr = Volumetric flow rate of exhaust gas from catalyst 
regenerator before entering the emission control system, dscm/min 
(dscf/min).

[[Page 61755]]

Qa = Volumetric flow rate of air to FCCU regenerator, as 
determined from the fluid catalytic cracking unit control room 
instrumentation, dscm/min (dscf/min).
%CO2 = Carbon dioxide concentration, percent by volume (dry 
basis).
%CO = Carbon monoxide concentration, percent by volume (dry basis).
%O2 = Oxygen concentration, percent by volume (dry basis).
K1 = Material balance and conversion factor, 2.982  x  
10-4 (Mg-min)/(hr-dscm-%) [9.31  x  10-6 (ton-
min)/(hr-dscf-%)].
K2 = Material balance and conversion factor, 2.088  x  
10-3 (Mg-min)/(hr-dscm-%) [6.52  x  10-5 (ton-
min)/(hr-dscf-%)].
K3 = Material balance and conversion factor, 9.94  x  
10-5 (Mg-min)/(hr-dscm-%) [3.1  x  10-6 (ton-
min)/(hr-dscf-%)].
* * * * *
    (c) * * *
    (1) * * *
    [GRAPHIC] [TIFF OMITTED] TR17OC00.002
    
Where:

Es = Emission rate of PM allowed, kg/Mg (lb/ton) of coke 
burn-off in catalyst regenerator.
F=Emission standard, 1.0 kg/Mg (2.0 lb/ton) of coke burn-off in 
catalyst regenerator.
A = Allowable incremental rate of PM emissions, 7.5  x  10-4 
kg/million J (0.10 lb/million Btu).
H = Heat input rate from solid or liquid fossil fuel, million J/hr 
(million Btu/hr).
Rc = Coke burn-off rate, Mg coke/hr (ton coke/hr).
* * * * *
    (e)(1) The owner or operator shall determine compliance with the 
H2S standard in Sec. 60.104(a)(1) as follows: Method 11, 15, 
15A, or 16 shall be used to determine the H2S concentration. 
The gases entering the sampling train should be at about atmospheric 
pressure. If the pressure in the refinery fuel gas lines is relatively 
high, a flow control valve may be used to reduce the pressure. If the 
line pressure is high enough to operate the sampling train without a 
vacuum pump, the pump may be eliminated from the sampling train. The 
sample shall be drawn from a point near the centroid of the fuel gas 
line.
    (i) For Method 11, the sampling time and sample volume shall be at 
least 10 minutes and 0.010 dscm (0.35 dscf). Two samples of equal 
sampling times shall be taken at about 1-hour intervals. The arithmetic 
average of these two samples shall constitute a run. For most fuel 
gases, sampling times exceeding 20 minutes may result in depletion of 
the collection solution, although fuel gases containing low 
concentrations of H2S may necessitate sampling for longer 
periods of time.
    (ii) For Method 15 or 16, at least three injects over a 1-hour 
period shall constitute a run.
    (iii) For Method 15A, a 1-hour sample shall constitute a run.
    (2) Where emissions are monitored by Sec. 60.105(a)(3), compliance 
with Sec. 60.105(a)(1) shall be determined using Method 6 or 6C and 
Method 3 or 3A. A 1-hour sample shall constitute a run. Method 6 
samples shall be taken at a rate of approximately 2 liters/min. The ppm 
correction factor (Method 6) and the sampling location in paragraph 
(f)(1) of this section apply. Method 4 shall be used to determine the 
moisture content of the gases. The sampling point for Method 4 shall be 
adjacent to the sampling point for Method 6 or 6C.
    (f) * * *
    (1) Method 6 shall be used to determine the SO2 
concentration. The concentration in mg/dscm obtained by Method 6 or 6C 
is multiplied by 0.3754 to obtain the concentration in ppm. The 
sampling point in the duct shall be the centroid of the cross section 
if the cross-sectional area is less than 5.00 m2 (53.8 
ft2) or at a point no closer to the walls than 1.00 m (39.4 
in.) if the cross-sectional area is 5.00 m2 or more and the 
centroid is more than 1 m from the wall. The sampling time and sample 
volume shall be at least 10 minutes and 0.010 dscm (0.35 dscf) for each 
sample. Eight samples of equal sampling times shall be taken at about 
30-minute intervals. The arithmetic average of these eight samples 
shall constitute a run. For Method 6C, a run shall consist of the 
arithmetic average of four 1-hour samples. Method 4 shall be used to 
determine the moisture content of the gases. The sampling point for 
Method 4 shall be adjacent to the sampling point for Method 6 or 6C. 
The sampling time for each sample shall be equal to the time it takes 
for two Method 6 samples. The moisture content from this sample shall 
be used to correct the corresponding Method 6 samples for moisture. For 
documenting the oxidation efficiency of the control device for reduced 
sulfur compounds, Method 15 shall be used following the procedures of 
paragraph (f)(2) of this section.
* * * * *
    (i) * * *
    (9) * * *
    [GRAPHIC] [TIFF OMITTED] TR17OC00.003
    
Where:

ESOx = sulfur oxides emission rate calculated as sulfur 
dioxide, kg/hr (lb/hr)
CSOx = sulfur oxides emission concentration calculated as 
sulfur dioxide, g/dscm (gr/dscf)
Qsd = dry volumetric stack gas flow rate corrected to 
standard conditions, dscm/hr (dscf/hr)
K=1,000 g/kg (7,000 gr/lb)

    (10) Sulfur oxides emissions calculated as sulfur dioxide shall be 
determined for each test run by the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.004

Where:

RSOx = Sulfur oxides emissions calculated as kg sulfur 
dioxide per Mg (lb/ton) coke burn-off.
ESOx = Sulfur oxides emission rate calculated as sulfur 
dioxide, kg/hr (lb/hr).
Rc = Coke burn-off rate, Mg/hr (ton/hr).
* * * * *


Sec. 60.107  [Amended]

    44. Section 60.107 is amended by revising paragraphs (c)(5) and 
(c)(6) as follows:


Sec. 60.107  Reporting and recordkeeping requirements.

* * * * *
    (c) * * *
    (5) If subject to Sec. 60.104(b)(2), for each day in which a Method 
8 sample result required by Sec. 60.106(i) was not obtained, the date 
for which and brief explanation as to why a Method 8 sample result was 
not obtained, for approval by the Administrator.
    (6) If subject to Sec. 60.104(b)(3), for each 8-hour period in 
which a feed sulfur measurement required by Sec. 60.106(j) was not 
obtained, the date for which and brief explanation as to why a feed 
sulfur measurement was not obtained, for approval by the Administrator.
* * * * *


Sec. 60.111  [Amended]

    45. Section 60.111 is amended as follows:

    a. In paragraph (b) by revising ``ASTM D396-78'' to read ``ASTM 
D396-78, 89, 90, 92, 96, or 98.''
    b. In paragraph (b) by revising ``ASTM D2880-78'' to read ``ASTM 
D2880-78 or 96.''
    c. In paragraph (b) by revising ``ASTM D975-78'' to read ``ASTM 
D975-78, 96, or 98a.''
    d. In paragraph (l) by revising ``ASTM D323-82'' to read ``ASTM 
D323-82 or 94.''

[[Page 61756]]

Sec. 60.111a  [Amended]

    46. Section 60.111a is amended as follows:
    a. In paragraph (b) by revising ``ASTM D396-78'' to read ``D396-78, 
89, 90, 92, 96, or 98.''
    b. In paragraph (b) by revising ``ASTM D2880-78'' to read ``ASTM 
D2880-78 or 96''; and by revising ``ASTM D975-78'' to read ``ASTM D975-
78, 96, or 98a.''
    c. In paragraph (g) by revising ``ASTM D323-82'' to read ``ASTM 
D323-82 or 94.''


Sec. 60.111b  [Amended]

    47. Section 60.111b is amended as follows:
    a. In paragraph (f)(3) by revising ``ASTM Method D2879-83'' to read 
``ASTM D2879-83, 96, or 97.''
    b. In paragraph (g) by revising ``ASTM D323-82'' to read ``ASTM 
D323-82 or 94.''


Sec. 60.116b  [Amended]

    48. Section 60.116b is amended as follows:
    a. In paragraph (e)(3)(ii) by revising ``ASTM Method D2879-83'' to 
read ``ASTM D2879-83, 96, or 97.''
    b. In paragraph (f)(2)(i) by revising ``ASTM Method D2879-83'' to 
read ``ASTM D2879-83, 96, or 97.''
    c. In paragraph (f)(2)(ii) by revising ``ASTM Method D323-82'' to 
read ``ASTM D323-82 or 94.''


Sec. 60.121  [Amended]

    49. In Sec. 60.121, paragraph (d) is added as follows:


Sec. 60.121  Definitions.

* * * * *
    (d) Blast furnace means any furnace used to recover metal from 
slag.
* * * * *


Sec. 60.133  [Amended]

    50. In Sec. 60.133, paragraph (b)(1), the first sentence is amended 
by revising the words ``pouring of the heat'' to read ``pouring of part 
of the production cycle.''


Sec. 60.144  [Amended]

    51. In Sec. 60.144, paragraph (c) is revised to read as follows:


Sec. 60.144  Test methods and procedures.

* * * * *
    (c) The owner or operator shall use the monitoring devices of 
Sec. 60.143(b)(1) and (2) for the duration of the particulate matter 
runs. The arithmetic average of all measurements taken during these 
runs shall be used to determine compliance with Sec. 60.143(c).
* * * * *


Sec. 60.143a  [Amended]

    52. Amend Sec. 60.143a, paragraph (c) as follows:
    a. The words ``All monitoring devices'' in the first sentence are 
revised to read ``All monitoring devices required by paragraph (a) of 
this section.''
    b. The words ``EPA Reference Method 2'' in the first sentence are 
revised to read ``Method 2 of Appendix A of this part.''
    c. The words ``EPA Reference Method 2'' in the second sentence are 
revised to read ``Method 2.''


Sec. 60.144a  [Amended]

    53. In Sec. 60.144a, paragraph (d) is amended by revising it to 
read as follows:


Sec. 60.144a  Test methods and procedures.

* * * * *
    (d) To comply with Sec. 60.143a(d) or (e), the owner or operator 
shall use the monitoring device of Sec. 60.143a(a) to determine the 
exhaust ventilation rates or levels during the particulate matter runs. 
Each owner or operator shall then use these rates or levels to 
determine the 3-hour averages required by Sec. 60.143a(d) and (e).
* * * * *


Sec. 60.145a  [Amended]

    54. In Sec. 60.145a, paragraph (f), in the first sentence by 
revising the words ``Reference Method 5'' to read ``Method 5.''


Sec. 60.153  [Amended]

    55. Amend Sec. 60.153 as follows:
    a. In paragraph (b)(3) by revising the word ``thermocouple'' or 
``thermocouples'' to read ``temperature measuring device'' or 
``temperature measuring devices'' wherever it occurs.
    b. In paragraph (b)(5), in the second sentence by revising the 
words ``with the method specified under Sec. 60.154(c)(2)'' to read 
``with the method specified under Sec. 60.154(b)(5).''


Sec. 60.154  [Amended]

    56. In Sec. 60.154, paragraphs (b)(1) and (b)(3) are revised, and 
in paragraph (b)(4), the equations and definitions are revised as 
follows:


Sec. 60.154  Test methods and procedures.

* * * * *
    (b) * * *
    (1) The emission rate (E) of particulate matter for each run shall 
be computed using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.005

Where:

E = Emission rate of particulate matter, g/kg (lb/ton) of dry sludge 
input.
cs = Concentration of particulate matter, g/dscm (gr/dscf).
Qsd = Volumetric flow rate of effluent gas, dscm/hr (dscf/
hr).
S = Charging rate of dry sludge during the run, kg/hr (ton/hr).
K = Conversion factor, 1.0 g/g (7,000 gr/lb).
* * * * *
    (3) The dry sludge charging rate (S) for each run shall be computed 
using either of the following equations:
[GRAPHIC] [TIFF OMITTED] TR17OC00.006

Where:

S = Charging rate of dry sludge, kg/hr (ton/hr).
Sm = Total mass of sludge charge, kg (ton).
Rdm = Average mass of dry sludge per unit mass of sludge 
charged, kg/kg (ton/ton).
 = Duration of run, hr.
Sv = Total volume of sludge charged, m3 (gal).
Rdv = Average mass of dry sludge per unit volume of sludge 
charged, kg/m3 (lb/gal).
Kv = Conversion factor, 1 g/g (2,000 lb/ton).

    (4) * * *
    [GRAPHIC] [TIFF OMITTED] TR17OC00.007
    
    [GRAPHIC] [TIFF OMITTED] TR17OC00.008
    
Where:

Sm = Total mass of sludge charged to the incinerator during 
the test run.
Sv = Total volume of sludge charged to the incinerator 
during the test run.
Qmi = Average mass flow rate calculated by averaging the 
flow rates at the beginning and end of each interval ``i,'' kg/hr (ton/
hr).
Qvi = Average volume flow rate calculated by averaging the 
flow rates at the beginning and end of each interval ``i,'' 
m3/hr (gal/hr).
i = Duration of interval ``i,'' hr.
* * * * *

    57. Paragraph (b)(5)(iii) is amended by revising the words ``mg/
liter (lb/ft3) or mg/mg (lb/lb)'' to read ``kg/m3 
(lb/gal) or kg/kg (ton/ton).''


Sec. 60.165  [Amended]

    58. In Sec. 60.165, paragraph (d)(2) is amended by revising the 
words

[[Page 61757]]

``installed under Sec. 60.163'' to read ``installed under paragraph (b) 
of this section.''


Sec. 60.192  [Amended]

    59. In Sec. 60.192, paragraph (a) is amended by revising the words 
``according to Sec. 60.8 above'' to read ``according to Sec. 60.195.''


Sec. 60.195  [Amended]

    60. Amend Sec. 60.195 as follows:
    a. In paragraph (b)(1) by revising the words ``(mg/dscf)'' in the 
definition of the term ``cs'' to read ``(gr/dscf)''; and 
revising the words ``(453,600 mg/lb)'' in the definition of the term 
``K'' to read ``(7,000 gr/lb).''
    b. In paragraph (b)(2) by revising the words ``(mg/dscf)'' in the 
definition of the symbol ``cs'' to read ``(gr/dscf)''; and 
revising the words ``(453,600 mg/lb)'' in the definition of the symbol 
``K'' to read ``(7,000 gr/lb).''


Sec. 60.201  [Amended]

    61. In Sec. 60.201 by revising paragraph (c) to read as follows:


Sec. 60.201  Definitions.

* * * * *
    (c) Equivalent P2O5 feed means the quantity 
of phosphorus, expressed as phosphorus pentoxide, fed to the process.
* * * * *


Sec. 60.202  [Amended]

    62. In Sec. 60.202, paragraph (a) is amended by revising the words 
``metric ton'' to read ``Mg.''


Sec. 60.203  [Amended]

    63. In Sec. 60.203, paragraph (b) is amended by revising the words 
``metric ton'' to read ``Mg.''


Sec. 60.204  [Amended]

    64. Amend Sec. 60.204 as follows:
    a. In paragraph (b)(1) by revising the words ``metric ton'' in the 
definition of the term ``E'' to read ``Mg''; revising the words ``(mg/
dscf)'' in the definition of the term ``csi'' to read ``(gr/
dscf)''; revising the words ``metric ton'' in the definition of the 
term ``P'' to read ``Mg''; and revising the words ``(453,600 mg/lb)'' 
in the definition of the term ``K'' to read ``(7,000 gr/lb).''
    b. In paragraph (b)(3) by revising the words ``metric ton'' in the 
definition of the term ``Mp'' to read ``Mg.''


Sec. 60.211  [Amended]

    65. In Sec. 60.211 by revising paragraph (c) to read as follows:


Sec. 60.211  Definitions.

* * * * *
    (c) Equivalent P2O5 feed means the quantity 
of phosphorus, expressed as phosphorus pentoxide, fed to the process.
* * * * *


Sec. 60.212  [Amended]

    66. In Sec. 60.212, paragraph (a) is amended by revising the words 
``metric ton'' to read ``megagram (Mg).''


Sec. 60.213  [Amended]

    67. In Sec. 60.213, paragraph (b) is amended by revising the words 
``metric ton'' to read ``Mg.''


Sec. 60.214  [Amended]

    68. Amend Sec. 60.214 as follows:
    a. In paragraph (b)(1) by revising the words ``metric ton'' in the 
definition of the term ``E'' to read ``Mg''; revising the words ``(mg/
dscf)'' in the definition of the term ``csi'' to read ``(gr/
dscf)''; revising the words ``metric ton'' in the definition of the 
term ``P'' to read ``Mg''; and revising the words ``(453,600 mg/lb)'' 
in the definition of the term ``K'' to read ``(7,000 gr/lb).''
    b. In paragraph (b)(3) by revising the words ``metric ton'' in the 
definition of the term ``Mp'' to read ``Mg.''


Sec. 60.222  [Amended]

    69. In Sec. 60.222, paragraph (a) is amended by revising the words 
``metric ton'' to read ``megagram (Mg).''


Sec. 60.223  [Amended]

    70. Amend Sec. 60.223 as follows:
    a. In paragraph (b) by revising the words ``metric ton'' to read 
``Mg.''
    b. In paragraph (c), in the first sentence by revising the word 
``part'' to read ``subpart.''


Sec. 60.224  [Amended]

    71. Amend Sec. 60.224 as follows:
    a. In paragraph (b)(1) by revising the words ``metric ton'' in the 
definition of the term ``E'' to read ``Mg''; revising the words ``(mg/
dscf)'' in the definition of the term ``csi'' to read ``(gr/
dscf)''; revising the words ``metric ton'' in the definition of the 
term ``P'' to read ``Mg''; and revising the words ``(453,600 mg/lb)'' 
in the definition of the term ``K'' to read ``(7,000 gr/lb).''
    b. In paragraph (b)(3) by revising the words ``metric ton'' in the 
definition of the term ``Mp'' to read ``Mg.''


Sec. 60.232  [Amended]

    72. Sec. 60.232 is amended by removing the paragraph designation 
and by revising the words ``metric ton'' to read ``megagram (Mg).''


Sec. 60.233  [Amended]

    73. Sec. 60.233 is amended by removing the paragraph designation 
and by revising the words ``metric ton'' to read ``Mg.''


Sec. 60.234  [Amended]

    74. Amend Sec. 60.234 as follows:
    a. In paragraph (b)(1) by revising the words ``metric ton'' in the 
definition of the term ``E'' to read ``Mg''; revising the words ``(mg/
dscf)'' in the definition of the term ``csi'' to read ``(gr/
dscf)''; revising the words ``metric ton'' in the definition of the 
term ``P'' to read ``Mg''; and revising the words ``(453,600 mg/lb)'' 
in the definition of the term ``K'' to read ``(7,000 gr/lb).''
    b. In paragraph (b)(3) by revising the words ``metric ton'' in the 
definition of the term ``Mp'' to read ``Mg.''


Sec. 60.241  [Amended]

    75. In Sec. 60.241, paragraph (c) is amended by italicizing the 
word ``stored.''


Sec. 60.242  [Amended]

    76-77. In Sec. 60.242, paragraph (a) is amended by revising the 
words ``metric ton'' to read ``megagram (Mg).''


Sec. 60.244  [Amended]

    78. Amend Sec. 60.244 as follows:
    a. In paragraph (c)(1) by revising the words ``metric ton'' in the 
definition of the term ``E'' to read ``Mg''; revising the words ``(mg/
dscf)'' in the definition of the term ``csi'' to read ``(gr/
dscf)''; revising the words ``metric ton'' the words ``(453,600 mg/
lb)'' in the definition of the term ``K'' to read ``(7,000 gr/lb).''
    b. In paragraph (b)(3) by revising the words ``metric ton'' in the 
definition of the term ``Mp''to read ``Mg.''


Sec. 60.250  [Amended]

    79. In Sec. 60.250, paragraph (a) is amended by revising the words 
``200 tons'' to read ``181 Mg (200 tons).''


Sec. 60.251  [Amended]

    80. In Sec. 60.251, paragraphs (b) and (c) are amended by revising 
``D388-77'' to read ``D388-77, 90, 91, 95, or 98a.''


Sec. 60.252  [Amended]

    81. In Sec. 60.252, paragraph (b)(1) is amended by revising the 
words ``0.040 g/dscm (0.018 gr/dscf)'' to read ``0.040 g/dscm (0.017 
gr/dscf).''


Sec. 60.253  [Amended]

    82. Amend Sec. 60.253 as follows:
    a. In paragraph (a)(1), the second sentence is amended by revising 
the words ``3 deg. Fahrenheit'' to read ``1.7 
deg.C (3  deg.F).''

[[Page 61758]]

    b. In paragraph (a)(2)(i), the second sentence is amended by 
revising the word ``gage'' to read ``gauge.''


Sec. 60.261  [Amended]

    83. Amend Sec. 60.261 as follows:
    a. Paragraph (n) is amended by revising ``ASTM Designation A99-76'' 
to read ``ASTM Designation A99-76 or 82 (Reapproved 1987).''
    b. Paragraphs (s) and (w) are amended by revising ``ASTM 
Designation A100-69 (Reapproved 1974)'' to read ``ASTM Designation 
A100-69, 74, or 93.''
    c. Paragraph (q) is amended by revising ``ASTM Designation A101-
73'' to read ``ASTM Designation A101-73 or 93.''
    d. Paragraph (t) is amended by revising ``ASTM Designation A482-
76'' to read ``ASTM Designation A482-76 or 93.''
    e. Paragraph (o) is amended by revising ``ASTM Designation A483-64 
(Reapproved 1974)'' to read ``ASTM Designation A483-64 or 74 
(Reapproved 1988).''
    f. Paragraph (v) is amended by revising ``ASTM Designation A495-
76'' to read ``ASTM Designation A495-76 or 94.''


Sec. 60.266  [Amended]

    84. Amend Sec. 60.266 as follows:
    a. Paragraph (c)(1) is amended by revising the words ``emissions is 
quantified'' in the definition of the term ``n'' to read ``emissions 
are quantified''; revising the words ``(g/dscf)'' in the definition of 
the term ``csi'' to read ``(gr/dscf)''; and revising the 
words ``(453.6 g/lb)'' in the definition of the term ``K'' to read 
``(7000 gr/lb).''
    b. Paragraph (c)(2)(ii) is amended by revising the words ``5.70 
dscm (200 dscf)'' to read ``5.66 dscm (200 dscf).''


Sec. 60.274  [Amended]

    85. Amend Sec. 60.274 as follows:
    a-b. Paragraph (a)(4) is amended by revising the words ``under 
paragraph (e) of this section'' to read ``under paragraph (f) of this 
section.''
    c. In Sec. 60.274, paragraph (i), the first sentence is amended by 
revising the words ``required by Sec. 60.275(c)'' to read ``required by 
Sec. 60.276(c).''
    d. In Sec. 60.274, by revising paragraph (i)(4) to read as follows:


Sec. 60.274  Monitoring of operations.

* * * * *
    (i) * * *
    (4) Continuous opacity monitor or Method 9 data.
* * * * *


Sec. 60.275  [Amended]

    86. Amend Sec. 60.275 as follows:
    a. Paragraph (e)(2) is amended by revising the words ``more then 
one control'' to read ``more than one control.''
    b. Paragraph (e)(4) is amended by revising the words ``the test 
runs shall be conducted concurrently'' to read ``the Method 9 test runs 
shall be conducted concurrently with the particulate matter test 
runs.''
    c. In paragraph (i), the fifth sentence is amended by revising the 
words ``In the case, Reference Method 9'' to read ``In this case, 
Method 9.''


Sec. 60.276  [Amended]

    87. Amend Sec. 60.276 by:
    a. Paragraphs (a) and (c)(6)(iv) are revised.
    b. In paragraph (b), the second sentence is amended by revising the 
words ``postmarked 30 days prior'' to read ``postmarked at least 30 
days prior.''
    The revisions read as follows:


Sec. 60.276  Recordkeeping and reporing requirements.

    (a) Operation at a furnace static pressure that exceeds the value 
established under Sec. 60.274(g) and either operation of control system 
fan motor amperes at values exceeding 15 percent of the 
value established under Sec. 60.274(c) or operation at flow rates lower 
than those established under Sec. 60.274(c) may be considered by the 
Administrator to be unacceptable operation and maintenance of the 
affected facility. Operation at such values shall be reported to the 
Administrator semiannually.
* * * * *
    (c) * * *
    (6) * * *
    (iv) Continuous opacity monitor or Method 9 data.
* * * * *


Sec. 60.274a  [Amended]

    88. Amend Sec. 60.274a by:
    a. In paragraph (c), the first sentence is revised, and paragraph 
(h)(4) is revised.
    b. Paragraph (f) is amended by adding the following sentence after 
the first sentence: ``The pressure shall be recorded as 15-minute 
integrated averages.''
    c. In paragraph (h), the first sentence is amended by revising the 
words ``required by Sec. 60.275a(d)'' to read ``required by 
Sec. 60.276a(f).''
    The revisions read as follows:


Sec. 60.274a  Monitoring of operations.

* * * * *
    (c) When the owner or operator of an EAF is required to demonstrate 
compliance with the standards under Sec. 60.272a(a)(3), and at any 
other time that the Administrator may require (under section 114 of the 
Act, as amended), either the control system fan motor amperes and all 
damper positions or the volumetric flow rate through each separately 
ducted hood shall be determined during all periods in which a hood is 
operated for the purpose of capturing emissions from the affected 
facility subject to paragraph (b)(1) or (b)(2) of this section. * * *
* * * * *
    (h) * * *
    (4) Continuous opacity monitor or Method 9 data.
* * * * *


Sec. 60.275a  [Amended]

    89. In Sec. 60.275a, paragraph (e)(4) is amended by revising the 
words ``the test runs shall be conducted concurrently'' to read ``the 
Method 9 test runs shall be conducted concurrently with the particulate 
matter test runs.''


Sec. 60.276a  [Amended]

    90. Amend Sec. 60.276a as follows:
    a. In paragraph (e), the second sentence is amended by revising the 
words ``postmarked 30 days prior'' to read ``postmarked at least 30 
days prior.''
    b. Paragraph (f)(6)(iv) is amended by revising as follows:


Sec. 60.276a  Recordkeeping and reporting requirements.

* * * * *
    (f) * * *
    (iv) Continuous opacity monitor or Method 9 data.
* * * * *


Sec. 60.281  [Amended]

    91. Amend Sec. 60.281 as follows:
    a. In paragraph (c) by revising the words ``Reference Method 16'' 
to read ``Method 16.''
    b. In paragraph (d) by revising the words ``below tank(s)'' to read 
``blow tank(s).''
    c. In paragraph (e) by revising the words ``digestion system'' to 
read ``digester system.''


Sec. 60.282  [Amended]

    92. In Sec. 60.282, paragraph (a)(3)(i) is amended by revising the 
words ``0.15 g/dscm (0.067 gr/dscf)'' to read ``0.15 g/dscm (0.066 gr/
dscf).''


Sec. 60.283  [Amended]

    93. Amend Sec. 60.283 as follows:
    a. In paragraph (a)(1)(iii) by revising the words ``1200 deg.F.'' 
to read ``650  deg.C (1200  deg.F).''

[[Page 61759]]

    b. In paragraph (a)(1)(v), in the second sentence by revising the 
words ``5 ppm by volume on a dry basis, corrected to the actual oxygen 
content of the untreated gas stream'' to read ``5 ppm by volume on a 
dry basis, uncorrected for oxygen content.''
    c. In paragraph (a)(1)(vi) by revising the words ``0.005 g/kg ADP'' 
to read ``0.005 g/kg air dried pulp (ADP).''


Sec. 60.284  [Amended]

    94. Amend Sec. 60.284 by:
    a. In paragraph (a)(2)(ii) by revising the words ``20 percent'' to 
read ``25 percent''
    b. Revising paragraph (c) introductory text.
    c. In paragraph (c)(3) by revising the words ``Correct all 12-hour 
average TRS concentrations to 10 volume percent oxygen, except that all 
12-hour average TRS concentration from a recovery furnace shall be 
corrected to 8 volume percent using the following equation:'' to read 
``Using the following equation, correct all 12-hour average TRS 
concentrations to 10 volume percent oxygen, except that all 12-hour 
average TRS concentrations from a recovery furnace shall be corrected 
to 8 volume percent oxygen instead of 10 percent, and all 12-hour 
average TRS concentrations from a facility to which the provisions of 
Sec. 60.283(a)(1)(v) apply shall not be corrected for oxygen content:''
    d. Paragraph (d)(3)(ii) is amended by revising the words 
``1200 deg.F'' to read ``650  deg.C (1200  deg.F).''
    e. Adding paragraph (f).
    The revisions and addition read as follows:


Sec. 60.284  Monitoring of emissions and operations.

* * * * *
    (c) Any owner or operator subject to the provisions of this subpart 
shall, except where the provisions of Sec. 60.283(a)(1)(iii) or (iv) 
apply, perform the following:
* * * * *
    (f) The procedures under Sec. 60.13 shall be followed for 
installation, evaluation, and operation of the continuous monitoring 
systems required under this section.
    (1) All continuous monitoring systems shall be operated in 
accordance with the applicable procedures under Performance 
Specifications 1, 3, and 5 of appendix B to this part.
    (2) Quarterly accuracy determinations and daily calibration drift 
tests shall be performed in accordance with Procedure 1 of appendix F 
to this part.


Sec. 60.285  [Amended]

    95. Amend Sec. 60.285 as follows:
    a. In paragraph (c)(1) by revising the definition of the term 
``cs'' to read ``cs = Concentration of 
particulate matter, g/dscm (lb/dscf).''
    b. In paragraph (d)(3) by revising the equation used to calculate 
``GLS'' as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.009

    c. In paragraph (e)(1) by revising the definition of ``F'' to read 
``F = conversion factor, 0.001417 g H2S/m3-ppm 
(8.846  x  10-8 lb H2S/ft3-ppm).''
    d. In paragraph (f)(1) by revising the words ``205  deg.C (400 
deg.F)'' to read ``204  deg.C (400  deg.F).''
    e. Revising paragraph (f)(2).
    The revisions read as follows:


Sec. 60.285  Test methods and procedures.

* * * * *
    (f) * * *
    (2) In place of Method 16, Method 16A or 16B may be used.
* * * * *


Sec. 60.290  [Amended]

    96. In Sec. 60.290, paragraph (c) is amended by revising the words 
``4,550 kilograms'' to read ``4.55 Mg (5 tons).''


Sec. 60.291  [Amended]

    97. Amend Sec. 60.291 as follows:
    a. The second sentence of the definition of the term ``Glass 
melting furnace'' is amended by revising the word ``appendaees'' to 
read ``appendages.''
    b. The definition of the term ``lead recipe'' is amended by 
revising the chemical formula ``Na2M'' to read 
``Na2O.''
    c. The second sentence of the definition of the term ``rebricking'' 
is amended by revising the word ``replacment'' to read ``replacement.''


Sec. 60.292  [Amended]

    98. In Sec. 60.292, paragraph (a)(2), the definition of the term 
STD is amended by revising the words ``g of particulate/kg'' to read 
``g of particulate/kg (lb of particulate/ton).''


Sec. 60.293  [Amended]

    99. Amend Sec. 60.293 as follows:
    a. In paragraph (d)(1) by revising the words ``specified in 
paragraph (b)(1) of this section'' to read ``specified in paragraph (b) 
of this section.''
    b. Paragraph (e) is redesignated as paragraph (f).
    c. Paragraph (d)(3) introductory text is redesignated as paragraph 
(e); paragraphs (d)(3)(i), (ii), and (iii) are redesignated as 
paragraphs (e)(1), (2), and (3).
    d. Newly designated paragraph (f) is amended by revising the words 
``12014 deg.C'' to read ``12014 deg.C 
(24825 deg.F).


Sec. 60.296  [Amended]

    100. Amend Sec. 60.296 as follows:
    In paragraph (b)(3) by revising the words ``American Society of 
Testing and Materials (ASTM) Method D240-76'' to read ``ASTM Method 
D240-76 or 92'' and by revising ``D1826-77'' to read ``D1826-77 or 
94.''


Sec. 60.301  [Amended]

    101. In Sec. 60.301, the first paragraph is amended by revising the 
words ``the act'' to read ``the Act.''


Sec. 60.313  [Amended]

    102. Amend Sec. 60.313 as follows:
    a. Paragraph (c)(1) is amended by revising the words ``Reference 
Method 24'' to read ``Method 24'' wherever they occur.
    b. In paragraph (c)(1)(i)(B), the third sentence is amended by 
revising the words ``other transfer efficiencies other than'' to read 
``transfer efficiencies other than.''
    c. Paragraph (c)(2)(i) is amended by revising the words ``in 
(c)(2)(i)(A), (B), and (C)'' to read ``in paragraphs (c)(2)(i)(A), (B), 
and (C)'' wherever they occur.


Sec. 60.315  [Amended]

    103. In Sec. 60.315, paragraph (a)(2) is amended by revising the 
words ``Reference Method 24'' to read ``Method 24.''


Sec. 60.330  [Amended]

    104. In Sec. 60.330, paragraph (a) is amended by revising the words 
``10.7 gigajoules'' to read ``10.7 gigajoules (10 million Btu).''


Sec. 60.331  [Amended]

    105. In Sec. 60.331, paragraph (s) is removed.


Sec. 60.332  [Amended]

    106. In Sec. 60.332, paragraph (a) is amended by revising the words 
``the date of the performance test'' to read ``the date on which the 
performance test.''


Sec. 60.334  [Amended]

    107. In Sec. 60.334, paragraph (c)(3), the first sentence is 
amended by revising the words ``provided in Sec. 60.332(g)'' to read 
``provided in Sec. 60.332(f).''


Sec. 60.335  [Amended]

    108. Amend Sec. 60.335 by:

[[Page 61760]]

    a. Paragraph (c)(1) is amended by revising the words:

``NOX = emission rate of NOX at 15 percent 
O2 and ISO standard ambient conditions, volume percent.
NOX = observed NOX concentration, ppm by 
volume.''

``NOX = emission rate of NOX at 15 percent O2 and 
ISO standard ambient conditions, ppm by volume.

NOX = observed NOX concentration, ppm by volume 
at 15 percent O2.''

    b. Paragraph (d) is revised.
    c. In paragraph (f)(1), the first sentence is amended by revising 
the words ``in paragraph (b)(1) of this section'' to read ``in 
paragraph (c)(1) of this section.''
    The revisions read as follows:


Sec. 60.335  Test methods and procedures.

* * * * *
    (d) The owner or operator shall determine compliance with the 
sulfur content standard in Sec. 60.333(b) as follows: ASTM D 2880-71, 
78, or 96 shall be used to determine the sulfur content of liquid fuels 
and ASTM D 1072-80 or 90 (Reapproved 1994), D 3031-81, D 4084-82 or 94, 
or D 3246-81, 92, or 96 shall be used for the sulfur content of gaseous 
fuels (incorporated by reference-see Sec. 60.17). The applicable ranges 
of some ASTM methods mentioned above are not adequate to measure the 
levels of sulfur in some fuel gases. Dilution of samples before 
analysis (with verification of the dilution ratio) may be used, subject 
to the approval of the Administrator.
* * * * *


Sec. 60.343  [Amended]

    109. In Sec. 60.343, paragraph (e), the first sentence is amended 
by revising the words ``in which the scrubber pressure drop is greater 
than 30 percent below the rate established during the performance 
test'' to read ``in which the scrubber pressure drop or scrubbing 
liquid supply pressure is greater than 30 percent below that 
established during the performance test.''


Sec. 60.344  [Amended]

    110. Amend Sec. 60.344 as follows:
    a. In paragraph (b)(1), the definition of the term 
``cs'' is amended by revising the words ``(g/dscf)'' to read 
``(gr/dscf).''
    b. In paragraph (b)(1), the definition of the term ``K'' is amended 
by revising the words ``(453.6 g/lb)'' to read ``(7000 gr/lb).''
    c. In paragraph (b)(2), the first sentence is amended by revising 
the words ``Method 5D shall be used as positive-pressure fabric 
filters'' to read ``Method 5D shall be used at positive-pressure fabric 
filters.''


Sec. 60.372  [Amended]

    111. Amend Sec. 60.372 as follows;
    a. In paragraph (a)(1) by revising the words ``0.40 milligram of 
lead per dry standard cubic meter of exhaust (0.000176 gr/dscf)'' to 
read ``0.40 milligram of lead per dry standard cubic meter of exhaust 
(0.000175 gr/dscf).''
    b. In paragraph (a)(2) by revising the words ``1.00 milligram of 
lead per dry standard cubic meter of exhaust (0.00044 gr/dscf)'' to 
read ``1.00 milligram of lead per dry standard cubic meter of exhaust 
(0.000437 gr/dscf).''
    c. In paragraph (a)(3) by revising the words ``1.00 milligram of 
lead per dry standard cubic meter of exhaust (0.00044 gr/dscf)'' to 
read ``1.00 milligram of lead per dry standard cubic meter of exhaust 
(0.000437 gr/dscf).''
    d. In paragraph (a)(5) by revising the words ``4.50 milligrams of 
lead per dry standard cubic meter of exhaust (0.00198 gr/dscf)'' to 
read ``4.50 milligrams of lead per dry standard cubic meter of exhaust 
(0.00197 gr/dscf).''
    e. In paragraph (a)(6) by revising the words ``1.00 milligram per 
dry standard cubic meter of exhaust (0.00044 gr/dscf)'' to read ``1.00 
milligram of lead per dry standard cubic meter of exhaust (0.000437 gr/
dscf).''


Sec. 60.374  [Amended]

    112. Amend Sec. 60.374 as follows:
    a. In paragraph (c)(1), in the definition of the term 
``cPbi'' by revising the words ``mg/dscm'' to read ``mg/dscm 
(gr/dscf).''
    b. In paragraph (c)(1), in the definition of the term ``K'' by 
revising the words ``453,600 mg/lb'' to read ``7000 gr/lb).''


Sec. 60.381  [Amended]

    113. In Sec. 60.381, in the definition of the term ``storage bin'' 
by revising the words ``or metallic minerals'' to read ``of metallic 
minerals.''


Sec. 60.382  [Amended]

    114. In Sec. 60.382, paragraph (a)(1) is amended by revising the 
words ``0.05 grams per dry standard cubic meter'' to read ``0.05 grams 
per dry standard cubic meter (0.02 g/dscm).''


Sec. 60.385  [Amended]

    115. In Sec. 60.385, paragraph (c) is amended by revising the words 
``scrubber pressure loss (or gain) and liquid flow rate'' to read 
``scrubber pressure loss (or gain) or liquid flow rate''.


Sec. 60.386  [Amended]

    116. In Sec. 60.386, paragraph (c) is amended by revising the words 
``Sec. 60.3284(a) and (b)'' to read ``Sec. 60.384(a) and (b).''


Sec. 60.391  [Amended]

    117. Amend Sec. 60.391 as follows:
    a. In paragraph (b), the definition of ``E'' is amended by revising 
the words ``destruction efficiency'' to read ``destruction or removal 
efficiency.''
    b. In paragraph (b), the eleventh definition is amended by revising 
the words

``Lcill = Volume of each coating (i) consumed by 
each application method (l), as received liters)''

to read

``Lcil = Volume of each coating (i) consumed by each 
application method (l), as received (liters).''


Sec. 60.393  [Amended]

    118. Amend Sec. 60.393 as follows:
    a. In paragraph (c)(1)(i) by revising the words ``Reference Method 
24'' to read ``Method 24'' wherever they occur.
    b. Paragraph (c)(2)(ii)(A) is amended by revising the term to read 
as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.010

to read as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.011

Sec. 60.395  [Amended]

    119. In Sec. 60.395, paragraph (d) is amended by revising the words 
``Reference Method 25'' to read ``Method 25.''


Sec. 60.396  [Amended]

    120. In Sec. 60.396, paragraphs (a)(1), (a)(2), (b), and (c) are 
amended by revising the words ``Reference Method'' to read ``Method.''


Sec. 60.401  [Amended]

    121. In Sec. 60.401, paragraph (b) is amended by revising the words 
``unit including, moisture'' to read ``unit, including moisture.''


Sec. 60.402  [Amended]

    122. In Sec. 60.402, paragraph (a)(2)(i) is amended by revising the 
word ``Contains'' to read ``Contain.''


Sec. 60.424  [Amended]

    123. Amend Sec. 60.424 to read as follows:
    a. In the first paragraph (b)(3), in the first sentence by revising 
the words

[[Page 61761]]

``scales or computed from material balance shall'' to read ``scales, or 
the result of computations using a material balance, shall.''
    b. The second paragraph (b)(3) is redesignated as (b)(4).


Sec. 60.431  [Amended]

    124. In Sec. 60.431, paragraph (b), the definition of the term 
``Ldi'' is amended by adding the words ``the subject 
facility (or facilities)'' to the end of the definition.


Sec. 60.433  [Amended]

    125. Amend Sec. 60.433 as follows:
    a. In paragraph (a)(5), the first sentence is amended by revising 
the words ``material or on at least'' to read ``material on at least.''
    b. Paragraph (a)(5)(ii) is amended by revising the punctuation at 
the end of the paragraph. The words ``according to Sec. 60.435.'' are 
revised to read ``according to Sec. 60.435;''
    c. Paragraphs(b)(1), (b)(2), (b)(3), (b)(5), (c)(2)(ii), and 
(c)(2)(iii) are amended by adding an ``='' between the ``i'' and the 
``1'' under the summation sign.
    d. Paragraph (c)(2)(v) is amended by replacing the ``e'' subscript 
with ``a'' wherever it occurs.
    e. Paragraph (e)(5)(ii) is amended by replacing the ``a'' subscript 
with ``e'' wherever it occurs.


Sec. 60.435  [Amended]

    126. Amend Sec. 60.435 as follows:

    a. Paragraphs (a)(1), (a)(2), and (b) are amended by revising the 
words ``Reference Method'' to read ``Method'' wherever they occur.
    b. Paragraph (d)(1) is amended by revising the words ``ASTM D1475-
60 (Reapproved 1980)'' to read ``ASTM D1475-60, 80, or 90.''


Sec. 60.440  [Amended]

    127. In Sec. 60.440, paragraph (b) is amended by revising the words 
``45 Mg'' to read ``45 Mg (50 tons)'' wherever they occur.


Sec. 60.441  [Amended]

    128. In Sec. 60.441, paragraphs (a) and (b) are amended by revising 
the words ``Reference Method'' to read ``Method'' wherever they occur.


Sec. 60.443  [Amended]

    129. Amend Sec. 60.443 as follows:
    a. In paragraph (b) by revising the words ``Rq less'' to 
read ``Rq is less.''
    b. In paragraph (d) by revising the words ``in paragraph (b)(1) of 
this section'' to read ``in paragraph (b) of this section.''
    c. In paragraph (e), in the third sentence by revising the words 
``38 deg.C (50 deg.F)'' to read ``28 deg.C (50 deg.F).''
    d. In paragraph (i) by revising the word ``devices'' to read 
``device(s).''


Sec. 60.446  [Amended]

    130. In Sec. 60.446, paragraphs (a) and (b) are amended by revising 
the words ``Reference Method'' to read ``Method'' wherever they occur.


Sec. 60.453  [Amended]

    131. Amend Sec. 60.453 as follows:
    a. In paragraph (b) by revising the words ``performance text'' to 
read ``performance test.''
    b. In paragraph (b)(1) by revising the words ``Reference Method'' 
to read ``Method'' wherever they occur.
    c. In paragraph (b)(1)(i)(B) by revising the word ``coatings'' to 
read ``coating.''
    d. In paragraph (b)(1)(i)(C) by revising equation (3).
    e. In paragraphs (b)(2)(i)(A) and (b)(2)(i)(B) by revising 
Equations (6) and (7).
    f. In paragraph (b)(2)(i)(B) by removing Equation (7) and its 
nomenclature, adding them to the end of paragraph (b)(2)(i)(A), and 
redesignating the equation as Equation (6).
    g. In paragraph (b)(3)(i) by revising the word ``assumed'' to read 
``consumed.''
    The revisions reads as follows:


Sec. 60.453  Test methods and procedures.

* * * * *
    (b) * * *
    (1) * * *
    (i) * * *
    (C) * * *
    [GRAPHIC] [TIFF OMITTED] TR17OC00.012
    
* * * * *
    (2) * * *
    (i) * * *
    (A) * * *
    [GRAPHIC] [TIFF OMITTED] TR17OC00.013
    
* * * * *
    (B) * * *
    [GRAPHIC] [TIFF OMITTED] TR17OC00.014
    
* * * * *


Sec. 60.454  [Amended]

    132. In Sec. 60.454, paragraph (a)(2) is amended by revising the 
words ``of the greater of 0.75 percent of the temperature being 
measured expressed in degrees Celsius or 2.5 deg.C'' to 
read ``of 0.75 percent of the temperature being measured, expressed in 
degrees Celsius, or 2.5  deg.C, whichever is greater.''


Sec. 60.455  [Amended]

    133. Amend Sec. 60.455 as follows:
    a. Paragraphs (c)(1) and (c)(2) are amended by revising the words 
``28  deg.C'' to read ``28  deg.C'' (50  deg.F)'' wherever they occur.
     b. In paragraph (d), the first sentence is amended by revising the 
word ``opreator'' to read ``operator.''


Sec. 60.456  [Amended]

    134. Amend Sec. 60.456 as follows:
    a. In paragraph (a)(1), the second sentence is amended by revising 
the words ``Reference Method 24'' to read ``Method 24.''
    b. In paragraph (a)(1), the third sentence is amended by revising 
the words ``subsection 4.4 of Method 24'' to read ``Section 12.6 of 
Method 24.''
    c. Paragraph (a)(4) is amended by revising the word ``volocity'' to 
read ``velocity.''
    d. Paragraph (c) is amended by revising the words ``0.003 dscm'' to 
read ``0.003 dscm (0.1 dscf).''


Sec. 60.463  [Amended]

    135. Amend Sec. 60.463 as follows:
    a. Paragraph (c)(1) is amended by revising the words ``Reference 
Method 24'' to read ``Method 24'' wherever they occur.
    b. Paragraph (c)(3)(iii) is amended by revising the word 
``computation'' to read ``computations.''
    c. Paragraph (c)(4)(ii) is amended by revising the defined term 
``m'' to read ``n.''


Sec. 60.464  [Amended]

    136. In Sec. 60.464, paragraph (c), the second sentence is amended 
by revising the words ``which is greater'' to read ``whichever is 
greater.''


Sec. 60.465  [Amended]

    137. Amend Sec. 60.465 as follows:
    a. In paragraph (c), the first sentence is amended by revising the 
reference ``Sec. 69.462'' to read ``Sec. 60.462.''
    b. In paragraph (d), the first sentence is amended by revising the 
reference ``Sec. 69.464'' to read ``Sec. 60.464.''


Sec. 60.466  [Amended]

    138. Amend Sec. 60.466 as follows:
    a. Paragraphs (a)(1) and (a)(2) are amended by revising the words

[[Page 61762]]

``Reference Method'' to read ``Method'' wherever they occur.
    b. In paragraph (a)(1), the first sentence is amended by revising 
the words ``coating for determining the VOC content'' to read 
``coating, shall be used for determining the VOC content.''
    c. In paragraph (a)(1), the third sentence is amended by revising 
the words ``section 4.4'' to read ``Section 12.6.''
    d. Paragraph (c) is amended by revising the words ``0.003 dry 
standard cubic meter (DSCM)'' to read ``0.003 dscm (0.11 dscf).''


Sec. 60.471  [Amended]

    139. In Sec. 60.471, the definition of the term ``Catalyst'' is 
amended by revising the words ``means means'' to read ``means.''


Sec. 60.472  [Amended]

    140. Amend Sec. 60.472 as follows:
    a. Paragraph (a)(1)(i) is amended by revising the words ``0.04 
kilograms of particulate per megagram'' to read ``0.04 kg/Mg (0.08 lb/
ton).''
    b. Paragraph (a)(1)(ii) is amended by revising the words ``0.04 
kilograms per megagram'' to read ``0.04 kg/Mg (0.08 lb/ton).''
    c. Paragraph (b)(1) is amended by revising the words ``0.67 
kilograms of particulate per megagram'' to read ``0.67 kg/Mg (1.3 lb/
ton).''
    d. Paragraph (b)(2) is amended by revising the words ``0.71 
kilograms of particulate per megagram'' to read ``0.71 kg/Mg (1.4 lb/
ton).''
    e. Paragraph (b)(3) is amended by revising the words ``0.60 
kilograms of particulate per megagram'' to read ``0.60 kg/Mg (1.2 lb/
ton).''
    f. Paragraph (b)(4) is amended by revising the words ``0.64 
kilograms of particulate per megagram'' to read ``0.64 kg/Mg (1.3 lb/
ton).''
    g. Paragraph (b)(5) is amended by revising the words ``procedures 
in Sec. 60.474(k)'' to read ``procedures in Sec. 60.474(g).''


Sec. 60.473  [Amended]

    141. Amend Sec. 60.473 as follows:
    a. In paragraph (a), the second sentence is amended by revising the 
words ``15 deg.C'' to read ``15 deg.C 
(25 deg.F).''
    b. In paragraph (b), the second sentence is amended by revising the 
words ``10  deg.C'' to read ``10  deg.C 
(18  deg.F).''
    c. In paragraph (c), the first sentence is amended by revising the 
words ``(a) and (b)'' to read ``(a) or (b)''


Sec. 60.474  [Amended]

    142. Amend Sec. 60.474 as follows:
    a. In paragraph (c)(1), the definition of the term ``E'' is amended 
by revising the words ``kg/Mg'' to read ``kg/Mg (lb/ton).''
    b. In paragraph (c)(1), the definition of the term 
``cs'' is amended by revising the words ``(g/dscf)'' to read 
``(gr/dscf).''
    c. In paragraph (c)(1), the definition of the term ``K'' is amended 
by revising the words ``907.2/(g-Mg)/(kg-ton)'' to read ``7000 gr/
lb).''
    d. In paragraph (c)(4), the definition of the term ``d'' is amended 
by revising the words ``llb/ft\3\'' to read ``lb/ft\3\.''
    e. Paragraphs (c)(4)(ii) and (f) are revised.
    The revisions read as follows:


Sec. 60.474  Test methods and procedures.

* * * * *
    (c) * * *
    (4) * * *
    (ii) The density (d) of the asphalt shall be computed using the 
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.015

Where:

d = Density of the asphalt, kg/m\3\ (lb/ft\3\)
K1 = 1056.1 kg/m\3\ (metric units)
    = 64.70 lb/ft\3\ (English Units)
K2 = 0.6176 kg/(m\3\  deg.C) (metric units)
    = 0.0694 lb/(ft\3\  deg.F) (English Units)
Ti = temperature at the start of the blow,  deg.C ( deg.F)
* * * * *
    (f) If at a later date the owner or operator believes that the 
emission limits in Sec. 60.472(a) and (b) are being met even though one 
of the conditions listed in this paragraph exist, he may submit a 
written request to the Administrator to repeat the performance test and 
procedure outlined in paragraph (c) of this section.
    (1) The temperature measured in accordance with Sec. 60.473(a) is 
exceeding that measured during the performance test.
    (2) The temperature measured in accordance with Sec. 60.473(b) is 
lower than that measured during the performance test.
* * * * *


Sec. 60.480  [Amended]

    143. In Sec. 60.480(d)(2), line 3, revise the words ``1,000 Mg/yr'' 
to read ``1,000 Mg/yr (1,102 ton/yr)''


Sec. 60.481  [Amended]

    144. Amend Sec. 60.481 as follows:
    a. Paragraph (a)(1) under the definition of ``Capital expenditure'' 
is amended by revising the words ``repair allowance, B, as reflected'' 
to ``repair allowance, B, divided by 100 as reflected''
    b. The definition for ``In vacuum service'' is amended by revising 
the words ``5 kilopascals (kPa)'' to ``5 kilopascals (kPa)(0.7 psia).''
    c. The definition of the term ``Repaired'' is amended by revising 
the words ``instrument reading or 10,000 ppm or greater'' to read 
``instrument reading of 10,000 ppm or greater.''


Sec. 60.482-2  [Amended]

    145. Amend Sec. 60.482-2 as follows:
    a. Paragraph (e) is amended by revising the words ``(a), (c), and 
(d) if the pump'' to read ``(a), (c), and (d) of this section if the 
pump.''
    b. Paragraph (e)(3) is amended by revising the words ``paragraph 
(e)(2)'' to read ``paragraph (e)(2) of this section.''
    c. Paragraph (f) is amended by revising the words ``exempt from the 
paragraphs (a) through (e)'' to read ``exempt from paragraphs (a) 
through (e) of this section.''


Sec. 60.482-3  [Amended]

    146. In Sec. 60.482-3, paragraph (i)(2) is amended by revising the 
words ``paragraph (i)(1)'' to read ``paragraph (i)(1) of this 
section.''


Sec. 60.482-4  [Amended]

    147. In Sec. 60.482-4, paragraph (c) is amended by revising the 
words ``paragraphs (a) and (b)'' to read ``paragraphs (a) and (b) of 
this section.''


Sec. 60.482-5  [Amended]

    148. In Sec. 60.482-5, paragraph (c) is amended by revising the 
words ``paragraphs (a) and (b).'' to read ``paragraphs (a) and (b) of 
this section.''


Sec. 60.482-7  [Amended]

    149. In Sec. 60.482-7, paragraph (f)(3) is amended by revising the 
words ``paragraph (f)(2)'' to read ``paragraph (f)(2) of this 
section.''


Sec. 60.482-10  [Amended]

    150. In Sec. 60.482-10, paragraph (c) is amended by revising the 
words ``temperature of 816  deg.C'' to read ``temperature of 816  deg.C 
(1500  deg.F).''


Sec. 60.483-1  [Amended]

    151. In Sec. 60.483-1, paragraph (b)(1) is amended by revising the 
words ``specified in Sec. 60.487(b)'' to read ``specified in 
Sec. 60.487(d).''


Sec. 60.483-2  [Amended]

    152. In Sec. 60.483-2, paragraph (a)(2) is amended by revising the 
words ``specified in Sec. 60.487(b)'' to read ``specified in 
Sec. 60.487(d).''


Sec. 60.484  [Amended]

    153. In Sec. 60.484, paragraph (f)(2) is amended by revising the 
words ``paragraphs (b), (c), (d), and (e)'' to read

[[Page 61763]]

``paragraphs (b), (c), (d), and (e) of this section.''


Sec. 60.485  [Amended]

    154. Amend Sec. 60.485 as follows:
    a. In paragraph (c)(2), in the third sentence by revising the word 
``indicates'' is revised to read ``indicated.''
    b. In paragraph (d), in the first sentence by revising the words 
``in VOC series'' to read ``in VOC service.''
    c. In paragraph (d)(1) by revising the words ``ASTM E-260, E-168, 
E-169'' to read ``ASTM E260-73, 91, or 96, E168-67, 77, or 92, E169-63, 
77, or 93.''
    d. In paragraphs (e)(1) and (e)(2) by revising the words ``0.3 kPa 
at 20 deg.C'' to read ``0.3 kPa at 20  deg.C (1.2 in. H2O at 
68  deg.F)'' wherever they occur.
    e. In paragraph (e)(1) by revising ``ASTM D-2879'' to read ``ASTM 
D2879-83, 96, or 97.''
    f. In paragraph (f) by revising the words ``paragraphs (d), (e), 
and (g)'' to read ``paragraphs (d), (e), and (g) of this section.''
    g. Paragraphs (g)(3) and (g)(4) are revised.
    h. In paragraph (g)(5) by revising ``ASTM D 2504-67'' to read 
``ASTM D2504-67, 77, or 88 (Reapproved 1993).''
    i. In paragraph (g)(6) by revising ``ASTM D 2382-76'' to read 
``ASTM D2382-76 or 88 or D4809-95.''
    The revisions read as follows:


Sec. 60.485  Test methods and procedures.

* * * * *
    (g) * * *
    (3) The maximum permitted velocity for air assisted flares shall be 
computed using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.016


Where:

Vmax = Maximum permitted velocity, m/sec (ft/sec)
HT = Net heating value of the gas being combusted, MJ/scm 
(Btu/scf).
K1 = 8.706 m/sec (metric units)
     = 28.56 ft/sec (English units)
K2 = 0.7084 m\4\/(MJ-sec) (metric units)
    = 0.087 ft\4\/(Btu-sec) (English units)

    (4) The net heating value (HT) of the gas being combusted in a 
flare shall be computed using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.017

Where:
K = Conversion constant, 1.740  x  10\7\ (g-mole)(MJ)/ (ppm-scm-kcal) 
(metric units)
    = 4.674  x  10\8\ [(g-mole)(Btu)/(ppm-scf-kcal)] (English units)
Ci = Concentration of sample component ``i,'' ppm
Hi = net heat of combustion of sample component ``i'' at 25 
deg.C and 760 mm Hg (77  deg.F and 14.7 psi), kcal/g-mole
* * * * *


Sec. 60.486  [Amended]

    155. In Sec. 60.486, paragraph (c)(8) is amended by revising the 
word ``shutdown'' to read ``shutdowns.''


Sec. 60.487  [Amended]

    156. In Sec. 60.487, paragraph (d) is amended by revising the words 
``An owner or operator electing to comply with the provisions of 
Secs. 60.483-1 and 60.483-2'' to read ``An owner or operator electing 
to comply with the provisions of Secs. 60.483-1 or 60.483-2.''


Sec. 60.489  [Amended]

    157. Amend the table in Sec. 60.489 as follows:
    a. Revise the chemical name ``Chlorbenzoyl chloride'' to read 
``Chlorobenzoyl chloride;''
    b. Revise the chemical name ``Chloronapthalene'' to read 
``Chloronaphthalene;''
    c. Revise the CAS No. for diethylene glycol monobutyl ether acetate 
to read 124-17-4;
    d. Revise the chemical name ``Ethylne carbonate'' to read 
``Ethylene carbonate;''
    e. Revise the chemical name ``Ethylene glycol monoethy ether'' to 
read ``Ethylene glycol monoethyl ether;''
    f. Revise the chemical name ``Propional dehyde'' to read 
``Propionaldehyde;'' and
    g. Revise the chemical name ``Tetrahydronapthalene'' to read 
``Tetrahydronaphthalene.''


Sec. 60.491  [Amended]

    158. In Sec. 60.491, paragraphs (a)(6) and (b) are amended by 
revising the word ``litre'' or ``litres'' to read ``liter'' or 
``liters'' wherever it occurs.


Sec. 60.493  [Amended]

    159. Amend Sec. 60.493 as follows:
    a. Paragraph (b)(1) is amended by revising the words ``Reference 
Method'' to read ``Method'' wherever they occur.
    b. Paragraph (b)(1)(i)(C) is amended by revising the words 
``volume-weighed average'' to read ``volume-weighted average.''
    c. In paragraph (b)(1)(i)(C), equation 3 is revised.
    d. Paragraph (b)(1)(iii) is amended by revising the words 
``weighted average of mass of VOC'' to read ``weighted average mass of 
VOC.''
    The revisions read as follows:


Sec. 60.493  Performance test and compliance provisions.

* * * * *
    (b) * * *
    (1) * * *
    (i) * * *
    (C) * * *
    [GRAPHIC] [TIFF OMITTED] TR17OC00.018
    
* * * * *


Sec. 60.494  [Amended]

    160. In Sec. 60.494, paragraph (b), the second sentence is amended 
by revising the words ``accuracy the greater of 0.75 
percent of the temperature being measured expressed in degrees Celsius 
or 2.5 deg.C to read ``accuracy of 0.75 percent of the 
temperature being measured, expressed in degrees Celsius, or 
2.5 deg.C, whichever is greater.''


Sec. 60.495  [Amended]

    161. In Sec. 60.495, paragraph (a)(1) is amended by revising the 
words ``from data determined using Reference Method 24 or supplies'' to 
read ``from data determined using Method 24 or supplied.''


Sec. 60.496  [Amended]

    162. Revise Sec. 60.496 as follows:
    a. Paragraph (a)(1) is revised.
    b. In paragraphs (a)(2), (b), and (c) by revising the words 
``Reference Method'' to read ``Method'' wherever they occur.
    c. In paragraph (a)(2) by revising the words ``30 days in advance'' 
to read ``at least 30 days in advance.''
    The revisions read as follows:


Sec. 60.496  Test methods and procedures.

    (a) * * *
    (1) Method 24, an equivalent or alternative method approved by the 
Administrator, or manufacturers' formulation data from which the VOC 
content of the coatings used for each affected facility can be 
calculated. In the event of a dispute, Method 24 data shall govern. 
When VOC content of water-borne coatings, determined from data 
generated by Method 24, is used to determine compliance of affected 
facilities, the results of the Method 24 analysis shall be adjusted as 
described in Section 12.6 of Method 24.
* * * * *


Sec. 60.501  [Amended]

    163. In Sec. 60.501, the definition of ``Vapor-tight gasoline tank 
truck'' is amended by revising the words ``Reference Method'' to read 
``Method.''


Sec. 60.531  [Amended]

    164. Amend Sec. 60.531 as follows:

[[Page 61764]]

    a. Under the definition of ``Coal-only heater'', the alphabetical 
designations of paragraphs (a) through (e) are removed and numerical 
designations (1) through (5) are added.
    b. Under the definition of ``Cookstove'', the alphabetical 
designations of paragraphs (a) through (g) are removed and numerical 
designations (1) through (7) are added.
    c. Under the definition of ``Wood heater'', paragraph (2) is 
amended by revising the words ``20 cubic feet'' to read ``0.57 cubic 
meters (20 cubic feet).''
    d. Under the definition of ``Wood heater'', paragraph (3) is 
amended by revising the words ``5 kg/hr'' to read ``5 kg/hr (11 lb/
hr).''
    e. Under the definition of ``Wood heater'', paragraph (4) is 
amended by revising the words ``800 kg'' to read ``800 kg (1,760 lb).''


Sec. 60.532  [Amended]

    165. Amend Sec. 60.532 as follows:
    a. In paragraph (b)(1) by revising the words ``4.1 g/hr'' to read 
``4.1 g/hr (0.009 lb/hr).''
    b. Paragraphs (b)(1)(i), (b)(1)(ii), and (b)(2) are revised.
    The revisions read as follows:


Sec. 60.532  Standards for particulate matter.

* * * * *
    (b) * * *
    (1) * * *
    (i) At burn rates less than or equal to 2.82 kg/hr (6.2 lb/hr),
    [GRAPHIC] [TIFF OMITTED] TR17OC00.019
    
Where:

BR = Burn rate in kg/hr (lb/hr)
K1 = 3.55 g/kg (0.00355 lb/lb)

K2 = 4.98 g/hr (0.0.011 lb/hr)

    (ii) At burn rates greater than 2.82 kg/hr (6.2 lb/hr), C = 15 g/hr 
(0.033 lb/hr).
    (2) An affected facility not equipped with a catalytic combustor 
shall not discharge into the atmosphere any gases which contain 
particulate matter in excess of a weighted average of 7.5 g/hr (0.017 
lb/hr). Particulate emissions shall not exceed 15 g/hr (0.033 lb/hr) 
during any test run at a burn rate less than or equal to 1.5 kg/hr (3.3 
lb/hr) that is required to be used in the weighted average and 
particulate emissions shall not exceed 18 g/hr (0.040 lb/hr) during any 
test run at a burn rate greater than 1.5 kg/hr (3.3 lb/hr) that is 
required to be used in the weighted average.
* * * * *


Sec. 60.533  [Amended]

    166. Amend Sec. 60.533 as follows:
    a. In paragraph (k)(1), the third sentence is amended by revising 
the words ``The grant of such a waiver'' to read ``The granting of such 
a waiver.''
    b. Paragraph (k)(2) is amended by revising the words `` 
\1/4\ inch'' to read `` 0.64 cm ( \1/4\ 
inch).''
    c. In paragraph (o)(4), the first sentence is amended by revising 
the word ``indicate'' to read ``indicates.''
    d. In paragraph (o)(4), the first sentence is amended by revising 
the words ``comply with applicable emission limit'' to read ``comply 
with the applicable emission limit.''
    e. In paragraph (p)(4)(ii)(A), the second sentence is amended by 
revising the words `` 1 gram per hour'' to read 
`` 1 gram per hour ( 0.0022 lb per hour).''


Sec. 60.535  [Amended]

    167. In Sec. 60.535, paragraph (b)(9) is amended by revising the 
words ``a reporting and recordkeeping requirements'' to read 
``reporting and recordkeeping requirements.''


Sec. 60.536  [Amended]

    168. Amend Sec. 60.536 as follows:
    a. Paragraph (a)(3)(ii) and the equation in (i)(4)(ii) are revised.
    b. Paragraph (j)(2)(v) is amended by revising the words ``five 
inches by seven inches'' to read ``12.7 centimeters by 17.8 centimeters 
(5 inches by 7 inches).''
    The revisions read as follows:


Sec. 60.536  Permanent label, temporary label, and owner's manual.

    (a) * * *
    (3) * * *
    (ii) Be at least 8.9 cm long and 5.1 cm wide (3\1/2\ inches long 
and 2 inches wide).
* * * * *
    (i) * * *
    (4) * * *
    (ii) * * *

HOE = Hv  x  (Estimated overall efficiency/100) 
x  BR

    Where:

    HOE = Estimated heat output in Btu/hr
    Hv = Heating value of fuel, 19,140 Btu/kg (8,700 Btu/lb)
    BR = Burn rate of dry test fuel per hour, kg (lb)
* * * * *


Sec. 60.541  [Amended]

    169. Amend Sec. 60.541 as follows:
    a. In paragraph (b), the definitions of the terms ``Dc'' 
and ``Dr'' are amended by revising the words ``(grams per 
liter)'' to read ``(grams per liter (lb per gallon)).''
    b. In paragraph (b), the definitions of the terms ``G'' and ``N'' 
are amended by revising the words ``(grams per tire)'' to read ``(grams 
(lb) per tire).''
    c. In paragraph (b), the definitions of the terms ``Gb'' 
and ``Nb'' are amended by revising the words ``(grams per 
bead)'' to read ``(grams (lb) per bead).''
    d. In paragraph (b), the definitions of the terms ``Lc'' 
and ``Lr'' are amended by revising the word ``(liters)'' to 
read ``(liters (gallons)).''
    e. In paragraph (b), the definitions of the terms ``M'', 
``Mo'', and ``Mr'' are amended by revising the 
word ``(grams)'' to read ``(grams (lb)).''
    f. In paragraph (b), the definitions of the terms 
``Qa'', ``Qb'', and ``Qf'' are amended 
by revising the words ``(dry standard cubic meters per hour)'' to read 
``(dry standard cubic meters (dry standard cubic feet) per hour).''


Sec. 60.542  [Amended]

    170. Amend Sec. 60.542 as follows:
    a. Paragraphs (a)(1)(ii)(A) through (E), (a)(2)(ii)(A) through (E), 
(a)(6)(ii)(A) through (E), (a)(8)(ii)(A) through (E), and (a)(9)(ii)(A) 
through (E) are revised.
    b. In paragraph (a)(3) by revising the words ``no more than 10 
grams of VOC per tire (g/tire)'' to read ``no more than 10 grams (0.022 
lb) of VOC per tire.''
    c. In paragraph (a)(4) by revising the words ``no more than 5 grams 
of VOC per bead (g/bead)'' to read ``no more than 5 grams (0.011 lb) of 
VOC per bead.''
    d. In paragraph (a)(5)(i) by revising the words ``1.2 grams of VOC 
per tire'' to read ``1.2 grams (0.0026 lb) of VOC per tire.''
    e. In paragraph (a)(5)(ii) by revising the words ``9.3 grams of VOC 
per tire'' to read ``9.3 grams (0.021 lb) of VOC per tire.''
    f. In paragraph (a)(7)(i) by revising the words ``1.2 grams of VOC 
per tire'' to read ``1.2 grams (0.0026 lb) of VOC per tire.''
    g. In paragraph (a)(7)(ii) by revising the words ``9.3 grams of VOC 
per tire'' to read ``9.3 grams (0.021 lb) of VOC per tire.''
    The revisions read as follows:


Sec. 60.542  Standards for volatile organic compounds.

    (a) * * *
    (1) * * *
    (ii) * * *
    (A) 3,870 kg (8,531 lb) of VOC per 28 days,
    (B) 4,010 kg (8,846 lb) of VOC per 29 days,
    (C) 4,150 kg (9,149 lb) of VOC per 30 days,
    (D) 4,280 kg (9,436 lb) of VOC per 31 days, or
    (E) 4,840 kg (10,670 lb) of VOC per 35 days.
* * * * *
    (2) * * *

[[Page 61765]]

    (ii) * * *
    (A) 3,220 kg (7,099 lb) of VOC per 28 days,
    (B) 3,340 kg (7,363 lb) of VOC per 29 days,
    (C) 3,450 kg (7,606 lb) of VOC per 30 days,
    (D) 3,570 kg (7,870 lb) of VOC per 31 days, or
    (E) 4,030 kg (8,885 lb) of VOC per 35 days.
* * * * *
    (6) * * *
    (ii) * * *
    (A) 3,220 kg (7,099 lb) of VOC per 28 days,
    (B) 3,340 kg (7,363 lb) of VOC per 29 days,
    (C) 3,450 kg (7,606 lb) of VOC per 30 days,
    (D) 3,570 kg (7,870 lb) of VOC per 31 days, or
    (E) 4,030 kg (8,885 lb) of VOC per 35 days.
* * * * *
    (8) * * *
    (ii) * * *
    (A) 1,570 kg (3,461 lb) of VOC per 28 days,
    (B) 1,630 kg (3,593 lb) of VOC per 29 days,
    (C) 1,690 kg (3,726 lb) of VOC per 30 days,
    (D) 1,740 kg (3,836 lb) of VOC per 31 days, or
    (E) 1,970 kg (4,343 lb) of VOC per 35 days.
* * * * *
    (9) * * *
    (ii) * * *
    (A) 1,310 kg (2,888 lb) of VOC per 28 days,
    (B) 1,360 kg (2,998 lb) of VOC per 29 days,
    (C) 1,400 kg (3,086 lb) of VOC per 30 days,
    (D) 1,450 kg (3,197 lb) of VOC per 31 days, or
    (E) 1,640 kg (3,616 lb) of VOC per 35 days.
* * * * *


Sec. 60.542a  [Amended]

    171. In Sec. 60.542a, paragraph (a) is amended by revising the 
words ``25 grams'' to read ``25 grams (0.055 lb)'' wherever they occur.


Sec. 60.543  [Amended]

    172. Amend Sec. 60.543 as follows:
    a. In paragraph (c), the first sentence is amended by deleting the 
abbreviation ``(kg/mo).''
    b. Paragraph (d) is amended by revising the words ``the g/tire 
limit'' to read ``the VOC emission per tire limit.''
    c. Paragraph (e) is amended by revising the words ``g/bead limit'' 
to read ``VOC emission per bead limit.''
    d. Paragraph (f) is amended by revising the words ``operation that 
use'' to read ``operation that uses.''
    e. Paragraphs (f)(2)(iv)(G) and (f)(2)(iv)(H) are amended by 
revising the definitions of the terms ``W'', ``V'', ``Qi'', 
and ``Mi'' following the equations as follows:

W = Molecular weight of the single VOC, mg/mg-mole (lb/lb-mole).
V = The volume occupied by one mole of ideal gas at standard conditions 
[20 deg.C, 760 mm Hg] on a wet basis, 2.405  x  10-5 
m3/mg-mole (385.3 ft3/lb-mole).
Qi = Volumetric flow in the capture system during run i, on 
a wet basis, adjusted to standard conditions, m3 
(ft3) (see Sec. 60.547(a)(5)).
Mi = Mass of the single VOC used during run i, mg (lb).

    f. Paragraphs (g) and (i) are amended by revising the words 
``operation that use'' to read ``operation that uses'' wherever they 
occur.
    g. Paragraphs (j)(4) and (j)(5)(ii) are amended by revising the 
words ``100 feet per minute'' to read ``30.5 meters (100 feet) per 
minute'' wherever they occur.
    h. Paragraphs (n) and (n)(5) are amended by revising the words ``25 
g/tire limit'' to read ``VOC emission per tire limit'' wherever they 
occur.


Sec. 60.544  [Amended]

    173. In Sec. 60.544, paragraph (a)(2) is amended by revising the 
word ``temperatrue'' to read ``temperature.''


Sec. 60.545  [Amended]

    174. Amend Sec. 60.545 as follows:
    a. Paragraph (b) is amended by revising the words ``28  deg.C'' to 
read ``28  deg.C (50  deg.F).''
    b. Paragraph (d) is amended by revising the words ``specified kg/mo 
uncontrolled VOC use'' to read ``specified VOC monthly usage.''
    c. Paragraph (f) is amended by revising the citation 
``Sec. 60.543(B)(4)'' to read ``Sec. 60.543(b)(4).''


Sec. 60.546  [Amended]

    175. Amend Sec. 60.546 as follows:
    a. Paragraph (a) is amended by revising the words ``green tires 
spraying operation where organic solvent-based spray are used'' to read 
``green tire spraying operation where organic solvent-based sprays are 
used.''
    b. Paragraph (c)(1) is amended by revising the words ``kg/mo 
uncontrolled VOC use'' to read ``VOC monthly usage.''
    c. Paragraph (c)(1) is amended by revising the words ``the number 
days'' to read ``the number of days.''
    d. Paragraphs (c)(2), (c)(3), and (c)(5) are amended by revising 
the words ``g/tire or g/bead limit'' to read ``VOC emission limit per 
tire or per bead'' wherever they occur.
    e. In paragraph (d), the second sentence is amended by revising the 
words ``(kg/hr)'' to read ``(kg/hr or lb/hr).''
    f. Paragraph (f)(1) is amended by revising the words ``g/tire or g/
bead limit'' to read ``VOC emission limit per tire or per bead.''
    g. Paragraph (f)(2) is amended by revising the words ``kg/mo VOC 
use'' to read ``monthly VOC usage.''
    h. In paragraph (j), the second sentence is amended by revising the 
words ``shall be reported within 30 days'' to read ``shall be reported 
within 30 days of the change.''


Sec. 60.547  [Amended]

    176. Amend Sec. 60.547 as follows:
    a. Paragraphs (a)(2) and (a)(5) are amended by revising the words 
``notify the Administrator 30 days in advance'' to read ``notify the 
Administrator at least 30 days in advance'' wherever they occur.
    b. Paragraphs (a)(2) and (a)(5) are amended by revising the words 
``1 meter'' to read ``1.0 meter (3.3 feet)'' wherever they occur.
    c. Paragraphs (a)(2) and (a)(5)(i) are amended by revising the 
words ``0.003 dry standard cubic meter'' to read ``0.003 dry standard 
cubic meter (dscm) (0.11 dry standard cubic feet (dscf))'' wherever 
they occur.


Sec. 60.560  [Amended]

    177. Amend Sec. 60.560 as follows:
    a. Paragraph (a)(4)(i) is amended by revising the words ``1,000 Mg/
yr'' to read ``1,000 Mg/yr (1,102 ton/yr).''
    b. In paragraph (b), Table 1 is revised to read as follows:

----------------------------------------------------------------------------------------------------------------
                                                                                            Emissions
           Polymer              Production  process(es)     Process section    ---------------------------------
                                                                                   Continuous      Intermittent
----------------------------------------------------------------------------------------------------------------
Polypropylene................  Liquid Phase............  Raw Materials                       X   ...............
                                                          Preparation.
                                                         Polymerization                      X   ...............
                                                          Reaction.

[[Page 61766]]

 
                                                         Material Recovery....               X                X
                                                         Product Finishing....               X   ...............
                                                         Product Storage......  ...............  ...............
Polypropylene................  Gas Phase...............  Raw Materials          ...............  ...............
                                                          Preparation.
                                                         Polymerization         ...............               X
                                                          Reaction.
                                                         Material Recovery....               X   ...............
                                                         Product Finishing....  ...............  ...............
                                                         Product Storage......  ...............  ...............
Low Density Polyethylene.....  High Pressure...........  Raw Materials          ...............               X
                                                          Preparation.
                                                         Polymerization         ...............               X
                                                          Reaction.
                                                         Material Recovery....  ...............               X
                                                         Product Finishing....  ...............               X
                                                         Product Storage......  ...............               X
Low Density Polyethylene.....  Low Pressure............  Raw Materials                       X                X
                                                          Preparation.
High Density Polyethylene....  Gas Phase...............  Polymerization         ...............               X
                                                          Reaction.
                                                         Material Recovery....  ...............  ...............
                                                         Product Finishing....               X   ...............
                                                         Product Storage......  ...............  ...............
High Density Polyethylene....  Liquid Phase Slurry.....  Raw Materials          ...............               X
                                                          Preparation.
                                                         Polymerization         ...............  ...............
                                                          Reaction.
                                                         Material Recovery....               X   ...............
                                                         Product Finishing....               X   ...............
                                                         Product Storage......  ...............  ...............
High Density Polyethylene....  Liquid Phase Solution...  Raw Materials                       X                X
                                                          Preparation.
                                                         Polymerization         ...............               X
                                                          Reaction.
                                                         Material Recovery....               X                X
                                                         Product Finishing....  ...............  ...............
                                                         Product Storage......  ...............  ...............
----------------------------------------------------------------------------------------------------------------


    c. In paragraph (d), Table 2 is revised.
    d. Paragraph (g) is amended by revising the words ``1.6 Mg/yr'' to 
read ``1.6 Mg/yr (1.76 ton/yr)'' wherever they occur.
    The revision reads as follows:


Sec. 60.560  Applicability and designation of affected facilities.

* * * * * * *
    (d) * * *

        Table 2.--Maximum Uncontrolled Threshold Emission Rates a
------------------------------------------------------------------------
                                                          Uncontrolled
                                                       emission rate, kg
      Production process           Process section       TOC/Mg product
                                                        (See associated
                                                           footnote)
------------------------------------------------------------------------
Polypropylene, liquid phase     Raw Materials          0.15 b
 process.                        Preparation.
                                Polymerization         0.14 b, 0.24 c
                                 Reaction.
                                Material Recovery....  0.19 b
                                Product Finishing....  1.57 b
Polypropylene, gas phase        Polymerization         0.12 c
 process.                        Reaction.
                                Material Recovery....  0.02 b
Low Density Polyethylene, low   Raw Materials          0.41 d
 pressure process.               Preparation.
                                Polymerization         (e)
                                 Reaction.
                                Material Recovery....  (e)
                                Product Finishing....  (e)
                                Product Storage......  (e)
Low Density Polythylene, low    Raw Materials          0.05 f
 pressure process.               Preparation.
                                Polymerization         0.03 g
                                 Reaction.
                                Product Finishing....  0.01 b
High Density Polyethylene,      Raw Materials          0.25 c
 liquid phase slurry process.    Preparation.
                                Material Recovery....  0.11 b
                                Product Finishing....  0.41 b
High Density Polyethylene,      Raw Materials          0.24 f
 liquid phase solution process.  Preparation.
                                Polymerization         0.16 c
                                 Reaction.
                                Material Recovery....  1.68 f
High Density Polyethylene, gas  Raw Materials          0.05 f
 phase process.                  Preparation.
                                Polymerization         0.03 g
                                 Reaction.

[[Page 61767]]

 
                                Product Finishing....  0.01 b
Polystyrene, continuous         Material Recovery....  0.05 b, h
 process.
Poly(ethylene terephalate),     Material Recovery....  0.12 b h
 dimethyl terephthalate
 process.
                                Polymerization         1.80 h i j,
                                 Reaction.
Poly(ethlyene terephthalate),   Raw Materials          (l)
 terephthalic acid process.      Preparation.
                                Polymerization         1.80 h j m
                                 Reaction.
                                                       3.92 h k m
------------------------------------------------------------------------
a ``Uncontrolled emission rate'' refers to the emission rate of a vent
  stream that vents directly to the atmosphere and to the emission rate
  of a vent stream to the atmosphere that would occur in the absence of
  any add-on control devices but after any material recovery devices
  that constitute part of the normal material recovery operations in a
  process line where potential emissions are recovered for recycle or
  resale.
b Emission rate applies to continuous emissions only.
c Emission rate applies to intermittent emissions only.
d Total emission rate for non-emergency intermittent emissions from raw
  materials preparation, polymerization reaction, material recovery,
  product finishing, and product storage process sections.
e See footnote d.
f Emission rate applies to both continuous and intermittent emissions.
 g Emission rate applies to non-emergency intermittent emissions only.
 h Applies to modified or reconstructed affected facilities only.
 i Includes emissions from the cooling water tower.
 j Applies to a process line producing low viscosity poly(ethylene
  terephthlalate).
 k Applies to a process line producing high viscosity poly(ethylene
  terephathalate).
 l See footnote m.
 m Applies to the sum of emissions to the atmosphere from the
  polymerization reaction section (including emissions from the cooling
  tower) and the raw materials preparation section (i.e., the
  esterifiers).

* * * * *


Sec. 60.561  [Amended]

    178. Amend Sec. 60.561 as follows:
    a. The definition of ``End finisher'' is amended as revising the 
words ``2 torr'' in the first sentence to read ``2 mm Hg (1 in. 
H2O)''; and by revising the words ``between 5 and 10 torr'' 
in the second sentence to read ``between 5 and 10 mm Hg (3 and 5 in. 
H2O).''
    b. The definition of ``High density polyethylene (HDPE)'' is 
amended by revising the words ``0.940 g/cm\3\'' to read ``0.940 gm/
cm\3\3 (58.7 lb/ft\3\).''
    c. The definition of ``High pressure process'' is amended by 
revising the words ``15,000 psig'' to read ``15,000 psig (103,000 kPa 
gauge).''
    d. The definition of ``Low density polyethylene (LDPE)'' is amended 
by revising the words ``0.940 g/cm\3\'' to read ``0.940 g/cm\3\ (58.7 
lb/ft\3\).''
    e. The definition of ``Low pressure process'' is amended by 
revising the words ``300 psig'' to read ``300 psig (2,070 kPa gauge).''


Sec. 60.562-1  [Amended]

    179. Amend Sec. 60.562-1 as follows:
    a. In paragraph (a)(1)(iii), the second sentence is amended by 
revising the words ``18.2 Mg/yr'' to read ``18.2 Mg/yr (20.1 ton/yr).''
    b. Paragraph (b)(1)(i) is amended by revising the words ``0.0036 kg 
TOC/Mg'' to read ``0.0036 kg TOC/Mg (0.0072 lb TOC/ton).''
    c. Paragraph (c)(1)(i)(A) is amended by revising the words ``0.018 
kg TOC/Mg'' to read ``0.018 kg TOC/Mg (0.036 lb TOC/ton).''
    d. Paragraph (c)(1)(ii)(A) is amended by revising the words ``0.02 
kg TOC/Mg'' to read ``0.02 kg TOC/Mg (0.04 lb TOC/ton).''
    e. Paragraph (c)(1)(ii)(C) is amended by inserting a comma after 
the word ``weight''.
    f. Paragraph (c)(2)(i) is amended by revising the words ``0.04 kg 
TOC/Mg'' to read ``0.04 kg TOC/Mg (0.08 lb TOC/ton).''
    g. Paragraph (c)(2)(ii)(A) is amended by revising the words ``0.02 
kg TOC/Mg'' to read ``0.02 kg TOC/Mg (0.04 lb TOC/ton).''
    h. Paragraph (c)(2)(ii)(C) is amended by inserting a comma after 
the word ``weight''.


Sec. 60.562-2  [Amended]

    180. In Sec. 60.562-2, paragraph (d) is amended by revising the 
words ``150  deg.C as determined by ASTM Method D86-78'' to read ``150 
deg.C (302  deg.F) as determined by ASTM Method D86-78, 82, 90, 95, or 
96.''


Sec. 60.564  [Amended]

    181. Amend Sec. 60.564 as follows:
    a. In paragraph (c)(1), the definitions of the terms 
``Einlet'' and ``Eoutlet'' are amended by 
revising the words ``kg TOC/hr'' to read ``kg TOC/hr (lb TOC/hr)'' 
wherever they occur.
    b. In Paragraphs (d)(1), (f) introductory text, and (j)(1)(iv), the 
equations and definitions are revised; and paragraphs (g)(2) and (g)(3) 
are revised.
    c. Paragraph (f)(1) is amended by revising ``ASTM D1946-77'' to 
read ``ASTM D1946-77 or 90 (Reapproved 1994).''
    d. Paragraph (f)(3) is amended by revising ``ASTM D2382-76'' to 
read ``ASTM D2382-76 or 88 or D4809-95.''
    e. In paragraph (h) designate the second paragraph as (h)(1), 
redesignate existing paragraphs (h)(1) and (h)(2) as paragraphs (h)(2) 
and (h)(3) and revise the equations and definitions in newly 
redesignated paragraph (h)(1).
    f. Paragraph (h)(3) is amended by revising the words ``The rate of 
polymer produced, Pp (kg/hr), shall be determined by 
dividing the weight of polymer pulled in kilograms (kg) from the 
process line during the performance test by the number of hours (hr) 
taken to perform the performance test. The polymer pulled, in 
kilograms, shall'' to read ``The rate of polymer production, 
Pp, shall be determined by dividing the weight of polymer 
pulled (in kg (lb)) from the process line during the performance test 
by the number of hours taken to perform the performance test. The 
weight of polymer pulled shall.''
    g. Paragraph (j)(1) introductory text is amended by revising ``ASTM 
D2908-74'' to read ``ASTM D2908-74 or 91.''

[[Page 61768]]

    h. Paragraph (j)(1)(i) is amended by revising ``ASTM D3370-76'' to 
read ``ASTM D3370-76 or 96a.''
    The revisions read as follows:


Sec. 60.564  Test methods and procedures.

* * * * *
    (d) * * *
    (1)
    [GRAPHIC] [TIFF OMITTED] TR17OC00.020
    
Where:

Eunc = uncontrolled annual emissions, Mg/yr (ton/yr)
Cj = concentration of sample component j of the gas stream, 
dry basis, ppmv
Mj = molecular weight of sample component j of the gas 
stream, g/g-mole (lb/lb-mole)
Q = flow rate of the gas stream, dscm/hr (dscf/hr)
K2 = 4.157  x  10-11 [(Mg)(g-mole)]/
[(g)(ppm)(dscm)] (metric units)
    = 1.298  x  10-12 [(ton)(lb-mole)]/[(lb)(ppm)(dscf)] 
(English units)
8,600 = operating hours per year
* * * * *
    (f) * * *
    [GRAPHIC] [TIFF OMITTED] TR17OC00.021
    
Where:

HT = Vent stream net heating value, MJ/scm (Btu/scf), where 
the net enthalpy per mole of offgas is based on combustion at 25  deg.C 
and 760 mm Hg (68  deg.F and 30 in. Hg), but the standard temperature 
for determining the volume corresponding to one mole is 20  deg.C (68 
deg.F).
K3 = 1.74  x  10-7 (1/ppm)(g-mole/scm)(MJ/kcal) 
(metric units), where standard temperature for (g-mole/scm) is 
20 deg.C.
    = 4.67  x  10-6 (1/ppm)(lb-mole/scf)(Btu/kcal) (English 
units) where standard temperature for (lb/mole/scf) is 68  deg.F.
Cj = Concentration on a wet basis of compound j in ppm.
Hj = Net heat of combustion of compound j, kcal/(g-mole) 
(kcal/(lb-mole)), based on combustion at 25  deg.C and 760 mm Hg (77 
deg.F and 30 in. Hg).
* * * * *
    (g) * * *
    (2) If applicable, the maximum permitted velocity (Vmax) 
for steam-assisted and nonassisted flares shall be computed using the 
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.022

Where:

Vmax = Maximum permitted velocity, m/sec (ft/sec)
K4 = 28.8 (metric units), 1212 (English units)
K5 = 31.7 (metric units), 850.8 (English units)
HT = The net heating value as determined in paragraph (f) of 
this section, MJ/scm (Btu/scf).

    (3) The maximum permitted velocity, Vmax, for air-
assisted flares shall be determined by the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.023

Where:
Vmax = Maximum permitted velocity, m/sec (ft/sec).
K6 = 8.706 m/sec (metric units)
     = 28.56 ft/sec (English units)
K7 = 0.7084 [(m/sec)/MJ/scm)] (metric units)
     = 0.00245 [(ft/sec)/Btu/scf)] (English units)
HT = The net heating value as determined in paragraph (f) of 
this section, MJ/scm (Btu/scf).
* * * * *
    (h) * * *
    (i) * * *
    [GRAPHIC] [TIFF OMITTED] TR17OC00.024
    
Where:

ERTOC = Emission rate of total organic compounds (minus 
methane and ethane), kg TOC/Mg (lb TOC/ton) product
ETOC = Emission rate of total organic compounds (minus 
methane and ethane) in the sample, kg/hr (lb/hr)
Pp = The rate of polymer production, kg/hr (lb/hr)
K5 = 1,000 kg/Mg (metric units)
     = 2,000 lb/ton (English units)
* * * * *
    (j) * * *
    (1) * * *
    (iv) * * *
    [GRAPHIC] [TIFF OMITTED] TR17OC00.025
    
Where:
Xi = daily ethylene glycol concentration for each day used 
to calculate the 14-day rolling average used in test results to justify 
implementing the reduced testing program.
n = number of ethylene glycol concentrations.
* * * * *


Sec. 60.565  [Amended]

    182. Amend Sec. 60.565 as follows:
    a. In paragraph (a)(1)(ii), the first sentence is amended by 
revising the words ``kilograms TOC (minus methane and ethane) per 
megagram of product'' to read ``kg TOC (minus methane and ethane) per 
Mg (lb TOC/ton) of product.''
    b. In paragraph (a)(2)(ii) by revising the word ``boiler'' to read 
``boilers.''
    c. In paragraph (f)(1)(i) by removing the words ``are exceeded.''


Sec. 60.581  [Amended]

    183. Amend Sec. 60.581 as follows:
    a. In paragraph (a), the definition of the term ``ink solids'' is 
amended by revising the words ``Reference Method'' to read ``Method.''
    b. In paragraph (b), the definitions of the terms 
``Woi'', ``Wsi'', and ``Woj'' are 
amended by revising the words ``Reference Method'' to read ``Method'' 
wherever they occur.


Sec. 60.583  [Amended]

    184. Amend Sec. 60.583 as follows:
    a. In paragraph (a) introductory text by revising the words 
``Reference Methods'' to read ``Methods.''
    b. In paragraphs (a)(1), (b)(4), (b)(5), (c)(2), (c)(3), and (c)(4) 
by revising the words ``Reference Method'' to read ``Method'' wherever 
they occur.


Sec. 60.584  [Amended]

    185. Amend Sec. 60.584 as follows:
    a. In paragraphs (b)(1) and (c)(1) by revising the words ``of 
0.75 percent of the temperature being measured or 
2.5 deg. C'' to read ``of 0.75 percent of the 
temperature being measured, expressed in degrees Celsius, or 
2.5 deg. C.''
    b. In paragraph (b)(2) by revising the words ``more than 28 deg. 
C'' to read ``more than 28 deg. C (50 deg. F).''


Sec. 60.593  [Amended]

    186. Amend Sec. 60.593 as follows:
    a. In paragraph (b)(2) by revising ``ASTM E-260, E-168, or E-169'' 
to read ``ASTM E260-73, 91, or 96, E168-67, 77, or 92, or E169-63, 77, 
or 93.''
    b. In paragraph (d) by revising ``ASTM Method D86'' to read ``ASTM 
Method D86-78, 82, 90, 95, or 96.''


Sec. 60.600  [Amended]

    187. In Sec. 60.600, paragraph (a) is amended by revising the words 
``500 megagrams'' to read ``500 Mg (551 ton).''


Sec. 60.602  [Amended]

    188. Amend Sec. 60.602 as follows:
    a. By removing the paragraph designation ``(a)''.
    b. In the first sentence, by revising the words ``10 kilograms (kg) 
VOC per megagram (Mg)'' to read ``10 kg/Mg (20 lb/ton).''

[[Page 61769]]

    c. In the second sentence, by revising the words ``10 kg VOC per 
Mg'' to read ``10 kg/Mg (20 lb/ton).''
    d. In the third sentence by revising the words ``17 kg VOC per Mg'' 
to read ``17 kg/Mg (34 lb/ton).''


Sec. 60.603  [Amended]

    189. Amend Sec. 60.603 as follows:
    a. In paragraph (b) introductory text, the first sentence is 
amended by revising the words ``VOC emissions per Mg solvent feed'' to 
read ``VOC emissions per unit mass solvent feed.''
    b. In paragraph (b)(2) by revising the second equation and by 
revising the definitions following the equations.
    c. Paragraph (b)(2)(i) is redesignated as paragraph (b)(3), and 
newly redesignated paragraph (b)(3) is amended by revising the words 
``13 kg per Mg solvent feed'' to read ``13 kg/Mg (26 lb/ton) solvent 
feed.''
    The revisions read as follows:


Sec. 60.603  Performance test and compliance provisions.

* * * * *
    (b) * * *
    (2) * * *
    [GRAPHIC] [TIFF OMITTED] TR17OC00.026
    
E = VOC Emissions, in kg/Mg (lb/ton) solvent;
SV = Measured or calculated volume of solvent feed, in 
liters (gallons);
SW = Weight of solvent feed, in Mg (ton);
MV = Measured volume of makeup solvent, in liters (gallons);
MW = Weight of makeup, in kg (lb);
N = Allowance for nongaseous losses, 13 kg/Mg (26 lb/ton) solvent feed;
SP = Fraction of measured volume that is actual solvent 
(excludes water);
D = Density of the solvent, in kg/liter (lb/gallon);
K = Conversion factor, 1,000 kg/Mg (2,000 lb/ton);
I = Allowance for solvent inventory variation or changes in the amount 
of solvent contained in the affected facility, in kg/Mg (lb/ton) 
solvent feed (may be positive or negative);
IS = Amount of solvent contained in the affected facility at 
the beginning of the test period, as determined by the owner or 
operator, in kg (lb);
IE = Amount of solvent contained in the affected facility at 
the close of the test period, as determined by the owner or operator, 
in kg (lb).
* * * * *


Sec. 60.604  [Amended]

    190. In Sec. 60.604, paragraph (b) is amended by revising the words 
``500 megagrams'' to read ``500 Mg (551 ton)'' wherever they occur.


Sec. 60.613  [Amended]

    191. Amend Sec. 60.613 as follows:
    a. In paragraph (c) introductory text by revising the words ``in 
the following equipment'' to read ``the following equipment.''
    b. Paragraphs (d) and (e) are redesignated as (e) and (f).
    c. Paragraph (c)(3) is redesignated as paragraph (d).


Sec. 60.614  [Amended]

    192. Amend Sec. 60.614 as follows:
    a. In paragraph (b)(4)(ii), the definitions of the terms 
``Ei'' and ``Eo'' are amended by revising the 
term ``kg TOC/hr'' to read ``kg/hr (lb/hr).''
    b. In paragraph (b)(4)(iii), the definition of the terms 
``Qi, Qo'' is amended by revising the units 
``dscf/hr'' to read ``dscf/min.''
    c. In paragraph (b)(4)(iii), the definition of the term 
``K2'' is revised.
    d. Paragraphs (b)(5), (c), (d), (e), and (f) are redesignated as 
paragraphs (c), (d), (e), (f), and (g), respectively.
    e. In newly redesignated paragraph (e)(1)(i), the second sentence 
is amended by revising ``Sec. 60.614(d)(2) and (3)'' to read 
``Sec. 60.614(e)(2) and (3)'' and by revising the section reference 
``(d)(1)(ii)'' to read ``(e)(1)(ii).''
    f. In newly redesignated paragraph (e)(1)(i), the last sentence is 
amended by revising the words ``4 inches'' to read ``10 centimeters (4 
inches).''
    g. In newly redesignated paragraph (e)(1)(ii)(C), the second 
sentence is amended by revising ``Sec. 60.614(d)(4) and (5)'' to read 
``Sec. 60.614(e)(4) and (5).''
    h. Newly redesignated paragraph (e)(2)(ii) is amended by revising 
``ASTM D1946-77'' to read ``D1946-77, or 90 (Reapproved 1994).''
    i. In newly redesignated paragraphs (e)(4) and (e)(5), the 
definitions of the equation terms are revised.
    j. Newly redesignated paragraphs (f)(1)(i), including Table 1, and 
(f)(1)(ii) are revised.
    k. In newly redesignated paragraph (f)(2) the definitions of the 
equation terms and Table 2 are revised.
    The revisions read as follows:


Sec. 60.614  Test methods and procedures.

* * * * *
    (b) * * *
    (4) * * *
    (iii) * * *

K2 = 2.494  x  10-6 (1/ppm)(g-mole/scm)(kg/
g)(min/hr) (metric units), where standard temperature for (g-mole/scm) 
is 20 deg.C.
    = 1.557  x  10-7 (1/ppm)(lb-mole/scf)(min/hr) (English 
units), where standard temperature for (lb-mole/scf) is 68 deg.F.
* * * * *
    (e) * * *
    (4) * * *

HT = Net heating value of the sample, MJ/scm (Btu/scf), 
where the net enthalpy per mole of vent stream is based on combustion 
at 25 deg.C and 760 mm Hg (77 deg.F and 30 in. Hg), but the standard 
temperature for determining the volume corresponding to one mole is 
20 deg.C (68 deg.F).
K1 = 1.74  x  10-7 (1/ppm)(g-mole/scm)(MJ/kcal) 
(metric units), where standard temperature for (g-mole/scm) is 
20 deg.C.
    = 1.03  x  10-11 (1/ppm)(lb-mole/scf)(Btu/kcal) (English 
units) where standard temperature for (lb/mole/scf) is 68 deg.F.
Cj = Concentration on a wet basis of compound j in ppm, as 
measured for organics by Method 18 and measured for hydrogen and carbon 
monoxide by ASTM D1946-77, 90, or 94 (incorporation by reference as 
specified in Sec. 60.17 of this part) as indicated in 
Sec. 60.614(e)(2).
Hj = Net heat of combustion of compound j, kcal/(g-mole) 
[kcal/(lb-mole)], based on combustion at 25 deg.C and 760 mm Hg (77 
deg.F and 30 in. Hg).
    (5) * * *
ETOC = Measured emission rate of TOC, kg/hr (lb/hr).
K2 = 2.494  x  10-6 (1/ppm)(g-mole/scm)(kg/
g)(min/hr) (metric units), where standard temperature for (g-mole/scm) 
is 20 deg.C.
    = 1.557  x  10-7 (1/ppm)(lb-mole/scf)(min/hr) (English 
units), where standard temperature for (lb-mole/scf) is 68 deg.F.
Cj = Concentration on a wet basis of compound j in ppm, as 
measured by Method 18 as indicated in Sec. 60.614(e)(2).
Mj = Molecular weight of sample j, g/g-mole (lb/lb-mole).
Qs = Vent stream flow rate, scm/hr (scf/hr), at a 
temperature of 20 deg.C (68 deg.F).
* * * * *
    (f) * * *
    (1) * * *
    (i) Where for a vent stream flow rate that is greater than or equal 
to 14.2 scm/min (501 scf/min) at a standard temperature of 20  deg.C 
(68  deg.F):
TRE = TRE index value.
Qs = Vent stream flow rate, scm/min (scf/min), at a 
temperature of 20 deg.C (68  deg.F).
HT = Vent stream net heating value, MJ/scm (Btu/scf), where 
the net enthalpy per mole of vent stream is

[[Page 61770]]

based on combustion at 25 deg.C and 760 mm Hg (68 deg.F and 30 in. Hg), 
but the standard temperature for determining the volume corresponding 
to one mole is 20 deg.C (68 deg.F) as in the definition of 
Qs.
Ys = Qs for all vent stream categories listed in 
Table 1 except for Category E vent streams where Ys = 
QsHT/3.6.
    ETOC = Hourly emissions of TOC, kg/hr (lb/hr). a, b, c, 
d, e, and f are coefficients.

    The set of coefficients which apply to a vent stream shall be 
obtained from Table 1.
BILLING CODE 6560-50-P

[[Page 61771]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.027


[[Page 61772]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.028

[GRAPHIC] [TIFF OMITTED] TR17OC00.029

BILLING CODE 6560-50-C

[[Page 61773]]

    (ii) Where for a vent stream flow rate that is less than 14.2 scm/
min (501 scf/min) at a standard temperature of 20 deg.C (68 deg.F):

TRE = TRE index value.
Qs = 14.2 scm/min (501 scf/min).
HT = (FLOW)(HVAL)/Qs.

    Where the following inputs are used:

FLOW = Vent stream flow rate, scm/min (scf/min), at a temperature of 20 
 deg.C (68  deg.F).
HVAL = Vent stream net heating value, MJ/scm (Btu/scf), where the net 
enthalpy per mole of vent stream is based on combustion at 25  deg.C 
and 760 mm Hg (68  deg.F and 30 in. Hg), but the standard temperature 
for determining the volume corresponding to one mole is 20  deg.C (68 
deg.F) as in the definition of Qs.
Ys = Qs for all vent stream categories listed in 
Table 1 except for Category E vent streams where Ys = 
QsHT/3.6.
ETOC = Hourly emissions of TOC, kg/hr (lb/hr).

    a, b, c, d, e, and f are coefficients.
    The set of coefficients that apply to a vent stream can be obtained 
from Table 1.
    (2) * * *

TRE = TRE index value.
ETOC = Hourly emissions of TOC, kg/hr (lb/hr).
Qs = Vent stream flow rate, scm/min (scf/min), at a standard 
temperature of 20  deg.C (68  deg.F).
HT = Vent stream net heating value, MJ/scm (Btu/scf), where 
the net enthalpy per mole of vent stream is based on combustion at 25 
deg.C and 760 mm Hg (68  deg.F and 30 in. Hg), but the standard 
temperature for determining the volume corresponding to one mole is 20 
deg.C (68  deg.F) as in the definition of Qs.

    a, b, c, d, and e are coefficients.
* * * * *

          Table 2.--Air Oxidation Processes NSPS TRE Coefficients for Vent Streams Controlled by a Flare
----------------------------------------------------------------------------------------------------------------
                                                  a             b             c             d             e
----------------------------------------------------------------------------------------------------------------
 HT  11.2 MJ/scm..........................          2.25         0.288        -0.193      (-0.0051          2.08
 (HT  301 Btu/scf)........................       (0.140)      (0.0367)   (-0.000448)     (-0.0051)        (4.59)
 HT  11.2 MJ/scm...............         0.309        0.0619       -0.0043       -0.0034          2.08
 HT  301 Btu/scf)..............      (0.0193)     (0.00788)   (-0.000010)     (-0.0034)        (4.59)
----------------------------------------------------------------------------------------------------------------

* * * * *


Sec. 60.615  [Amended]

    193. Amend Sec. 60.615 as follows:
    a. In paragraph (e), the first sentence is amended by revising the 
words ``44 MW'' to read ``44 MW (150 million Btu/hour).''
    b. In paragraph (g), the first sentence is amended by revising 
``Sec. 60.613(c)'' to read ``Sec. 60.613(e).''


Sec. 60.620  [Amended]

    194. In Sec. 60.620, paragraph (b), the second sentence is amended 
by revising the words ``4,700 gallons'' to read ``17,791 liters (4,700 
gallons).''


Sec. 60.624  [Amended]

    195. In Sec. 60.624, the third sentence is amended by revising the 
words ``is from the outlet'' to read ``is the outlet.''


Sec. 60.632  [Amended]

    196. Amend Sec. 60.632 as follows:
    a. In paragraph (f), the second sentence is amended by revising the 
words ``percent VOC content'' to read ``VOC content.''
    b. Paragraph (f) is amended by revising ``ASTM Methods E169, E168, 
or E260'' to read ``ASTM E169-63, 77, or 93, E168-67, 77, or 92, or 
E260-73, 91, or 96.''


Sec. 60.633  [Amended]

    197. Amend Sec. 60.633 as follows:
    a. Paragraph (b)(4)(i) is amended by revising ``Sec. 60.482-
(b)(1)'' to read ``Sec. 60.482-4(b)(1).''
    b. Paragraph (d) is amended by revising the words ``283,000 
standard cubic meters per day (scmd) (10 million standard cubic feet 
per day (scfd))'' to read ``283,200 standard cubic meters per day (10 
million standard cubic feet per day).''
    c. Paragraphs (h)(1) and (2) are amended by revising the words ``at 
150  deg.C'' to read ``at 150  deg.C (302  deg.F).''
    d. Paragraphs (h)(1) and (2) are amended by revising the words 
``ASTM Method D86'' to read ``ASTM Method D86-78, 82, 90, 95, or 96.''


Sec. 60.641  [Amended]

    198. Amend Sec. 60.641 as follows:
    a. The definition for ``Total SO2'' is amended by 
revising the words ``(ppmv or kg/DSCM)'' to read ``(ppmv or kg/dscm 
(lb/dscf)).''
    b. The definitions for ``E'', ``S'', and ``X'' are amended to read 
as follows:


Sec. 60.641  Definitions.

* * * * *
E = The sulfur emission rate expressed as elemental sulfur, kilograms 
per hour (kg/hr) [pounds per hour (lb/hr)], rounded to one decimal 
place.
* * * * *
S = The sulfur production rate, kilograms per hour (kg/hr) [pounds per 
hour (lb/hr)], rounded to one decimal place.
X = The sulfur feed rate from the sweetening unit (i.e., the 
H2S in the acid gas), expressed as sulfur, Mg/D(LT/D), 
rounded to one decimal place.
* * * * *


Sec. 60.644  [Amended]

    199. Amend Sec. 60.644 as follows:
    a. Paragraphs (b)(1), (c)(3), and (c)(4)(iii) are revised.
    b. In paragraph (b)(2), the first sentence is amended by revising 
the words ``dscf/day'' to read ``dscm/day (dscf/day).''
    c. In paragraph (c)(2), the second sentence is amended by revising 
the words ``kg/hr'' to read ``kg/hr (lb/hr).''
    d. In the paragraph (c)(4) introductory text, the first sentence is 
revised.
    e. Paragraph (c)(4)(i) is amended by deleting the words ``in mg/
dscm'' in the third sentence and by revising the last sentence.
    f. In paragraph (c)(4)(ii), the last sentence is revised.
    g. In paragraph (c)(4)(iv), the fifth sentence is amended by 
revising the words ``(0.35 dscf)'' to read ``(3.5 dscf).''
    h. Paragraph (d) is amended by revising the words ``(b) of (c)'' to 
read ``(b) or (c).''
    The revisions read as follows:


Sec. 60.644  Test methods and procedures.

* * * * *
    (b) * * *
    (1) The average sulfur feed rate (X) shall be computed as follows:
    [GRAPHIC] [TIFF OMITTED] TR17OC00.030
    
Where:

X = average sulfur feed rate, Mg/D (LT/D).
Qa = average volumetric flow rate of acid gas from 
sweetening unit, dscm/day (dscf/day).
Y = average H2S concentration in acid gas feed from 
sweetening unit, percent by volume, expressed as a decimal.

[[Page 61774]]

K = (32 kg S/kg-mole)/((24.04 dscm/kg-mole)(1000 kg S/ Mg)) = 1.331  x  
10-3 Mg/dscm, for metric units
    = (32 lb S/lb-mole)/((385.36 dscf/lb-mole)(2240 lb S/long ton))
    = 3.707  x  10-5 long ton/dscf, for English units.
* * * * *
    (c) * * *
    (3) The emission rate of sulfur shall be computed for each run as 
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.031

Where:

E = emission rate of sulfur per run, kg/hr.
Ce = concentration of sulfur equivalent (SO2 + 
reduced sulfur), g/dscm (lb/dscf).
Qsd = volumetric flow rate of effluent gas, dscm/hr (dscf/
hr).
K1 = conversion factor, 1000 g/kg (7000 gr/lb).

    (4) The concentration of sulfur equivalent (Ce) shall be 
the sum of the SO2 and reduced sulfur concentrations, after 
being converted to sulfur equivalents. * * *
    (i) * * * The concentration shall be multiplied by 0.5  x  
10-\3\ to convert the results to sulfur equivalent.
    (ii) * * * The concentration in ppm reduced sulfur as sulfur shall 
be multiplied by 1.333  x  10-3 to convert the results to 
sulfur equivalent.
    (iii) Method 16A or 15 shall be used to determine the reduced 
sulfur concentration from oxidation-type devices or where the oxygen 
content of the effluent gas is greater than 1.0 percent by volume. 
Eight samples of 20 minutes each shall be taken at 30-minute intervals. 
The arithmetic average shall be the concentration for the run. The 
concentration in ppm reduced sulfur as sulfur shall be multiplied by 
1.333  x  10-3 to convert the results to sulfur equivalent.
* * * * *


Sec. 60.646  [Amended]

    200. Amend Sec. 60.646 as follows:
    a. In paragraph (b)(1), the second sentence is amended by revising 
the words ``(kg/hr)'' to read ``(kg/hr (lb/hr)).''
    b. In paragraph (c), the second sentence is amended by revising the 
words ``(kg/hr)'' to read ``(kg/hr (lb/hr)).''
    c. In paragraph (e), the first sentence is amended by revising the 
words ``150 LT/D'' to read ``152 Mg/D (150 LT/D).''
    d. In paragraph (e), the equation and definitions are amended by 
revising as follows:


Sec. 60.646  Monitoring of emissions and operations.

* * * * *
    (e) * * *
    [GRAPHIC] [TIFF OMITTED] TR17OC00.032
    
Where:

R = The sulfur dioxide removal efficiency achieved during the 24-hour 
period, percent.
K2 = Conversion factor, 0.02400 Mg/D per kg/hr (0.01071 LT/D 
per lb/hr).
S = The sulfur production rate during the 24-hour period, kg/hr (lb/
hr).
X = The sulfur feed rate in the acid gas, Mg/D (LT/D).
* * * * *


Sec. 60.663  [Amended]

    201. Amend Sec. 60.663 as follows:
    a. In paragraph (c) introductory text by revising the words ``in 
the following equipment'' to read ``the following equipment.''
    b. Paragraphs (d) and (e) are redesignated as (e) and (f) and 
paragraph (c)(3) is redesignated as paragraph (d).
    c. In newly redesignated paragraph (f) by revising the words 
``carbon absorber'' to read ``carbon adsorber.''


Sec. 60.664  [Amended]

    202. Amend Sec. 60.664 as follows:
    a. In paragraph (b)(4)(ii), the definitions of the terms 
``Ei'' and ``Eo'' are amended by revising the 
term ``kg TOC/hr'' to read ``kg/hr (lb/hr).''
    b. In paragraph (b)(4)(iii), the definitions of the terms 
``Qi'' and ``Qo'' are amended by revising the 
units ``dscf/hr'' to read ``dscf/min.''
    c. In paragraph (b)(4)(iii), the definition of the term 
``K2'' is revised.
    d. Paragraphs (b)(5), (c), (d), (e), (f), and (g) are redesignated 
as paragraphs (c), (d), (e), (f), (g), and (h), respectively.
    e. In newly redesignated paragraph (e)(1)(i), the second sentence 
is amended by revising ``Sec. 60.664(d)(2) and (3)'' to read 
``Sec. 60.664(e)(2) and (3).''
    f. In newly redesignated paragraph (e)(1)(i), the second sentence 
is amended by revising ``(d)(1)(ii)'' to read ``(e)(1)(ii).''
    g. In newly redesignated paragraph (e)(1)(i), the third sentence is 
amended by revising the words ``4 inches'' to read ``10 centimeters (4 
inches).''
    h. In newly redesignated paragraph (e)(1)(ii)(C), the second 
sentence is amended by revising ``Sec. 60.664(d)(4) and (5)'' to read 
``Sec. 60.664(e)(4) and (5).''
    i. Newly redesignated paragraph (e)(2)(ii) is amended by revising 
``ASTM D1946-77'' to read ``ASTM D1946-77 or 90 (Reapproved 1994).''
    j. In newly redesignated paragraphs (e)(4), (e)(5) and (f)(2), the 
equation definitions are revised; and newly redesignated paragraphs 
(f)(1)(i), (f)(1)(ii) including Table 1, and Table 2 of (f)(2)are 
revised.
    k. The last sentence in the newly redesignated paragraph (e)(4) is 
amended by revising ``ASTM D2382-76'' to read ``ASTM D2382-76 or 88 or 
D4809-95.''
    The revisions read as follows:


Sec. 60.664  Test methods and procedures.

* * * * *
    (b) * * *
    (4) * * *
    (iii) * * *

K2 = 2.494  x  10-6 (1/ppm)(g-mole/scm) (kg/g) 
(min/hr) (metric units), where standard temperature for (g-mole/scm) is 
20  deg.C.
    = 1.557  x  10-7 (1/ppm) (lb-mole/scf) (min/hr) (English 
units), where standard temperature for (lb-mole/scf) is 68  deg.F.
* * * * *
    (e) * * *
    (4) * * *
HT = Net heating value of the sample, MJ/scm (Btu/scf), 
where the net enthalpy per mole of vent stream is based on combustion 
at 25  deg.C and 760 mm Hg (77  deg.F and 30 in. Hg), but the standard 
temperature for determining the volume corresponding to one mole is 20 
deg.C (68  deg.F).
K1 = 1.74  x  10-7 (1/ppm) (g-mole/scm) (MJ/kcal) 
(metric units), where standard temperature for (g-mole/scm) is 20 
deg.C.
    = 1.03  x  10-11 (1/ppm) (lb-mole/scf) (Btu/kcal) 
(English units) where standard temperature for (lb/mole/scf) is 68 
deg.F.
Cj = Concentration on a wet basis of compound j in ppm, as 
measured for organics by Method 18 and measured for hydrogen and carbon 
monoxide by ASTM D1946-77 or 90 (Reapproved 1994) (incorporation by 
reference as specified in Sec. 60.17 of this part) as indicated in 
Sec. 60.664(e)(2).
Hj = Net heat of combustion of compound j, kcal/(g-mole) 
[kcal/(lb-mole)], based on combustion at 25  deg.C and 760 mm Hg (77 
deg.F and 30 in. Hg).
* * * * *
    (5) * * *

ETOC = Measured emission rate of TOC, kg/hr (lb/hr).
K2 = 2.494 x 10-6 (1/ppm) (g-mole/scm) (kg/g) 
(min/hr) (metric units), where standard temperature for (g-mole/scm) is 
20  deg.C.
= 1.557  x  10-7 (1/ppm) (lb-mole/scf) (min/hr) (English 
units), where

[[Page 61775]]

standard temperature for (lb-mole/scf) is 68  deg.F.
Cj = Concentration on a wet basis of compound j in ppm, as 
measured by Method 18 as indicated in Sec. 60.664(e)(2).
Mj = Molecular weight of sample j, g/g-mole (lb/lb-mole).
Qs = Vent stream flow rate, scm/min (scf/min), at a 
temperature of 20  deg.C (68  deg.F).
* * * * *
    (f) * * *
    (1) * * *
    (i) Where for a vent stream flow rate that is greater than or equal 
to 14.2 scm/min (501 scf/min) at a standard temperature of 20  deg.C 
(68  deg.F):

TRE = TRE index value.
Qs = Vent stream flow rate, scm/min (scf/min), at a 
temperature of 20  deg.C (68  deg.F).
HT = Vent stream net heating value, MJ/scm (Btu/scf), where 
the net enthalpy per mole of vent stream is based on combustion at 25 
deg.C and 760 mm Hg (68  deg.F and 30 in. Hg), but the standard 
temperature for determining the volume corresponding to one mole is 20 
deg.C (68  deg.F) as in the definition of Qs.
Ys = Qs for all vent stream categories listed in 
Table 1 except for Category E vent streams where Ys = 
QsHT/3.6.
ETOC = Hourly emissions of TOC, kg/hr (lb/hr).

    a, b, c, d, e, and f are coefficients.
    The set of coefficients that apply to a vent stream can be obtained 
from Table 1.
BILLING CODE 6560-50-P
[GRAPHIC] [TIFF OMITTED] TR17OC00.033


[[Page 61776]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.034


[[Page 61777]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.035

[GRAPHIC] [TIFF OMITTED] TR17OC00.036

BILLING CODE 6560-50-C
    (ii) Where for a vent stream flow rate that is less than 14.2 scm/
min (501 scf/min) at a standard temperature of 20  deg.C (68  deg.F):

TRE = TRE index value.
Qs = 14.2 scm/min (501 scf/min).
HT = (FLOW) (HVAL)/Qs.
Where the following inputs are used:
FLOW = Vent stream flow rate, scm/min (scf/min), at a temperature of 20 
 deg.C (68  deg.F).
HVAL = Vent stream net heating value, MJ/scm (Btu/scf), where the net 
enthalpy per mole of vent stream is based on combustion at 25  deg.C 
and 760 mm Hg (68  deg.F and 30 in. Hg), but the standard temperature 
for determining the volume corresponding to one mole is 20  deg.C (68 
deg.F) as in the definition of Qs.
Ys = Qs for all vent stream categories listed in 
Table 1 except for Category E vent streams where Ys = 
QsHT/3.6.
ETOC = Hourly emissions of TOC, kg/hr (lb/hr).

    a, b, c, d, e, and f are coefficients

[[Page 61778]]

    The set of coefficients that apply to a vent stream can be obtained 
from Table 1.
    (2) * * *

TRE = TRE index value.
ETOC = Hourly emissions of TOC, kg/hr (lb/hr).
Qs = Vent stream flow rate, scm/min (scf/min), at a standard 
temperature of 20  deg.C (68  deg.F).
HT = Vent stream net heating value, MJ/scm (Btu/scf), where 
the net enthalpy per mole of vent stream is based on combustion at 25 
deg.C and 760 mm Hg (68  deg.F and 30 in. Hg), but the standard 
temperature for determining the volume corresponding to one mole is 20 
deg.C (68  deg.F) as in the definition of Qs.

    a, b, c, d, and e are coefficients.
* * * * *

               Table 2.--Distillation NSPS TRE Coefficients for Vent Streams Controlled By a Flare
----------------------------------------------------------------------------------------------------------------
                                         a               b               c               d               e
----------------------------------------------------------------------------------------------------------------
HT  11.2 MJ/scm.................            2.25           0.288          -0.193         -0.0051            2.08
(HT  301 Btu/scf)...............         (0.140)        (0.0367)     (-0.000448)       (-0.0051)          (4.59)
HT  11.2 MJ/scm......           0.309          0.0619         -0.0043         -0.0034            2.08
(HT  301 Btu/scf)....        (0.0193)       (0.00788)    (-0.0000010)       (-0.0034)          (4.59)
----------------------------------------------------------------------------------------------------------------

* * * * *


Sec. 60.665  [Amended]

    203. Amend Sec. 60.665 as follows:
    a. Paragraph (b)(4)(i) is amended by revising the word 
``adsorbing'' to read ``absorbing.''
    b. In paragraph (e), the first sentence is amended by revising the 
words ``44 MW'' to read ``44 MW (150 million Btu/hour).''
    c. In paragraph (g), the first sentence is amended by revising the 
section reference ``Sec. 60.663(d)'' to read ``Sec. 60.663(e).''
    d. Paragraph (i) is amended by revising the words ``0.008 
m3/min'' to read ``0.008 scm/min (0.3 scf/min).''
    e. In paragraph (l)(6), the fourth sentence is amended by revising 
the words ``vent stream flow rate, heating value, ETOC'' to 
read ``vent stream flow rate, heating value, and ETOC.''
    f. Paragraph (n) is amended by revising the word ``capcity'' to 
read ``capacity.''


Sec. 60.672  [Amended]

    204. In Sec. 60.672, paragraph (a)(1) is amended by revising the 
words ``0.05 g/dscm'' to read ``0.05 g/dscm (0.022 gr/dscf).''


Sec. 60.676  [Amended]

    205. In Sec. 60.676, paragraphs (a)(1)(i), (a)(4)(i), and 
(a)(4)(ii) are amended by revising the word ``tons'' to read 
``megagrams or tons'' wherever it occurs.


Sec. 60.685  [Amended]

    206. Amend Sec. 60.685 as follows:
    a. In paragraph (c)(1), the equation definitions are revised.
    b. In paragraph (c)(2) by revising the words ``2.55 dscm (90 
dscf)'' to read ``2.55 dscm (90.1 dscf).''
    c. In paragraph (c)(3)(i) by revising the words ``ASTM Standard 
Test Method D2584-68 (Reapproved 1979)'' to read ``ASTM D2584-68 
(Reapproved 1985) or 94.''
    The revisions read as follows:


Sec. 60.685  Test methods and procedures.

* * * * *
    (c) * * *
    (1) * * *

E = emission rate of particulate matter, kg/Mg (lb/ton).
Ct = concentration of particulate matter, g/dscm (gr/dscf).
Qsd = volumetric flow rate of effluent gas, dscm/hr (dscf/
hr).
Pavg = average glass pull rate, Mg/hr (ton/hr).
K = 1,000 g/kg (7,000 gr/lb).
* * * * *


Sec. 60.692-3  [Amended]

    207. In Sec. 60.692-3, paragraph (b) is amended by revising the 
words ``16 liters per second (250 gpm)'' to read ``16 liters per second 
(250 gallons per minute (gpm)).''


Sec. 60.695  [Amended]

    208. In Sec. 60.695, paragraphs (a)(1) and (2) are amended by 
revising the words ``an accuracy of 1 percent of the temperature being 
measured in  deg.C or 0.5  deg.C (1.0  deg.F), 
whichever is greater'' to read ``an accuracy of 1 percent 
of the temperature being measured, expressed in  deg.C, or 
0.5  deg.C (0.9  deg.F), whichever is greater.''


Sec. 60.697  [Amended]

    209. Amend Sec. 60.697 by adding paragraph (k) as follows:


Sec. 60.697  Recordkeeping requirements.

* * * * *
    (k) For oil-water separators subject to Sec. 60.693-2, the 
location, date, and corrective action shall be recorded for inspections 
required by Secs. 60.693-2(a)(1)(iii)(A) and (B), and shall be 
maintained for the time period specified in paragraphs (k)(1) and (2) 
of this section.
    (1) For inspections required by Sec. 60.693-2(a)(1)(iii)(A), ten 
years after the information is recorded.
    (2) For inspections required by Sec. 60.693-2(a)(1)(iii)(B), two 
years after the information is recorded.


Sec. 60.704  [Amended]

    210. Amend Sec. 60.704 as follows:
    a. Paragraph (d)(2)(ii) is amended by revising ``ASTM D1946-77'' to 
read ``ASTM D1946-77 or 90 (Reapproved 1994).''
    b. The definition of ``Cj'' in paragraph (d)(4) is 
amended by revising ``ASTM D1946-77'' to read ``ASTM D1946-77 or 90 
(Reapproved 1994).''
    c. The definition of ``Hj'' in paragraph (d)(4) is 
amended by revising ``ASTM D2382-76'' to read ``ASTM D2382-76 or 88 or 
D4809-95.''


Sec. 60.723  [Amended]

    211. In Sec. 60.723, paragraph (b)(1) is amended by revising the 
words ``Reference Method'' to read ``Method'' wherever they occur.


Sec. 60.724  [Amended]

    212. In Sec. 60.724, paragraph (a)(2) is amended by revising the 
words ``Reference Method'' to read ``Method.''


Sec. 60.732  [Amended]

    213. In Sec. 60.732, paragraph (a) is amended by revising the words 
``0.057 g/dscm for dryers'' to read ``0.057 g/dscm (0.025 gr/dscf) for 
dryers.''


Sec. 60.753  [Amended]

    214. In Sec. 60.753, paragraph (c)(2) introductory text is amended 
by revising the words ``Method 3A'' to read ``Method 3A or 3C.''


Sec. 60.754  [Amended]

    215. Amend Sec. 60.754 as follows;
    a. In paragraphs (a)(1)(i) and (a)(1)(ii), the equations are 
amended by revising ``CNMOC'' to read ``CNMOC.''

[[Page 61779]]

    b. In paragraph (a)(3), the introductory text is revised; and in 
paragraph (d), the first sentence is removed and three sentences are 
added in its place to read as follows:


Sec. 60.754  Test methods and procedures.

    (a) * * *
    (3) Tier 2. The landfill owner or operator shall determine the NMOC 
concentration using the following sampling procedure. The landfill 
owner or operator shall install at least two sample probes per hectare 
of landfill surface that has retained waste for at least 2 years. If 
the landfill is larger than 25 hectares in area, only 50 samples are 
required. The sample probes should be located to avoid known areas of 
nondegradable solid waste. The owner or operator shall collect and 
analyze one sample of landfill gas from each probe to determine the 
NMOC concentration using Method 25 or 25C of Appendix A of this part. 
Method 18 of Appendix A of this part may be used to analyze the samples 
collected by the Method 25 or 25C sampling procedure. Taking composite 
samples from different probes into a single cylinder is allowed; 
however, equal sample volumes must be taken from each probe. For each 
composite, the sampling rate, collection times, beginning and ending 
cylinder vacuums, or alternative volume measurements must be recorded 
to verify that composite volumes are equal. Composite sample volumes 
should not be less than one liter unless evidence can be provided to 
substantiate the accuracy of smaller volumes. Terminate compositing 
before the cylinder approaches ambient pressure where measurement 
accuracy diminishes. If using Method 18, the owner or operator must 
identify all compounds in the sample and, as a minimum, test for those 
compounds published in the most recent Compilation of Air Pollutant 
Emission Factors (AP-42), minus carbon monoxide, hydrogen sulfide, and 
mercury. As a minimum, the instrument must be calibrated for each of 
the compounds on the list. Convert the concentration of each Method 18 
compound to CNMOC as hexane by multiplying by the ratio of 
its carbon atoms divided by six. If more than the required number of 
samples are taken, all samples must be used in the analysis. The 
landfill owner or operator must divide the NMOC concentration from 
Method 25 or 25C of Appendix A of this part by six to convert from 
CNMOC as carbon to CNMOC as hexane. If the 
landfill has an active or passive gas removal system in place, Method 
25 or 25C samples may be collected from these systems instead of 
surface probes provided the removal system can be shown to provide 
sampling as representative as the two sampling probe per hectare 
requirement. For active collection systems, samples may be collected 
from the common header pipe before the gas moving or condensate removal 
equipment. For these systems, a minimum of three samples must be 
collected from the header pipe.
* * * * *
    (d) For the performance test required in Sec. 60.752(b)(2)(iii)(B), 
Method 25, 25C, or Method 18 of Appendix A of this part must be used to 
determine compliance with the 98 weight-percent efficiency or the 20 
ppmv outlet concentration level, unless another method to demonstrate 
compliance has been approved by the Administrator as provided by 
Sec. 60.752(b)(2)(i)(B). Method 3 or 3A shall be used to determine 
oxygen for correcting the NMOC concentration as hexane to 3 percent. In 
cases where the outlet concentration is less than 50 ppm NMOC as carbon 
(8 ppm NMOC as hexane), Method 25A should be used in place of Method 
25. * * *
* * * * *

    216. In Part 60, Appendix A is amended by revising Methods 1, 1A, 
2, 2A, 2B, 2C, 2D, 2E, 3, 3B, 4, 5, 5A, 5B, 5D, 5E, 5F, 5G, 5H, 6, 6A, 
6B, 7, 7A, 7B, 7C, 7D, 8, 10A, 10B, 11, 12, 13A, 13B, 14, 15, 15A, 16, 
16A, 16B, 17, 18, 19, 21, 22, 24, 24A, 25, 25A, 25B, 25C, 25D, 25E, 26, 
26A, 27, 28, 28A, and 29 to read as follows:

METHOD 1--Sample and Velocity Traverses for Stationary Sources

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

1.0  Scope and Application

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

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

2.0  Summary of Method

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

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety

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

6.0  Equipment and Supplies.

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

[[Page 61780]]

plugging when used in particulate-laden gas streams. Therefore, a 
procedure for cleaning the pressure holes by ``back-purging'' with 
pressurized air is required.
    6.1.2  Differential Pressure Gauges. Inclined manometers, U-tube 
manometers, or other differential pressure gauges (e.g., magnehelic 
gauges) that meet the specifications described in Method 2, Section 
6.2.

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

7.0  Reagents and Standards [Reserved]

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

9.0  Quality Control [Reserved]

10.0  Calibration and Standardization [Reserved]

11.0  Procedure

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

Square Area = D1  x  D2  x  0.7854

Where: D1 = Stack diameter 1

D2 = Stack diameter 2
    11.3.1.4  In addition, for stacks having diameters greater than 
0.61 m (24 in.), no traverse points shall be within 2.5 centimeters 
(1.00 in.) of the stack walls; and for stack diameters equal to or less 
than 0.61 m (24 in.), no traverse points shall be located within 1.3 cm 
(0.50 in.) of the stack walls. To meet these criteria, observe the 
procedures given below.
    11.3.2  Stacks With Diameters Greater Than 0.61 m (24 in.).
    11.3.2.1  When any of the traverse points as located in Section 
11.3.1 fall within 2.5 cm (1.0 in.) of the stack walls, relocate them 
away from the stack walls to: (1) a distance of 2.5 cm (1.0 in.); or 
(2) a distance equal to the nozzle inside diameter, whichever is 
larger. These relocated traverse points (on each end of a diameter) 
shall be the ``adjusted'' traverse points.
    11.3.2.2  Whenever two successive traverse points are combined to 
form a single adjusted traverse point, treat the adjusted point as two 
separate traverse points, both in the sampling and/or velocity 
measurement procedure, and in recording of the data.
    11.3.3  Stacks With Diameters Equal To or Less Than 0.61 m (24 
in.). Follow the procedure in Section 11.3.1.1, noting only that any 
``adjusted'' points should be relocated away from the stack walls to: 
(1) a distance of 1.3 cm (0.50 in.); or (2) a distance equal to the 
nozzle inside diameter, whichever is larger.
    11.3.4  Rectangular Stacks.
    11.3.4.1  Determine the number of traverse points as explained in 
Sections 11.1 and 11.2 of this method. From Table 1-1, determine the 
grid configuration. Divide the stack cross-section into as many equal 
rectangular elemental areas as traverse points, and then locate a 
traverse point at the centroid of each equal area according to the 
example in Figure 1-4.
    11.3.4.2  To use more than the minimum number of traverse points, 
expand the ``minimum number of traverse points'' matrix (see Table 1-1) 
by adding the extra traverse points along one or the other or both legs 
of the matrix; the final matrix need not be balanced. For example, if a 
4  x  3 ``minimum number of points'' matrix were expanded to 36 points, 
the final matrix could be 9  x  4 or 12  x  3, and would not 
necessarily have to be 6  x  6. After constructing the final matrix, 
divide the stack cross-section into as many equal rectangular, 
elemental areas as traverse points, and locate a traverse point at the 
centroid of each equal area.
    11.3.4.3  The situation of traverse points being too close to the 
stack walls is not expected to arise with rectangular stacks. If this 
problem should ever arise, the Administrator must be contacted for 
resolution of the matter.
    11.4  Verification of Absence of Cyclonic Flow.
    11.4.1  In most stationary sources, the direction of stack gas flow 
is essentially parallel to the stack walls. However, cyclonic flow may 
exist (1) after such devices as cyclones and inertial demisters 
following venturi

[[Page 61781]]

scrubbers, or (2) in stacks having tangential inlets or other duct 
configurations which tend to induce swirling; in these instances, the 
presence or absence of cyclonic flow at the sampling location must be 
determined. The following techniques are acceptable for this 
determination.
    11.4.2  Level and zero the manometer. Connect a Type S pitot tube 
to the manometer and leak-check system. Position the Type S pitot tube 
at each traverse point, in succession, so that the planes of the face 
openings of the pitot tube are perpendicular to the stack cross-
sectional plane; when the Type S pitot tube is in this position, it is 
at ``0 deg. reference.'' Note the differential pressure (p) 
reading at each traverse point. If a null (zero) pitot reading is 
obtained at 0 deg. reference at a given traverse point, an acceptable 
flow condition exists at that point. If the pitot reading is not zero 
at 0 deg. reference, rotate the pitot tube (up to 90 deg. 
yaw angle), until a null reading is obtained. Carefully determine and 
record the value of the rotation angle () to the nearest 
degree. After the null technique has been applied at each traverse 
point, calculate the average of the absolute values of ; 
assign  values of 0 deg. to those points for which no rotation 
was required, and include these in the overall average. If the average 
value of  is greater than 20 deg., the overall flow condition 
in the stack is unacceptable, and alternative methodology, subject to 
the approval of the Administrator, must be used to perform accurate 
sample and velocity traverses.
    11.5  The alternative site selection procedure may be used to 
determine the rotation angles in lieu of the procedure outlined in 
Section 11.4.
    11.5.1  Alternative Measurement Site Selection Procedure. This 
alternative applies to sources where measurement locations are less 
than 2 equivalent or duct diameters downstream or less than one-half 
duct diameter upstream from a flow disturbance. The alternative should 
be limited to ducts larger than 24 in. in diameter where blockage and 
wall effects are minimal. A directional flow-sensing probe is used to 
measure pitch and yaw angles of the gas flow at 40 or more traverse 
points; the resultant angle is calculated and compared with acceptable 
criteria for mean and standard deviation.


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


    11.5.2  Traverse Points. Use a minimum of 40 traverse points for 
circular ducts and 42 points for rectangular ducts for the gas flow 
angle determinations. Follow the procedure outlined in Section 11.3 and 
Table 1-1 or 1-2 for the location and layout of the traverse points. If 
the measurement location is determined to be acceptable according to 
the criteria in this alternative procedure, use the same traverse point 
number and locations for sampling and velocity measurements.
    11.5.3  Measurement Procedure.
    11.5.3.1  Prepare the directional probe and differential pressure 
gauges as recommended by the manufacturer. Capillary tubing or surge 
tanks may be used to dampen pressure fluctuations. It is recommended, 
but not required, that a pretest leak check be conducted. To perform a 
leak check, pressurize or use suction on the impact opening until a 
reading of at least 7.6 cm (3 in.) H2O registers on the 
differential pressure gauge, then plug the impact opening. The pressure 
of a leak-free system will remain stable for at least 15 seconds.
    11.5.3.2  Level and zero the manometers. Since the manometer level 
and zero may drift because of vibrations and temperature changes, 
periodically check the level and zero during the traverse.
    11.5.3.3  Position the probe at the appropriate locations in the 
gas stream, and rotate until zero deflection is indicated for the yaw 
angle pressure gauge. Determine and record the yaw angle. Record the 
pressure gauge readings for the pitch angle, and determine the pitch 
angle from the calibration curve. Repeat this procedure for each 
traverse point. Complete a ``back-purge'' of the pressure lines and the 
impact openings prior to measurements of each traverse point.
    11.5.3.4  A post-test check as described in Section 11.5.3.1 is 
required. If the criteria for a leak-free system are not met, repair 
the equipment, and repeat the flow angle measurements.
    11.5.4  Calibration. Use a flow system as described in Sections 
10.1.2.1 and 10.1.2.2 of Method 2. In addition, the flow system shall 
have the capacity to generate two test-section velocities: one between 
365 and 730 m/min (1,200 and 2,400 ft/min) and one between 730 and 
1,100 m/min (2,400 and 3,600 ft/min).
    11.5.4.1  Cut two entry ports in the test section. The axes through 
the entry ports shall be perpendicular to each other and intersect in 
the centroid of the test section. The ports should be elongated slots 
parallel to the axis of the test section and of sufficient length to 
allow measurement of pitch angles while maintaining the pitot head 
position at the test-section centroid. To facilitate alignment of the 
directional probe during calibration, the test section should be 
constructed of plexiglass or some other transparent material. All 
calibration measurements should be made at the same point in the test 
section, preferably at the centroid of the test section.
    11.5.4.2  To ensure that the gas flow is parallel to the central 
axis of the test section, follow the procedure outlined in Section 11.4 
for cyclonic flow determination to measure the gas flow angles at the 
centroid of the test section from two test ports located 90 deg. apart. 
The gas flow angle measured in each port must be 2 deg. of 
0 deg.. Straightening vanes should be installed, if necessary, to meet 
this criterion.
    11.5.4.3  Pitch Angle Calibration. Perform a calibration traverse 
according to the manufacturer's recommended protocol in 5 deg. 
increments for angles from -60 deg. to +60 deg. at one velocity in each 
of the two ranges specified above. Average the pressure ratio values 
obtained for each angle in the two flow ranges, and plot a calibration 
curve with the average values of the pressure ratio (or other suitable 
measurement factor as recommended by the manufacturer) versus the pitch 
angle. Draw a smooth line through the data points. Plot also the data 
values for each traverse point. Determine the differences between the 
measured data values and the angle from the calibration curve at the 
same pressure ratio. The difference at each comparison must be within 
2 deg. for angles between 0 deg. and 40 deg. and within 3 deg. for 
angles between 40 deg. and 60 deg..
    11.5.4.4  Yaw Angle Calibration. Mark the three-dimensional probe 
to allow the determination of the yaw position of the probe. This is 
usually a line extending the length of the probe and aligned with the 
impact opening. To determine the accuracy of measurements of the yaw 
angle, only the zero or null position need be calibrated as follows: 
Place the directional probe in the test section, and rotate the probe 
until the zero position is found. With a protractor or other angle 
measuring device, measure the angle indicated by the yaw angle 
indicator on the three-dimensional probe. This should be within 2 deg. 
of 0 deg.. Repeat this measurement for any other points along the 
length of the pitot where yaw angle measurements could be read in order 
to account for

[[Page 61782]]

variations in the pitot markings used to indicate pitot head positions.

12.0  Data Analysis and Calculations

    12.1  Nomenclature.

L = length.
n = total number of traverse points.
Pi = pitch angle at traverse point i, degree.
Ravg = average resultant angle, degree.
Ri = resultant angle at traverse point i, degree.
Sd = standard deviation, degree.

W = width.
Yi = yaw angle at traverse point i, degree.
    12.2  For a rectangular cross section, an equivalent diameter 
(De) shall be calculated using the following equation, to 
determine the upstream and downstream distances:
[GRAPHIC] [TIFF OMITTED] TR17OC00.037

    12.3  If use of the alternative site selection procedure (Section 
11.5 of this method) is required, perform the following calculations 
using the equations below: the resultant angle at each traverse point, 
the average resultant angle, and the standard deviation. Complete the 
calculations retaining at least one extra significant figure beyond 
that of the acquired data. Round the values after the final 
calculations.
    12.3.1  Calculate the resultant angle at each traverse point:
    [GRAPHIC] [TIFF OMITTED] TR17OC00.038
    
    12.3.2  Calculate the average resultant for the measurements:
    [GRAPHIC] [TIFF OMITTED] TR17OC00.039
    
    12.3.3  Calculate the standard deviations:
    [GRAPHIC] [TIFF OMITTED] TR17OC00.040
    
    12.3.4  Acceptability Criteria. The measurement location is 
acceptable if Ravg  20 deg. and Sd 
 10 deg..

13.0  Method Performance [Reserved]

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

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

[[Page 61783]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data

[GRAPHIC] [TIFF OMITTED] TR17OC00.041


[[Page 61784]]



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


[[Page 61785]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.042


[[Page 61786]]


                                               Table 1-2.--Location of Traverse Points in Circular Stacks
                                             [Percent of stack diameter from inside wall to tranverse point]
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                                                                      Number of traverse points on a diameter
         Traverse  point  number on  a diameter          -----------------------------------------------------------------------------------------------
                                                             2       4       6       8      10      12      14      16      18      20      22      24
--------------------------------------------------------------------------------------------------------------------------------------------------------
1.......................................................    14.6     6.7     4.4     3.2     2.6     2.1     1.8     1.6     1.4     1.3     1.1     1.1
2.......................................................    85.4    25.0    14.6    10.5     8.2     6.7     5.7     4.9     4.4     3.9     3.5     3.2
3.......................................................            75.0    29.6    19.4    14.6    11.8     9.9     8.5     7.5     6.7     6.0     5.5
4.......................................................            93.3    70.4    32.3    22.6    17.7    14.6    12.5    10.9     9.7     8.7     7.9
5.......................................................                    85.4    67.7    34.2    25.0    20.1    16.9    14.6    12.9    11.6    10.5
6.......................................................                    95.6    80.6    65.8    35.6    26.9    22.0    18.8    16.5    14.6    13.2
7.......................................................                            89.5    77.4    64.4    36.6    28.3    23.6    20.4    18.0    16.1
8.......................................................                            96.8    85.4    75.0    63.4    37.5    29.6    25.0    21.8    19.4
9.......................................................                                    91.8    82.3    73.1    62.5    38.2    30.6    26.2    23.0
10......................................................                                    97.4    88.2    79.9    71.7    61.8    38.8    31.5    27.2
11......................................................                                            93.3    85.4    78.0    70.4    61.2    39.3    32.3
12......................................................                                            97.9    90.1    83.1    76.4    69.4    60.7    39.8
13......................................................                                                    94.3    87.5    81.2    75.0    68.5    60.2
14......................................................                                                    98.2    91.5    85.4    79.6    73.8    67.7
15......................................................                                                            95.1    89.1    83.5    78.2    72.8
16......................................................                                                            98.4    92.5    87.1    82.0    77.0
17......................................................                                                                    95.6    90.3    85.4    80.6
18......................................................                                                                    98.6    93.3    88.4    83.9
19......................................................                                                                            96.1    91.3    86.8
20......................................................                                                                            98.7    94.0    89.5
21......................................................                                                                                    96.5    92.1
22......................................................                                                                                    98.9    94.5
23......................................................                                                                                            96.8
24......................................................                                                                                            99.9
--------------------------------------------------------------------------------------------------------------------------------------------------------


[[Page 61787]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.043


[[Page 61788]]

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

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

1.0  Scope and Application

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

2.0  Summary of Method

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

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety

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

6.0  Equipment and Supplies [Reserved]

7.0  Reagents and Standards [Reserved]

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

9.0  Quality Control [Reserved]

10.0  Calibration and Standardization [Reserved]

11.0  Procedure

    11.1  Selection of Measurement Site.
    11.1.1  Particulate Measurements--Steady or Unsteady Flow. Select a 
particulate measurement site located preferably at least eight 
equivalent stack or duct diameters downstream and 10 equivalent 
diameters upstream from any flow disturbances such as bends, 
expansions, or contractions in the stack, or from a visible flame. 
Next, locate the velocity measurement site eight equivalent diameters 
downstream of the particulate measurement site (see Figure 1A-1). If 
such locations are not available, select an alternative particulate 
measurement location at least two equivalent stack or duct diameters 
downstream and two and one-half diameters upstream from any flow 
disturbance. Then, locate the velocity measurement site two equivalent 
diameters downstream from the particulate measurement site. (See 
Section 12.2 of Method 1 for calculating equivalent diameters for a 
rectangular cross-section.)
    11.1.2  PM Sampling (Steady Flow) or Velocity (Steady or Unsteady 
Flow) Measurements. For PM sampling when the volumetric flow rate in a 
duct is constant with respect to time, Section 11.1.1 of Method 1 may 
be followed, with the PM sampling and velocity measurement performed at 
one location. To demonstrate that the flow rate is constant (within 10 
percent) when PM measurements are made, perform complete velocity 
traverses before and after the PM sampling run, and calculate the 
deviation of the flow rate derived after the PM sampling run from the 
one derived before the PM sampling run. The PM sampling run is 
acceptable if the deviation does not exceed 10 percent.
    11.2  Determining the Number of Traverse Points.
    11.2.1  Particulate Measurements (Steady or Unsteady Flow). Use 
Figure 1-1 of Method 1 to determine the number of traverse points to 
use at both the velocity measurement and PM sampling locations. Before 
referring to the figure, however, determine the distances between both 
the velocity measurement and PM sampling sites to the nearest upstream 
and downstream disturbances. Then divide each distance by the stack 
diameter or equivalent diameter to express the distances in terms of 
the number of duct diameters. Then, determine the number of traverse 
points from Figure 1-1 of Method 1 corresponding to each of these four 
distances. Choose the highest of the four numbers of traverse points 
(or a greater number) so that, for circular ducts the number is a 
multiple of four; and for rectangular ducts, the number is one of those 
shown in Table 1-1 of Method 1. When the optimum duct diameter location 
criteria can be satisfied, the minimum number of traverse points 
required is eight for circular ducts and nine for rectangular ducts.
    11.2.2  PM Sampling (Steady Flow) or only Velocity (Non-
Particulate) Measurements. Use Figure 1-2 of Method 1 to determine 
number of traverse points, following the same procedure used for PM 
sampling as described in Section 11.2.1 of Method 1. When the optimum 
duct diameter location criteria can be satisfied, the minimum number of 
traverse points required is eight for circular ducts and nine for 
rectangular ducts.
    11.3  Cross-sectional Layout, Location of Traverse Points, and 
Verification of the Absence of Cyclonic Flow. Same as Method 1, 
Sections 11.3 and 11.4, respectively.

12.0  Data Analysis and Calculations [Reserved]

13.0  Method Performance [Reserved]

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

    Same as Method 1, Section 16.0, References 1 through 6, with the 
addition of the following:
    1. Vollaro, Robert F. Recommended Procedure for Sample Traverses in 
Ducts Smaller Than 12 Inches in

[[Page 61789]]

Diameter. U.S. Environmental Protection Agency, Emission Measurement 
Branch, Research Triangle Park, North Carolina. January 1977.

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

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

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

1.0  Scope and Application.

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

2.0  Summary of Method.

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

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety

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

6.0  Equipment and Supplies

    Specifications for the apparatus are given below. Any other 
apparatus that has been demonstrated (subject to approval of the 
Administrator) to be capable of meeting the specifications will be 
considered acceptable.
    6.1  Type S Pitot Tube.
    6.1.1  Pitot tube made of metal tubing (e.g., stainless steel) as 
shown in Figure 2-1. It is recommended that the external tubing 
diameter (dimension Dt, Figure 2-2b) be between 0.48 and 
0.95 cm (\3/16\ and \3/8\ inch). There shall be an equal distance from 
the base of each leg of the pitot tube to its face-opening plane 
(dimensions PA and PB, Figure 2-2b); it is 
recommended that this distance be between 1.05 and 1.50 times the 
external tubing diameter. The face openings of the pitot tube shall, 
preferably, be aligned as shown in Figure 2-2; however, slight 
misalignments of the openings are permissible (see Figure 2-3).
    6.1.2  The Type S pitot tube shall have a known coefficient, 
determined as outlined in Section 10.0. An identification number shall 
be assigned to the pitot tube; this number shall be permanently marked 
or engraved on the body of the tube. A standard pitot tube may be used 
instead of a Type S, provided that it meets the specifications of 
Sections 6.7 and 10.2. Note, however, that the static and impact 
pressure holes of standard pitot tubes are susceptible to plugging in 
particulate-laden gas streams. Therefore, whenever a standard pitot 
tube is used to perform a traverse, adequate proof must be furnished 
that the openings of the pitot tube have not plugged up during the 
traverse period. This can be accomplished by comparing the velocity 
head (p) measurement recorded at a selected traverse point 
(readable p value) with a second p measurement 
recorded after ``back purging'' with pressurized air to clean the 
impact and static holes of the standard pitot tube. If the before and

[[Page 61790]]

after p measurements are within 5 percent, then the traverse 
data are acceptable. Otherwise, the data should be rejected and the 
traverse measurements redone. Note that the selected traverse point 
should be one that demonstrates a readable p value. If ``back 
purging'' at regular intervals is part of a routine procedure, then 
comparative p measurements shall be conducted as above for the 
last two traverse points that exhibit suitable p measurements.
    6.2  Differential Pressure Gauge. An inclined manometer or 
equivalent device. Most sampling trains are equipped with a 10 in. 
(water column) inclined-vertical manometer, having 0.01 in. 
H20 divisions on the 0 to 1 in. inclined scale, and 0.1 in. 
H20 divisions on the 1 to 10 in. vertical scale. This type 
of manometer (or other gauge of equivalent sensitivity) is satisfactory 
for the measurement of p values as low as 1.27 mm (0.05 in.) 
H20. However, a differential pressure gauge of greater 
sensitivity shall be used (subject to the approval of the 
Administrator), if any of the following is found to be true: (1) the 
arithmetic average of all p readings at the traverse points in 
the stack is less than 1.27 mm (0.05 in.) H20; (2) for 
traverses of 12 or more points, more than 10 percent of the individual 
p readings are below 1.27 mm (0.05 in.) H20; or (3) 
for traverses of fewer than 12 points, more than one p reading 
is below 1.27 mm (0.05 in.) H20. Reference 18 (see Section 
17.0) describes commercially available instrumentation for the 
measurement of low-range gas velocities.
    6.2.1  As an alternative to criteria (1) through (3) above, 
Equation 2-1 (Section 12.2) may be used to determine the necessity of 
using a more sensitive differential pressure gauge. If T is greater 
than 1.05, the velocity head data are unacceptable and a more sensitive 
differential pressure gauge must be used.

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

    6.3  Temperature Sensor. A thermocouple, liquid-filled bulb 
thermometer, bimetallic thermometer, mercury-in-glass thermometer, or 
other gauge capable of measuring temperatures to within 1.5 percent of 
the minimum absolute stack temperature. The temperature sensor shall be 
attached to the pitot tube such that the sensor tip does not touch any 
metal; the gauge shall be in an interference-free arrangement with 
respect to the pitot tube face openings (see Figure 2-1 and Figure 2-
4). Alternative positions may be used if the pitot tube-temperature 
gauge system is calibrated according to the procedure of Section 10.0. 
Provided that a difference of not more than 1 percent in the average 
velocity measurement is introduced, the temperature gauge need not be 
attached to the pitot tube. This alternative is subject to the approval 
of the Administrator.
    6.4  Pressure Probe and Gauge. A piezometer tube and mercury- or 
water-filled U-tube manometer capable of measuring stack pressure to 
within 2.5 mm (0.1 in.) Hg. The static tap of a standard type pitot 
tube or one leg of a Type S pitot tube with the face opening planes 
positioned parallel to the gas flow may also be used as the pressure 
probe.
    6.5  Barometer. A mercury, aneroid, or other barometer capable of 
measuring atmospheric pressure to within 2.54 mm (0.1 in.) Hg.


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


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

7.0  Reagents and Standards [Reserved]

8.0  Sample Collection and Analysis

    8.1  Set up the apparatus as shown in Figure 2-1. Capillary tubing 
or surge tanks installed between the manometer and pitot tube may be 
used to dampen p fluctuations. It is recommended, but not 
required, that a pretest leak-check be conducted as follows: (1) blow 
through the pitot impact opening until at least 7.6 cm (3.0 in.) 
H20 velocity head registers on the manometer; then, close 
off the impact opening. The pressure shall remain stable for at least 
15 seconds; (2) do the same for the static pressure side, except using 
suction to obtain the minimum of 7.6 cm (3.0 in.) H20. Other 
leak-check procedures, subject to the approval of the Administrator, 
may be used.
    8.2  Level and zero the manometer. Because the manometer level and 
zero

[[Page 61791]]

may drift due to vibrations and temperature changes, make periodic 
checks during the traverse (at least once per hour). Record all 
necessary data on a form similar to that shown in Figure 2-6.
    8.3  Measure the velocity head and temperature at the traverse 
points specified by Method 1. Ensure that the proper differential 
pressure gauge is being used for the range of p values 
encountered (see Section 6.2). If it is necessary to change to a more 
sensitive gauge, do so, and remeasure the p and temperature 
readings at each traverse point. Conduct a post-test leak-check 
(mandatory), as described in Section 8.1 above, to validate the 
traverse run.
    8.4  Measure the static pressure in the stack. One reading is 
usually adequate.
    8.5  Determine the atmospheric pressure.
    8.6  Determine the stack gas dry molecular weight. For combustion 
processes or processes that emit essentially CO2, 
O2, CO, and N2, use Method 3. For processes 
emitting essentially air, an analysis need not be conducted; use a dry 
molecular weight of 29.0. For other processes, other methods, subject 
to the approval of the Administrator, must be used.
    8.7  Obtain the moisture content from Method 4 (reference method, 
or equivalent) or from Method 5.
    8.8  Determine the cross-sectional area of the stack or duct at the 
sampling location. Whenever possible, physically measure the stack 
dimensions rather than using blueprints. Do not assume that stack 
diameters are equal. Measure each diameter distance to verify its 
dimensions.

9.0  Quality Control

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

10.0  Calibration and Standardization

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


    Note: Do not use a Type S pitot tube assembly that is 
constructed such that the impact pressure opening plane of the pitot 
tube is below the entry plane of the nozzle (see Figure 2-6B).


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


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


    10.1.2.3  The flow system shall have the capacity to generate a 
test-section velocity around 910 m/min (3,000 ft/min). This velocity 
must be constant with time to guarantee steady flow during calibration. 
Note that Type S pitot tube coefficients obtained by single-velocity 
calibration at 910 m/min (3,000 ft/min) will generally be valid to 
3 percent for the measurement of velocities above 300 m/min 
(1,000 ft/min) and to 6 percent for the measurement of 
velocities between 180 and 300 m/min (600 and 1,000 ft/min). If a more 
precise correlation between the pitot tube coefficient, 
(Cp), and velocity is desired, the flow system should have 
the capacity to generate at least four distinct, time-invariant test-
section velocities covering the velocity range from 180 to 1,500 m/min 
(600 to 5,000 ft/min), and calibration data shall be taken at regular 
velocity intervals over this range (see References 9 and 14 in Section 
17.0 for details).
    10.1.2.4  Two entry ports, one for each of the standard and Type S 
pitot tubes, shall be cut in the test section. The standard pitot entry 
port shall be located slightly downstream of the Type S port, so that 
the standard and Type S

[[Page 61792]]

impact openings will lie in the same cross-sectional plane during 
calibration. To facilitate alignment of the pitot tubes during 
calibration, it is advisable that the test section be constructed of 
PlexiglasTM or some other transparent material.
    10.1.3  Calibration Procedure. Note that this procedure is a 
general one and must not be used without first referring to the special 
considerations presented in Section 10.1.5. Note also that this 
procedure applies only to single-velocity calibration. To obtain 
calibration data for the A and B sides of the Type S pitot tube, 
proceed as follows:
    10.1.3.1  Make sure that the manometer is properly filled and that 
the oil is free from contamination and is of the proper density. 
Inspect and leak-check all pitot lines; repair or replace if necessary.
    10.1.3.2  Level and zero the manometer. Switch on the fan, and 
allow the flow to stabilize. Seal the Type S pitot tube entry port.
    10.1.3.3  Ensure that the manometer is level and zeroed. Position 
the standard pitot tube at the calibration point (determined as 
outlined in Section 10.1.5.1), and align the tube so that its tip is 
pointed directly into the flow. Particular care should be taken in 
aligning the tube to avoid yaw and pitch angles. Make sure that the 
entry port surrounding the tube is properly sealed.
    10.1.3.4  Read pstd, and record its value in a 
data table similar to the one shown in Figure 2-9. Remove the standard 
pitot tube from the duct, and disconnect it from the manometer. Seal 
the standard entry port.
    10.1.3.5  Connect the Type S pitot tube to the manometer and leak-
check. Open the Type S tube entry port. Check the manometer level and 
zero. Insert and align the Type S pitot tube so that its A side impact 
opening is at the same point as was the standard pitot tube and is 
pointed directly into the flow. Make sure that the entry port 
surrounding the tube is properly sealed.
    10.1.3.6  Read ps, and enter its value in the 
data table. Remove the Type S pitot tube from the duct, and disconnect 
it from the manometer.
    10.1.3.7  Repeat Steps 10.1.3.3 through 10.1.3.6 until three pairs 
of p readings have been obtained for the A side of the Type S 
pitot tube.
    10.1.3.8  Repeat Steps 10.1.3.3 through 10.1.3.7 for the B side of 
the Type S pitot tube.
    10.1.3.9  Perform calculations as described in Section 12.4. Use 
the Type S pitot tube only if the values of A and 
B are less than or equal to 0.01 and if the 
absolute value of the difference between Cp(A) and 
Cp(B) is 0.01 or less.
    10.1.4  Special Considerations.
    10.1.4.1  Selection of Calibration Point.
    10.1.4.1.1  When an isolated Type S pitot tube is calibrated, 
select a calibration point at or near the center of the duct, and 
follow the procedures outlined in Section 10.1.3. The Type S pitot 
coefficients measured or calculated, (i.e. Cp(A) and 
Cp(B)) will be valid, so long as either: (1) the isolated 
pitot tube is used; or (2) the pitot tube is used with other components 
(nozzle, thermocouple, sample probe) in an arrangement that is free 
from aerodynamic interference effects (see Figures 2-4, 2-7, and 2-8).
    10.1.4.1.2  For Type S pitot tube-thermocouple combinations 
(without probe assembly), select a calibration point at or near the 
center of the duct, and follow the procedures outlined in Section 
10.1.3. The coefficients so obtained will be valid so long as the pitot 
tube-thermocouple combination is used by itself or with other 
components in an interference-free arrangement (Figures 2-4, 2-7, and 
2-8).
    10.1.4.1.3  For Type S pitot tube combinations with complete probe 
assemblies, the calibration point should be located at or near the 
center of the duct; however, insertion of a probe sheath into a small 
duct may cause significant cross-sectional area interference and 
blockage and yield incorrect coefficient values (Reference 9 in Section 
17.0). Therefore, to minimize the blockage effect, the calibration 
point may be a few inches off-center if necessary. The actual blockage 
effect will be negligible when the theoretical blockage, as determined 
by a projected-area model of the probe sheath, is 2 percent or less of 
the duct cross-sectional area for assemblies without external sheaths 
(Figure 2-10a), and 3 percent or less for assemblies with external 
sheaths (Figure 2-10b).
    10.1.4.2  For those probe assemblies in which pitot tube-nozzle 
interference is a factor (i.e., those in which the pitot-nozzle 
separation distance fails to meet the specifications illustrated in 
Figure 2-7A), the value of Cp(s) depends upon the amount of 
free space between the tube and nozzle and, therefore, is a function of 
nozzle size. In these instances, separate calibrations shall be 
performed with each of the commonly used nozzle sizes in place. Note 
that the single-velocity calibration technique is acceptable for this 
purpose, even though the larger nozzle sizes (>0.635 cm or \1/4\ in.) 
are not ordinarily used for isokinetic sampling at velocities around 
910 m/min (3,000 ft/min), which is the calibration velocity. Note also 
that it is not necessary to draw an isokinetic sample during 
calibration (see Reference 19 in Section 17.0).
    10.1.4.3  For a probe assembly constructed such that its pitot tube 
is always used in the same orientation, only one side of the pitot tube 
need be calibrated (the side which will face the flow). The pitot tube 
must still meet the alignment specifications of Figure 2-2 or 2-3, 
however, and must have an average deviation () value of 0.01 
or less (see Section 10.1.4.4).
    10.1.5  Field Use and Recalibration.
    10.1.5.1  Field Use.
    10.1.5.1.1  When a Type S pitot tube (isolated or in an assembly) 
is used in the field, the appropriate coefficient value (whether 
assigned or obtained by calibration) shall be used to perform velocity 
calculations. For calibrated Type S pitot tubes, the A side coefficient 
shall be used when the A side of the tube faces the flow, and the B 
side coefficient shall be used when the B side faces the flow. 
Alternatively, the arithmetic average of the A and B side coefficient 
values may be used, irrespective of which side faces the flow.
    10.1.5.1.2  When a probe assembly is used to sample a small duct, 
30.5 to 91.4 cm (12 to 36 in.) in diameter, the probe sheath sometimes 
blocks a significant part of the duct cross-section, causing a 
reduction in the effective value of Cp(s). Consult Reference 
9 (see Section 17.0) for details. Conventional pitot-sampling probe 
assemblies are not recommended for use in ducts having inside diameters 
smaller than 30.5 cm (12 in.) (see Reference 16 in Section 17.0).
    10.1.5.2  Recalibration.
    10.1.5.2.1  Isolated Pitot Tubes. After each field use, the pitot 
tube shall be carefully reexamined in top, side, and end views. If the 
pitot face openings are still aligned within the specifications 
illustrated in Figure 2-2 and Figure 2-3, it can be assumed that the 
baseline coefficient of the pitot tube has not changed. If, however, 
the tube has been damaged to the extent that it no longer meets the 
specifications of Figure 2-2 and Figure 2-3, the damage shall either be 
repaired to restore proper alignment of the face openings, or the tube 
shall be discarded.
    10.1.5.2.2  Pitot Tube Assemblies. After each field use, check the 
face opening alignment of the pitot tube, as in Section 10.1.5.2.1. 
Also, remeasure the intercomponent spacings of the assembly. If the 
intercomponent spacings have not changed and the face opening alignment 
is acceptable, it can be assumed that the coefficient of the assembly 
has not changed. If the face

[[Page 61793]]

opening alignment is no longer within the specifications of Figure 2-2 
and Figure 2-3, either repair the damage or replace the pitot tube 
(calibrating the new assembly, if necessary). If the intercomponent 
spacings have changed, restore the original spacings, or recalibrate 
the assembly.
    10.2  Standard Pitot Tube (if applicable). If a standard pitot tube 
is used for the velocity traverse, the tube shall be constructed 
according to the criteria of Section 6.7 and shall be assigned a 
baseline coefficient value of 0.99. If the standard pitot tube is used 
as part of an assembly, the tube shall be in an interference-free 
arrangement (subject to the approval of the Administrator).
    10.3  Temperature Sensors.
    10.3.1  After each field use, calibrate dial thermometers, liquid-
filled bulb thermometers, thermocouple-potentiometer systems, and other 
sensors at a temperature within 10 percent of the average absolute 
stack temperature. For temperatures up to 405  deg.C (761  deg.F), use 
an ASTM mercury-in-glass reference thermometer, or equivalent, as a 
reference. Alternatively, either a reference thermocouple and 
potentiometer (calibrated against NIST standards) or thermometric fixed 
points (e.g., ice bath and boiling water, corrected for barometric 
pressure) may be used. For temperatures above 405 deg.C (761  deg.F), 
use a reference thermocouple-potentiometer system calibrated against 
NIST standards or an alternative reference, subject to the approval of 
the Administrator.
    10.3.2  The temperature data recorded in the field shall be 
considered valid. If, during calibration, the absolute temperature 
measured with the sensor being calibrated and the reference sensor 
agree within 1.5 percent, the temperature data taken in the field shall 
be considered valid. Otherwise, the pollutant emission test shall 
either be considered invalid or adjustments (if appropriate) of the 
test results shall be made, subject to the approval of the 
Administrator.
    10.4  Barometer. Calibrate the barometer used against a mercury 
barometer.

11.0  Analytical Procedure

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

12.0  Data Analysis and Calculations

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

A = Cross-sectional area of stack, m\2\ (ft\2\).
Bws = Water vapor in the gas stream (from Method 4 
(reference method) or Method 5), proportion by volume.
Cp = Pitot tube coefficient, dimensionless.
Cp(s) = Type S pitot tube coefficient, dimensionless.
Cp(std) = Standard pitot tube coefficient; use 0.99 if the 
coefficient is unknown and the tube is designed according to the 
criteria of Sections 6.7.1 to 6.7.5 of this method.
De = Equivalent diameter.
K = 0.127 mm H2O (metric units). 0.005 in. H2O 
(English units).
Kp = Velocity equation constant.
L = Length.
Md = Molecular weight of stack gas, dry basis (see Section 
8.6), g/g-mole (lb/lb-mole).
Ms = Molecular weight of stack gas, wet basis, g/g-mole (lb/
lb-mole).
n = Total number of traverse points.
Pbar = Barometric pressure at measurement site, mm Hg (in. 
Hg).
Pg = Stack static pressure, mm Hg (in. Hg).
Ps = Absolute stack pressure (Pbar + 
Pg), mm Hg (in. Hg),
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
Qsd = Dry volumetric stack gas flow rate corrected to 
standard conditions, dscm/hr (dscf/hr).
T = Sensitivity factor for differential pressure gauges.
Ts = Stack temperature,  deg.C ( deg.F).
Ts(abs) = Absolute stack temperature,  deg.K ( deg.R).
= 273 + Ts for metric units,
= 460 + Ts for English units.
Tstd = Standard absolute temperature, 293  deg.K (528 
deg.R).
Vs = Average stack gas velocity, m/sec (ft/sec).
W = Width.
p = Velocity head of stack gas, mm H2O (in. 
H20).
pi = Individual velocity head reading at traverse 
point ``i'', mm (in.) H2O.
pstd = Velocity head measured by the standard pitot 
tube, cm (in.) H2O.
ps = Velocity head measured by the Type S pitot 
tube, cm (in.) H2O.
3600 = Conversion Factor, sec/hr.
18.0 = Molecular weight of water, g/g-mole (lb/lb-mole).

    12.2  Calculate T as follows:
    [GRAPHIC] [TIFF OMITTED] TR17OC00.045
    
    12.3  Calculate De as follows:
    [GRAPHIC] [TIFF OMITTED] TR17OC00.046
    
    12.4  Calibration of Type S Pitot Tube.
    12.4.1  For each of the six pairs of p readings (i.e., 
three from side A and three from side B) obtained in Section 10.1.3, 
calculate the value of the Type S pitot tube coefficient according to 
Equation 2-3:
[GRAPHIC] [TIFF OMITTED] TR17OC00.047

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

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

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

    12.6  Average Stack Gas Velocity.

[[Page 61794]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.051

[GRAPHIC] [TIFF OMITTED] TR17OC00.052

[GRAPHIC] [TIFF OMITTED] TR17OC00.053

    12.7  Average Stack Gas Dry Volumetric Flow Rate.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.054
    
13.0  Method Performance [Reserved]

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

    1. Mark, L.S. Mechanical Engineers' Handbook. New York. McGraw-
Hill Book Co., Inc. 1951.
    2. Perry, J.H., ed. Chemical Engineers' Handbook. New York. 
McGraw-Hill Book Co., Inc. 1960.
    3. Shigehara, R.T., W.F. Todd, and W.S. Smith. Significance of 
Errors in Stack Sampling Measurements. U.S. Environmental Protection 
Agency, Research Triangle Park, N.C. (Presented at the Annual 
Meeting of the Air Pollution Control Association, St. Louis, MO., 
June 14-19, 1970).
    4. Standard Method for Sampling Stacks for Particulate Matter. 
In: 1971 Book of ASTM Standards, Part 23. Philadelphia, PA. 1971. 
ASTM Designation D 2928-71.
    5. Vennard, J.K. Elementary Fluid Mechanics. New York. John 
Wiley and Sons, Inc. 1947.
    6. Fluid Meters--Their Theory and Application. American Society 
of Mechanical Engineers, New York, N.Y. 1959.
    7. ASHRAE Handbook of Fundamentals. 1972. p. 208.
    8. Annual Book of ASTM Standards, Part 26. 1974. p. 648.
    9. Vollaro, R.F. Guidelines for Type S Pitot Tube Calibration. 
U.S. Environmental Protection Agency, Research Triangle Park, N.C. 
(Presented at 1st Annual Meeting, Source Evaluation Society, Dayton, 
OH, September 18, 1975.)
    10. Vollaro, R.F. A Type S Pitot Tube Calibration Study. U.S. 
Environmental Protection Agency, Emission Measurement Branch, 
Research Triangle Park, N.C. July 1974.
    11. Vollaro, R.F. The Effects of Impact Opening Misalignment on 
the Value of the Type S Pitot Tube Coefficient. U.S. Environmental 
Protection Agency, Emission Measurement Branch, Research Triangle 
Park, NC. October 1976.
    12. Vollaro, R.F. Establishment of a Baseline Coefficient Value 
for Properly Constructed Type S Pitot Tubes. U.S. Environmental 
Protection Agency, Emission Measurement Branch, Research Triangle 
Park, NC. November 1976.
    13. Vollaro, R.F. An Evaluation of Single-Velocity Calibration 
Technique as a Means of Determining Type S Pitot Tube Coefficients. 
U.S. Environmental Protection Agency, Emission Measurement Branch, 
Research Triangle Park, NC. August 1975.
    14. Vollaro, R.F. The Use of Type S Pitot Tubes for the 
Measurement of Low Velocities. U.S. Environmental Protection Agency, 
Emission Measurement Branch, Research Triangle Park, NC. November 
1976.
    15. Smith, Marvin L. Velocity Calibration of EPA Type Source 
Sampling Probe. United Technologies Corporation, Pratt and Whitney 
Aircraft Division, East Hartford, CT. 1975.
    16. Vollaro, R.F. Recommended Procedure for Sample Traverses in 
Ducts Smaller than 12 Inches in Diameter. U.S. Environmental 
Protection Agency, Emission Measurement Branch, Research Triangle 
Park, NC. November 1976.
    17. Ower, E. and R.C. Pankhurst. The Measurement of Air Flow, 
4th Ed. London, Pergamon Press. 1966.
    18. Vollaro, R.F. A Survey of Commercially Available 
Instrumentation for the Measurement of Low-Range Gas Velocities. 
U.S. Environmental Protection Agency, Emission Measurement Branch, 
Research Triangle Park, NC. November 1976. (Unpublished Paper).
    19. Gnyp, A.W., et al. An Experimental Investigation of the 
Effect of Pitot Tube-Sampling Probe Configurations on the Magnitude 
of the S Type Pitot Tube Coefficient for Commercially Available 
Source Sampling Probes. Prepared by the University of Windsor for 
the Ministry of the Environment, Toronto, Canada. February 1975.

[[Page 61795]]

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


[[Page 61796]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.056


[[Page 61797]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.057


[[Page 61798]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.058


[[Page 61799]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.059

PLANT-----------------------------------------------------------------
DATE------------------------------------------------------------------
RUN NO.---------------------------------------------------------------
STACK DIA. OR DIMENSIONS, m (in.)-------------------------------------
BAROMETRIC PRESS., mm Hg (in. Hg)-------------------------------------
CROSS SECTIONAL AREA, m\2\ (ft\2\)------------------------------------
OPERATORS-------------------------------------------------------------
PITOT TUBE I.D. NO.---------------------------------------------------
AVG. COEFFICIENT, Cp =------------------------------------------------
LAST DATE CALIBRATED--------------------------------------------------

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

SCHEMATIC OF STACK CROSS SECTION

[[Page 61800]]



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

Figure 2-6. Velocity Traverse Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.060


[[Page 61801]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.061


[[Page 61802]]


PITOT TUBE IDENTIFICATION NUMBER:-------------------------------------
DATE:-----------------------------------------------------------------
CALIBRATED BY:--------------------------------------------------------

                                             ``A'' Side Calibration
----------------------------------------------------------------------------------------------------------------
                                  Pstd  cm   P(s)  cm                       Deviation  Cp(s)--
            Run No.                 H2O  (in H2O)       H2O  (in H2O)            Cp(s)               Cp(A)
----------------------------------------------------------------------------------------------------------------
1
----------------------------------------------------------------------------------------------------------------
2
----------------------------------------------------------------------------------------------------------------
3
----------------------------------------------------------------------------------------------------------------
                                                     Cp, avg
                                                     (SIDE A)
----------------------------------------------------------------------------------------------------------------


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

                                                     [GRAPHIC] [TIFF OMITTED] TR17OC00.062
                                                     
[Cp, avg (side A)--Cp, avg (side B)]*

    *Must be less than or equal to 0.01
Figure 2-9. Pitot Tube Calibration Data

[[Page 61803]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.063

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

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

1.0  Scope and Application

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

2.0  Summary of Method

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

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may

[[Page 61804]]

not address all of the safety problems associated with its use. It is 
the responsibility of the user of this test method to establish 
appropriate safety and health practices and determine the applicability 
of regulatory limitations prior to performing this test method.

6.0  Equipment and Supplies

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

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

    6.3  Stopwatch. Capable of measurement to within 1 second.

7.0  Reagents and Standards [Reserved]

8.0  Sample Collection and Analysis

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

9.0  Quality Control

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

10.0  Calibration and Standardization

    10.1  Volume Meter.
    10.1.1  The volume meter is calibrated against a standard reference 
meter prior to its initial use in the field. The reference meter is a 
spirometer or liquid displacement meter with a capacity consistent with 
that of the test meter.
    10.1.2  Alternatively, a calibrated, standard pitot may be used as 
the reference meter in conjunction with a wind tunnel assembly. Attach 
the test meter to the wind tunnel so that the total flow passes through 
the test meter. For each calibration run, conduct a 4-point traverse 
along one stack diameter at a position at least eight diameters of 
straight tunnel downstream and two diameters upstream of any bend, 
inlet, or air mover. Determine the traverse point locations as 
specified in Method 1. Calculate the reference volume using the 
velocity values following the procedure in Method 2, the wind tunnel 
cross-sectional area, and the run time.
    10.1.3  Set up the test meter in a configuration similar to that 
used in the field installation (i.e., in relation to the flow moving 
device). Connect the temperature sensor and pressure gauge as they are 
to be used in the field. Connect the reference meter at the inlet of 
the flow line, if appropriate for the meter, and begin gas flow through 
the system to condition the meters. During this conditioning operation, 
check the system for leaks.
    10.1.4  The calibration shall be performed during at least three 
different flow rates. The calibration flow rates shall be about 0.3, 
0.6, and 0.9 times the rated maximum flow rate of the test meter.
    10.1.5  For each calibration run, the data to be collected include: 
reference meter initial and final volume readings, the test meter 
initial and final volume reading, meter average temperature and 
pressure, barometric pressure, and run time. Repeat the runs at each 
flow rate at least three times.
    10.1.6  Calculate the test meter calibration coefficient as 
indicated in Section 12.2.
    10.1.7  Compare the three Ym values at each of the flow 
rates tested and determine the maximum and minimum values. The 
difference between the maximum and minimum values at each flow rate 
should be no greater than 0.030. Extra runs may be required to complete 
this requirement. If this specification cannot be met in six successive 
runs, the test meter is not suitable for use. In addition, the meter 
coefficients should be between 0.95 and 1.05. If these specifications 
are met at all the flow rates, average all the Ym values 
from runs meeting the specifications to obtain an average meter 
calibration coefficient, Ym.
    10.1.8  The procedure above shall be performed at least once for 
each volume meter. Thereafter, an abbreviated calibration check shall 
be completed

[[Page 61805]]

following each field test. The calibration of the volume meter shall be 
checked with the meter pressure set at the average value encountered 
during the field test. Three calibration checks (runs) shall be 
performed using this average flow rate value. Calculate the average 
value of the calibration factor. If the calibration has changed by more 
than 5 percent, recalibrate the meter over the full range of flow as 
described above.


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

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

11.0  Analytical Procedure

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

12.0  Data Analysis and Calculations

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

    12.1  Nomenclature.

f = Final reading.
i = Initial reading.
Pbar = Barometric pressure, mm Hg.
Pg = Average static pressure in volume meter, mm Hg.
Qs = Gas flow rate, m3/min, standard conditions.
s = Standard conditions, 20 deg.C and 760 mm Hg.
Tr = Reference meter average temperature,  deg.K ( deg.R).
Tm = Test meter average temperature,  deg.K ( deg.R).
Vr = Reference meter volume reading, m3.
Vm = Test meter volume reading, m3.
Ym = Test meter calibration coefficient, dimensionless.
 = Elapsed test period time, min.

    12.2  Test Meter Calibration Coefficient.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.064
    
    12.3  Volume.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.065
    
    12.4  Gas Flow Rate.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.066
    
13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

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

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

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

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

1.0  Scope and Application

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

2.0  Summary of Method

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

3.0  Definitions

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

4.0  Interferences

    Same as Section 4.0 of Method 10.

[[Page 61806]]

5.0  Safety

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

6.0  Equipment and Supplies

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

7.0  Reagents and Standards

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

8.0  Sample Collection and Analysis

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

9.0  Quality Control

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

10.0  Calibration and Standardization

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

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

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

11.0  Analytical Procedure

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

12.0  Data Analysis and Calculations

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

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

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


[[Page 61807]]


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

13.0  Method Performance [Reserved]

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

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

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

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

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

1.0  Scope and Application

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

2.0  Summary of Method

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

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety

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

6.0  Equipment and Supplies

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

7.0  Reagents and Standards [Reserved]

8.0  Sample Collection and Analysis

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

9.0  Quality Control

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

10.0  Calibration and Standardization

    Same as Method 2, Sections 10.2 through 10.4.

11.0  Analytical Procedure

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

12.0  Calculations and Data Analysis

    Same as Method 2, Section 12.0.

13.0  Method Performance [Reserved]

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

    Same as Method 2, Section 16.0.

[[Page 61808]]

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

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

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

1.0  Scope and Application

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

2.0  Summary of Method

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

3.0  Definitions. [Reserved]

4.0  Interferences. [Reserved]

5.0  Safety

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

6.0  Equipment and Supplies

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

7.0  Reagents and Standards. [Reserved]

8.0  Sample Collection and Analysis

    8.1  Installation and Leak Check. Same as Method 2A, Sections 8.1 
and 8.2, respectively.
    8.2  Volume Rate Measurement.
    8.2.1  Continuous, Steady Flow. At least once an hour, record the 
metering device flow rate or pressure drop reading, and the metering 
device temperature and pressure. Make a minimum of 12 equally spaced 
readings of each parameter during the test period. Record the 
barometric pressure at the beginning and end of the test period. Record 
the data on a table similar to that shown in Figure 2D-1.
    8.2.2  Noncontinuous and Nonsteady Flow. Use volume rate devices 
with particular caution. Calibration will be affected by variation in 
stack gas temperature, pressure and molecular

[[Page 61809]]

weight. Use the procedure in Section 8.2.1 with the addition of the 
following: Record all the metering device parameters on a time interval 
frequency sufficient to adequately profile each process cyclical or 
noncontinuous event. A multichannel continuous recorder may be used.

9.0  Quality Control

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

10.0  Calibration and Standardization

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

11.0  Analytical Procedure.

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

12.0  Data Analysis and Calculations

    12.1  Nomenclature.

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

    [GRAPHIC] [TIFF OMITTED] TR17OC00.069
    
    12.3  Test Meter Device Calibration Coefficient. Calculation for 
testing metering device calibration coefficient, Ym.
[GRAPHIC] [TIFF OMITTED] TR17OC00.070

13.0  Method Performance [Reserved]

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

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

17.0  Tables, Diagrams, Flowcharts, and Validation Data

Plant-----------------------------------------------------------------
Date------------------------------------------------------------------
Run No.---------------------------------------------------------------
Sample location-------------------------------------------------------
Barometric pressure (mm Hg):
Start-----------------------------------------------------------------
Finish----------------------------------------------------------------
Operators-------------------------------------------------------------
Metering device No.---------------------------------------------------
Calibration coefficient-----------------------------------------------
Calibration gas-------------------------------------------------------
Date to recalibrate---------------------------------------------------

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

Figure 2D-1. Volume Flow Rate Measurement Data

[[Page 61810]]

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

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

1.0  Scope and Application

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

2.0  Summary of Method

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

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety

    5.1  Since this method is complex, only experienced personnel 
should perform the test. Landfill gas contains methane, therefore 
explosive mixtures may exist at or near the landfill. It is advisable 
to take appropriate safety precautions when testing landfills, such as 
refraining from smoking and installing explosion-proof equipment.

6.0  Equipment and Supplies

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

7.0  Reagents and Standards. Not Applicable

8.0  Sample Collection, Preservation, Storage, and Transport

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

[[Page 61811]]

extend to a depth equal to the top of the perforated section of the 
extraction wells. All other probes (shallow probes) shall extend to a 
depth equal to half the depth of the deep probes.
    8.3.1  Use an auger to dig a hole, 0.15- to 0.23-m (6-to 9-in.) in 
diameter, for each pressure probe. Perforate the bottom two thirds of 
the pressure probe. A minimum requirement for perforations is holes or 
slots with an open area equivalent to four 0.006-m (0.25-in.) diameter 
holes spaced 90 deg. apart every 0.15 m (6 in.). Place the pressure 
probe in the center of the hole and backfill with gravel to a level 
0.30 m (1 ft) above the perforated section. Add a layer of backfill 
material at least 1.2 m (4 ft) thick. Add a layer of bentonite at least 
0.3 m (1 ft) thick, and backfill the remainder of the hole with cover 
material or material equal in permeability to the existing cover 
material. The specifications for pressure probe installation are shown 
in Figure 2E-5.
    8.4  LFG Flow Rate Measurement. Place the flow measurement device, 
such as an orifice meter, as shown in Figure 2E-1. Attach the wells to 
the blower and flare assembly. The individual wells may be ducted to a 
common header so that a single blower, flare assembly, and flow meter 
may be used. Use the procedures in Section 10.1 to calibrate the flow 
meter.
    8.5  Leak-Check. A leak-check of the above ground system is 
required for accurate flow rate measurements and for safety. Sample LFG 
at the well head sample port and at the outlet sample port. Use Method 
3C to determine nitrogen (N2) concentrations. Determine the 
difference between the well head and outlet N2 
concentrations using the formula in Section 12.3. The system passes the 
leak-check if the difference is less than 10,000 ppmv.
    8.6  Static Testing. Close the control valves on the well heads 
during static testing. Measure the gauge pressure (Pg) at 
each deep pressure probe and the barometric pressure (Pbar) 
every 8 hours (hr) for 3 days. Convert the gauge pressure of each deep 
pressure probe to absolute pressure using the equation in Section 12.4. 
Record as Pi (initial absolute pressure).
    8.6.1  For each probe, average all of the 8-hr deep pressure probe 
readings (Pi) and record as Pia (average absolute 
pressure). Pia is used in Section 8.7.5 to determine the 
maximum radius of influence.
    8.6.2  Measure the static flow rate of each well once during static 
testing.
    8.7  Short-Term Testing. The purpose of short-term testing is to 
determine the maximum vacuum that can be applied to the wells without 
infiltration of ambient air into the landfill. The short-term testing 
is performed on one well at a time. Burn all LFG with a flare or 
incinerator.
    8.7.1  Use the blower to extract LFG from a single well at a rate 
at least twice the static flow rate of the respective well measured in 
Section 8.6.2. If using a single blower and flare assembly and a common 
header system, close the control valve on the wells not being measured. 
Allow 24 hr for the system to stabilize at this flow rate.
    8.7.2  Test for infiltration of air into the landfill by measuring 
the gauge pressures of the shallow pressure probes and using Method 3C 
to determine the LFG N2 concentration. If the LFG 
N2 concentration is less than 5 percent and all of the 
shallow probes have a positive gauge pressure, increase the blower 
vacuum by 3.7 mm Hg (2 in. H2O), wait 24 hr, and repeat the 
tests for infiltration. Continue the above steps of increasing blower 
vacuum by 3.7 mm Hg (2 in. H2O), waiting 24 hr, and testing 
for infiltration until the concentration of N2 exceeds 5 
percent or any of the shallow probes have a negative gauge pressure. 
When this occurs,reduce the blower vacuum to the maximum setting at 
which the N2 concentration was less than 5 percent and the 
gauge pressures of the shallow probes are positive.
    8.7.3  At this blower vacuum, measure atmospheric pressure 
(Pbar) every 8 hr for 24 hr, and record the LFG flow rate 
(Qs) and the probe gauge pressures (Pf) for all 
of the probes. Convert the gauge pressures of the deep probes to 
absolute pressures for each 8-hr reading at Qs as shown in 
Section 12.4.
    8.7.4  For each probe, average the 8-hr deep pressure probe 
absolute pressure readings and record as Pfa (the final 
average absolute pressure).
    8.7.5  For each probe, compare the initial average pressure 
(Pia) from Section 8.6.1 to the final average pressure 
(Pfa). Determine the furthermost point from the well head 
along each radial arm where Pfa  Pia. 
This distance is the maximum radius of influence (Rm), which 
is the distance from the well affected by the vacuum. Average these 
values to determine the average maximum radius of influence 
(Rma).
    8.7.6  Calculate the depth (Dst) affected by the 
extraction well during the short term test as shown in Section 12.6. If 
the computed value of Dst exceeds the depth of the landfill, 
set Dst equal to the landfill depth.
    8.7.7  Calculate the void volume (V) for the extraction well as 
shown in Section 12.7.
    8.7.8  Repeat the procedures in Section 8.7 for each well.
    8.8  Calculate the total void volume of the test wells 
(Vv) by summing the void volumes (V) of each well.
    8.9  Long-Term Testing. The purpose of long-term testing is to 
extract two void volumes of LFG from the extraction wells. Use the 
blower to extract LFG from the wells. If a single Blower and flare 
assembly and common header system are used, open all control valves and 
set the blower vacuum equal to the highest stabilized blower vacuum 
demonstrated by any individual well in Section 8.7. Every 8 hr, sample 
the LFG from the well head sample port, measure the gauge pressures of 
the shallow pressure probes, the blower vacuum, the LFG flow rate, and 
use the criteria for infiltration in Section 8.7.2 and Method 3C to 
test for infiltration. If infiltration is detected, do not reduce the 
blower vacuum, instead reduce the LFG flow rate from the well by 
adjusting the control valve on the well head. Adjust each affected well 
individually. Continue until the equivalent of two total void volumes 
(Vv) have been extracted, or until Vt = 
2Vv.
    8.9.1  Calculate Vt, the total volume of LFG extracted 
from the wells, as shown in Section 12.8.
    8.9.2  Record the final stabilized flow rate as Qf and 
the gauge pressure for each deep probe. If, during the long term 
testing, the flow rate does not stabilize, calculate Qf by 
averaging the last 10 recorded flow rates.
    8.9.3  For each deep probe, convert each gauge pressure to absolute 
pressure as in Section 12.4. Average these values and record as 
Psa. For each probe, compare Pia to 
Psa. Determine the furthermost point from the well head 
along each radial arm where Psa  Pia. 
This distance is the stabilized radius of influence. Average these 
values to determine the average stabilized radius of influence 
(Rsa).
    8.10 Determine the NMOC mass emission rate using the procedures in 
Section 12.9 through 12.15.

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

[[Page 61812]]



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

10.0  Calibration and Standardization

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

11.0  Procedures [Reserved]

12.0  Data Analysis and Calculations

    12.1  Nomenclature.

A = Age of landfill, yr.
Aavg = Average age of the refuse tested, yr.
Ai = Age of refuse in the ith fraction, yr.
Ar = Acceptance rate, Mg/yr.
CNMOC = NMOC concentration, ppmv as hexane (CNMOC 
= Ct/6).
Co = Concentration of N2 at the outlet, ppmv.
Ct = NMOC concentration, ppmv (carbon equivalent) from 
Method 25C.
Cw = Concentration of N2 at the wellhead, ppmv.
D = Depth affected by the test wells, m.
Dst = Depth affected by the test wells in the short-term 
test, m.
e = Base number for natural logarithms (2.718).
f = Fraction of decomposable refuse in the landfill.
fi = Fraction of the refuse in the ith section.
k = Landfill gas generation constant, yr-\1\.
Lo = Methane generation potential, m\3\/Mg.
Lo' = Revised methane generation potential to account for 
the amount of nondecomposable material in the landfill, m\3\/Mg.
Mi = Mass of refuse in the ith section, Mg.
Mr = Mass of decomposable refuse affected by the test well, 
Mg.
Pbar = Atmospheric pressure, mm Hg.
Pf = Final absolute pressure of the deep pressure probes 
during short-term testing, mm Hg.
Pfa = Average final absolute pressure of the deep pressure 
probes during short-term testing, mm Hg.
Pgf = final gauge pressure of the deep pressure probes, mm 
Hg.
Pgi = Initial gauge pressure of the deep pressure probes, mm 
Hg.
Pi = Initial absolute pressure of the deep pressure probes 
during static testing, mm Hg.
Pia = Average initial absolute pressure of the deep pressure 
probes during static testing, mm Hg.
Ps = Final absolute pressure of the deep pressure probes 
during long-term testing, mm Hg.
Psa = Average final absolute pressure of the deep pressure 
probes during long-term testing, mm Hg.
Qf = Final stabilized flow rate, m\3\/min.
Qi = LFG flow rate measured at orifice meter during the ith 
interval, m\3\/min.
Qs = Maximum LFG flow rate at each well determined by short-
term test, m\3\/min.
Qt = NMOC mass emission rate, m\3\/min.
Rm = Maximum radius of influence, m.
Rma = Average maximum radius of influence, m.
Rs = Stabilized radius of influence for an individual well, 
m.
Rsa = Average stabilized radius of influence, m.
ti = Age of section i, yr.
tt = Total time of long-term testing, yr.
tvi = Time of the ith interval (usually 8), hr.
V = Void volume of test well, m\3\.
Vr = Volume of refuse affected by the test well, m\3\.
Vt = Total volume of refuse affected by the long-term 
testing, m\3\.
Vv = Total void volume affected by test wells, m\3\.
WD = Well depth, m.
 = Refuse density, Mg/m\3\ (Assume 0.64 Mg/m\3\ if data are 
unavailable).

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

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

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

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

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

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

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

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

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

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

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

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

[[Page 61813]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.082

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

    12.15  Use the following equation to determine landfill NMOC mass 
emission rate if the acceptance rate has not been consistent over the 
life of the landfill.
[GRAPHIC] [TIFF OMITTED] TR17OC00.084

13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    1. Same as Method 2, Appendix A, 40 CFR Part 60.
    2. Emcon Associates, Methane Generation and Recovery from 
Landfills. Ann Arbor Science, 1982.
    3. The Johns Hopkins University, Brown Station Road Landfill Gas 
Resource Assessment, Volume 1: Field Testing and Gas Recovery 
Projections. Laurel, Maryland: October 1982.
    4. Mandeville and Associates, Procedure Manual for Landfill 
Gases Emission Testing.
    5. Letter and attachments from Briggum, S., Waste Management of 
North America, to Thorneloe, S., EPA. Response to July 28, 1988 
request for additional information. August 18, 1988.
    6. Letter and attachments from Briggum, S., Waste Management of 
North America, to Wyatt, S., EPA. Response to December 7, 1988 
request for additional information. January 16, 1989.
BILLING CODE 6560-50-C

[[Page 61814]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.085


[[Page 61815]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.086


[[Page 61816]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.087


[[Page 61817]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.088


[[Page 61818]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.089

BILLING CODE 6560-50-C

[[Page 61819]]

* * * * *

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

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

1.0  Scope and Application

    1.1  Analytes.

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

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

2.0  Summary of Method

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

3.0  Definitions [Reserved]

4.0  Interferences

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

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Corrosive Reagents.
    5.2.1  A typical Orsat analyzer requires four reagents: a gas-
confining solution, CO2 absorbent, O2 absorbent, 
and CO absorbent. These reagents may contain potassium hydroxide, 
sodium hydroxide, cuprous chloride, cuprous sulfate, alkaline 
pyrogallic acid, and/or chromous chloride. Follow manufacturer's 
operating instructions and observe all warning labels for reagent use.
    5.2.2  A typical Fyrite analyzer contains zinc chloride, 
hydrochloric acid, and either potassium hydroxide or chromous chloride. 
Follow manufacturer's operating instructions and observe all warning 
labels for reagent use.

6.0  Equipment and Supplies

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

    6.1  Grab Sampling (See Figure 3-1).
    6.1.1  Probe. Stainless steel or borosilicate glass tubing equipped 
with an in-stack or out-of-stack filter to remove particulate matter (a 
plug of glass wool is satisfactory for this purpose). Any other 
materials, resistant to temperature at sampling conditions and inert to 
all components of the gas stream, may be used for the probe. Examples 
of such materials may include aluminum, copper, quartz glass, and 
Teflon.
    6.1.2  Pump. A one-way squeeze bulb, or equivalent, to transport 
the gas sample to the analyzer.
    6.2  Integrated Sampling (Figure 3-2).
    6.2.1  Probe. Same as in Section 6.1.1.
    6.2.2  Condenser. An air-cooled or water-cooled condenser, or other 
condenser no greater than 250 ml that will not remove O2, 
CO2, CO, and N2, to remove excess moisture which 
would interfere with the operation of the pump and flowmeter.
    6.2.3  Valve. A needle valve, to adjust sample gas flow rate.
    6.2.4  Pump. A leak-free, diaphragm-type pump, or equivalent, to 
transport sample gas to the flexible bag. Install a small surge tank 
between the pump and rate meter to eliminate the pulsation effect of 
the diaphragm pump on the rate meter.
    6.2.5  Rate Meter. A rotameter, or equivalent, capable of measuring 
flow rate to  2 percent of the selected flow rate. A flow 
rate range of 500 to 1000 ml/min is suggested.
    6.2.6  Flexible Bag. Any leak-free plastic (e.g., Tedlar, Mylar, 
Teflon) or plastic-coated aluminum (e.g., aluminized Mylar) bag, or 
equivalent, having a capacity consistent with the selected flow rate 
and duration of the test run. A capacity in the range of 55 to 90 
liters (1.9 to 3.2 ft3) is suggested. To leak-check the bag, 
connect it to a water manometer, and pressurize the bag to 5 to 10 cm 
H2O (2 to 4 in. H2O). Allow to stand for 10 
minutes. Any displacement in the water manometer indicates a leak. An 
alternative leak-check method is to pressurize the bag to

[[Page 61820]]

5 to 10 cm (2 to 4 in.) H2O and allow to stand overnight. A 
deflated bag indicates a leak.
    6.2.7  Pressure Gauge. A water-filled U-tube manometer, or 
equivalent, of about 30 cm (12 in.), for the flexible bag leak-check.
    6.2.8  Vacuum Gauge. A mercury manometer, or equivalent, of at 
least 760 mm (30 in.) Hg, for the sampling train leak-check.
    6.3  Analysis. An Orsat or Fyrite type combustion gas analyzer.

7.0  Reagents and Standards

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

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Single Point, Grab Sampling Procedure.
    8.1.1  The sampling point in the duct shall either be at the 
centroid of the cross section or at a point no closer to the walls than 
1.0 m (3.3 ft), unless otherwise specified by the Administrator.
    8.1.2  Set up the equipment as shown in Figure 3-1, making sure all 
connections ahead of the analyzer are tight. If an Orsat analyzer is 
used, it is recommended that the analyzer be leak-checked by following 
the procedure in Section 11.5; however, the leak-check is optional.
    8.1.3  Place the probe in the stack, with the tip of the probe 
positioned at the sampling point. Purge the sampling line long enough 
to allow at least five exchanges. Draw a sample into the analyzer, and 
immediately analyze it for percent CO2 and percent 
O2 according to Section 11.2.
    8.2  Single-Point, Integrated Sampling Procedure.
    8.2.1  The sampling point in the duct shall be located as specified 
in Section 8.1.1.
    8.2.2  Leak-check (optional) the flexible bag as in Section 6.2.6. 
Set up the equipment as shown in Figure 3-2. Just before sampling, 
leak-check (optional) the train by placing a vacuum gauge at the 
condenser inlet, pulling a vacuum of at least 250 mm Hg (10 in. Hg), 
plugging the outlet at the quick disconnect, and then turning off the 
pump. The vacuum should remain stable for at least 0.5 minute. Evacuate 
the flexible bag. Connect the probe, and place it in the stack, with 
the tip of the probe positioned at the sampling point. Purge the 
sampling line. Next, connect the bag, and make sure that all 
connections are tight.
    8.2.3  Sample Collection. Sample at a constant rate (10 
percent). The sampling run should be simultaneous with, and for the 
same total length of time as, the pollutant emission rate 
determination. Collection of at least 28 liters (1.0 ft3) of 
sample gas is recommended; however, smaller volumes may be collected, 
if desired.
    8.2.4  Obtain one integrated flue gas sample during each pollutant 
emission rate determination. Within 8 hours after the sample is taken, 
analyze it for percent CO2 and percent O2 using 
either an Orsat analyzer or a Fyrite type combustion gas analyzer 
according to Section 11.3.

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

    8.3  Multi-Point, Integrated Sampling Procedure.
    8.3.1  Unless otherwise specified in an applicable regulation, or 
by the Administrator, a minimum of eight traverse points shall be used 
for circular stacks having diameters less than 0.61 m (24 in.), a 
minimum of nine shall be used for rectangular stacks having equivalent 
diameters less than 0.61 m (24 in.), and a minimum of 12 traverse 
points shall be used for all other cases. The traverse points shall be 
located according to Method 1.
    8.3.2  Follow the procedures outlined in Sections 8.2.2 through 
8.2.4, except for the following: Traverse all sampling points, and 
sample at each point for an equal length of time. Record sampling data 
as shown in Figure 3-3.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.2...........................  Use of Fyrite to   Ensures the accurate
                                 confirm Orsat      measurement of CO2
                                 results.           and O2.
10.1..........................  Periodic audit of  Ensures that the
                                 analyzer and       analyzer is
                                 operator           operating properly
                                 technique.         and that the
                                                    operator performs
                                                    the sampling
                                                    procedure correctly
                                                    and accurately.
11.3..........................  Replicable         Minimizes
                                 analyses of        experimental error.
                                 integrated
                                 samples.
------------------------------------------------------------------------

10.0  Calibration and Standardization

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

11.0  Analytical Procedure

    11.1  Maintenance. The Orsat or Fyrite-type analyzer should be 
maintained and operated according to the manufacturers specifications.
    11.2  Grab Sample Analysis. Use either an Orsat analyzer or a 
Fyrite-type combustion gas analyzer to measure O2 and 
CO2 concentration for dry molecular weight determination, 
using procedures as specified in the analyzer user's manual. If an 
Orsat analyzer is used, it is recommended that the Orsat leak-check, 
described in Section 11.5, be performed before this determination; 
however, the check is optional. Calculate the dry molecular weight as 
indicated in Section 12.0. Repeat the sampling, analysis, and 
calculation procedures until the dry molecular weights of any three 
grab samples differ from their mean by no more than 0.3 g/g-mole (0.3 
lb/lb-mole). Average these three molecular weights, and report the 
results to the nearest 0.1 g/g-mole (0.1 lb/lb-mole).
    11.3  Integrated Sample Analysis. Use either an Orsat analyzer or a 
Fyrite-type combustion gas analyzer to measure O2 and 
CO2 concentration for dry molecular weight determination, 
using procedures as specified in the analyzer user's manual. If an 
Orsat analyzer is used, it is recommended that the Orsat leak-check, 
described in Section 11.5, be performed before this determination; 
however, the check is

[[Page 61821]]

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

12.0  Calculations and Data Analysis

    12.1  Nomenclature.

Md = Dry molecular weight, g/g-mole (lb/lb-mole).
%CO2 = Percent CO2 by volume, dry basis.
%O2 = Percent O2 by volume, dry basis.
%CO = Percent CO by volume, dry basis.
%N2 = Percent N2 by volume, dry basis.
0.280   = Molecular weight of N2 or CO, divided by 100.
0.320   = Molecular weight of O2 divided by 100.
0.440   = Molecular weight of CO2 divided by 100.
    12.2  Nitrogen, Carbon Monoxide Concentration. Determine the 
percentage of the gas that is N2 and CO by subtracting the 
sum of the percent CO2 and percent O2 from 100 
percent.
    12.3  Dry Molecular Weight. Use Equation 3-1 to calculate the dry 
molecular weight of the stack gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.090


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

13.0  Method Performance [Reserved]

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

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

[[Page 61822]]

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


[[Page 61823]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.092


----------------------------------------------------------------------------------------------------------------
                 Time                       Traverse point           Q (liter/min)            % Deviation a
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
Average
----------------------------------------------------------------------------------------------------------------
a % Dev.=[(Q-Qavg)/Qavg] x 100 (Must be >10%)

Figure 3-3. Sampling Rate Data

[[Page 61824]]

* * * * *

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

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

1.0  Scope and Application

    1.1  Analytes.

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

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

2.0  Summary of Method

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

3.0  Definitions [Reserved]

4.0  Interferences

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

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Corrosive Reagents. A typical Orsat analyzer requires four 
reagents: a gas-confining solution, CO2 absorbent, 
O2 absorbent, and CO absorbent. These reagents may contain 
potassium hydroxide, sodium hydroxide, cuprous chloride, cuprous 
sulfate, alkaline pyrogallic acid, and/or chromous chloride. Follow 
manufacturer's operating instructions and observe all warning labels 
for reagent use.

6.0  Equipment and Supplies

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

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

7.0  Reagents and Standards

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

8.0  Sample Collection, Preservation, Storage, and Transport

    Note: Each of the three procedures below shall be used only when 
specified in an applicable subpart of the standards. The use of 
these procedures for other purposes must have specific prior 
approval of the Administrator. A Fyrite-type combustion gas analyzer 
is not acceptable for excess air or emission rate correction factor 
determinations, unless approved by the Administrator. If both 
percent CO2 and percent O2 are measured, the 
analytical results of any of the three procedures given below may 
also be used for calculating the dry molecular weight (see Method 
3).

8.1  Single-Point, Grab Sampling and Analytical Procedure.

    8.1.1  The sampling point in the duct shall either be at the 
centroid of the cross section or at a point no closer to the walls than 
1.0 m (3.3 ft), unless otherwise specified by the Administrator.
    8.1.2  Set up the equipment as shown in Figure 3-1 of Method 3, 
making sure all connections ahead of the analyzer are tight. Leak-check 
the Orsat analyzer according to the procedure described in Section 11.5 
of Method 3. This leak-check is mandatory.
    8.1.3  Place the probe in the stack, with the tip of the probe 
positioned at the sampling point; purge the sampling line long enough 
to allow at least five exchanges. Draw a sample into the analyzer. For 
emission rate correction factor determinations, immediately analyze the 
sample for percent CO2 or

[[Page 61825]]

percent O2, as outlined in Section 11.2. For excess air 
determination, immediately analyze the sample for percent 
CO2, O2, and CO, as outlined in Section 11.2, and 
calculate excess air as outlined in Section 12.2.
    8.1.4  After the analysis is completed, leak-check (mandatory) the 
Orsat analyzer once again, as described in Section 11.5 of Method 3. 
For the results of the analysis to be valid, the Orsat analyzer must 
pass this leak-test before and after the analysis.

8.2  Single-Point, Integrated Sampling and Analytical Procedure.

    8.2.1  The sampling point in the duct shall be located as specified 
in Section 8.1.1.
    8.2.2  Leak-check (mandatory) the flexible bag as in Section 6.2.6 
of Method 3. Set up the equipment as shown in Figure 3-2 of Method 3. 
Just before sampling, leak-check (mandatory) the train by placing a 
vacuum gauge at the condenser inlet, pulling a vacuum of at least 250 
mm Hg (10 in. Hg), plugging the outlet at the quick disconnect, and 
then turning off the pump. The vacuum should remain stable for at least 
0.5 minute. Evacuate the flexible bag. Connect the probe, and place it 
in the stack, with the tip of the probe positioned at the sampling 
point; purge the sampling line. Next, connect the bag, and make sure 
that all connections are tight.
    8.2.3  Sample at a constant rate, or as specified by the 
Administrator. The sampling run must be simultaneous with, and for the 
same total length of time as, the pollutant emission rate 
determination. Collect at least 28 liters (1.0 ft\3\) of sample gas. 
Smaller volumes may be collected, subject to approval of the 
Administrator.
    8.2.4  Obtain one integrated flue gas sample during each pollutant 
emission rate determination. For emission rate correction factor 
determination, analyze the sample within 4 hours after it is taken for 
percent CO2 or percent O2 (as outlined in Section 
11.2).

8.3  Multi-Point, Integrated Sampling and Analytical Procedure.

    8.3.1  Unless otherwise specified in an applicable regulation, or 
by the Administrator, a minimum of eight traverse points shall be used 
for circular stacks having diameters less than 0.61 m (24 in.), a 
minimum of nine shall be used for rectangular stacks having equivalent 
diameters less than 0.61 m (24 in.), and a minimum of 12 traverse 
points shall be used for all other cases. The traverse points shall be 
located according to Method 1.
    8.3.2  Follow the procedures outlined in Sections 8.2.2 through 
8.2.4, except for the following: Traverse all sampling points, and 
sample at each point for an equal length of time. Record sampling data 
as shown in Figure 3-3 of Method 3.

9.0  Quality Control

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


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

10.0  Calibration and Standardization

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

11.0  Analytical Procedure

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


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


    11.3  Integrated Sample Analysis. The Orsat analyzer must be leak-
checked (see Section 11.5 of Method 3) before the analysis. If excess 
air is desired, proceed as follows: (1) within 4 hours after the sample 
is taken, analyze it (as in Sections 11.3.1 through 11.3.3) for percent 
CO2, O2, and CO; (2) determine the percentage of 
the gas that is N2 by subtracting the sum of the percent 
CO2, percent O2, and percent CO from 100 percent; 
and (3) calculate percent excess air, as outlined in Section 12.2.
    11.3.1  To ensure complete absorption of the CO2, 
O2, or if applicable, CO, follow the procedure described in 
Section 11.2.


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


    11.3.2  Repeat the analysis until the following criteria are met:
    11.3.2.1  For percent CO2, repeat the analytical 
procedure until the results of any three analyses differ by no more 
than (a) 0.3 percent by volume when CO2 is greater than 4.0 
percent or (b) 0.2 percent by volume when CO2 is less than 
or equal to 4.0 percent. Average three acceptable values of percent 
CO2, and report the results to the nearest 0.2 percent.
    11.3.2.2  For percent O2, repeat the analytical 
procedure until the results of any three analyses differ by no more 
than (a) 0.3 percent by volume when O2 is less than 15.0 
percent or (b) 0.2 percent by volume when O2 is greater than 
or equal to 15.0 percent. Average the three acceptable values of 
percent O2, and report the results to the nearest 0.1 
percent.
    11.3.2.3  For percent CO, repeat the analytical procedure until the 
results of any three analyses differ by no more than 0.3 percent. 
Average the three acceptable values of percent CO, and

[[Page 61826]]

report the results to the nearest 0.1 percent.
    11.3.3  After the analysis is completed, leak-check (mandatory) the 
Orsat analyzer once again, as described in Section 11.5 of Method 3. 
For the results of the analysis to be valid, the Orsat analyzer must 
pass this leak-test before and after the analysis.
    11.4  Standardization. A periodic check of the reagents and of 
operator technique should be conducted at least once every three series 
of test runs as indicated in Section 10.1.

12.0  Calculations and Data Analysis

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

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


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

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

Where:

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

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

[GRAPHIC] [TIFF OMITTED] TR17OC00.096

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

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

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

13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    Same as Method 3, Section 16.0.

17.0  Tables, Diagrams, Flowcharts, and Validation Data

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

* * * * *

Method 4--Determination of Moisture Content in Stack Gases

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

1.0  Scope and Application

    1.1  Analytes.

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

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

[[Page 61827]]

2.0  Summary of Method

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

3.0  Definitions [Reserved]

4.0  Interferences

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

5.0  Safety

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

6.0  Equipment and Supplies

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

7.0  Reagents and Standards [Reserved]

8.0  Sample Collection, Preservation, Transport, and Storage

    8.1  Reference Method. The following procedure is intended for a 
condenser system (such as the impinger system described in Section 
6.1.1.8 of Method 5) incorporating volumetric analysis to measure the 
condensed moisture, and silica gel and gravimetric analysis to measure 
the moisture leaving the condenser.
    8.1.1  Preliminary Determinations.
    8.1.1.1  Unless otherwise specified by the Administrator, a minimum 
of eight traverse points shall be used for circular stacks having 
diameters less than 0.61 m (24 in.), a minimum of nine points shall be 
used for rectangular stacks having equivalent diameters less than 0.61 
m (24 in.), and a minimum of twelve traverse points shall be used in 
all other cases. The traverse points shall be located according to 
Method 1. The use of fewer points is subject to the approval of the 
Administrator. Select a suitable probe and probe length such that all 
traverse points can be sampled. Consider sampling from opposite sides 
of the stack (four total sampling ports) for large stacks, to permit 
use of shorter probe lengths. Mark the probe with heat resistant tape 
or by some other method to denote the proper distance into the stack or 
duct for each sampling point.
    8.1.1.2  Select a total sampling time such that a minimum total gas 
volume of 0.60 scm (21 scf) will be collected, at a rate no greater 
than 0.021 m\3\/min (0.75 cfm). When both moisture content and 
pollutant emission rate are to be determined, the moisture 
determination shall be simultaneous with, and for the same total length 
of time as, the pollutant emission rate run, unless otherwise specified 
in an applicable subpart of the standards.

[[Page 61828]]

    8.1.2  Preparation of Sampling Train.
    8.1.2.1  Place known volumes of water in the first two impingers; 
alternatively, transfer water into the first two impingers and record 
the weight of each impinger (plus water) to the nearest 0.5 g. Weigh 
and record the weight of the silica gel to the nearest 0.5 g, and 
transfer the silica gel to the fourth impinger; alternatively, the 
silica gel may first be transferred to the impinger, and the weight of 
the silica gel plus impinger recorded.
    8.1.2.2  Set up the sampling train as shown in Figure 4-1. Turn on 
the probe heater and (if applicable) the filter heating system to 
temperatures of approximately 120  deg.C (248  deg.F), to prevent water 
condensation ahead of the condenser. Allow time for the temperatures to 
stabilize. Place crushed ice and water in the ice bath container.
    8.1.3  Leak Check Procedures. It is recommended, but not required, 
that the volume metering system and sampling train be leak-checked as 
follows:
    8.1.3.1  Metering System. Same as Method 5, Section 8.4.1.
    8.1.3.2  Sampling Train. Disconnect the probe from the first 
impinger or (if applicable) from the filter holder. Plug the inlet to 
the first impinger (or filter holder), and pull a 380 mm (15 in.) Hg 
vacuum. A lower vacuum may be used, provided that it is not exceeded 
during the test. A leakage rate in excess of 4 percent of the average 
sampling rate or 0.00057 m\3\/min (0.020 cfm), whichever is less, is 
unacceptable. Following the leak check, reconnect the probe to the 
sampling train.
    8.1.4  Sampling Train Operation. During the sampling run, maintain 
a sampling rate within 10 percent of constant rate, or as specified by 
the Administrator. For each run, record the data required on a data 
sheet similar to that shown in Figure 4-3. Be sure to record the dry 
gas meter reading at the beginning and end of each sampling time 
increment and whenever sampling is halted. Take other appropriate 
readings at each sample point at least once during each time increment.


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


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

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


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

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


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

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

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

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

10.0  Calibration and Standardization

    Note: Maintain a laboratory log of all calibrations.

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

11.0  Analytical Procedure

    11.1  Reference Method. Measure the volume of the moisture 
condensed in each of the impingers to the nearest ml. Alternatively, if 
the impingers were weighed prior to sampling, weigh the impingers after 
sampling and record the difference in weight to the nearest 0.5 g. 
Determine the increase in weight of the silica gel (or silica gel plus 
impinger) to the nearest 0.5 g. Record this information (see example 
data sheet, Figure 4-5), and calculate the moisture content, as 
described in Section 12.0.
    11.2  Approximation Method. Combine the contents of the two 
impingers, and measure the volume to the nearest 0.5 ml.

12.0  Data Analysis and Calculations

    Carry out the following calculations, retaining at least one extra 
significant figure beyond that of the acquired data. Round off figures 
after final calculation.
    12.1  Reference Method.
    12.1.1  Nomenclature.
Bws = Proportion of water vapor, by volume, in the gas 
stream.
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 lb/lb-
mole).
Pm = Absolute pressure (for this method, same as barometric 
pressure) at the dry gas meter, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
R = Ideal gas constant, 0.06236 (mm Hg)(m\3\)/(g-mole)( deg.K) for 
metric units and 21.85 (in. Hg)(ft\3\)/(lb-mole)( deg.R) for English 
units.
Tm = Absolute temperature at meter,  deg.K ( deg.R).
Tstd = Standard absolute temperature, 293  deg.K (528 
deg.R).

[[Page 61829]]

Vf = Final volume of condenser water, ml.
Vi = Initial volume, if any, of condenser water, ml.
Vm = Dry gas volume measured by dry gas meter, dcm (dcf).
Vm(std) = Dry gas volume measured by the dry gas meter, 
corrected to standard conditions, dscm (dscf).
Vwc(std) = Volume of water vapor condensed, corrected to 
standard conditions, scm (scf).
Vwsg(std) = Volume of water vapor collected in silica gel, 
corrected to standard conditions, scm (scf).
Wf = Final weight of silica gel or silica gel plus impinger, 
g.
Wi = Initial weight of silica gel or silica gel plus 
impinger, g.
Y = Dry gas meter calibration factor.
Vm = Incremental dry gas volume measured by dry gas 
meter at each traverse point, dcm (dcf).
w = Density of water, 0.9982 g/ml (0.002201 lb/ml).

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

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

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

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

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

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

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

    12.1.5  Moisture Content.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.101
    
    12.1.6  Verification of Constant Sampling Rate. For each time 
increment, determine the Vm. Calculate the average. 
If the value for any time increment differs from the average by more 
than 10 percent, reject the results, and repeat the run.
    12.1.7  In saturated or moisture droplet-laden gas streams, two 
calculations of the moisture content of the stack gas shall be made, 
one using a value based upon the saturated conditions (see Section 
4.1), and another based upon the results of the impinger analysis. The 
lower of these two values of Bws shall be considered 
correct.
    12.2  Approximation Method. The approximation method presented is 
designed to estimate the moisture in the stack gas; therefore, other 
data, which are only necessary for accurate moisture determinations, 
are not collected. The following equations adequately estimate the 
moisture content for the purpose of determining isokinetic sampling 
rate settings.
    12.2.1  Nomenclature.
Bwm = Approximate proportion by volume of water vapor in the 
gas stream leaving the second impinger, 0.025.
Bws = Water vapor in the gas stream, proportion by volume.
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 lb/lb-
mole).
Pm = Absolute pressure (for this method, same as barometric 
pressure) at the dry gas meter, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
R = Ideal gas constant, 0.06236 [(mm Hg)(m\3\)]/[(g-mole)(K)] for 
metric units and 21.85 [(in. Hg)(ft\3\)]/[(lb-mole)( deg.R)] for 
English units.
Tm = Absolute temperature at meter,  deg.K ( deg.R).
Tstd = Standard absolute temperature, 293  deg.K (528 
deg.R).
Vf = Final volume of impinger contents, ml.
Vi = Initial volume of impinger contents, ml.
Vm = Dry gas volume measured by dry gas meter, dcm (dcf).
Vm(std) = Dry gas volume measured by dry gas meter, 
corrected to standard conditions, dscm (dscf).
Vwc(std) = Volume of water vapor condensed, corrected to 
standard conditions, scm (scf).
Y = Dry gas meter calibration factor.
w = Density of water, 0.09982 g/ml (0.002201 lb/
ml).

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

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

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

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

    12.2.4  Approximate Moisture Content.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.104
    
13.0  Method Performance [Reserved]

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  Alternative Procedures

    The procedure described in Method 5 for determining moisture 
content is acceptable as a reference method.

17.0  References

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

[[Page 61830]]

18.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.105


[[Page 61831]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.106


[[Page 61832]]


Plant-----------------------------------------------------------------
Location--------------------------------------------------------------
Operator--------------------------------------------------------------
Date------------------------------------------------------------------
Run No.---------------------------------------------------------------
Ambient temperature---------------------------------------------------
Barometric pressure---------------------------------------------------
Probe Length----------------------------------------------------------

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

SCHEMATIC OF STACK CROSS SECTION

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

Location--------------------------------------------------------------
Test------------------------------------------------------------------
Date------------------------------------------------------------------
Operator--------------------------------------------------------------
Barometric pressure---------------------------------------------------
Comments:-------------------------------------------------------------
----------------------------------------------------------------------
Figure 4-3. Moisture Determination--Reference Method

----------------------------------------------------------------------------------------------------------------
                                          Gas Volume through     Rate meter setting m3/     Meter temperature
              Clock time                meter, (Vm), m3 (ft3)        min (ft3/min)            deg.C ( deg.F)
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
----------------------------------------------------------------------------------------------------------------

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

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

Figure 4-5. Analytical Data--Reference Method

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

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


[[Page 61833]]



1.0  Scope and Application

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

2.0  Summary of Method

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

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety

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

6.0  Equipment and Supplies

    6.1  Sample Collection. The following items are required for sample 
collection:
    6.1.1  Sampling Train. A schematic of the sampling train used in 
this method is shown in Figure 5-1 in Section 18.0. Complete 
construction details are given in APTD-0581 (Reference 2 in Section 
17.0); commercial models of this train are also available. For changes 
from APTD-0581 and for allowable modifications of the train shown in 
Figure 5-1, see the following subsections.

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

    6.1.1.1  Probe Nozzle. Stainless steel (316) or glass with a sharp, 
tapered leading edge. The angle of taper shall be 30 deg., 
and the taper shall be on the outside to preserve a constant internal 
diameter. The probe nozzle shall be of the button-hook or elbow design, 
unless otherwise specified by the Administrator. If made of stainless 
steel, the nozzle shall be constructed from seamless tubing. Other 
materials of construction may be used, subject to the approval of the 
Administrator. A range of nozzle sizes suitable for isokinetic sampling 
should be available. Typical nozzle sizes range from 0.32 to 1.27 cm 
(\1/8\ to \1/2\ in) inside diameter (ID) in increments of 0.16 cm (\1/
16\ in). Larger nozzles sizes are also available if higher volume 
sampling trains are used. Each nozzle shall be calibrated, according to 
the procedures outlined in Section 10.1.
    6.1.1.2  Probe Liner. Borosilicate or quartz glass tubing with a 
heating system capable of maintaining a probe gas temperature during 
sampling of 120  14  deg.C (248  25  deg.F), or 
such other temperature as specified by an applicable subpart of the 
standards or as approved by the Administrator for a particular 
application. Since the actual temperature at the outlet of the probe is 
not usually monitored during sampling, probes constructed according to 
APTD-0581 and utilizing the calibration curves of APTD-0576 (or 
calibrated according to the procedure outlined in APTD-0576) will be 
considered acceptable. Either borosilicate or quartz glass probe liners 
may be used for stack temperatures up to about 480  deg.C (900  deg.F); 
quartz glass liners shall be used for temperatures between 480 and 900 
deg.C (900 and 1,650  deg.F). Both types of liners may be used at 
higher temperatures than specified for short periods of time, subject 
to the approval of the Administrator. The softening temperature for 
borosilicate glass is 820  deg.C (1500 deg.F), and for quartz glass it 
is 1500  deg.C (2700  deg.F). Whenever practical, every effort should 
be made to use borosilicate or quartz glass probe liners. 
Alternatively, metal liners (e.g., 316 stainless steel, Incoloy 825 or 
other corrosion resistant metals) made of seamless tubing may be used, 
subject to the approval of the Administrator.
    6.1.1.3  Pitot Tube. Type S, as described in Section 6.1 of Method 
2, or other device approved by the Administrator. The pitot tube shall 
be attached to the probe (as shown in Figure 5-1) to allow constant 
monitoring of the stack gas velocity. The impact (high pressure) 
opening plane of the pitot tube shall be even with or above the nozzle 
entry plane (see Method 2, Figure 2-7) during sampling. The Type S 
pitot tube assembly shall have a known coefficient, determined as 
outlined in Section 10.0 of Method 2.
    6.1.1.4  Differential Pressure Gauge. Inclined manometer or 
equivalent device (two), as described in Section 6.2 of Method 2. One 
manometer shall be used for velocity head (p) readings, and 
the other, for orifice differential pressure readings.
    6.1.1.5  Filter Holder. Borosilicate glass, with a glass frit 
filter support and a silicone rubber gasket. Other materials of 
construction (e.g., stainless steel, Teflon, or Viton) may be used, 
subject to the approval of the Administrator. The holder design shall 
provide a positive seal against leakage from the outside or around the 
filter. The holder shall be attached immediately at the outlet of the 
probe (or cyclone, if used).
    6.1.1.6  Filter Heating System. Any heating system capable of 
maintaining a temperature around the filter holder of 120 
14  deg.C (248 25  deg.F) during sampling, or 
such other temperature as specified by an applicable subpart of the 
standards or approved by the Administrator for a particular 
application.
    6.1.1.7  Temperature Sensor. A temperature sensor capable of 
measuring temperature to within 3  deg.C (5.4  deg.F) shall 
be installed so that the sensing tip of the temperature sensor is in 
direct contact with the sample gas, and the temperature around the 
filter holder can be regulated and monitored during sampling.
    6.1.1.8  Condenser. The following system shall be used to determine 
the stack gas moisture content: Four impingers connected in series with 
leak-free ground glass fittings or any similar leak-free 
noncontaminating fittings. The first, third, and fourth impingers shall 
be of the Greenburg-Smith design, modified by replacing the tip with a 
1.3 cm (\1/2\ in.) ID glass tube extending to about 1.3 cm (\1/2\ in.) 
from the bottom of the flask. The second impinger shall be of the 
Greenburg-Smith design with the standard tip. Modifications (e.g., 
using flexible connections between the impingers, using materials other 
than glass, or using flexible vacuum lines to connect the filter holder 
to the condenser) may be used, subject to the approval of the 
Administrator. The first and second impingers shall contain known 
quantities of water (Section 8.3.1), the third shall be empty, and the 
fourth shall contain a known weight of silica gel, or equivalent 
desiccant. A temperature sensor, capable of measuring temperature to 
within 1  deg.C (2  deg.F) shall be placed at the outlet of the fourth 
impinger for monitoring purposes. Alternatively, any system that cools 
the sample gas stream and allows

[[Page 61834]]

measurement of the water condensed and moisture leaving the condenser, 
each to within 1 ml or 1 g may be used, subject to the approval of the 
Administrator. An acceptable technique involves the measurement of 
condensed water either gravimetrically or volumetrically and the 
determination of the moisture leaving the condenser by: (1) monitoring 
the temperature and pressure at the exit of the condenser and using 
Dalton's law of partial pressures; or (2) passing the sample gas stream 
through a tared silica gel (or equivalent desiccant) trap with exit 
gases kept below 20  deg.C (68  deg.F) and determining the weight gain. 
If means other than silica gel are used to determine the amount of 
moisture leaving the condenser, it is recommended that silica gel (or 
equivalent) still be used between the condenser system and pump to 
prevent moisture condensation in the pump and metering devices and to 
avoid the need to make corrections for moisture in the metered volume.


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


    6.1.1.9  Metering System. Vacuum gauge, leak-free pump, temperature 
sensors capable of measuring temperature to within 3  deg.C (5.4 
deg.F), dry gas meter (DGM) capable of measuring volume to within 2 
percent, and related equipment, as shown in Figure 5-1. Other metering 
systems capable of maintaining sampling rates within 10 percent of 
isokinetic and of determining sample volumes to within 2 percent may be 
used, subject to the approval of the Administrator. When the metering 
system is used in conjunction with a pitot tube, the system shall allow 
periodic checks of isokinetic rates.
    6.1.1.10 Sampling trains utilizing metering systems designed for 
higher flow rates than that described in APTD-0581 or APTD-0576 may be 
used provided that the specifications of this method are met.
    6.1.2  Barometer. Mercury, aneroid, or other barometer capable of 
measuring atmospheric pressure to within 2.5 mm Hg (0.1 in.).

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


    6.1.3  Gas Density Determination Equipment. Temperature sensor and 
pressure gauge, as described in Sections 6.3 and 6.4 of Method 2, and 
gas analyzer, if necessary, as described in Method 3. The temperature 
sensor shall, preferably, be permanently attached to the pitot tube or 
sampling probe in a fixed configuration, such that the tip of the 
sensor extends beyond the leading edge of the probe sheath and does not 
touch any metal. Alternatively, the sensor may be attached just prior 
to use in the field. Note, however, that if the temperature sensor is 
attached in the field, the sensor must be placed in an interference-
free arrangement with respect to the Type S pitot tube openings (see 
Method 2, Figure 2-4). As a second alternative, if a difference of not 
more than 1 percent in the average velocity measurement is to be 
introduced, the temperature sensor need not be attached to the probe or 
pitot tube. (This alternative is subject to the approval of the 
Administrator.)
    6.2  Sample Recovery. The following items are required for sample 
recovery:
    6.2.1  Probe-Liner and Probe-Nozzle Brushes. Nylon bristle brushes 
with stainless steel wire handles. The probe brush shall have 
extensions (at least as long as the probe) constructed of stainless 
steel, Nylon, Teflon, or similarly inert material. The brushes shall be 
properly sized and shaped to brush out the probe liner and nozzle.
    6.2.2  Wash Bottles. Two Glass wash bottles are recommended. 
Alternatively, polyethylene wash bottles may be used. It is recommended 
that acetone not be stored in polyethylene bottles for longer than a 
month.
    6.2.3  Glass Sample Storage Containers. Chemically resistant, 
borosilicate glass bottles, for acetone washes, 500 ml or 1000 ml. 
Screw cap liners shall either be rubber-backed Teflon or shall be 
constructed so as to be leak-free and resistant to chemical attack by 
acetone. (Narrow mouth glass bottles have been found to be less prone 
to leakage.) Alternatively, polyethylene bottles may be used.
    6.2.4  Petri Dishes. For filter samples; glass or polyethylene, 
unless otherwise specified by the Administrator.
    6.2.5  Graduated Cylinder and/or Balance. To measure condensed 
water to within 1 ml or 0.5 g. Graduated cylinders shall have 
subdivisions no greater than 2 ml.
    6.2.6  Plastic Storage Containers. Air-tight containers to store 
silica gel.
    6.2.7  Funnel and Rubber Policeman. To aid in transfer of silica 
gel to container; not necessary if silica gel is weighed in the field.
    6.2.8  Funnel. Glass or polyethylene, to aid in sample recovery.
    6.3  Sample Analysis. The following equipment is required for 
sample analysis:
    6.3.1  Glass Weighing Dishes.
    6.3.2  Desiccator.
    6.3.3  Analytical Balance. To measure to within 0.1 mg.
    6.3.4  Balance. To measure to within 0.5 g.
    6.3.5  Beakers. 250 ml.
    6.3.6  Hygrometer. To measure the relative humidity of the 
laboratory environment.
    6.3.7  Temperature Sensor. To measure the temperature of the 
laboratory environment.

7.0  Reagents and Standards

    7.1  Sample Collection. The following reagents are required for 
sample collection:
    7.1.1  Filters. Glass fiber filters, without organic binder, 
exhibiting at least 99.95 percent efficiency (0.05 percent penetration) 
on 0.3 micron dioctyl phthalate smoke particles. The filter efficiency 
test shall be conducted in accordance with ASTM Method D 2986-71, 78, 
or 95a (incorporated by reference--see Sec. 60.17). Test data from the 
supplier's quality control program are sufficient for this purpose. In 
sources containing SO2 or SO3, the filter 
material must be of a type that is unreactive to SO2 or 
SO3. Reference 10 in Section 17.0 may be used to select the 
appropriate filter.
    7.1.2  Silica Gel. Indicating type, 6 to 16 mesh. If previously 
used, dry at 175  deg.C (350  deg.F) for 2 hours. New silica gel may be 
used as received. Alternatively, other types of desiccants (equivalent 
or better) may be used, subject to the approval of the Administrator.
    7.1.3  Water. When analysis of the material caught in the impingers 
is required, deionized distilled water (to conform to ASTM D 1193-77 or 
91 Type 3 (incorporated by reference--see Sec. 60.17)) shall be used. 
Run blanks prior to field use to eliminate a high blank on test 
samples.
    7.1.4  Crushed Ice.
    7.1.5  Stopcock Grease. Acetone-insoluble, heat-stable silicone 
grease. This is not necessary if screw-on connectors with Teflon 
sleeves, or similar, are used. Alternatively, other types of stopcock 
grease may be used, subject to the approval of the Administrator.
    7.2  Sample Recovery. Acetone, reagent grade, 0.001 
percent residue, in glass bottles, is required. Acetone from metal 
containers generally has a high

[[Page 61835]]

residue blank and should not be used. Sometimes, suppliers transfer 
acetone to glass bottles from metal containers; thus, acetone blanks 
shall be run prior to field use and only acetone with low blank values 
(0.001 percent) shall be used. In no case shall a blank 
value of greater than 0.001 percent of the weight of acetone used be 
subtracted from the sample weight.
    7.3  Sample Analysis. The following reagents are required for 
sample analysis:
    7.3.1  Acetone. Same as in Section 7.2.
    7.3.2  Desiccant. Anhydrous calcium sulfate, indicating type. 
Alternatively, other types of desiccants may be used, subject to the 
approval of the Administrator.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Pretest Preparation. It is suggested that sampling equipment 
be maintained according to the procedures described in APTD-0576.
    8.1.1  Place 200 to 300 g of silica gel in each of several air-
tight containers. Weigh each container, including silica gel, to the 
nearest 0.5 g, and record this weight. As an alternative, the silica 
gel need not be preweighed, but may be weighed directly in its impinger 
or sampling holder just prior to train assembly.
    8.1.2  Check filters visually against light for irregularities, 
flaws, or pinhole leaks. Label filters of the proper diameter on the 
back side near the edge using numbering machine ink. As an alternative, 
label the shipping containers (glass or polyethylene petri dishes), and 
keep each filter in its identified container at all times except during 
sampling.
    8.1.3  Desiccate the filters at 20  5.6  deg.C (68 
 10  deg.F) and ambient pressure for at least 24 hours. 
Weigh each filter (or filter and shipping container) at intervals of at 
least 6 hours to a constant weight (i.e., 0.5 mg change from 
previous weighing). Record results to the nearest 0.1 mg. During each 
weighing, the period for which the filter is exposed to the laboratory 
atmosphere shall be less than 2 minutes. Alternatively (unless 
otherwise specified by the Administrator), the filters may be oven 
dried at 105  deg.C (220  deg.F) for 2 to 3 hours, desiccated for 2 
hours, and weighed. Procedures other than those described, which 
account for relative humidity effects, may be used, subject to the 
approval of the Administrator.
    8.2  Preliminary Determinations.
    8.2.1  Select the sampling site and the minimum number of sampling 
points according to Method 1 or as specified by the Administrator. 
Determine the stack pressure, temperature, and the range of velocity 
heads using Method 2; it is recommended that a leak check of the pitot 
lines (see Method 2, Section 8.1) be performed. Determine the moisture 
content using Approximation Method 4 or its alternatives for the 
purpose of making isokinetic sampling rate settings. Determine the 
stack gas dry molecular weight, as described in Method 2, Section 8.6; 
if integrated Method 3 sampling is used for molecular weight 
determination, the integrated bag sample shall be taken simultaneously 
with, and for the same total length of time as, the particulate sample 
run.
    8.2.2  Select a nozzle size based on the range of velocity heads, 
such that it is not necessary to change the nozzle size in order to 
maintain isokinetic sampling rates. During the run, do not change the 
nozzle size. Ensure that the proper differential pressure gauge is 
chosen for the range of velocity heads encountered (see Section 8.3 of 
Method 2).
    8.2.3  Select a suitable probe liner and probe length such that all 
traverse points can be sampled. For large stacks, consider sampling 
from opposite sides of the stack to reduce the required probe length.
    8.2.4  Select a total sampling time greater than or equal to the 
minimum total sampling time specified in the test procedures for the 
specific industry such that (l) the sampling time per point is not less 
than 2 minutes (or some greater time interval as specified by the 
Administrator), and (2) the sample volume taken (corrected to standard 
conditions) will exceed the required minimum total gas sample volume. 
The latter is based on an approximate average sampling rate.
    8.2.5  The sampling time at each point shall be the same. It is 
recommended that the number of minutes sampled at each point be an 
integer or an integer plus one-half minute, in order to avoid 
timekeeping errors.
    8.2.6  In some circumstances (e.g., batch cycles) it may be 
necessary to sample for shorter times at the traverse points and to 
obtain smaller gas sample volumes. In these cases, the Administrator's 
approval must first be obtained.
    8.3  Preparation of Sampling Train.
    8.3.1  During preparation and assembly of the sampling train, keep 
all openings where contamination can occur covered until just prior to 
assembly or until sampling is about to begin. Place 100 ml of water in 
each of the first two impingers, leave the third impinger empty, and 
transfer approximately 200 to 300 g of preweighed silica gel from its 
container to the fourth impinger. More silica gel may be used, but care 
should be taken to ensure that it is not entrained and carried out from 
the impinger during sampling. Place the container in a clean place for 
later use in the sample recovery. Alternatively, the weight of the 
silica gel plus impinger may be determined to the nearest 0.5 g and 
recorded.
    8.3.2  Using a tweezer or clean disposable surgical gloves, place a 
labeled (identified) and weighed filter in the filter holder. Be sure 
that the filter is properly centered and the gasket properly placed so 
as to prevent the sample gas stream from circumventing the filter. 
Check the filter for tears after assembly is completed.
    8.3.3  When glass probe liners are used, install the selected 
nozzle using a Viton A O-ring when stack temperatures are less than 260 
 deg.C (500  deg.F) or a heat-resistant string gasket when temperatures 
are higher. See APTD-0576 for details. Other connecting systems using 
either 316 stainless steel or Teflon ferrules may be used. When metal 
liners are used, install the nozzle as discussed above or by a leak-
free direct mechanical connection. Mark the probe with heat resistant 
tape or by some other method to denote the proper distance into the 
stack or duct for each sampling point.
    8.3.4  Set up the train as shown in Figure 5-1, using (if 
necessary) a very light coat of silicone grease on all ground glass 
joints, greasing only the outer portion (see APTD-0576) to avoid the 
possibility of contamination by the silicone grease. Subject to the 
approval of the Administrator, a glass cyclone may be used between the 
probe and filter holder when the total particulate catch is expected to 
exceed 100 mg or when water droplets are present in the stack gas.
    8.3.5  Place crushed ice around the impingers.
    8.4  Leak-Check Procedures.
    8.4.1  Leak Check of Metering System Shown in Figure 5-1. That 
portion of the sampling train from the pump to the orifice meter should 
be leak-checked prior to initial use and after each shipment. Leakage 
after the pump will result in less volume being recorded than is 
actually sampled. The following procedure is suggested (see Figure 5-
2): Close the main valve on the meter box. Insert a one-hole rubber 
stopper with rubber tubing attached into the orifice exhaust pipe. 
Disconnect and vent the

[[Page 61836]]

low side of the orifice manometer. Close off the low side orifice tap. 
Pressurize the system to 13 to 18 cm (5 to 7 in.) water column by 
blowing into the rubber tubing. Pinch off the tubing, and observe the 
manometer for one minute. A loss of pressure on the manometer indicates 
a leak in the meter box; leaks, if present, must be corrected.
    8.4.2  Pretest Leak Check. A pretest leak check of the sampling 
train is recommended, but not required. If the pretest leak check is 
conducted, the following procedure should be used.
    8.4.2.1  After the sampling train has been assembled, turn on and 
set the filter and probe heating systems to the desired operating 
temperatures. Allow time for the temperatures to stabilize. If a Viton 
A O-ring or other leak-free connection is used in assembling the probe 
nozzle to the probe liner, leak-check the train at the sampling site by 
plugging the nozzle and pulling a 380 mm (15 in.) Hg vacuum.


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


    8.4.2.2  If a heat-resistant string is used, do not connect the 
probe to the train during the leak check. Instead, leak-check the train 
by first plugging the inlet to the filter holder (cyclone, if 
applicable) and pulling a 380 mm (15 in.) Hg vacuum (see Note in 
Section 8.4.2.1). Then connect the probe to the train, and leak-check 
at approximately 25 mm (1 in.) Hg vacuum; alternatively, the probe may 
be leak-checked with the rest of the sampling train, in one step, at 
380 mm (15 in.) Hg vacuum. Leakage rates in excess of 4 percent of the 
average sampling rate or 0.00057 m\3\/min (0.020 cfm), whichever is 
less, are unacceptable.
    8.4.2.3  The following leak-check instructions for the sampling 
train described in APTD-0576 and APTD-0581 may be helpful. Start the 
pump with the bypass valve fully open and the coarse adjust valve 
completely closed. Partially open the coarse adjust valve, and slowly 
close the bypass valve until the desired vacuum is reached. Do not 
reverse the direction of the bypass valve, as this will cause water to 
back up into the filter holder. If the desired vacuum is exceeded, 
either leak-check at this higher vacuum, or end the leak check and 
start over.
    8.4.2.4  When the leak check is completed, first slowly remove the 
plug from the inlet to the probe, filter holder, or cyclone (if 
applicable), and immediately turn off the vacuum pump. This prevents 
the water in the impingers from being forced backward into the filter 
holder and the silica gel from being entrained backward into the third 
impinger.
    8.4.3  Leak Checks During Sample Run. If, during the sampling run, 
a component (e.g., filter assembly or impinger) change becomes 
necessary, a leak check shall be conducted immediately before the 
change is made. The leak check shall be done according to the procedure 
outlined in Section 8.4.2 above, except that it shall be done at a 
vacuum equal to or greater than the maximum value recorded up to that 
point in the test. If the leakage rate is found to be no greater than 
0.00057 m3/min (0.020 cfm) or 4 percent of the average 
sampling rate (whichever is less), the results are acceptable, and no 
correction will need to be applied to the total volume of dry gas 
metered; if, however, a higher leakage rate is obtained, either record 
the leakage rate and plan to correct the sample volume as shown in 
Section 12.3 of this method, or void the sample run.


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


    8.4.4  Post-Test Leak Check. A leak check of the sampling train is 
mandatory at the conclusion of each sampling run. The leak check shall 
be performed in accordance with the procedures outlined in Section 
8.4.2, except that it shall be conducted at a vacuum equal to or 
greater than the maximum value reached during the sampling run. If the 
leakage rate is found to be no greater than 0.00057 m3 min 
(0.020 cfm) or 4 percent of the average sampling rate (whichever is 
less), the results are acceptable, and no correction need be applied to 
the total volume of dry gas metered. If, however, a higher leakage rate 
is obtained, either record the leakage rate and correct the sample 
volume as shown in Section 12.3 of this method, or void the sampling 
run.
    8.5  Sampling Train Operation. During the sampling run, maintain an 
isokinetic sampling rate (within 10 percent of true isokinetic unless 
otherwise specified by the Administrator) and a temperature around the 
filter of 120  14  deg.C (248  25  deg.F), or 
such other temperature as specified by an applicable subpart of the 
standards or approved by the Administrator.
    8.5.1  For each run, record the data required on a data sheet such 
as the one shown in Figure 5-3. Be sure to record the initial DGM 
reading. Record the DGM readings at the beginning and end of each 
sampling time increment, when changes in flow rates are made, before 
and after each leak check, and when sampling is halted. Take other 
readings indicated by Figure 5-3 at least once at each sample point 
during each time increment and additional readings when significant 
changes (20 percent variation in velocity head readings) necessitate 
additional adjustments in flow rate. Level and zero the manometer. 
Because the manometer level and zero may drift due to vibrations and 
temperature changes, make periodic checks during the traverse.
    8.5.2  Clean the portholes prior to the test run to minimize the 
chance of collecting deposited material. To begin sampling, verify that 
the filter and probe heating systems are up to temperature, remove the 
nozzle cap, verify that the pitot tube and probe are properly 
positioned. Position the nozzle at the first traverse point with the 
tip pointing directly into the gas stream. Immediately start the pump, 
and adjust the flow to isokinetic conditions. Nomographs are available 
which aid in the rapid adjustment of the isokinetic sampling rate 
without excessive computations. These nomographs are designed for use 
when the Type S pitot tube coefficient (Cp) is 0.85 
 0.02, and the stack gas equivalent density [dry molecular 
weight (Md)] is equal to 29  4. APTD-0576 
details the procedure for using the nomographs. If Cp and 
Md are outside the above stated ranges, do not use the 
nomographs unless appropriate steps (see Reference 7 in Section 17.0) 
are taken to compensate for the deviations.
    8.5.3  When the stack is under significant negative pressure (i.e., 
height of impinger stem), take care to close the coarse adjust valve 
before inserting the probe into the stack to prevent water from backing 
into the filter holder. If necessary, the pump may be turned on with 
the coarse adjust valve closed.
    8.5.4  When the probe is in position, block off the openings around 
the probe and porthole to prevent unrepresentative dilution of the gas 
stream.
    8.5.5  Traverse the stack cross-section, as required by Method 1 or 
as specified by the Administrator, being careful not to bump the probe 
nozzle into the stack walls when sampling near the walls or when 
removing or inserting the probe through the portholes; this minimizes 
the chance of extracting deposited material.
    8.5.6  During the test run, make periodic adjustments to keep the 
temperature around the filter holder at the proper level; add more ice 
and, if necessary, salt to maintain a temperature of less than 20 
deg.C (68  deg.F) at the condenser/silica gel outlet. Also,

[[Page 61837]]

periodically check the level and zero of the manometer.
    8.5.7  If the pressure drop across the filter becomes too high, 
making isokinetic sampling difficult to maintain, the filter may be 
replaced in the midst of the sample run. It is recommended that another 
complete filter assembly be used rather than attempting to change the 
filter itself. Before a new filter assembly is installed, conduct a 
leak check (see Section 8.4.3). The total PM weight shall include the 
summation of the filter assembly catches.
    8.5.8  A single train shall be used for the entire sample run, 
except in cases where simultaneous sampling is required in two or more 
separate ducts or at two or more different locations within the same 
duct, or in cases where equipment failure necessitates a change of 
trains. In all other situations, the use of two or more trains will be 
subject to the approval of the Administrator.


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


    8.5.9  At the end of the sample run, close the coarse adjust valve, 
remove the probe and nozzle from the stack, turn off the pump, record 
the final DGM meter reading, and conduct a post-test leak check, as 
outlined in Section 8.4.4. Also, leak-check the pitot lines as 
described in Method 2, Section 8.1. The lines must pass this leak 
check, in order to validate the velocity head data.
    8.6  Calculation of Percent Isokinetic. Calculate percent 
isokinetic (see Calculations, Section 12.11) to determine whether the 
run was valid or another test run should be made. If there was 
difficulty in maintaining isokinetic rates because of source 
conditions, consult with the Administrator for possible variance on the 
isokinetic rates.
    8.7  Sample Recovery.
    8.7.1  Proper cleanup procedure begins as soon as the probe is 
removed from the stack at the end of the sampling period. Allow the 
probe to cool.
    8.7.2  When the probe can be safely handled, wipe off all external 
PM near the tip of the probe nozzle, and place a cap over it to prevent 
losing or gaining PM. Do not cap off the probe tip tightly while the 
sampling train is cooling down. This would create a vacuum in the 
filter holder, thereby drawing water from the impingers into the filter 
holder.
    8.7.3  Before moving the sample train to the cleanup site, remove 
the probe from the sample train, wipe off the silicone grease, and cap 
the open outlet of the probe. Be careful not to lose any condensate 
that might be present. Wipe off the silicone grease from the filter 
inlet where the probe was fastened, and cap it. Remove the umbilical 
cord from the last impinger, and cap the impinger. If a flexible line 
is used between the first impinger or condenser and the filter holder, 
disconnect the line at the filter holder, and let any condensed water 
or liquid drain into the impingers or condenser. After wiping off the 
silicone grease, cap off the filter holder outlet and impinger inlet. 
Either ground-glass stoppers, plastic caps, or serum caps may be used 
to close these openings.
    8.7.4  Transfer the probe and filter-impinger assembly to the 
cleanup area. This area should be clean and protected from the wind so 
that the chances of contaminating or losing the sample will be 
minimized.
    8.7.5  Save a portion of the acetone used for cleanup as a blank. 
Take 200 ml of this acetone directly from the wash bottle being used, 
and place it in a glass sample container labeled ``acetone blank.''
    8.7.6  Inspect the train prior to and during disassembly, and note 
any abnormal conditions. Treat the samples as follows:
    8.7.6.1  Container No. 1. Carefully remove the filter from the 
filter holder, and place it in its identified petri dish container. Use 
a pair of tweezers and/or clean disposable surgical gloves to handle 
the filter. If it is necessary to fold the filter, do so such that the 
PM cake is inside the fold. Using a dry Nylon bristle brush and/or a 
sharp-edged blade, carefully transfer to the petri dish any PM and/or 
filter fibers that adhere to the filter holder gasket. Seal the 
container.
    8.7.6.2  Container No. 2. Taking care to see that dust on the 
outside of the probe or other exterior surfaces does not get into the 
sample, quantitatively recover PM or any condensate from the probe 
nozzle, probe fitting, probe liner, and front half of the filter holder 
by washing these components with acetone and placing the wash in a 
glass container. Deionized distilled water may be used instead of 
acetone when approved by the Administrator and shall be used when 
specified by the Administrator. In these cases, save a water blank, and 
follow the Administrator's directions on analysis. Perform the acetone 
rinse as follows:
    8.7.6.2.1  Carefully remove the probe nozzle. Clean the inside 
surface by rinsing with acetone from a wash bottle and brushing with a 
Nylon bristle brush. Brush until the acetone rinse shows no visible 
particles, after which make a final rinse of the inside surface with 
acetone.
    8.7.6.2.2  Brush and rinse the inside parts of the fitting with 
acetone in a similar way until no visible particles remain.
    8.7.6.2.3  Rinse the probe liner with acetone by tilting and 
rotating the probe while squirting acetone into its upper end so that 
all inside surfaces will be wetted with acetone. Let the acetone drain 
from the lower end into the sample container. A funnel (glass or 
polyethylene) may be used to aid in transferring liquid washes to the 
container. Follow the acetone rinse with a probe brush. Hold the probe 
in an inclined position, squirt acetone into the upper end as the probe 
brush is being pushed with a twisting action through the probe; hold a 
sample container underneath the lower end of the probe, and catch any 
acetone and particulate matter that is brushed from the probe. Run the 
brush through the probe three times or more until no visible PM is 
carried out with the acetone or until none remains in the probe liner 
on visual inspection. With stainless steel or other metal probes, run 
the brush through in the above prescribed manner at least six times 
since metal probes have small crevices in which particulate matter can 
be entrapped. Rinse the brush with acetone, and quantitatively collect 
these washings in the sample container. After the brushing, make a 
final acetone rinse of the probe.
    8.7.6.2.4  It is recommended that two people clean the probe to 
minimize sample losses. Between sampling runs, keep brushes clean and 
protected from contamination.
    8.7.6.2.5  After ensuring that all joints have been wiped clean of 
silicone grease, clean the inside of the front half of the filter 
holder by rubbing the surfaces with a Nylon bristle brush and rinsing 
with acetone. Rinse each surface three times or more if needed to 
remove visible particulate. Make a final rinse of the brush and filter 
holder. Carefully rinse out the glass cyclone, also (if applicable). 
After all acetone washings and particulate matter have been collected 
in the sample container, tighten the lid on the sample container so 
that acetone will not leak out when it is shipped to the laboratory. 
Mark the height of the fluid level to allow determination of whether 
leakage

[[Page 61838]]

occurred during transport. Label the container to identify clearly its 
contents.
    8.7.6.3  Container No. 3. Note the color of the indicating silica 
gel to determine whether it has been completely spent, and make a 
notation of its condition. Transfer the silica gel from the fourth 
impinger to its original container, and seal. A funnel may make it 
easier to pour the silica gel without spilling. A rubber policeman may 
be used as an aid in removing the silica gel from the impinger. It is 
not necessary to remove the small amount of dust particles that may 
adhere to the impinger wall and are difficult to remove. Since the gain 
in weight is to be used for moisture calculations, do not use any water 
or other liquids to transfer the silica gel. If a balance is available 
in the field, follow the procedure for Container No. 3 in Section 
11.2.3.
    8.7.6.4  Impinger Water. Treat the impingers as follows: Make a 
notation of any color or film in the liquid catch. Measure the liquid 
that is in the first three impingers to within 1 ml by using a 
graduated cylinder or by weighing it to within 0.5 g by using a 
balance. Record the volume or weight of liquid present. This 
information is required to calculate the moisture content of the 
effluent gas. Discard the liquid after measuring and recording the 
volume or weight, unless analysis of the impinger catch is required 
(see NOTE, Section 6.1.1.8). If a different type of condenser is used, 
measure the amount of moisture condensed either volumetrically or 
gravimetrically.
    8.8  Sample Transport. Whenever possible, containers should be 
shipped in such a way that they remain upright at all times.

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

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

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

Where:

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

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

where:

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

10.0  Calibration and Standardization

    Note: Maintain a laboratory log of all calibrations.

    10.1  Probe Nozzle. Probe nozzles shall be calibrated before their 
initial use in the field. Using a micrometer, measure the ID of the 
nozzle to the nearest 0.025 mm (0.001 in.). Make three separate 
measurements using different diameters each time, and obtain the 
average of the measurements. The difference between the high and low 
numbers shall not exceed 0.1 mm (0.004 in.). When nozzles become 
nicked, dented, or corroded, they shall be reshaped, sharpened, and 
recalibrated before use. Each nozzle shall be permanently and uniquely 
identified.
    10.2  Pitot Tube Assembly. The Type S pitot tube assembly shall be 
calibrated according to the procedure outlined in Section 10.1 of 
Method 2.
    10.3  Metering System.
    10.3.1  Calibration Prior to Use. Before its initial use in the 
field, the metering system shall be calibrated as follows: Connect the 
metering system inlet to the outlet of a wet test meter that is 
accurate to within 1 percent. Refer to Figure 5-4. The wet test meter 
should have a capacity of 30 liters/rev (1 ft3/rev). A 
spirometer of 400 liters (14 ft3) or more capacity, or 
equivalent, may be used for this calibration, although a wet test meter 
is usually more practical. The wet test meter should be periodically 
calibrated with a spirometer or a liquid displacement meter to ensure 
the accuracy of the wet test meter. Spirometers or wet test meters of 
other sizes may be used, provided that the specified accuracies of the 
procedure are maintained. Run the metering system pump for about 15 
minutes with the orifice manometer indicating a median reading as 
expected in field use to allow the pump to warm up and to permit the 
interior surface of the wet test meter to be thoroughly wetted. Then, 
at each of a minimum of three orifice manometer settings, pass an exact 
quantity of gas through the wet test meter and note the gas volume 
indicated by the DGM. Also note the barometric pressure and the 
temperatures of the wet test meter, the inlet of the DGM, and the 
outlet of the DGM. Select the highest and lowest orifice settings to 
bracket the expected field operating range of the orifice. Use a 
minimum volume of 0.14 m3 (5 ft3) at all orifice 
settings. Record all the data on a form similar to Figure 5-5 and 
calculate Y, the DGM calibration factor, and H@, 
the orifice calibration factor, at each orifice setting as shown on 
Figure 5-5. Allowable tolerances for

[[Page 61839]]

individual Y and H@ values are given in Figure 5-5. 
Use the average of the Y values in the calculations in Section 12.0.
    10.3.1.1  Before calibrating the metering system, it is suggested 
that a leak check be conducted. For metering systems having diaphragm 
pumps, the normal leak-check procedure will not detect leakages within 
the pump. For these cases the following leak-check procedure is 
suggested: make a 10-minute calibration run at 0.00057 m3/
min (0.020 cfm). At the end of the run, take the difference of the 
measured wet test meter and DGM volumes. Divide the difference by 10 to 
get the leak rate. The leak rate should not exceed 0.00057 
m3/min (0.020 cfm).
    10.3.2  Calibration After Use. After each field use, the 
calibration of the metering system shall be checked by performing three 
calibration runs at a single, intermediate orifice setting (based on 
the previous field test), with the vacuum set at the maximum value 
reached during the test series. To adjust the vacuum, insert a valve 
between the wet test meter and the inlet of the metering system. 
Calculate the average value of the DGM calibration factor. If the value 
has changed by more than 5 percent, recalibrate the meter over the full 
range of orifice settings, as detailed in Section 10.3.1.


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


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

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


    10.5  Temperature Sensors. Use the procedure in Section 10.3 of 
Method 2 to calibrate in-stack temperature sensors. Dial thermometers, 
such as are used for the DGM and condenser outlet, shall be calibrated 
against mercury-in-glass thermometers.
    10.6  Barometer. Calibrate against a mercury barometer.

11.0  Analytical Procedure

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


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

12.0  Data Analysis and Calculations

    Carry out calculations, retaining at least one extra significant 
figure beyond that of the acquired data. Round off figures after the 
final calculation. Other forms of the equations may be used, provided 
that they give equivalent results.
    12.1  Nomenclature.
An = Cross-sectional area of nozzle, m2 
(ft2).
Bws = Water vapor in the gas stream, proportion by volume.
Ca = Acetone blank residue concentration, mg/mg.
cs = Concentration of particulate matter in stack gas, dry 
basis, corrected to standard conditions, g/dscm (gr/dscf).
I = Percent of isokinetic sampling.
L1 = Individual leakage rate observed during the leak-check 
conducted prior to the first component change, m3/min 
(ft3/min)
La = Maximum acceptable leakage rate for either a pretest 
leak-check or for a leak-check following a component change; equal to 
0.00057 m3/min (0.020 cfm) or 4 percent of the average 
sampling rate, whichever is less.
Li = Individual leakage rate observed during the leak-check 
conducted prior to the ``i\th\'' component change (i = 1, 2, 3 . . . 
n), m3/min (cfm).
Lp = Leakage rate observed during the post-test leak-check, 
m3/min (cfm).
ma = Mass of residue of acetone after evaporation, mg.
mn = Total amount of particulate matter collected, mg.
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 lb/lb-
mole).
Pbar = Barometric pressure at the sampling site, mm Hg (in. 
Hg).
Ps = Absolute stack gas pressure, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
R = Ideal gas constant, 0.06236 ((mm Hg)(m \3\))/((K)(g-mole)) {21.85 
((in. Hg) (ft \3\))/(( deg.R) (lb-mole))}.

[[Page 61840]]

Tm = Absolute average DGM temperature (see Figure 5-3), K 
( deg.R).
Ts = Absolute average stack gas temperature (see Figure 5-
3), K ( deg.R).
Tstd = Standard absolute temperature, 293 K (528  deg.R).
Va = Volume of acetone blank, ml.
Vaw = Volume of acetone used in wash, ml.
V1c = Total volume of liquid collected in impingers and 
silica gel (see Figure 5-6), ml.
Vm = Volume of gas sample as measured by dry gas meter, dcm 
(dcf).
Vm(std) = Volume of gas sample measured by the dry gas 
meter, corrected to standard conditions, dscm (dscf).
Vw(std) = Volume of water vapor in the gas sample, corrected 
to standard conditions, scm (scf).
Vs = Stack gas velocity, calculated by Method 2, Equation 2-
7, using data obtained from Method 5, m/sec (ft/sec).
Wa = Weight of residue in acetone wash, mg.
Y = Dry gas meter calibration factor.
H = Average pressure differential across the orifice meter 
(see Figure 5-4), mm H2O (in. H2O).
a = Density of acetone, mg/ml (see label on 
bottle).
w = Density of water, 0.9982 g/ml.(0.002201 lb/ml).
 = Total sampling time, min.
1 = Sampling time interval, from the beginning of 
a run until the first component change, min.
i = Sampling time interval, between two successive 
component changes, beginning with the interval between the first and 
second changes, min.
p = Sampling time interval, from the final (n 
\th\) component change until the end of the sampling run, min.
13.6   = Specific gravity of mercury.
60 = Sec/min.
100 = Conversion to percent.

    12.2  Average Dry Gas Meter Temperature and Average Orifice 
Pressure Drop. See data sheet (Figure 5-3).
    12.3  Dry Gas Volume. Correct the sample volume measured by the dry 
gas meter to standard conditions (20  deg.C, 760 mm Hg or 68  deg.F, 
29.92 in. Hg) by using Equation 5-1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.109

Where:

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


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

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

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

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

K2 = 0.001333 m \3\/ml for metric units, = 0.04706 ft \3\/ml 
for English units.
    12.5  Moisture Content.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.113
    

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


    12.6  Acetone Blank Concentration.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.114
    
    12.7  Acetone Wash Blank.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.115
    
    12.8  Total Particulate Weight. Determine the total particulate 
matter

[[Page 61841]]

catch from the sum of the weights obtained from Containers 1 and 2 less 
the acetone blank (see Figure 5-6).


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

    12.9  Particulate Concentration.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.116
    
Where:

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

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

    12.11  Isokinetic Variation.
    12.11.1  Calculation from Raw Data.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.117
    
Where:
K4 = 0.003454 ((mm Hg)(m\3\))/((ml)( deg.K)) for metric 
units,
= 0.002669 ((in. Hg)(ft\3\))/((ml)( deg.R)) for English units.

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

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

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

16.0  Alternative Procedures

    16.1  Dry Gas Meter as a Calibration Standard. A DGM may be used as 
a calibration standard for volume measurements in place of the wet test 
meter specified in Section 10.3, provided that it is calibrated 
initially and recalibrated periodically as follows:
    16.1.1  Standard Dry Gas Meter Calibration.
    16.1.1.1.  The DGM to be calibrated and used as a secondary 
reference meter should be of high quality and have an appropriately 
sized capacity (e.g., 3 liters/rev (0.1 ft\3\/rev)). A spirometer (400 
liters (14 ft\3\) or more capacity), or equivalent, may be used for 
this calibration, although a wet test meter is usually more practical. 
The wet test meter should have a capacity of 30 liters/rev (1 ft\3\/
rev) and capable of measuring volume to within 1.0 percent. Wet test 
meters should be checked against a spirometer or a liquid displacement 
meter to ensure the accuracy of the wet test meter. Spirometers or wet 
test meters of other sizes may be used, provided that the specified 
accuracies of the procedure are maintained.
    16.1.1.2  Set up the components as shown in Figure 5-7. A 
spirometer, or equivalent, may be used in place of the wet test meter 
in the system. Run the pump for at least 5 minutes at a flow rate of 
about 10 liters/min (0.35 cfm) to condition the interior surface of the 
wet test meter. The pressure drop indicated by the manometer at the 
inlet side of the DGM should be minimized (no greater than 100 mm 
H2O (4 in. H2O) at a flow rate of 30 liters/min 
(1 cfm)). This can be accomplished by using large diameter tubing 
connections and straight pipe fittings.
    16.1.1.3  Collect the data as shown in the example data sheet (see 
Figure 5-8). Make triplicate runs at each of the flow rates and at no 
less than five different flow rates. The range of flow rates should be 
between 10 and 34 liters/min (0.35 and 1.2 cfm) or over the expected 
operating range.
    16.1.1.4  Calculate flow rate, Q, for each run using the wet test 
meter volume, VW, and the run time, . Calculate 
the DGM coefficient, Yds, for each run. These calculations 
are as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.119

[GRAPHIC] [TIFF OMITTED] TR17OC00.120

Where:

K1 = 0.3858  deg.C/mm Hg for metric units=17.64  deg.F/in. 
Hg for English units.
VW = Wet test meter volume, liter (ft\3\).
Vds = Dry gas meter volume, liter (ft\3\).
Tds = Average dry gas meter temperature,  deg.C ( deg.F).
Tadj = 273  deg.C for metric units = 460  deg.F for English 
units.
TW = Average wet test meter temperature,  deg.C ( deg.F)

[[Page 61842]]

Pbar = Barometric pressure, mm Hg (in. Hg).
p = Dry gas meter inlet differential pressure, mm 
H2O (in. H2O).
 = Run time, min.

    16.1.1.5  Compare the three Yds values at each of the 
flow rates and determine the maximum and minimum values. The difference 
between the maximum and minimum values at each flow rate should be no 
greater than 0.030. Extra sets of triplicate runs may be made in order 
to complete this requirement. In addition, the meter coefficients 
should be between 0.95 and 1.05. If these specifications cannot be met 
in three sets of successive triplicate runs, the meter is not suitable 
as a calibration standard and should not be used as such. If these 
specifications are met, average the three Yds values at each 
flow rate resulting in no less than five average meter coefficients, 
Yds.
    16.1.1.6  Prepare a curve of meter coefficient, Yds, 
versus flow rate, Q, for the DGM. This curve shall be used as a 
reference when the meter is used to calibrate other DGMs and to 
determine whether recalibration is required.
    16.1.2  Standard Dry Gas Meter Recalibration.
    16.1.2.1  Recalibrate the standard DGM against a wet test meter or 
spirometer annually or after every 200 hours of operation, whichever 
comes first. This requirement is valid provided the standard DGM is 
kept in a laboratory and, if transported, cared for as any other 
laboratory instrument. Abuse to the standard meter may cause a change 
in the calibration and will require more frequent recalibrations.
    16.1.2.2  As an alternative to full recalibration, a two-point 
calibration check may be made. Follow the same procedure and equipment 
arrangement as for a full recalibration, but run the meter at only two 
flow rates [suggested rates are 14 and 30 liters/min (0.5 and 1.0 
cfm)]. Calculate the meter coefficients for these two points, and 
compare the values with the meter calibration curve. If the two 
coefficients are within 1.5 percent of the calibration curve values at 
the same flow rates, the meter need not be recalibrated until the next 
date for a recalibration check.
    16.2  Critical Orifices As Calibration Standards. Critical orifices 
may be used as calibration standards in place of the wet test meter 
specified in Section 16.1, provided that they are selected, calibrated, 
and used as follows:
    16.2.1  Selection of Critical Orifices.
    16.2.1.1  The procedure that follows describes the use of 
hypodermic needles or stainless steel needle tubings which have been 
found suitable for use as critical orifices. Other materials and 
critical orifice designs may be used provided the orifices act as true 
critical orifices (i.e., a critical vacuum can be obtained, as 
described in Section 16.2.2.2.3). Select five critical orifices that 
are appropriately sized to cover the range of flow rates between 10 and 
34 liters/min (0.35 and 1.2 cfm) or the expected operating range. Two 
of the critical orifices should bracket the expected operating range. A 
minimum of three critical orifices will be needed to calibrate a Method 
5 DGM; the other two critical orifices can serve as spares and provide 
better selection for bracketing the range of operating flow rates. The 
needle sizes and tubing lengths shown in Table 5-1 in Section 18.0 give 
the approximate flow rates.
    16.2.1.2  These needles can be adapted to a Method 5 type sampling 
train as follows: Insert a serum bottle stopper, 13 by 20 mm sleeve 
type, into a \1/2\-inch Swagelok (or equivalent) quick connect. Insert 
the needle into the stopper as shown in Figure 5-9.
    16.2.2  Critical Orifice Calibration. The procedure described in 
this section uses the Method 5 meter box configuration with a DGM as 
described in Section 6.1.1.9 to calibrate the critical orifices. Other 
schemes may be used, subject to the approval of the Administrator.
    16.2.2.1  Calibration of Meter Box. The critical orifices must be 
calibrated in the same configuration as they will be used (i.e., there 
should be no connections to the inlet of the orifice).
    16.2.2.1.1  Before calibrating the meter box, leak check the system 
as follows: Fully open the coarse adjust valve, and completely close 
the by-pass valve. Plug the inlet. Then turn on the pump, and determine 
whether there is any leakage. The leakage rate shall be zero (i.e., no 
detectable movement of the DGM dial shall be seen for 1 minute).
    16.2.2.1.2  Check also for leakages in that portion of the sampling 
train between the pump and the orifice meter. See Section 8.4.1 for the 
procedure; make any corrections, if necessary. If leakage is detected, 
check for cracked gaskets, loose fittings, worn O-rings, etc., and make 
the necessary repairs.
    16.2.2.1.3  After determining that the meter box is leakless, 
calibrate the meter box according to the procedure given in Section 
10.3. Make sure that the wet test meter meets the requirements stated 
in Section 16.1.1.1. Check the water level in the wet test meter. 
Record the DGM calibration factor, Y.
    16.2.2.2  Calibration of Critical Orifices. Set up the apparatus as 
shown in Figure 5-10.
    16.2.2.2.1  Allow a warm-up time of 15 minutes. This step is 
important to equilibrate the temperature conditions through the DGM.
    16.2.2.2.2  Leak check the system as in Section 16.2.2.1.1. The 
leakage rate shall be zero.
    16.2.2.2.3  Before calibrating the critical orifice, determine its 
suitability and the appropriate operating vacuum as follows: Turn on 
the pump, fully open the coarse adjust valve, and adjust the by-pass 
valve to give a vacuum reading corresponding to about half of 
atmospheric pressure. Observe the meter box orifice manometer reading, 
H. Slowly increase the vacuum reading until a stable reading 
is obtained on the meter box orifice manometer. Record the critical 
vacuum for each orifice. Orifices that do not reach a critical value 
shall not be used.
    16.2.2.2.4  Obtain the barometric pressure using a barometer as 
described in Section 6.1.2. Record the barometric pressure, 
Pbar, in mm Hg (in. Hg).
    16.2.2.2.5  Conduct duplicate runs at a vacuum of 25 to 50 mm Hg (1 
to 2 in. Hg) above the critical vacuum. The runs shall be at least 5 
minutes each. The DGM volume readings shall be in increments of 
complete revolutions of the DGM. As a guideline, the times should not 
differ by more than 3.0 seconds (this includes allowance for changes in 
the DGM temperatures) to achieve  0.5 percent in K' (see 
Eq. 5-11). Record the information listed in Figure 5-11.
16.2.2.2.6  Calculate K' using Equation 5-11.
[GRAPHIC] [TIFF OMITTED] TR17OC00.121

Where:

K' = Critical orifice coefficient,
[m \3\)( deg.K)\1/2\]/

[[Page 61843]]

[(mm Hg)(min)] {[(ft \3\)( deg.R)\1/2\)] [(in. Hg)(min)].
Tamb = Absolute ambient temperature,  deg.K ( deg.R).
    Calculate the arithmetic mean of the K' values. The individual K' 
values should not differ by more than 0.5 percent from the 
mean value.
    16.2.3  Using the Critical Orifices as Calibration Standards.
    16.2.3.1  Record the barometric pressure.
    16.2.3.2  Calibrate the metering system according to the procedure 
outlined in Section 16.2.2. Record the information listed in Figure 5-
12.
    16.2.3.3  Calculate the standard volumes of air passed through the 
DGM and the critical orifices, and calculate the DGM calibration 
factor, Y, using the equations below:
[GRAPHIC] [TIFF OMITTED] TR17OC00.122

[GRAPHIC] [TIFF OMITTED] TR17OC00.123

[GRAPHIC] [TIFF OMITTED] TR17OC00.124

Where:

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

    16.2.3.4  Average the DGM calibration values for each of the flow 
rates. The calibration factor, Y, at each of the flow rates should not 
differ by more than  2 percent from the average.
    16.2.3.5  To determine the need for recalibrating the critical 
orifices, compare the DGM Y factors obtained from two adjacent orifices 
each time a DGM is calibrated; for example, when checking orifice 13/
2.5, use orifices 12/10.2 and 13/5.1. If any critical orifice yields a 
DGM Y factor differing by more than 2 percent from the others, 
recalibrate the critical orifice according to Section 16.2.2.

17.0  References.

    1. Addendum to Specifications for Incinerator Testing at Federal 
Facilities. PHS, NCAPC. December 6, 1967.
    2. Martin, Robert M. Construction Details of Isokinetic Source-
Sampling Equipment. Environmental Protection Agency. Research 
Triangle Park, NC. APTD-0581. April 1971.
    3. Rom, Jerome J. Maintenance, Calibration, and Operation of 
Isokinetic Source Sampling Equipment. Environmental Protection 
Agency. Research Triangle Park, NC. APTD-0576. March 1972.
    4. Smith, W.S., R.T. Shigehara, and W.F. Todd. A Method of 
Interpreting Stack Sampling Data. Paper Presented at the 63rd Annual 
Meeting of the Air Pollution Control Association, St. Louis, MO. 
June 14-19, 1970.
    5. Smith, W.S., et al. Stack Gas Sampling Improved and 
Simplified With New Equipment. APCA Paper No. 67-119. 1967.
    6. Specifications for Incinerator Testing at Federal Facilities. 
PHS, NCAPC. 1967.
    7. Shigehara, R.T. Adjustment in the EPA Nomograph for Different 
Pitot Tube Coefficients and Dry Molecular Weights. Stack Sampling 
News 2:4-11. October 1974.
    8. Vollaro, R.F. A Survey of Commercially Available 
Instrumentation for the Measurement of Low-Range Gas Velocities. 
U.S. Environmental Protection Agency, Emission Measurement Branch. 
Research Triangle Park, NC. November 1976 (unpublished paper).
    9. Annual Book of ASTM Standards. Part 26. Gaseous Fuels; Coal 
and Coke; Atmospheric Analysis. American Society for Testing and 
Materials. Philadelphia, PA. 1974. pp. 617-622.
    10. Felix, L.G., G.I. Clinard, G.E. Lacy, and J.D. McCain. 
Inertial Cascade Impactor Substrate Media for Flue Gas Sampling. 
U.S. Environmental Protection Agency. Research Triangle Park, NC 
27711. Publication No. EPA-600/7-77-060. June 1977. 83 pp.
    11. Westlin, P.R. and R.T. Shigehara. Procedure for Calibrating 
and Using Dry Gas Volume Meters as Calibration Standards. Source 
Evaluation Society Newsletter. 3(1):17-30. February 1978.
    12. Lodge, J.P., Jr., J.B. Pate, B.E. Ammons, and G.A. Swanson. 
The Use of Hypodermic Needles as Critical Orifices in Air Sampling. 
J. Air Pollution Control Association. 16:197-200. 1966.

18.0  Tables, Diagrams, Flowcharts, and Validation Data

----------------------------------------------------------------------------------------------------------------
                                                                     Flow rate                       Flow rate
                            Gauge/cm                                liters/min.      Gauge/cm       liters/min.
----------------------------------------------------------------------------------------------------------------
12/7.6..........................................................           32.56          14/2.5           19.54
12/10.2.........................................................           30.02          14/5.1           17.27
13/2.5..........................................................           25.77          14/7.6           16.14
13/5.1..........................................................           23.50          15/3.2           14.16
13/7.6..........................................................           22.37          15/7.6           11.61
13/10.2.........................................................           20.67         15/10.2           10.48
----------------------------------------------------------------------------------------------------------------


[[Page 61844]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.125


[[Page 61845]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.126


[[Page 61846]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.127


[[Page 61847]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.128


[[Page 61848]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.129


[[Page 61849]]

Plant-----------------------------------------------------------------
Date------------------------------------------------------------------
Run No.---------------------------------------------------------------
Filter No.------------------------------------------------------------
Amount liquid lost during transport-----------------------------------
Acetone blank volume, m1----------------------------------------------
Acetone blank concentration, mg/mg (Equation 5-4)---------------------
Acetone wash blank, mg (Equation 5-5)---------------------------------

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


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

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


[[Page 61850]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.130


[[Page 61851]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.131


[[Page 61852]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.132


[[Page 61853]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.133


[[Page 61854]]


----------------------------------------------------------------------
Date------------------------------------------------------------------
Train ID--------------------------------------------------------------
DGM cal. factor-------------------------------------------------------
Critical orifice ID---------------------------------------------------

------------------------------------------------------------------------
                                                         Run No.
        Dry gas meter                          -------------------------
                                                     1            2
------------------------------------------------------------------------
Final reading................  m3 (ft3).......  ...........  ...........
Initial reading..............  m3 (ft3).......  ...........  ...........
Difference, Vm...............  m 3 (ft 3).....  ...........  ...........
Inlet/Outlet.................  ...............  ...........  ...........
    Temperatures:............   deg.C ( deg.F)       /            /
    Initial..................   deg.C ( deg.F)       /            /
    Final....................  min/sec........       /            /
    Av. Temeperature, t m....  min............  ...........  ...........
Time, .............  ...............  ...........  ...........
Orifice man. rdg., H  mm (in.) H 2...  ...........  ...........
Bar. pressure, P bar.........  mm (in.) Hg....  ...........  ...........
Ambient temperature, tamb....  mm (in.) Hg....  ...........  ...........
Pump vacuum..................  ...............  ...........  ...........
K' factor....................  ...............  ...........  ...........
    Average..................  ...............  ...........  ...........
------------------------------------------------------------------------

Figure 5-11. Data sheet of determining K' factor.
Date------------------------------------------------------------------
Train ID--------------------------------------------------------------
Critical orifice ID---------------------------------------------------
Critical orifice K' factor--------------------------------------------

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

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

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

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

1.0  Scope and Applications

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

2.0  Summary of Method

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

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test

[[Page 61855]]

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

6.0  Equipment and Supplies

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


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


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

7.0.  Reagents and Standards

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

8.0.  Sample Collection, Preservation, Storage, and Transport

    8.1.  Pretest Preparation. Unless otherwise specified, maintain and 
calibrate all components according to the procedure described in APTD-
0576, ``Maintenance, Calibration, and Operation of Isokinetic Source-
Sampling Equipment'' (Reference 3 in Method 5, Section 17.0).
    8.1.1  Prepare probe liners and sampling nozzles as needed for use. 
Thoroughly clean each component with soap and water followed by a 
minimum of three TCE rinses. Use the probe and nozzle brushes during at 
least one of the TCE rinses (refer to Section 8.7 for rinsing 
techniques). Cap or seal the open ends of the probe liners and nozzles 
to prevent contamination during shipping.
    8.1.2  Prepare silica gel portions and glass filters as specified 
in Method 5, Section 8.1.
    8.2  Preliminary Determinations. Select the sampling site, probe 
nozzle, and probe length as specified in Method 5, Section 8.2. Select 
a total sampling time greater than or equal to the minimum total 
sampling time specified in the ``Test Methods and Procedures'' section 
of the applicable subpart of the regulations. Follow the guidelines 
outlined in Method 5, Section 8.2 for sampling time per point and total 
sample volume collected.
    8.3  Preparation of Sampling Train. Prepare the sampling train as 
specified in Method 5, Section 8.3, with the addition of the 
precollector cyclone, if used, between the probe and filter holder. The 
temperature of the precollector cyclone, if used, should be maintained 
in the same range as that of the filter, i.e., 42  10 
deg.C (108  18  deg.F). Use no stopcock grease on ground 
glass joints unless grease is insoluble in TCE.
    8.4  Leak-Check Procedures. Same as Method 5, Section 8.4.
    8.5  Sampling Train Operation. Operate the sampling train as 
described in Method 5, Section 8.5, except maintain the temperature of 
the gas exiting the filter holder at 42  10  deg.C (108 
 18  deg.F).
    8.6  Calculation of Percent Isokinetic. Same as Method 5, Section 
8.6.
    8.7  Sample Recovery. Same as Method 5, Section 8.7.1 through 
8.7.6.1, with the addition of the following:
    8.7.1  Container No. 2 (Probe to Filter Holder).
    8.7.1.1  Taking care to see that material on the outside of the 
probe or other exterior surfaces does not get into the sample, 
quantitatively recover PM or any condensate from the probe nozzle, 
probe fitting, probe liner, precollector cyclone and collector flask 
(if used), and front half of the filter holder by washing these 
components with TCE and placing the wash in a glass container. 
Carefully measure the total amount of TCE used in the rinses. Perform 
the TCE rinses as described in Method 5, Section 8.7.6.2, using TCE 
instead of acetone.
    8.7.1.2  Brush and rinse the inside of the cyclone, cyclone 
collection flask, and the front half of the filter holder. Brush and 
rinse each surface three times or more, if necessary, to remove visible 
PM.
    8.7.2  Container No. 3 (Silica Gel). Same as in Method 5, Section 
8.7.6.3.
    8.7.3  Impinger Water. Same as Method 5, Section 8.7.6.4.
    8.8  Blank. Save a portion of the TCE used for cleanup as a blank. 
Take 200 ml of this TCE directly from the wash bottle being used, and 
place it in a glass sample container labeled ``TCE Blank.''

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.4, 10.0.....................  Sampling           Ensures accurate
                                 equipment leak     measurement of stack
                                 check and          gas flow rate,
                                 calibration.       sample volume.
------------------------------------------------------------------------


[[Page 61856]]

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

10.0  Calibration and Standardization

    Same as Method 5, Section 10.0.

11.0  Analytical Procedures

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


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

12.0  Data Analysis and Calculations

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

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

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

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

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

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


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

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


    12.6  TCE Wash Blank.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.137
    
    12.7  Total PM Weight. Determine the total PM catch from the sum of 
the weights obtained from Containers 1 and 2, less the TCE blank.
    12.8  PM Concentration.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.138
    
Where:

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

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

13.0  Method Performance [Reserved]

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

    Same as Method 5, Section 17.0.

17.0  Tables, Diagrams, Flowcharts, and Validation Data

[[Page 61857]]

Plant-----------------------------------------------------------------
Date------------------------------------------------------------------
Run No.---------------------------------------------------------------
Filter No.------------------------------------------------------------
Amount liquid lost during transport-----------------------------------
Acetone blank volume, m1----------------------------------------------
Acetone blank concentration, mg/mg (Equation 5-4)---------------------
Acetone wash blank, mg (Equation 5-5)---------------------------------

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


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

  [GRAPHIC] [TIFF OMITTED] TR17OC00.139
  
Method 5B--Determination of Nonsulfuric Acid Particulate Matter 
Emissions From Stationary Sources

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

1.0  Scope and Application

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

2.0  Summary of Method

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

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety

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

6.0  Equipment and Supplies

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

7.0  Reagents and Standards

    Same as Method 5, Section 7.0.

8.0  Sample Collection, Preservation, Storage, and Transport.

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

9.0  Quality Control

    Same as Method 5, Section 9.0.

10.0  Calibration and Standardization

    Same as Method 5, Section 10.0.

11.0  Analytical Procedure

    Same as Method 5, Section 11.0, except replace Section
    11.2.2  With the following:
    11.1  Container No. 2. Note the level of liquid in the container, 
and confirm on the analysis sheet whether leakage occurred during 
transport. If a noticeable amount of leakage has occurred, either void 
the sample or use methods, subject to the approval of the 
Administrator, to correct the final results. Measure the liquid in this 
container either volumetrically to 1 ml or gravimetrically 
to 0.5 g. Transfer the

[[Page 61858]]

contents to a tared 250 ml beaker, and evaporate to dryness at ambient 
temperature and pressure. Then oven dry the probe and filter samples at 
a temperature of 160  5  deg.C (320  10  deg.F) 
for 6 hours. Cool in a desiccator for 2 hours, and weigh to constant 
weight. Report the results to the nearest 0.1 mg.

12.0  Data Analysis and Calculations

    Same as in Method 5, Section 12.0.

13.0  Method Performance [Reserved]

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

    Same as Method 5, Section 17.0.

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

* * * * *

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

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

1.0  Scope and Application

    1.1  Analyte. Particulate matter (PM). No CAS number assigned.
    1.2  Applicability.
    1.2.1  This method is applicable for the determination of PM 
emissions from positive pressure fabric filters. Emissions are 
determined in terms of concentration (mg/m3 or gr/
ft3) and emission rate (kg/hr or lb/hr).
    1.2.2  The General Provisions of 40 CFR part 60, Sec. 60.8(e), 
require that the owner or operator of an affected facility shall 
provide performance testing facilities. Such performance testing 
facilities include sampling ports, safe sampling platforms, safe access 
to sampling sites, and utilities for testing. It is intended that 
affected facilities also provide sampling locations that meet the 
specification for adequate stack length and minimal flow disturbances 
as described in Method 1. Provisions for testing are often overlooked 
factors in designing fabric filters or are extremely costly. The 
purpose of this procedure is to identify appropriate alternative 
locations and procedures for sampling the emissions from positive 
pressure fabric filters. The requirements that the affected facility 
owner or operator provide adequate access to performance testing 
facilities remain in effect.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

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

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety

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

6.0  Equipment and Supplies

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

7.0  Reagents and Standards

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

8.0  Sample Collection, Preservation, Storage, and Transport

    Same Section 8.0 of either Method 5 or Method 17, except replace 
Section 8.2.1 of Method 5 with the following:
    8.1  Determination of Measurement Site. The configuration of 
positive pressure fabric filter structures frequently are not amenable 
to emission testing according to the requirements of Method 1. 
Following are several alternatives for determining measurement sites 
for positive pressure fabric filters.
    8.1.1  Stacks Meeting Method 1 Criteria. Use a measurement site as 
specified in Method 1, Section 11.1.
    8.1.2  Short Stacks Not Meeting Method 1 Criteria. Use stack 
extensions and the procedures in Method 1. Alternatively, use flow 
straightening vanes of the ``egg-crate'' type (see Figure 5D-1). Locate 
the measurement site downstream of the straightening vanes at a 
distance equal to or greater than two times the average equivalent 
diameter of the vane openings and at least one-half of the overall 
stack diameter upstream of the stack outlet.
    8.1.3  Roof Monitor or Monovent. (See Figure 5D-2). For a positive 
pressure fabric filter equipped with a peaked roof monitor, ridge vent, 
or other type of monovent, use a measurement site at the base of the 
monovent. Examples of such locations are shown in Figure 5D-2. The 
measurement site must be upstream of any exhaust point (e.g., louvered 
vent).
    8.1.4  Compartment Housing. Sample immediately downstream of the 
filter bags directly above the tops of the bags as shown in the 
examples in Figure 5D-2. Depending on the housing design, use sampling 
ports in the housing walls or locate the sampling equipment within the 
compartment housing.
    8.2  Determination of Number and Location of Traverse Points. 
Locate the traverse points according to Method 1, Section 11.3. Because 
a performance test consists of at least three test runs and because of 
the varied configurations of positive pressure fabric filters, there 
are several schemes by which the number of traverse points can be 
determined and the three test runs can be conducted.
    8.2.1  Single Stacks Meeting Method 1 Criteria. Select the number 
of traverse points according to Method 1. Sample all traverse points 
for each test run.
    8.2.2  Other Single Measurement Sites. For a roof monitor or 
monovent, single compartment housing, or other stack not meeting Method 
1 criteria, use at least 24 traverse points. For example, for a 
rectangular measurement site, such as a monovent, use a balanced 5 x 5 
traverse point matrix. Sample all traverse points for each test run.
    8.2.3  Multiple Measurement Sites. Sampling from two or more stacks 
or measurement sites may be combined for a test run, provided the 
following guidelines are met:
    8.2.3.1  All measurement sites up to 12 must be sampled. For more 
than 12 measurement sites, conduct sampling on at least 12 sites or 50 
percent of the sites, whichever is greater. The measurement sites 
sampled should be evenly, or nearly evenly, distributed among the 
available sites; if not, all sites are to be sampled.
    8.2.3.2  The same number of measurement sites must be sampled for 
each test run.
    8.2.3.3  The minimum number of traverse points per test run is 24. 
An exception to the 24-point minimum would be a test combining the 
sampling from two stacks meeting Method 1 criteria for acceptable stack 
length, and

[[Page 61859]]

Method 1 specifies fewer than 12 points per site.
    8.2.3.4  As long as the 24 traverse points per test run criterion 
is met, the number of traverse points per measurement site may be 
reduced to eight.
    8.2.3.5  Alternatively, conduct a test run for each measurement 
site individually using the criteria in Section 8.2.1 or 8.2.2 to 
determine the number of traverse points. Each test run shall count 
toward the total of three required for a performance test. If more than 
three measurement sites are sampled, the number of traverse points per 
measurement site may be reduced to eight as long as at least 72 
traverse points are sampled for all the tests.
    8.2.3.6  The following examples demonstrate the procedures for 
sampling multiple measurement sites.
    8.2.3.6.1  Example 1: A source with nine circular measurement sites 
of equal areas may be tested as follows: For each test run, traverse 
three measurement sites using four points per diameter (eight points 
per measurement site). In this manner, test run number 1 will include 
sampling from sites 1,2, and 3; run 2 will include samples from sites 
4, 5, and 6; and run 3 will include sites 7, 8, and 9. Each test area 
may consist of a separate test of each measurement site using eight 
points. Use the results from all nine tests in determining the emission 
average.
    8.2.3.6.2  Example 2: A source with 30 rectangular measurement 
sites of equal areas may be tested as follows: For each of the three 
test runs, traverse five measurement sites using a 3 x 3 matrix of 
traverse points for each site. In order to distribute the sampling 
evenly over all the available measurement sites while sampling only 50 
percent of the sites, number the sites consecutively from 1 to 30 and 
sample all the even numbered (or odd numbered) sites. Alternatively, 
conduct a separate test of each of 15 measurement sites using Section 
8.2.1 or 8.2.2 to determine the number and location of traverse points, 
as appropriate.
    8.2.3.6.3  Example 3: A source with two measurement sites of equal 
areas may be tested as follows: For each test of three test runs, 
traverse both measurement sites, using Section 8.2.3 in determining the 
number of traverse points. Alternatively, conduct two full emission 
test runs for each measurement site using the criteria in Section 8.2.1 
or 8.2.2 to determine the number of traverse points.
    8.2.3.7  Other test schemes, such as random determination of 
traverse points for a large number of measurement sites, may be used 
with prior approval from the Administrator.
    8.3  Velocity Determination.
    8.3.1  The velocities of exhaust gases from positive pressure 
baghouses are often too low to measure accurately with the type S pitot 
tube specified in Method 2 (i.e., velocity head 1.3 mm H2O 
(0.05 in. H2O)). For these conditions, measure the gas flow 
rate at the fabric filter inlet following the procedures outlined in 
Method 2. Calculate the average gas velocity at the measurement site as 
shown in Section 12.2 and use this average velocity in determining and 
maintaining isokinetic sampling rates.
    8.3.2  Velocity determinations to determine and maintain isokinetic 
rates at measurement sites with gas velocities within the range 
measurable with the type S pitot tube (i.e., velocity head greater than 
1.3 mm H2O (0.05 in. H2O)) shall be conducted 
according to the procedures outlined in Method 2.
    8.4  Sampling. Follow the procedures specified in Sections 8.1 
through 8.6 of Method 5 or Sections 8.1 through 8.25 in Method 17 with 
the exceptions as noted above.
    8.5  Sample Recovery. Follow the procedures specified in Section 
8.7 of Method 5 or Section 8.2 of Method 17.

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

 
------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.0, 10.0.....................  Sampling           Ensures accurate
                                 equipment leak     measurement of stack
                                 check and          gas flow rate,
                                 calibration.       sample volume.
------------------------------------------------------------------------

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

10.0  Calibration and Standardization

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

11.0  Analytical Procedure

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

12.0  Data Analysis and Calculations

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

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

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

    12.4  Dilution Air Flow Rate.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.142
    
    12.5  Average PM Concentration. For multiple measurement sites, 
calculate the average PM concentration as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.143

13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    Same as Method 5, Section 17.0.

[[Page 61860]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.144


[[Page 61861]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.145


[[Page 61862]]



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

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

1.0  Scope and Applications

    1.1  Analyte. Particulate matter (PM). No CAS number assigned.
    1.2  Applicability. This method is applicable for the determination 
of PM emissions from wool fiberglass insulation manufacturing sources.

2.0  Summary of Method

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

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and to determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Corrosive Reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burn as thermal burn.
    5.2.1  Hydrochloric Acid (HCl). Highly toxic. Vapors are highly 
irritating to eyes, skin, nose, and lungs, causing severe damage. May 
cause bronchitis, pneumonia, or edema of lungs. Exposure to 
concentrations of 0.13 to 0.2 percent in air can be lethal in minutes. 
Will react with metals, producing hydrogen.
    5.2.2  Sodium Hydroxide (NaOH). Causes severe damage to eye tissues 
and to skin. Inhalation causes irritation to nose, throat, and lungs. 
Reacts exothermically with limited amounts of water.

6.0  Equipment and Supplies

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

7.0  Reagents and Standards

    Unless otherwise indicated, it is intended that all reagents 
conform to the specifications established by the Committee on 
Analytical Reagents of the American Chemical Society, where such 
specifications are available; otherwise, use the best available grade.
    7.1  Sample Collection. Same as Method 5, Section 7.1, with the 
addition of 0.1 N NaOH (Dissolve 4 g of NaOH in water and dilute to 1 
liter).
    7.2  Sample Recovery. Same as Method 5, Section 7.2, with the 
addition of the following:
    7.2.1  Water. Deionized distilled to conform to ASTM Specification 
D 1193-77 or 91 Type 3 (incorporated by reference--see Sec. 60.17). The 
potassium permanganate (KMnO4) test for oxidizable organic 
matter may be omitted when high concentrations of organic matter are 
not expected to be present.
    7.2.2  Sodium Hydroxide. Same as described in Section 7.1.
    7.3  Sample Analysis. Same as Method 5, Section 7.3, with the 
addition of the following:
    7.3.1  Carbon Dioxide-Free Water. Distilled or deionized water that 
has been freshly boiled for 15 minutes and cooled to room temperature 
while preventing exposure to ambient air by using a cover vented with 
an Ascarite tube.
    7.3.2  Hydrochloric Acid. HCl, concentrated, with a dropper.
    7.3.3  Organic Carbon Stock Solution. Dissolve 2.1254 g of dried 
potassium biphthalate (HOOCC6H4COOK) in 
CO2-free water, and dilute to 1 liter in a volumetric flask. 
This solution contains 1000 mg/L organic carbon.
    7.3.4  Inorganic Carbon Stock Solution. Dissolve 4.404 g anhydrous 
sodium carbonate (Na2CO3.) in about 500 ml of 
CO2-free water in a 1-liter volumetric flask. Add 3.497 g 
anhydrous sodium bicarbonate (NaHCO3) to the flask, and 
dilute to 1 liter with CO2 -free water. This solution 
contains 1000 mg/L inorganic carbon.
    7.3.5  Oxygen Gas. CO2 -free.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Pretest Preparation and Preliminary Determinations. Same as 
Method 5, Sections 8.1 and 8.2, respectively.
    8.2  Preparation of Sampling Train. Same as Method 5, Section 8.3, 
except that 0.1 N NaOH is used in place of water in the impingers. The 
volumes of the solutions are the same as in Method 5.
    8.3  Leak-Check Procedures, Sampling Train Operation, Calculation 
of Percent Isokinetic. Same as Method 5, Sections 8.4 through 8.6, 
respectively.
    8.4  Sample Recovery. Same as Method 5, Sections 8.7.1 through 
8.7.4, with the addition of the following:
    8.4.1  Save portions of the water, acetone, and 0.1 N NaOH used for 
cleanup as blanks. Take 200 ml of each liquid directly from the wash 
bottles being used, and place in glass sample containers labeled 
``water blank,'' ``acetone blank,'' and ``NaOH blank,'' respectively.

[[Page 61863]]

    8.4.2  Inspect the train prior to and during disassembly, and note 
any abnormal conditions. Treat the samples as follows:
    8.4.2.1  Container No. 1. Same as Method 5, Section 8.7.6.1.
    8.4.2.2  Container No. 2. Use water to rinse the sample nozzle, 
probe, and front half of the filter holder three times in the manner 
described in Section 8.7.6.2 of Method 5 except that no brushing is 
done. Put all the water wash in one container, seal, and label.
    8.4.2.3  Container No. 3. Rinse and brush the sample nozzle, probe, 
and front half of the filter holder with acetone as described for 
Container No. 2 in Section 8.7.6.2 of Method 5.
    8.4.2.4  Container No. 4. Place the contents of the silica gel 
impinger in its original container as described for Container No. 3 in 
Section 8.7.6.3 of Method 5.
    8.4.2.5  Container No. 5. Measure the liquid in the first three 
impingers and record the volume or weight as described for the Impinger 
Water in Section 8.7.6.4 of Method 5. Do not discard this liquid, but 
place it in a sample container using a glass funnel to aid in the 
transfer from the impingers or graduated cylinder (if used) to the 
sample container. Rinse each impinger thoroughly with 0.1 N NaOH three 
times, as well as the graduated cylinder (if used) and the funnel, and 
put these rinsings in the same sample container. Seal the container and 
label to clearly identify its contents.
    8.5  Sample Transport. Whenever possible, containers should be 
shipped in such a way that they remain upright at all times.

9.0  Quality Control.

    9.1  Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.3, 10.0.....................  Sampling           Ensures accurate
                                 equipment leak-    measurement of stack
                                 check and          gas flow rate,
                                 calibration.       sample volume.
10.1.2, 11.2.5.3..............  Repetitive         Ensures precise
                                 analyses.          measurement of total
                                                    carbon and inorganic
                                                    carbon concentration
                                                    of samples, blank,
                                                    and standards.
10.1.4........................  TOC analyzer       Ensures linearity of
                                 calibration.       analyzer response to
                                                    standards.
------------------------------------------------------------------------

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

10.0  Calibration and Standardization

    Same as Method 5, Section 10.0, with the addition of the following 
procedures for calibrating the total organic carbon analyzer:
    10.1  Preparation of Organic Carbon Standard Curve.
    10.1.1  Add 10 ml, 20 ml, 30 ml, 40 ml, and 50 ml of the organic 
carbon stock solution to a series of five 1000-ml volumetric flasks. 
Add 30 ml, 40 ml, and 50 ml of the same solution to a series of three 
500-ml volumetric flasks. Dilute the contents of each flask to the mark 
using CO2-free water. These flasks contain 10, 20, 30, 40, 
50, 60, 80, and 100 mg/L organic carbon, respectively.
    10.1.2  Use a hypodermic syringe to withdraw a 20- to 50-l 
aliquot from the 10 mg/L standard solution and inject it into the total 
carbon port of the analyzer. Measure the peak height. Repeat the 
injections until three consecutive peaks are obtained within 10 percent 
of their arithmetic mean. Repeat this procedure for the remaining 
organic carbon standard solutions.
    10.1.3  Calculate the corrected peak height for each standard by 
deducting the blank correction (see Section 11.2.5.3) as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.146

Where:

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

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

11.0  Analytical Procedure

    11.1  Record the data required on a sheet such as the one shown in 
Figure 5-6 of Method 5.
    11.2  Handle each sample container as follows:
    11.2.1  Container No. 1. Same as Method 5, Section 11.2.1, except 
that the filters must be dried at 20  6  deg.C (68 
 10  deg.F) and ambient pressure.
    11.2.2  Containers No. 2 and No. 3. Same as Method 5, Section 
11.2.2, except that evaporation of the samples must be at 20 
 6  deg.C (68  10  deg.F) and ambient pressure.
    11.2.3  Container No. 4. Same as Method 5, Section 11.2.3.
    11.2.4  ``Water Blank'' and ``Acetone Blank'' Containers. Determine 
the water and acetone blank values following the procedures for the 
``Acetone Blank'' container in Section 11.2.4 of Method 5. Evaporate 
the samples at ambient temperature (20  6  deg.C (68 
 10  deg.F)) and pressure.
    11.2.5  Container No. 5. For the determination of total organic 
carbon, perform two analyses on successive identical samples, i.e., 
total carbon and inorganic carbon. The desired quantity is the 
difference between the two values obtained. Both analyses are based on 
conversion of sample carbon into carbon dioxide for measurement by a 
nondispersive infrared analyzer. Results of analyses register as peaks 
on a strip chart recorder.
    11.2.5.1  The principal differences between the operating 
parameters for the two channels involve the combustion tube packing 
material and temperature. In the total carbon channel, a high 
temperature (950  deg.C (1740  deg.F)) furnace heats a Hastelloy 
combustion tube packed with cobalt oxide-impregnated asbestos fiber. 
The oxygen in the carrier gas, the elevated temperature, and the 
catalytic effect of the packing result in oxidation of both organic and 
inorganic carbonaceous material to CO2, and steam. In the

[[Page 61864]]

inorganic carbon channel, a low temperature (150  deg.C (300  deg.F)) 
furnace heats a glass tube containing quartz chips wetted with 85 
percent phosphoric acid. The acid liberates CO2 and steam 
from inorganic carbonates. The operating temperature is below that 
required to oxidize organic matter. Follow the manufacturer's 
instructions for assembly, testing, calibration, and operation of the 
analyzer.
    11.2.5.2  As samples collected in 0.1 N NaOH often contain a high 
measure of inorganic carbon that inhibits repeatable determinations of 
TOC, sample pretreatment is necessary. Measure and record the liquid 
volume of each sample (or impinger contents). If the sample contains 
solids or immiscible liquid matter, homogenize the sample with a 
blender or ultrasonics until satisfactory repeatability is obtained. 
Transfer a representative portion of 10 to 15 ml to a 30-ml beaker, and 
acidify with about 2 drops of concentrated HCl to a pH of 2 or less. 
Warm the acidified sample at 50  deg.C (120  deg.F) in a water bath for 
15 minutes.
    11.2.5.3  While stirring the sample with a magnetic stirrer, use a 
hypodermic syringe to withdraw a 20-to 50-1 aliquot from the 
beaker. Analyze the sample for total carbon and calculate its corrected 
mean peak height according to the procedures outlined in Sections 
10.1.2 and 10.1.3. Similarly analyze an aliquot of the sample for 
inorganic carbon. Repeat the analyses for all the samples and for the 
0.1 N NaOH blank.
    11.2.5.4  Ascertain the total carbon and inorganic carbon 
concentrations (CTC and CIC, respectively) of 
each sample and blank by comparing the corrected mean peak heights for 
each sample and blank to the appropriate standard curve.


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

12.0  Data Analysis and Calculations

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

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

    12.2  Concentration of Condensed TOC in Liquid Sample.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.148
    
    12.3 Mass of Condensed TOC Collected.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.149
    
Where:

0.001  = Liters per milliliter.

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

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

    12.5  Total Particulate Concentration.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.151
    
13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References.

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

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

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

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

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

1.0  Scope and Applications

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

2.0  Summary of Method

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

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety

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

6.0  Equipment and Supplies

    6.1  Sample Collection and Recovery. Same as Method 5, Sections 6.1 
and 6.2, respectively.
    6.2  Sample Analysis. Same as Method 5, Section 6.3, with the 
addition of the following:
    6.2.1  Erlenmeyer Flasks. 125-ml, with ground glass joints.
    6.2.2  Air Condenser. With ground glass joint compatible with the 
Erlenmeyer flasks.
    6.2.3  Beakers. 600-ml.
    6.2.4  Volumetric Flasks. 1-liter, 500-ml (one for each sample), 
200-ml, and 50-ml (one for each sample and standard).
    6.2.5  Pipet. 5-ml (one for each sample and standard).
    6.2.6  Ion Chromatograph. The ion chromatograph should have at 
least the following components.
    6.2.6.1  Columns. An anion separation column or other column

[[Page 61865]]

capable of resolving the sulfate ion from other species present and a 
standard anion suppressor column. Suppressor columns are produced as 
proprietary items; however, one can be produced in the laboratory using 
the resin available from BioRad Company, 32nd and Griffin Streets, 
Richmond, California. Other systems which do not use suppressor columns 
may also be used.
    6.2.6.2  Pump. Capable of maintaining a steady flow as required by 
the system.
    6.2.6.3  Flow Gauges. Capable of measuring the specified system 
flow rate.
    6.2.6.4  Conductivity Detector.
    6.2.6.5  Recorder. Compatible with the output voltage range of the 
detector.

7.0  Reagents and Standards

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

8.0  Sample Collection, Preservation, Storage, and Transport

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

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.3, 10.0.....................  Sampling           Ensures accurate
                                 equipment leak     measurement of stack
                                 check and          gas flow rate,
                                 calibration.       sample volume.
10.1.2, 11.2.5.3..............  Repetitive         Ensures precise
                                 analyses.          measurement of total
                                                    carbon and inorganic
                                                    carbon concentration
                                                    of samples, blank,
                                                    and standards.
------------------------------------------------------------------------

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

10.0  Calibration and Standardization

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

11.0  Analytical Procedure

    11.1  Sample Extraction.
    11.1.1  Note on the analytical data sheet, the level of the liquid 
in the container, and whether any sample was lost during shipment. If a 
noticeable amount of leakage has occurred, either void the sample or 
use methods, subject to the approval of the Administrator, to correct 
the final results.
    11.1.2  Cut the filter into small pieces, and place it in a 125-ml 
Erlenmeyer flask with a ground glass joint equipped with an air 
condenser. Rinse the shipping container with water, and pour the rinse 
into the flask. Add additional water to the flask until it contains 
about 75 ml, and place the flask on a hot plate. Gently reflux the 
contents for 6 to 8 hours. Cool the solution, and transfer it to a 500-
ml volumetric flask. Rinse the Erlenmeyer flask with water, and 
transfer the rinsings to the volumetric flask including the pieces of 
filter.
    11.1.3  Transfer the probe rinse to the same 500-ml volumetric 
flask with the filter sample. Rinse the sample bottle with water, and 
add the rinsings to the volumetric flask. Dilute the contents of the 
flask to the mark with water.
    11.1.4  Allow the contents of the flask to settle until all solid 
material is at the bottom of the flask. If necessary, remove and 
centrifuge a portion of the sample.
    11.1.5  Repeat the procedures outlined in Sections 11.1.1 through 
11.1.4 for each sample and for the filter blank.
    11.2  Sulfate (SO4) Analysis.

[[Page 61866]]

    11.2.1  Prepare a standard calibration curve according to the 
procedures outlined in Section 10.1.
    11.2.2  Pipet 5 ml of the sample into a 50-ml volumetric flask, and 
dilute to 50 ml with water. (Alternatively, eluent solution may be used 
instead of water in all sample, standard, and blank dilutions.) Analyze 
the set of standards followed by the set of samples, including the 
filter blank, using the same injection volume used for the standards.
    11.2.3  Repeat the analyses of the standards and the samples, with 
the standard set being done last. The two peak height or peak area 
responses for each sample must agree within 5 percent of their 
arithmetic mean for the analysis to be valid. Perform this analysis 
sequence on the same day. Dilute any sample and the blank with equal 
volumes of water if the concentration exceeds that of the highest 
standard.
    11.2.4  Document each sample chromatogram by listing the following 
analytical parameters: injection point, injection volume, sulfate 
retention time, flow rate, detector sensitivity setting, and recorder 
chart speed.
    11.3  Sample Residue.
    11.3.1  Transfer the remaining contents of the volumetric flask to 
a tared 600-ml beaker or similar container. Rinse the volumetric flask 
with water, and add the rinsings to the tared beaker. Make certain that 
all particulate matter is transferred to the beaker. Evaporate the 
water in an oven at 105  deg.C (220  deg.F) until only about 100 ml of 
water remains. Remove the beakers from the oven, and allow them to 
cool.
    11.3.2  After the beakers have cooled, add five drops of 
phenolphthalein indicator, and then add concentrated ammonium hydroxide 
until the solution turns pink. Return the samples to the oven at 105 
deg.C (220  deg.F), and evaporate the samples to dryness. Cool the 
samples in a desiccator, and weigh the samples to constant weight.

12.0  Data Analysis and Calculations

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

CW = Water blank residue concentration, mg/ml.
F = Dilution factor (required only if sample dilution was needed to 
reduce the concentration into the range of calibration).
HS = Arithmetic mean response of duplicate sample analyses, 
mm for height or mm2 for area.
Hb = Arithmetic mean response of duplicate filter blank 
analyses, mm for height or mm2 for area.
mb = Mass of beaker used to dry sample, mg.
mf = Mass of sample filter, mg.
mn = Mass of nonsulfate particulate matter in the sample as 
collected, mg.
ms = Mass of ammonium sulfate in the sample as collected, 
mg.
mt = Mass of beaker, filter, and dried sample, mg.
mw = Mass of residue after evaporation of water blank, mg.
S = Calibration factor, g/mm.
Vb = Volume of water blank, ml.
VS = Volume of sample collected, 500 ml.

    12.2  Water Blank Concentration.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.152
    
    12.3  Mass of Ammonium Sulfate.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.153
    
Where:

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

    12.4  Mass of Nonsulfate Particulate Matter.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.154
    
13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  Alternative Procedures  

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

[[Page 61867]]

    16.1.3.3.2  Assemble the vacuum filter apparatus, and place one of 
the clean, tared glass fiber filters in the Buchner funnel. Decant the 
liquid portion of the extracted sample (Section 16.1.3.2) through the 
tared glass fiber filter into a clean, dry, 500-ml filter flask. Rinse 
all the particulate matter remaining in the volumetric flask onto the 
glass fiber filter with water. Rinse the particulate matter with 
additional water. Transfer the filtrate to a 500-ml volumetric flask, 
and dilute to 500 ml with water. Dry the filter overnight at 105 
 5 deg. C (221  9 deg.F), cool in a desiccator, 
and weigh to the nearest 0.1 mg.
    16.1.3.3.3  Dry a 250-ml beaker at 75  5 deg. C (167 
 9 deg. F), and cool in a desiccator; then weigh to 
constant weight to the nearest 0.1 mg. Pipette 200 ml of the filtrate 
that was saved into a tared 250-ml beaker; add five drops of 
phenolphthalein indicator and sufficient concentrated ammonium 
hydroxide to turn the solution pink. Carefully evaporate the contents 
of the beaker to dryness at 75  5 deg. C (167  
9 deg. F). Check for dryness every 30 minutes. Do not continue to bake 
the sample once it has dried. Cool the sample in a desiccator, and 
weigh to constant weight to the nearest 0.1 mg.
    16.1.3.4  Sulfate Analysis. Adjust the flow rate through the ion 
exchange column to 3 ml/min. Pipette a 20-ml aliquot of the filtrate 
onto the top of the ion exchange column, and collect the eluate in a 
50-ml volumetric flask. Rinse the column with two 15-ml portions of 
water. Stop collection of the eluate when the volume in the flask 
reaches 50-ml. Pipette a 20-ml aliquot of the eluate into a 250-ml 
Erlenmeyer flask, add 80 ml of 100 percent isopropanol and two to four 
drops of thorin indicator, and titrate to a pink end point using 0.0100 
N barium perchlorate. Repeat and average the titration volumes. Run a 
blank with each series of samples. Replicate titrations must agree 
within 1 percent or 0.2 ml, whichever is larger. Perform the ion 
exchange and titration procedures on duplicate portions of the 
filtrate. Results should agree within 5 percent. Regenerate or replace 
the ion exchange resin after 20 sample aliquots have been analyzed or 
if the end point of the titration becomes unclear.


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


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

ma = Mass of clean analytical filter, mg.
md = Mass of dissolved particulate matter, mg.
me = Mass of beaker and dissolved particulate matter after 
evaporation of filtrate, mg.
mp = Mass of insoluble particulate matter, mg.
mr = Mass of analytical filter, sample filter, and insoluble 
particulate matter, mg.
mbk = Mass of nonsulfate particulate matter in blank sample, 
mg.
mn = Mass of nonsulfate particulate matter, mg.
ms = Mass of Ammonium sulfate, mg.
N = Normality of Ba(ClO4) titrant, meq/ml.
Va = Volume of aliquot taken for titration, 20 ml.
Vc = Volume of titrant used for titration blank, ml.
Vd = Volume of filtrate evaporated, 200 ml.
Ve = Volume of eluate collected, 50 ml.
Vf = Volume of extracted sample, 500 ml.
Vi = Volume of filtrate added to ion exchange column, 20 ml.
Vt = Volume of Ba(C104)2 titrant, ml.
W = Equivalent weight of ammonium sulfate, 66.07 mg/meq.
    16.1.5.2  Mass of Insoluble Particulate Matter.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.155
    
    16.1.5.3  Mass of Dissolved Particulate Matter.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.156
    
    16.1.5.4  Mass of Ammonium Sulfate.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.157
    
    16.1.5.5  Mass of Nonsulfate Particulate Matter.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.158
    
17.0  References

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

    1. Mulik, J.D. and E. Sawicki. Ion Chromatographic Analysis of 
Environmental Pollutants. Ann Arbor, Ann Arbor Science Publishers, 
Inc. Vol. 2, 1979.
    2. Sawicki, E., J.D. Mulik, and E. Wittgenstein. Ion 
Chromatographic Analysis of Environmental Pollutants. Ann Arbor, Ann 
Arbor Science Publishers, Inc. Vol. 1. 1978.
    3. Siemer, D.D. Separation of Chloride and Bromide from Complex 
Matrices Prior to Ion Chromatographic Determination. Analytical 
Chemistry 52(12): 1874-1877. October 1980.
    4. Small, H., T.S. Stevens, and W.C. Bauman. Novel Ion Exchange 
Chromatographic Method Using Conductimetric Determination. 
Analytical Chemistry. 47(11):1801. 1975.

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

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

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

1.0  Scope and Application

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

2.0  Summary of Method

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

[[Page 61868]]

(2) and (3) are referenced in Section 16.0 of this method. The dual-
filter dry sampling train equipment and operation, option (1), are 
described in detail in this method.

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety

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

6.0  Equipment and Supplies

    6.1  Sample Collection. The following items are required for sample 
collection:
    6.1.1  Sampling Train. The sampling train configuration is shown in 
Figure 5G-1 and consists of the following components:
    6.1.1.1  Probe. Stainless steel (e.g., 316 or grade more corrosion 
resistant) or glass about 9.5 mm (\3/8\ in.) I.D., 0.6 m (24 in.) in 
length. If made of stainless steel, the probe shall be constructed from 
seamless tubing.
    6.1.1.2  Pitot Tube. Type S, as described in Section 6.1 of Method 
2. The Type S pitot tube assembly shall have a known coefficient, 
determined as outlined in Method 2, Section 10. Alternatively, a 
standard pitot may be used as described in Method 2, Section 6.1.2.
    6.1.1.3  Differential Pressure Gauge. Inclined manometer or 
equivalent device, as described in Method 2, Section 6.2. One manometer 
shall be used for velocity head (p) readings and another 
(optional) for orifice differential pressure readings (H).
    6.1.1.4  Filter Holders. Two each made of borosilicate glass, 
stainless steel, or Teflon, with a glass frit or stainless steel filter 
support and a silicone rubber, Teflon, or Viton gasket. The holder 
design shall provide a positive seal against leakage from the outside 
or around the filters. The filter holders shall be placed in series 
with the backup filter holder located 25 to 100 mm (1 to 4 in.) 
downstream from the primary filter holder. The filter holder shall be 
capable of holding a filter with a 100 mm (4 in.) diameter, except as 
noted in Section 16.
    6.1.1.5  Filter Temperature Monitoring System. A temperature sensor 
capable of measuring temperature to within  3  deg.C 
( 5  deg.F). The sensor shall be installed at the exit side 
of the front filter holder so that the sensing tip of the temperature 
sensor is in direct contact with the sample gas or in a thermowell as 
shown in Figure 5G-1. The temperature sensor shall comply with the 
calibration specifications in Method 2, Section 10.3. Alternatively, 
the sensing tip of the temperature sensor may be installed at the inlet 
side of the front filter holder.
    6.1.1.6  Dryer. Any system capable of removing water from the 
sample gas to less than 1.5 percent moisture (volume percent) prior to 
the metering system. The system shall include a temperature sensor for 
demonstrating that sample gas temperature exiting the dryer is less 
than 20  deg.C (68  deg.F).
    6.1.1.7  Metering System. Same as Method 5, Section 6.1.1.9.
    6.1.2  Barometer. Same as Method 5, Section 6.1.2.
    6.1.3  Dilution Tunnel Gas Temperature Measurement. A temperature 
sensor capable of measuring temperature to within  3  deg.C 
( 5  deg.F).
    6.1.4  Dilution Tunnel. The dilution tunnel apparatus is shown in 
Figure 5G-2 and consists of the following components:
    6.1.4.1  Hood. Constructed of steel with a minimum diameter of 0.3 
m (1 ft) on the large end and a standard 0.15 to 0.3 m (0.5 to 1 ft) 
coupling capable of connecting to standard 0.15 to 0.3 m (0.5 to 1 ft) 
stove pipe on the small end.
    6.1.4.2  90 deg. Elbows. Steel 90 deg. elbows, 0.15 to 0.3 m (0.5 
to 1 ft) in diameter for connecting mixing duct, straight duct and 
optional damper assembly. There shall be at least two 90 deg. elbows 
upstream of the sampling section (see Figure 5G-2).
    6.1.4.3  Straight Duct. Steel, 0.15 to 0.3 m (0.5 to 1 ft) in 
diameter to provide the ducting for the dilution apparatus upstream of 
the sampling section. Steel duct, 0.15 m (0.5 ft) in diameter shall be 
used for the sampling section. In the sampling section, at least 1.2 m 
(4 ft) downstream of the elbow, shall be two holes (velocity traverse 
ports) at 90 deg. to each other of sufficient size to allow entry of 
the pitot for traverse measurements. At least 1.2 m (4 ft) downstream 
of the velocity traverse ports, shall be one hole (sampling port) of 
sufficient size to allow entry of the sampling probe. Ducts of larger 
diameter may be used for the sampling section, provided the 
specifications for minimum gas velocity and the dilution rate range 
shown in Section 8 are maintained. The length of duct from the hood 
inlet to the sampling ports shall not exceed 9.1 m (30 ft).
    6.1.4.4  Mixing Baffles. Steel semicircles (two) attached at 
90 deg. to the duct axis on opposite sides of the duct midway between 
the two elbows upstream of sampling section. The space between the 
baffles shall be about 0.3 m (1 ft).
    6.1.4.5  Blower. Squirrel cage or other fan capable of extracting 
gas from the dilution tunnel of sufficient flow to maintain the 
velocity and dilution rate specifications in Section 8 and exhausting 
the gas to the atmosphere.
    6.2  Sample Recovery. The following items are required for sample 
recovery: probe brushes, wash bottles, sample storage containers, petri 
dishes, and funnel. Same as Method 5, Sections 6.2.1 through 6.2.4, and 
6.2.8, respectively.
    6.3  Sample Analysis. The following items are required for sample 
analysis: glass weighing dishes, desiccator, analytical balance, 
beakers (250-ml or smaller), hygrometer, and temperature sensor. Same 
as Method 5, Sections 6.3.1 through 6.3.3 and 6.3.5 through 6.3.7, 
respectively.

7.0  Reagents and Standards

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

8.0  Sample Collection, Preservation, Transport, and Storage

    8.1  Dilution Tunnel Assembly and Cleaning. A schematic of a 
dilution tunnel is shown in Figure 5G-2. The dilution tunnel dimensions 
and other features are described in Section 6.1.4. Assemble the 
dilution tunnel, sealing joints and seams to prevent air leakage. Clean 
the dilution tunnel with an appropriately sized wire chimney brush 
before each certification test.
    8.2  Draft Determination. Prepare the wood heater as in Method 28, 
Section 6.2.1. Locate the dilution tunnel hood centrally over the wood 
heater stack

[[Page 61869]]

exhaust. Operate the dilution tunnel blower at the flow rate to be used 
during the test run. Measure the draft imposed on the wood heater by 
the dilution tunnel (i.e., the difference in draft measured with and 
without the dilution tunnel operating) as described in Method 28, 
Section 6.2.3. Adjust the distance between the top of the wood heater 
stack exhaust and the dilution tunnel hood so that the dilution tunnel 
induced draft is less than 1.25 Pa (0.005 in. H2O). Have no 
fire in the wood heater, close the wood heater doors, and open fully 
the air supply controls during this check and adjustment.
    8.3  Pretest Ignition. Same as Method 28, Section 8.7.
    8.4  Smoke Capture. During the pretest ignition period, operate the 
dilution tunnel and visually monitor the wood heater stack exhaust. 
Operate the wood heater with the doors closed and determine that 100 
percent of the exhaust gas is collected by the dilution tunnel hood. If 
less than 100 percent of the wood heater exhaust gas is collected, 
adjust the distance between the wood heater stack and the dilution 
tunnel hood until no visible exhaust gas is escaping. Stop the pretest 
ignition period, and repeat the draft determination procedure described 
in Section 8.2.
    8.5  Velocity Measurements. During the pretest ignition period, 
conduct a velocity traverse to identify the point of average velocity. 
This single point shall be used for measuring velocity during the test 
run.
    8.5.1  Velocity Traverse. Measure the diameter of the duct at the 
velocity traverse port location through both ports. Calculate the duct 
area using the average of the two diameters. A pretest leak-check of 
pitot lines as in Method 2, Section 8.1, is recommended. Place the 
calibrated pitot tube at the centroid of the stack in either of the 
velocity traverse ports. Adjust the damper or similar device on the 
blower inlet until the velocity indicated by the pitot is approximately 
220 m/min (720 ft/min). Continue to read the p and temperature 
until the velocity has remained constant (less than 5 percent change) 
for 1 minute. Once a constant velocity is obtained at the centroid of 
the duct, perform a velocity traverse as outlined in Method 2, Section 
8.3 using four points per traverse as outlined in Method 1. Measure the 
p and tunnel temperature at each traverse point and record the 
readings. Calculate the total gas flow rate using calculations 
contained in Method 2, Section 12. Verify that the flow rate is 4 
 0.40 dscm/min (140  14 dscf/min); if not, 
readjust the damper, and repeat the velocity traverse. The moisture may 
be assumed to be 4 percent (100 percent relative humidity at 85 
deg.F). Direct moisture measurements (e.g., according to Method 4) are 
also permissible.


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


    8.5.2  Testing Velocity Measurements. After obtaining velocity 
traverse results that meet the flow rate requirements, choose a point 
of average velocity and place the pitot and temperature sensor at that 
location in the duct. Alternatively, locate the pitot and the 
temperature sensor at the duct centroid and calculate a velocity 
correction factor for the centroidal position. Mount the pitot to 
ensure no movement during the test run and seal the port holes to 
prevent any air leakage. Align the pitot opening to be parallel with 
the duct axis at the measurement point. Check that this condition is 
maintained during the test run (about 30-minute intervals). Monitor the 
temperature and velocity during the pretest ignition period to ensure 
that the proper flow rate is maintained. Make adjustments to the 
dilution tunnel flow rate as necessary.
    8.6  Pretest Preparation. Same as Method 5, Section 8.1.
    8.7  Preparation of Sampling Train. During preparation and assembly 
of the sampling train, keep all openings where contamination can occur 
covered until just prior to assembly or until sampling is about to 
begin.
    Using a tweezer or clean disposable surgical gloves, place one 
labeled (identified) and weighed filter in each of the filter holders. 
Be sure that each filter is properly centered and that the gasket is 
properly placed so as to prevent the sample gas stream from 
circumventing the filter. Check each filter for tears after assembly is 
completed.
    Mark the probe with heat resistant tape or by some other method to 
denote the proper distance into the stack or duct. Set up the train as 
shown in Figure 5G-1.
    8.8  Leak-Check Procedures.
    8.8.1  Leak-Check of Metering System Shown in Figure 5G-1. That 
portion of the sampling train from the pump to the orifice meter shall 
be leak-checked prior to initial use and after each certification or 
audit test. Leakage after the pump will result in less volume being 
recorded than is actually sampled. Use the procedure described in 
Method 5, Section 8.4.1. Similar leak-checks shall be conducted for 
other types of metering systems (i.e., without orifice meters).
    8.8.2  Pretest Leak-Check. A pretest leak-check of the sampling 
train is recommended, but not required. If the pretest leak check is 
conducted, the procedures outlined in Method 5, Section 8.4.2 should be 
used. A vacuum of 130 mm Hg (5 in. Hg) may be used instead of 380 mm Hg 
(15 in. Hg).
    8.8.3  Post-Test Leak-Check. A leak-check of the sampling train is 
mandatory at the conclusion of each test run. The leak-check shall be 
performed in accordance with the procedures outlined in Method 5, 
Section 8.4.2. A vacuum of 130 mm Hg (5 in. Hg) or the highest vacuum 
measured during the test run, whichever is greater, may be used instead 
of 380 mm Hg (15 in. Hg).
    8.9  Preliminary Determinations. Determine the pressure, 
temperature and the average velocity of the tunnel gases as in Section 
8.5. Moisture content of diluted tunnel gases is assumed to be 4 
percent for making flow rate calculations; the moisture content may be 
measured directly as in Method 4.
    8.10  Sampling Train Operation. Position the probe inlet at the 
stack centroid, and block off the openings around the probe and 
porthole to prevent unrepresentative dilution of the gas stream. Be 
careful not to bump the probe into the stack wall when removing or 
inserting the probe through the porthole; this minimizes the chance of 
extracting deposited material.
    8.10.1  Begin sampling at the start of the test run as defined in 
Method 28, Section 8.8.1. During the test run, maintain a sample flow 
rate proportional to the dilution tunnel flow rate (within 10 percent 
of the initial proportionality ratio) and a filter holder temperature 
of no greater than 32  deg.C (90  deg.F). The initial sample flow rate 
shall be approximately 0.015 m\3\/min (0.5 cfm).
    8.10.2  For each test run, record the data required on a data sheet 
such as the one shown in Figure 5G-3. Be sure to record the initial dry 
gas meter reading. Record the dry gas meter readings at the beginning 
and end of each sampling time increment and when sampling is halted. 
Take other readings as indicated on Figure 5G-3 at least once each 10 
minutes during the test run. Since the manometer level and zero may 
drift because of vibrations and temperature changes, make periodic 
checks during the test run.
    8.10.3  For the purposes of proportional sampling rate

[[Page 61870]]

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


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

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

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

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

10.0  Calibration and Standardization

    Note: Maintain a laboratory record of all calibrations.


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


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


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


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


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

11.0  Analytical Procedure

    11.1  Record the data required on a sheet such as the one shown in 
Figure 5G-4. Use the same analytical balance for determining tare 
weights and final sample weights.
    11.2  Handle each sample container as follows:

[[Page 61871]]

    11.2.1  Container Nos. 1 and 1A. Treat the two filters according to 
the procedures outlined in Method 5, Section 11.2.1.
    11.2.2  Container No. 2. Same as Method 5, Section 11.2.2, except 
that the beaker may be smaller than 250 ml.
    11.2.3  Acetone Blank Container. Same as Method 5, Section 11.2.4, 
except that the beaker may be smaller than 250 ml.

12.0  Data Analysis and Calculations

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

Bws = Water vapor in the gas stream, proportion by volume 
(assumed to be 0.04).
cs = Concentration of particulate matter in stack gas, dry 
basis, corrected to standard conditions, g/dscm (gr/dscf).
E = Particulate emission rate, g/hr (lb/hr).
Eadj = Adjusted particulate emission rate, g/hr (lb/hr).
La = Maximum acceptable leakage rate for either a pretest or 
post-test leak-check, equal to 0.00057 m\3\/min (0.020 cfm) or 4 
percent of the average sampling rate, whichever is less.
Lp = Leakage rate observed during the post-test leak-check, 
m\3\/min (cfm).
ma = Mass of residue of acetone blank after evaporation, mg.
maw = Mass of residue from acetone wash after evaporation, 
mg.
mn = Total amount of particulate matter collected, mg.
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 lb/lb-
mole).
Pbar = Barometric pressure at the sampling site, mm Hg (in. 
Hg).
PR = Percent of proportional sampling rate.
Ps = Absolute gas pressure in dilution tunnel, mm Hg (in. 
Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
Qsd = Average gas flow rate in dilution tunnel, calculated 
as in Method 2, Equation 2-8, dscm/hr (dscf/hr).
Tm = Absolute average dry gas meter temperature (see Figure 
5G-3),  deg.K ( deg.R).
Tmi = Absolute average dry gas meter temperature during each 
10-minute interval, i, of the test run,  deg.K ( deg.R).
Ts = Absolute average gas temperature in the dilution tunnel 
(see Figure 5G-3),  deg.K ( deg.R).
Tsi = Absolute average gas temperature in the dilution 
tunnel during each 10 minute interval, i, of the test run,  deg.K 
( deg.R).
Tstd = Standard absolute temperature, 293  deg.K (528 
deg.R).
Va = Volume of acetone blank, ml.
Vaw = Volume of acetone used in wash, ml.
Vm = Volume of gas sample as measured by dry gas meter, dcm 
(dcf).
Vmi = Volume of gas sample as measured by dry gas meter 
during each 10-minute interval, i, of the test run, dcm.
Vm(std) = Volume of gas sample measured by the dry gas 
meter, corrected to standard conditions, dscm (dscf).
Vs = Average gas velocity in the dilution tunnel, calculated 
by Method 2, Equation 2-7, m/sec (ft/sec). The dilution tunnel dry gas 
molecular weight may be assumed to be 29 g/g mole (lb/lb mole).
Vsi = Average gas velocity in dilution tunnel during each 
10-minute interval, i, of the test run, calculated by Method 2, 
Equation 2-7, m/sec (ft/sec).
Y = Dry gas meter calibration factor.
H = Average pressure differential across the orifice meter, if 
used (see Figure 5G-2), mm H\2\O (in. H\2\O).
U = Total sampling time, min.
10 = 10 minutes, length of first sampling period.
13.6 = Specific gravity of mercury.
100 = Conversion to percent.
    12.2  Dry Gas Volume. Same as Method 5, Section 12.2, except that 
component changes are not allowable.
    12.3  Solvent Wash Blank.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.159
    
    12.4  Total Particulate Weight. Determine the total particulate 
catch, mn, from the sum of the weights obtained from Container Nos. 1, 
1A, and 2, less the acetone blank (see Figure 5G-4).
    12.5  Particulate Concentration.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.160
    
Where:
K2 = 0.001 g/mg for metric units.
     = 0.0154 gr/mg for English units.
    12.6 Particulate Emission Rate.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.161
    

    Note: Particulate emission rate results produced using the 
sampling train described in Section 6 and shown in Figure 5G-1 shall 
be adjusted for reporting purposes by the following method 
adjustment factor:

[GRAPHIC] [TIFF OMITTED] TR17OC00.162

Where:

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

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

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

13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  Alternative Procedures

    16.1  Method 5H Sampling Train. The sampling train and sample 
collection, recovery, and analysis procedures described in Method 5H, 
Sections 6.1.1, 7.1, 7.2, 8.1, 8.10, 8.11, and 11.0, respectively, may 
be used in lieu of similar sections in Method 5G.

[[Page 61872]]

Operation of the Method 5H sampling train in the dilution tunnel is as 
described in Section 8.10 of this method. Filter temperatures and 
condenser conditions are as described in Method 5H. No adjustment to 
the measured particulate matter emission rate (Equation 5G-4, Section 
12.6) is to be applied to the particulate emission rate measured by 
this alternative method.
    16.2  Dual Sampling Trains. Two sampling trains may be operated 
simultaneously at sample flow rates other than that specified in 
Section 8.10, provided that the following specifications are met.
    16.2.1  Sampling Train. The sampling train configuration shall be 
the same as specified in Section 6.1.1, except the probe, filter, and 
filter holder need not be the same sizes as specified in the applicable 
sections. Filter holders of plastic materials such as Nalgene or 
polycarbonate materials may be used (the Gelman 1119 filter holder has 
been found suitable for this purpose). With such materials, it is 
recommended that solvents not be used in sample recovery. The filter 
face velocity shall not exceed 150 mm/sec (30 ft/min) during the test 
run. The dry gas meter shall be calibrated for the same flow rate range 
as encountered during the test runs. Two separate, complete sampling 
trains are required for each test run.
    16.2.2  Probe Location. Locate the two probes in the dilution 
tunnel at the same level (see Section 6.1.4.3). Two sample ports are 
necessary. Locate the probe inlets within the 50 mm (2 in.) diameter 
centroidal area of the dilution tunnel no closer than 25 mm (1 in.) 
apart.
    16.2.3  Sampling Train Operation. Operate the sampling trains as 
specified in Section 8.10, maintaining proportional sampling rates and 
starting and stopping the two sampling trains simultaneously. The pitot 
values as described in Section 8.5.2 shall be used to adjust sampling 
rates in both sampling trains.
    16.2.4  Recovery and Analysis of Sample. Recover and analyze the 
samples from the two sampling trains separately, as specified in 
Sections 8.12 and 11.0, respectively.
    16.2.4.1  For this alternative procedure, the probe and filter 
holder assembly may be weighed without sample recovery (use no 
solvents) described above in order to determine the sample weight 
gains. For this approach, weigh the clean, dry probe and filter holder 
assembly upstream of the front filter (without filters) to the nearest 
0.1 mg to establish the tare weights. The filter holder section between 
the front and second filter need not be weighed. At the end of the test 
run, carefully clean the outside of the probe, cap the ends, and 
identify the sample (label). Remove the filters from the filter holder 
assemblies as described for container Nos. 1 and 1A in Section 
8.12.2.1. Reassemble the filter holder assembly, cap the ends, identify 
the sample (label), and transfer all the samples to the laboratory 
weighing area for final weighing. Requirements for capping and 
transport of sample containers are not applicable if sample recovery 
and analysis occur in the same room.
    16.2.4.2  For this alternative procedure, filters may be weighed 
directly without a petri dish. If the probe and filter holder assembly 
are to be weighed to determine the sample weight, rinse the probe with 
acetone to remove moisture before desiccating prior to the test run. 
Following the test run, transport the probe and filter holder to the 
desiccator, and uncap the openings of the probe and the filter holder 
assembly. Desiccate for 24 hours and weigh to a constant weight. Report 
the results to the nearest 0.1 mg.
    16.2.5  Calculations. Calculate an emission rate (Section 12.6) for 
the sample from each sampling train separately and determine the 
average emission rate for the two values. The two emission rates shall 
not differ by more than 7.5 percent from the average emission rate, or 
7.5 percent of the weighted average emission rate limit in the 
applicable subpart of the regulations, whichever is greater. If this 
specification is not met, the results are unacceptable. Report the 
results, but do not include the results in calculating the weighted 
average emission rate. Repeat the test run until acceptable results are 
achieved, report the average emission rate for the acceptable test run, 
and use the average in calculating the weighted average emission rate.

17.0  References

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

    1. Oregon Department of Environmental Quality. Standard Method 
for Measuring the Emissions and Efficiencies of Woodstoves. June 8, 
1984. Pursuant to Oregon Administrative Rules Chapter 340, Division 
21.
    2. American Society for Testing and Materials. Proposed Test 
Methods for Heating Performance and Emissions of Residential Wood-
fired Closed Combustion-Chamber Heating Appliances. E-6 Proposal P 
180. August 1986.
BILLING CODE 6560-50-P

[[Page 61873]]

18.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.164


[[Page 61874]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.165


[[Page 61875]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.166


[[Page 61876]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.167

BILLING CODE 6560-50-C

[[Page 61877]]

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

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

1.0  Scope and Application

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

2.0  Summary of Method

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

3.0  Definitions

    Same as in Method 6C, Section 3.0.

4.0  Interferences. [Reserved]

5.0  Safety

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

6.0  Equipment and Supplies

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


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


    6.1.3.6  Manifold. A sampling tube capable of delivering the sample 
gas to two analyzers and handling an excess of the total amount used by 
the analyzers. The excess gas is exhausted through a separate port.
    6.1.3.7  Recorders (optional). To provide a permanent record of the 
analyzer outputs.
    6.1.4  Proportional Gas Flow Rate System. To monitor stack flow 
rate changes and provide a measurement that can be used to adjust and 
maintain particulate sampling flow rates proportional to the stack gas 
flow rate. A schematic of the proportional flow rate system is shown in 
Figure 5H-2 and consists of the following components:
    6.1.4.1  Tracer Gas Injection System. To inject a known 
concentration of sulfur dioxide (SO2) into the flue. The 
tracer gas injection system consists of a cylinder of SO2, a 
gas cylinder regulator, a stainless steel needle valve or flow 
controller, a nonreactive (stainless steel and glass) rotameter, and an 
injection loop to disperse the SO2 evenly in the flue.
    6.1.4.2  Sample Probe. A glass or stainless steel sampling probe.
    6.1.4.3  Gas Conditioning System. A combustor as described in 
Method 16A, Sections 6.1.5 and 6.1.6, followed by a high density filter 
to remove particulate matter, and a condenser capable of lowering the 
dew point of the gas to less than 5  deg.C (40  deg.F). Desiccant, such 
as Drierite, may be used to dry the sample gas. Do not use silica gel.
    6.1.4.4  Pump. Same as described in Section 6.1.3.3.
    6.1.4.5  SO2 Analyzer. Any analyzer capable of providing 
a measure of the SO2 concentration in the range of 0 to 
1,000 ppm by volume (or other range necessary to measure the 
SO2 concentration) at least once every 10 minutes.
    6.1.4.6  Recorder (optional). To provide a permanent record of the 
analyzer outputs.


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


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

[[Page 61878]]

7.0  Reagents and Standards

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

8.0  Sample Collection, Preservation, Transport, and Storage

    8.1  Pretest Preparation. Same as Method 5, Section 8.1.
    8.2  Calibration Gas and SO2 Injection Gas Concentration 
Verification, Sampling System Bias Check, Response Time Test, and Zero 
and Calibration Drift Tests. Same as Method 6C, Sections 8.2.1, 8.2.3, 
8.2.4, and 8.5, respectively, except that for verification of CO and 
CO2 gas concentrations, substitute Method 3 for Method 6.
    8.3  Preliminary Determinations.
    8.3.1  Sampling Location. The sampling location for the particulate 
sampling probe shall be 2.45  0.15 m (8  0.5 
ft) above the platform upon which the wood heater is placed (i.e., the 
top of the scale).
    8.3.2  Sampling Probe and Nozzle. Select a nozzle, if used, sized 
for the range of velocity heads, such that it is not necessary to 
change the nozzle size in order to maintain proportional sampling 
rates. During the run, do not change the nozzle size. Select a suitable 
probe liner and probe length to effect minimum blockage.
    8.4  Preparation of Particulate Sampling Train. Same as Method 5, 
Section 8.3, with the exception of the following:
    8.4.1  The train should be assembled as shown in Figure 5H-1.
    8.4.2  A glass cyclone may not be used between the probe and filter 
holder.
    8.5  Leak-Check Procedures.
    8.5.1  Leak-Check of Metering System Shown in Figure 5H-1. That 
portion of the sampling train from the pump to the orifice meter shall 
be leak-checked after each certification or audit test. Use the 
procedure described in Method 5, Section 8.4.1.
    8.5.2  Pretest Leak-Check. A pretest leak-check of the sampling 
train is recommended, but not required. If the pretest leak-check is 
conducted, the procedures outlined in Method 5, Section 8.5.2 should be 
used. A vacuum of 130 mm Hg (5 in. Hg) may be used instead of 380 mm Hg 
(15 in. Hg).
    8.5.2  Leak-Checks During Sample Run. If, during the sampling run, 
a component (e.g., filter assembly or impinger) change becomes 
necessary, conduct a leak-check as described in Method 5, Section 
8.4.3.
    8.5.3  Post-Test Leak-Check. A leak-check is mandatory at the 
conclusion of each sampling run. The leak-check shall be performed in 
accordance with the procedures outlined in Method 5, Section 8.4.4, 
except that a vacuum of 130 mm Hg (5 in. Hg) or the greatest vacuum 
measured during the test run, whichever is greater, may be used instead 
of 380 mm Hg (15 in. Hg).
    8.6  Tracer Gas Procedure. A schematic of the tracer gas injection 
and sampling systems is shown in Figure 5H-2.
    8.6.1  SO2 Injection Probe. Install the SO2 
injection probe and dispersion loop in the stack at a location 2.9 
 0.15 m (9.5  0.5 ft) above the sampling 
platform.
    8.6.2  SO2 Sampling Probe. Install the SO2 
sampling probe at the centroid of the stack at a location 4.1 
 0.15 m (13.5  0.5 ft) above the sampling 
platform.
    8.7  Flow Rate Measurement System. A schematic of the flow rate 
measurement system is shown in Figure 5H-2. Locate the flow rate 
measurement sampling probe at the centroid of the stack at a location 
2.3  0.3 m (7.5  1 ft) above the sampling 
platform.
    8.8  Tracer Gas Procedure. Within 1 minute after closing the wood 
heater door at the start of the test run (as defined in Method 28, 
Section 8.8.1), meter a known concentration of SO2 tracer 
gas at a constant flow rate into the wood heater stack. Monitor the 
SO2 concentration in the stack, and record the 
SO2 concentrations at 10-minute intervals or more often. 
Adjust the particulate sampling flow rate proportionally to the 
SO2 concentration changes using Equation 5H-6 (e.g., the 
SO2 concentration at the first 10-minute reading is measured 
to be 100 ppm; the next 10 minute SO2 concentration is 
measured to be 75 ppm: the particulate sample flow rate is adjusted 
from the initial 0.15 cfm to 0.20 cfm). A check for proportional rate 
variation shall be made at the completion of the test run using 
Equation 5H-10.
    8.9  Volumetric Flow Rate Procedure. Apply stoichiometric 
relationships to the wood combustion process in determining the exhaust 
gas flow rate as follows:
    8.9.1  Test Fuel Charge Weight. Record the test fuel charge weight 
(wet) as specified in Method 28, Section 8.8.2. The wood is assumed to 
have the following weight percent composition: 51 percent carbon, 7.3 
percent hydrogen, 41 percent oxygen. Record the wood moisture for each 
fuel charge as described in Method 28, Section 8.6.5. The ash is 
assumed to have negligible effect on associated C, H, and O 
concentrations after the test burn.
    8.9.2  Measured Values. Record the CO and CO2 
concentrations in the stack on a dry basis every 10 minutes during the 
test run or more often. Average these values for the test run. Use as a 
mole fraction (e.g., 10 percent CO2 is recorded as 0.10) in 
the calculations to express total flow (see Equation 5H-6).
    8.10  Sampling Train Operation.
    8.10.1  For each run, record the data required on a data sheet such 
as the one shown in Figure 5H-3. Be sure to record the initial dry gas 
meter reading. Record the dry gas meter readings at the beginning and 
end of each sampling time increment, when changes in flow rates are 
made, before and after each leak-check, and when sampling is halted. 
Take other readings as indicated on Figure 5H-3 at least once each 10 
minutes during the test run.
    8.10.2  Remove the nozzle cap, verify that the filter and probe 
heating systems are up to temperature, and that the probe is properly 
positioned. Position the nozzle, if used, facing into gas stream, or 
the probe tip in the 50 mm (2 in.) centroidal area of the stack.
    8.10.3  Be careful not to bump the probe tip into the stack wall 
when removing or inserting the probe through the porthole; this 
minimizes the chance of extracting deposited material.

[[Page 61879]]

    8.10.4  When the probe is in position, block off the openings 
around the probe and porthole to prevent unrepresentative dilution of 
the gas stream.
    8.10.5  Begin sampling at the start of the test run as defined in 
Method 28, Section 8.8.1, start the sample pump, and adjust the sample 
flow rate to between 0.003 and 0.014 m\3\/min (0.1 and 0.5 cfm). Adjust 
the sample flow rate proportionally to the stack gas flow during the 
test run according to the procedures outlined in Section 8. Maintain a 
proportional sampling rate (within 10 percent of the desired value) and 
a filter holder temperature no greater than 120  deg.C (248  deg.F).
    8.10.6  During the test run, make periodic adjustments to keep the 
temperature around the filter holder at the proper level. Add more ice 
to the impinger box and, if necessary, salt to maintain a temperature 
of less than 20  deg.C (68  deg.F) at the condenser/silica gel outlet.
    8.10.7  If the pressure drop across the filter becomes too high, 
making proportional sampling difficult to maintain, either filter may 
be replaced during a sample run. It is recommended that another 
complete filter assembly be used rather than attempting to change the 
filter itself. Before a new filter assembly is installed, conduct a 
leak-check (see Section 8.5.2). The total particulate weight shall 
include the summation of all filter assembly catches. The total time 
for changing sample train components shall not exceed 10 minutes. No 
more than one component change is allowed for any test run.
    8.10.8  At the end of the test run, turn off the coarse adjust 
valve, remove the probe and nozzle from the stack, turn off the pump, 
record the final dry gas meter reading, and conduct a post-test leak-
check, as outlined in Section 8.5.3.
    8.11  Sample Recovery. Same as Method 5, Section 8.7, with the 
exception of the following:
    8.11.1  Blanks. The volume of the acetone blank may be about 50-ml, 
rather than 200-ml; a 200-ml water blank shall also be saved for 
analysis.
    8.11.2  Samples.
    8.11.2.1  Container Nos. 1 and 1A. Treat the two filters according 
to the procedures outlined in Method 5, Section 8.7.6.1. The filters 
may be stored either in a single container or in separate containers.
    8.11.2.2  Container No. 2. Same as Method 5, Section 8.7.6.2, 
except that the container should not be sealed until the impinger rinse 
solution is added (see Section 8.10.2.4).
    8.11.2.3  Container No. 3. Treat the impingers as follows: Measure 
the liquid which is in the first three impingers to within 1-ml by 
using a graduated cylinder or by weighing it to within 0.5 g by using a 
balance (if one is available). Record the volume or weight of liquid 
present. This information is required to calculate the moisture content 
of the effluent gas. Transfer the water from the first, second, and 
third impingers to a glass container. Tighten the lid on the sample 
container so that water will not leak out.
    8.11.2.4  Rinse impingers and graduated cylinder, if used, with 
acetone three times or more. Avoid direct contact between the acetone 
and any stopcock grease or collection of any stopcock grease in the 
rinse solutions. Add these rinse solutions to sample Container No. 2.
    8.11.2.5  Container No. 4. Same as Method 5, Section 8.7.6.3
    8.12  Sample Transport. Whenever possible, containers should be 
transferred in such a way that they remain upright at all times.


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

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

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

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

10.0  Calibration and Standardization

    Note: Maintain a laboratory record of all calibrations.


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

11.0  Analytical Procedure

    11.1  Record the data required on a sheet such as the one shown in 
Figure 5H-4.
    11.2  Handle each sample container as follows:
    11.2.1  Container Nos. 1 and 1A. Treat the two filters according to 
the procedures outlined in Method 5, Section 11.2.1.
    11.2.2  Container No. 2. Same as Method 5, Section 11.2.2, except 
that the beaker may be smaller than 250-ml.
    11.2.3  Container No. 3. Note the level of liquid in the container 
and confirm on the analysis sheet whether leakage occurred during 
transport. If a noticeable amount of leakage has occurred, either void 
the sample or use methods, subject to the approval of the 
Administrator, to correct the final results. Determination of sample 
leakage is not applicable if sample recovery and analysis occur in the 
same room. Measure the liquid in this container either volumetrically 
to within 1-ml or gravimetrically to within 0.5 g. Transfer the 
contents to a 500-ml or larger separatory funnel. Rinse the container 
with water, and add to the separatory

[[Page 61880]]

funnel. Add 25-ml of dichloromethane to the separatory funnel, stopper 
and vigorously shake 1 minute, let separate and transfer the 
dichloromethane (lower layer) into a tared beaker or evaporating dish. 
Repeat twice more. It is necessary to rinse Container No. 3 with 
dichloromethane. This rinse is added to the impinger extract container. 
Transfer the remaining water from the separatory funnel to a tared 
beaker or evaporating dish and evaporate to dryness at 104  deg.C (220 
deg.F). Desiccate and weigh to a constant weight. Evaporate the 
combined impinger water extracts at ambient temperature and pressure. 
Desiccate and weigh to a constant weight. Report both results to the 
nearest 0.1 mg.
    11.2.4  Container No. 4. Weigh the spent silica gel (or silica gel 
plus impinger) to the nearest 0.5 g using a balance.
    11.2.5  Acetone Blank Container. Same as Method 5, Section 11.2.4, 
except that the beaker may be smaller than 250 ml.
    11.2.6  Dichloromethane Blank Container. Treat the same as the 
acetone blank.
    11.2.7  Water Blank Container. Transfer the water to a tared 250 ml 
beaker and evaporate to dryness at 104  deg.C (220  deg.F). Desiccate 
and weigh to a constant weight.

12.0  Data Analysis and Calculations

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

a = Sample flow rate adjustment factor.
BR = Dry wood burn rate, kg/hr (lb/hr), from Method 28, Section 8.3.
Bws = Water vapor in the gas stream, proportion by volume.
Cs = Concentration of particulate matter in stack gas, dry 
basis, corrected to standard conditions, g/dscm (g/dscf).
E = Particulate emission rate, g/hr (lb/hr).
H = Average pressure differential across the orifice meter 
(see Figure 5H-1), mm H2O (in. H2O).
La = Maximum acceptable leakage rate for either a post-test 
leak-check or for a leak-check following a component change; equal to 
0.00057 cmm (0.020 cfm) or 4 percent of the average sampling rate, 
whichever is less.
L1 = Individual leakage rate observed during the leak-check 
conducted before a component change, cmm (cfm).
Lp = Leakage rate observed during the post-test leak-check, 
cmm (cfm).
mn = Total amount of particulate matter collected, mg.
Ma = Mass of residue of solvent after evaporation, mg.
NC = Grams of carbon/gram of dry fuel (lb/lb), equal to 
0.0425.
NT = Total dry moles of exhaust gas/kg of dry wood burned, 
g-moles/kg (lb-moles/lb).
PR = Percent of proportional sampling rate.
Pbar = Barometric pressure at the sampling site, mm Hg 
(in.Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in.Hg).
Qsd = Total gas flow rate, dscm/hr (dscf/hr).
S1 = Concentration measured at the SO2 analyzer 
for the first 10-minute interval, ppm.
Si = Concentration measured at the SO2 analyzer 
for the ``ith'' 10 minute interval, ppm.
Tm = Absolute average dry gas meter temperature (see Figure 
5H-3),  deg.K ( deg.R).
Tstd = Standard absolute temperature, 293  deg.K (528 
deg.R).
Va = volume of solvent blank, ml.
Vaw = Volume of solvent used in wash, ml.
Vlc = Total volume of liquid collected in impingers and 
silica gel (see Figure 5H-4), ml.
Vm = Volume of gas sample as measured by dry gas meter, dcm 
(dcf).
Vm(std) = Volume of gas sample measured by the dry gas 
meter, corrected to standard conditions, dscm (dscf).
Vmi(std) = Volume of gas sample measured by the dry gas 
meter during the ``ith'' 10-minute interval, dscm (dscf).
Vw(std) = Volume of water vapor in the gas sample, corrected 
to standard conditions, scm (scf).
Wa = Weight of residue in solvent wash, mg.
Y = Dry gas meter calibration factor.
YCO = Measured mole fraction of CO (dry), average from 
Section 8.2, g/g-mole (lb/lb-mole).
YCO2 = Measured mole fraction of CO2 (dry), 
average from Section 8.2, g/g-mole (lb/lb-mole).
YHC = Assumed mole fraction of HC (dry), g/g-mole (lb/lb-
mole); = 0.0088 for catalytic wood heaters; = 0.0132 for non-catalytic 
wood heaters; = 0.0080 for pellet-fired wood heaters.
10 = Length of first sampling period, min.
13.6 = Specific gravity of mercury.
100 = Conversion to percent.
 = Total sampling time, min.
1 = Sampling time interval, from the beginning of 
a run until the first component change, min.
    12.2  Average Dry Gas Meter Temperature and Average Orifice 
Pressure Drop. See data sheet (Figure 5H-3).
    12.3  Dry Gas Volume. Same as Method 5, Section 12.3.
    12.4  Volume of Water Vapor.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.168
    
Where:

K2 = 0.001333 m3/ml for metric units.
K2 = 0.04707 ft3/ml for English units.

    12.5  Moisture Content.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.169
    
    12.6  Solvent Wash Blank.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.170
    
    12.7  Total Particulate Weight. Determine the total particulate 
catch from the sum of the weights obtained from containers 1, 2, 3, and 
4 less the appropriate solvent blanks (see Figure 5H-4).


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

    12.8  Particulate Concentration.

    [GRAPHIC] [TIFF OMITTED] TR17OC00.171
    
    12.9  Sample Flow Rate Adjustment.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.172
    
    12.10  Carbon Balance for Total Moles of Exhaust Gas (dry)/kg of 
Wood Burned in the Exhaust Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.173

Where:

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

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


    12.11  Total Stack Gas Flow Rate.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.174
    
Where:
K4 = 0.02406 dscm/g-mole for metric units.
K4 = 384.8 dscf/lb-mole for English units.
    12.12  Particulate Emission Rate.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.175
    

[[Page 61881]]


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

    12.14  Acceptable Results. If no more than 15 percent of the PR 
values for all the intervals fall outside the range 90 percent 
 PR  110 percent, and if no PR value for any 
interval falls outside the range 75  PR  125 
percent, the results are acceptable. If the PR values for the test runs 
are judged to be unacceptable, report the test run emission results, 
but do not include the test run results in calculating the weighted 
average emission rate, and repeat the test.

13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    Same as Method 5G, Section 17.0.
BILLING CODE 6560-50-P

[[Page 61882]]

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


[[Page 61883]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.178


[[Page 61884]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.179


[[Page 61885]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.180


[[Page 61886]]



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

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

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
              Analyte                   CAS No.          Sensitivity
------------------------------------------------------------------------
SO2...............................       7449-09-5  3.4 mg SO2/m3
                                                    (2.12  x  10)-7 lb/
                                                     ft3
------------------------------------------------------------------------

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

2.  0  Summary of Method

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

3.0  Definitions. [Reserved]

4.0  Interferences

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

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user to establish appropriate safety and health practices and 
determine the applicability of regulatory limitations before performing 
this test method.
    5.2  Corrosive reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water for at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burns as thermal 
burns.
    5.2.1  Hydrogen Peroxide (H2O2). Irritating 
to eyes, skin, nose, and lungs. 30% H2O2 is a 
strong oxidizing agent. Avoid contact with skin, eyes, and combustible 
material. Wear gloves when handling.
    5.2.2  Sodium Hydroxide (NaOH). Causes severe damage to eyes and 
skin. Inhalation causes irritation to nose, throat, and lungs. Reacts 
exothermically with limited amounts of water.
    5.2.3  Sulfuric Acid (H2SO4). Rapidly 
destructive to body tissue. Will cause third degree burns. Eye damage 
may result in blindness. Inhalation may be fatal from spasm of the 
larynx, usually within 30 minutes. May cause lung tissue damage with 
edema. 1 mg/m3 for 8 hours will cause lung damage or, in 
higher concentrations, death. Provide ventilation to limit inhalation. 
Reacts violently with metals and organics.

6.0  Equipment and Supplies

    6.1  Sample Collection. The following items are required for sample 
collection:
    6.1.1  Sampling Train. A schematic of the sampling train is shown 
in Figure 6-1. The sampling equipment described in Method 8 may be 
substituted in place of the midget impinger equipment of Method 6. 
However, the Method 8 train must be modified to include a heated filter 
between the probe and isopropanol impinger, and the operation of the 
sampling train and sample analysis must be at the flow rates and 
solution volumes defined in Method 8. Alternatively, SO2 may 
be determined simultaneously with particulate matter and moisture 
determinations by either (1) replacing the water in a Method 5 impinger 
system with a 3 percent H2O2 solution, or (2) 
replacing the Method 5 water impinger system with a Method 8 
isopropanol-filter-H2O2 system. The analysis for 
SO2 must be consistent with the procedure of Method 8. The 
Method 6 sampling train consists of the following components:
    6.1.1.1  Probe. Borosilicate glass or stainless steel (other 
materials of construction may be used, subject to the approval of the 
Administrator), approximately 6 mm (0.25 in.) inside diameter, with a 
heating system to prevent water condensation and a filter (either in-
stack or heated out-of-stack) to remove particulate matter, including 
sulfuric acid mist. A plug of glass wool is a satisfactory filter.
    6.1.1.2  Bubbler and Impingers. One midget bubbler with medium-
coarse glass frit and borosilicate or quartz glass wool packed in top 
(see Figure 6-1) to prevent sulfuric acid mist carryover, and three 30-
ml midget impingers. The midget bubbler and midget impingers must be 
connected in series with leak-free glass connectors. Silicone grease 
may be used, if necessary, to prevent leakage. A midget impinger may be 
used in place of the midget bubbler.


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

    6.1.1.3  Glass Wool. Borosilicate or quartz.
    6.1.1.4  Stopcock Grease. Acetone-insoluble, heat-stable silicone 
grease may be used, if necessary.
    6.1.1.5  Temperature Sensor. Dial thermometer, or equivalent, to 
measure temperature of gas leaving impinger train to within 1  deg.C (2 
 deg.F).
    6.1.1.6  Drying Tube. Tube packed with 6- to 16- mesh indicating-
type silica gel, or equivalent, to dry the gas sample and to protect 
the meter and pump. If silica gel is previously used, dry at 177  deg.C 
(350  deg.F) for 2 hours. New silica gel may be used as received. 
Alternatively, other types of desiccants

[[Page 61887]]

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

7.0  Reagents and Standards

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


    7.1  Sample Collection. The following reagents are required for 
sample collection:
    7.1.1  Water. Deionized distilled to conform to ASTM Specification 
D 1193-77 or 91 Type 3 (incorporated by reference--see Sec. 60.17). The 
KMnO4 test for oxidizable organic matter may be omitted when 
high concentrations of organic matter are not expected to be present.
    7.1.2  Isopropanol, 80 Percent by Volume. Mix 80 ml of isopropanol 
with 20 ml of water.
    7.1.2.1  Check each lot of isopropanol for peroxide impurities as 
follows: Shake 10 ml of isopropanol with 10 ml of freshly prepared 10 
percent potassium iodide solution. Prepare a blank by similarly 
treating 10 ml of water. After 1 minute, read the absorbance at 352 nm 
on a spectrophotometer using a 1-cm path length. If absorbance exceeds 
0.1, reject alcohol for use.
    7.1.2.2  Peroxides may be removed from isopropanol by redistilling 
or by passage through a column of activated alumina; however, reagent 
grade isopropanol with suitably low peroxide levels may be obtained 
from commercial sources. Rejection of contaminated lots may, therefore, 
be a more efficient procedure.
    7.1.3  Hydrogen Peroxide (H2O2), 3 Percent by 
Volume. Add 10 ml of 30 percent H2O2 to 90 ml of 
water. Prepare fresh daily.
    7.1.4  Potassium Iodide Solution, 10 Percent Weight by Volume (w/
v). Dissolve 10.0 g of KI in water, and dilute to 100 ml. Prepare when 
needed.
    7.2  Sample Recovery. The following reagents are required for 
sample recovery:
    7.2.1  Water. Same as in Section 7.1.1.
    7.2.2  Isopropanol, 80 Percent by Volume. Same as in Section 7.1.2.
    7.3  Sample Analysis. The following reagents and standards are 
required for sample analysis:
    7.3.1  Water. Same as in Section 7.1.1.
    7.3.2  Isopropanol, 100 Percent.
    7.3.3  Thorin Indicator. 1-(o-arsonophenylazo)-2-naphthol-3,6-
disulfonic acid, disodium salt, or equivalent. Dissolve 0.20 g in 100 
ml of water.
    7.3.4  Barium Standard Solution, 0.0100 N. Dissolve 1.95 g of 
barium perchlorate trihydrate [Ba(ClO4)2 
3H2O] in 200 ml water, and dilute to 1 liter with 
isopropanol. Alternatively, 1.22 g of barium chloride dihydrate 
[BaCl2 2H2O] may be used instead of the barium 
perchlorate trihydrate. Standardize as in Section 10.5.
    7.3.5  Sulfuric Acid Standard, 0.0100 N. Purchase or standardize to 
0.0002 N against 0.0100 N NaOH which has previously been 
standardized against potassium acid phthalate (primary standard grade).
    7.3.6  Quality Assurance Audit Samples. When making compliance 
determinations, audit samples, if available must be obtained from the 
appropriate EPA Regional Office or from the responsible enforcement 
authority and analyzed in conjunction with the field samples.


    Note: The responsible enforcement authority should be notified 
at least 30 days prior to the test date to allow sufficient time for 
sample delivery.

8.0  Sample Collection, Preservation, Storage and Transport

    8.1  Preparation of Sampling Train. Measure 15 ml of 80 percent 
isopropanol into the midget bubbler and 15 ml of 3 percent 
H2O2 into each of the first two midget impingers. 
Leave the final midget impinger dry. Assemble the train as shown in 
Figure 6-1. Adjust the probe heater to a temperature sufficient to 
prevent water condensation. Place crushed ice and water around the 
impingers.
    8.2  Sampling Train Leak-Check Procedure. A leak-check prior to the 
sampling run is recommended, but not required. A leak-check after the 
sampling run is mandatory. The leak-check procedure is as follows:
    8.2.1  Temporarily attach a suitable (e.g., 0- to 40- ml/min) 
rotameter to the outlet of the DGM, and place a vacuum gauge at or near 
the probe inlet. Plug the probe inlet, pull a vacuum of at least 250 mm 
Hg (10 in. Hg), and note the flow rate as indicated by the rotameter. A 
leakage rate in excess of 2 percent of the average sampling rate is not 
acceptable.


    Note: Carefully (i.e., slowly) release the probe inlet plug 
before turning off the pump.


    8.2.2  It is suggested (not mandatory) that the pump be leak-
checked separately, either prior to or after the sampling run. To leak-
check the pump, proceed as follows: Disconnect the drying tube from the 
probe-impinger assembly. Place a vacuum gauge at the inlet to either 
the drying tube or the pump, pull a vacuum of 250 mm Hg (10 in. Hg), 
plug or pinch off the outlet of the flow meter, and then turn off the 
pump. The vacuum should remain stable for at least 30 seconds.

[[Page 61888]]

    If performed prior to the sampling run, the pump leak-check shall 
precede the leak-check of the sampling train described immediately 
above; if performed after the sampling run, the pump leak-check shall 
follow the sampling train leak-check.
    8.2.3  Other leak-check procedures may be used, subject to the 
approval of the Administrator.
    8.3  Sample Collection.
    8.3.1  Record the initial DGM reading and barometric pressure. To 
begin sampling, position the tip of the probe at the sampling point, 
connect the probe to the bubbler, and start the pump. Adjust the sample 
flow to a constant rate of approximately 1.0 liter/min as indicated by 
the rate meter. Maintain this constant rate ( 10 percent) 
during the entire sampling run.
    8.3.2  Take readings (DGM volume, temperatures at DGM and at 
impinger outlet, and rate meter flow rate) at least every 5 minutes. 
Add more ice during the run to keep the temperature of the gases 
leaving the last impinger at 20 deg.C (68  deg.F) or less.
    8.3.3  At the conclusion of each run, turn off the pump, remove the 
probe from the stack, and record the final readings. Conduct a leak-
check as described in Section 8.2. (This leak-check is mandatory.) If a 
leak is detected, void the test run or use procedures acceptable to the 
Administrator to adjust the sample volume for the leakage.
    8.3.4  Drain the ice bath, and purge the remaining part of the 
train by drawing clean ambient air through the system for 15 minutes at 
the sampling rate. Clean ambient air can be provided by passing air 
through a charcoal filter or through an extra midget impinger 
containing 15 ml of 3 percent H2O2. 
Alternatively, ambient air without purification may be used.
    8.4  Sample Recovery. Disconnect the impingers after purging. 
Discard the contents of the midget bubbler. Pour the contents of the 
midget impingers into a leak-free polyethylene bottle for shipment. 
Rinse the three midget impingers and the connecting tubes with water, 
and add the rinse to the same storage container. Mark the fluid level. 
Seal and identify the sample container.

9.0  Quality Control

------------------------------------------------------------------------
                             Quality control
         Section                 measure                 Effect
------------------------------------------------------------------------
7.1.2....................  Isopropanol check..  Ensure acceptable level
                                                 of peroxide impurities
                                                 in isopropanol.
8.2, 10.1-10.4...........  Sampling equipment   Ensure accurate
                            leak-check and       measurement of stack
                            calibration.         gas flow rate, sample
                                                 volume.
10.5.....................  Barium standard      Ensure precision of
                            solution             normality
                            standardization.     determination.
11.2.3...................  Replicate            Ensure precision of
                            titrations.          titration
                                                 determinations
11.3.....................  Audit sample         Evaluate analyst's
                            analysis.            technique and standards
                                                 preparation.
------------------------------------------------------------------------

10.0  Calibration and Standardization

    10.1  Volume Metering System.
    10.1.1  Initial Calibration.
    10.1.1.1  Before its initial use in the field, leak-check the 
metering system (drying tube, needle valve, pump, rate meter, and DGM) 
as follows: Place a vacuum gauge at the inlet to the drying tube and 
pull a vacuum of 250 mm Hg (10 in. Hg). Plug or pinch off the outlet of 
the flow meter, and then turn off the pump. The vacuum must remain 
stable for at least 30 seconds. Carefully release the vacuum gauge 
before releasing the flow meter end.
    10.1.1.2  Remove the drying tube, and calibrate the metering system 
(at the sampling flow rate specified by the method) as follows: Connect 
an appropriately sized wet-test meter (e.g., 1 liter per revolution) to 
the inlet of the needle valve. Make three independent calibration runs, 
using at least five revolutions of the DGM per run. Calculate the 
calibration factor Y (wet-test meter calibration volume divided by the 
DGM volume, both volumes adjusted to the same reference temperature and 
pressure) for each run, and average the results (Yi). If any 
Y-value deviates by more than 2 percent from (Yi), the 
metering system is unacceptable for use. If the metering system is 
acceptable, use (Yi) as the calibration factor for 
subsequent test runs.
    10.1.2  Post-Test Calibration Check. After each field test series, 
conduct a calibration check using the procedures outlined in Section 
10.1.1.2, except that three or more revolutions of the DGM may be used, 
and only two independent runs need be made. If the average of the two 
post-test calibration factors does not deviate by more than 5 percent 
from Yi, then Yi is accepted as the DGM 
calibration factor (Y), which is used in Equation 6-1 to calculate 
collected sample volume (see Section 12.2). If the deviation is more 
than 5 percent, recalibrate the metering system as in Section 10.1.1, 
and determine a post-test calibration factor (Yf). Compare 
Yi and Yf; the smaller of the two factors is 
accepted as the DGM calibration factor. If recalibration indicates that 
the metering system is unacceptable for use, either void the test run 
or use methods, subject to the approval of the Administrator, to 
determine an acceptable value for the collected sample volume.
    10.1.3  DGM as a Calibration Standard. A DGM may be used as a 
calibration standard for volume measurements in place of the wet-test 
meter specified in Section 10.1.1.2, provided that it is calibrated 
initially and recalibrated periodically according to the same 
procedures outlined in Method 5, Section 10.3 with the following 
exceptions: (a) the DGM is calibrated against a wet-test meter having a 
capacity of 1 liter/rev (0.035 ft3/rev) or 3 liters/rev (0.1 
ft3/rev) and having the capability of measuring volume to 
within 1 percent; (b) the DGM is calibrated at 1 liter/min (0.035 cfm); 
and (c) the meter box of the Method 6 sampling train is calibrated at 
the same flow rate.
    10.2  Temperature Sensors. Calibrate against mercury-in-glass 
thermometers.
    10.3  Rate Meter. The rate meter need not be calibrated, but should 
be cleaned and maintained according to the manufacturer's instructions.
    10.4  Barometer. Calibrate against a mercury barometer.
    10.5  Barium Standard Solution. Standardize the barium perchlorate 
or chloride solution against 25 ml of standard sulfuric acid to which 
100 ml of 100 percent isopropanol has been added. Run duplicate 
analyses. Calculate the normality using the average of duplicate 
analyses where the titrations agree within 1 percent or 0.2 ml, 
whichever is larger.

11.0  Analytical Procedure

    11.1  Sample Loss Check. Note level of liquid in container and 
confirm whether any sample was lost during shipment; note this finding 
on the analytical data sheet. If a noticeable amount of leakage has 
occurred, either void the sample or use methods, subject to the 
approval of the Administrator, to correct the final results.
    11.2  Sample Analysis.
    11.2.1  Transfer the contents of the storage container to a 100-ml 
volumetric flask, dilute to exactly 100 ml with water, and mix the 
diluted sample.

[[Page 61889]]

    11.2.2  Pipette a 20-ml aliquot of the diluted sample into a 250-ml 
Erlenmeyer flask and add 80 ml of 100 percent isopropanol plus two to 
four drops of thorin indicator. While stirring the solution, titrate to 
a pink endpoint using 0.0100 N barium standard solution.
    11.2.3  Repeat the procedures in Section 11.2.2, and average the 
titration volumes. Run a blank with each series of samples. Replicate 
titrations must agree within 1 percent or 0.2 ml, whichever is larger.


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


    11.3  Audit Sample Analysis.
    11.3.1  When the method is used to analyze samples to demonstrate 
compliance with a source emission regulation, an audit sample, if 
available, must be analyzed.
    11.3.2  Concurrently analyze the audit sample and the compliance 
samples in the same manner to evaluate the technique of the analyst and 
the standards preparation.
    11.3.3  The same analyst, analytical reagents, and analytical 
system must be used for the compliance samples and the audit sample. If 
this condition is met, duplicate auditing of subsequent compliance 
analyses for the same enforcement agency within a 30-day period is 
waived. An audit sample set may not be used to validate different sets 
of compliance samples under the jurisdiction of separate enforcement 
agencies, unless prior arrangements have been made with both 
enforcement agencies.
    11.4  Audit Sample Results.
    11.4.1  Calculate the audit sample concentrations and submit 
results using the instructions provided with the audit samples.
    11.4.2  Report the results of the audit samples and the compliance 
determination samples along with their identification numbers, and the 
analyst's name to the responsible enforcement authority. Include this 
information with reports of any subsequent compliance analyses for the 
same enforcement authority during the 30-day period.
    11.4.3  The concentrations of the audit samples obtained by the 
analyst must agree within 5 percent of the actual concentration. If the 
5 percent specification is not met, reanalyze the compliance and audit 
samples, and include initial and reanalysis values in the test report.
    11.4.4  Failure to meet the 5-percent specification may require 
retests until the audit problems are resolved. However, if the audit 
results do not affect the compliance or noncompliance status of the 
affected facility, the Administrator may waive the reanalysis 
requirement, further audits, or retests and accept the results of the 
compliance test. While steps are being taken to resolve audit analysis 
problems, the Administrator may also choose to use the data to 
determine the compliance or noncompliance status of the affected 
facility.

12.0  Data Analysis and Calculations

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

Ca = Actual concentration of SO2 in audit sample, 
mg/dscm.
Cd = Determined concentration of SO2 in audit 
sample, mg/dscm.
CSO2 = Concentration of SO2, dry basis, corrected 
to standard conditions, mg/dscm (lb/dscf).
N = Normality of barium standard titrant, meq/ml.
Pbar = Barometric pressure, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
RE = Relative error of QA audit sample analysis, percent
Tm = Average DGM absolute temperature,  deg.K ( deg.R).
Tstd = Standard absolute temperature, 293  deg.K (528 
deg.R).
Va = Volume of sample aliquot titrated, ml.
Vm = Dry gas volume as measured by the DGM, dcm (dcf).
Vm(std) = Dry gas volume measured by the DGM, corrected to 
standard conditions, dscm (dscf).
Vsoln = Total volume of solution in which the SO2 sample is 
contained, 100 ml.
Vt = Volume of barium standard titrant used for the sample 
(average of replicate titration), ml.
Vtb = Volume of barium standard titrant used for the blank, 
ml.
Y = DGM calibration factor.

    12.2  Dry Sample Gas Volume, Corrected to Standard Conditions.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.181
    
Where:

K1 = 0.3855  deg.K/mm Hg for metric units,
K1 = 17.65  deg.R/in. Hg for English units.

    12.3  SO2 Concentration.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.182
    
Where:

K2 = 32.03 mg SO2/meq for metric units,
K2 = 7.061  x  10-5 lb SO2/meq for 
English units.

    12.4  Relative Error for QA Audit Samples.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.183
    
13.0  Method Performance

    13.1  Range. The minimum detectable limit of the method has been 
determined to be 3.4 mg SO2/m3 (2.12  x  
10-7 lb/ft3). Although no upper limit has been 
established, tests have shown that concentrations as high as 80,000 mg/
m3 (0.005 lb/ft3) of SO2 can be 
collected efficiently at a rate of 1.0 liter/min (0.035 cfm) for 20 
minutes in two midget impingers, each containing 15 ml of 3 percent 
H2O2. Based on theoretical calculations, the 
upper concentration limit in a 20 liter (0.7 ft3) sample is 
about 93,300 mg/m3 (0.00583 lb/ft3).

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  Alternative Procedures

    16.1  Nomenclature. Same as Section 12.1, with the following 
additions:

Bwa = Water vapor in ambient air, proportion by volume.
Ma = Molecular weight of the ambient air saturated at 
impinger temperature, g/g-mole (lb/lb-mole).
Ms = Molecular weight of the sample gas saturated at 
impinger temperature, g/g-mole (lb/lb-mole).

[[Page 61890]]

Pc = Inlet vacuum reading obtained during the calibration 
run, mm Hg (in. Hg).
Psr = Inlet vacuum reading obtained during the sampling run, 
mm Hg (in. Hg).
Qstd = Volumetric flow rate through critical orifice, scm/
min (scf/min).
Qstd = Average flow rate of pre-test and post-test 
calibration runs, scm/min (scf/min).
Tamb = Ambient absolute temperature of air,  deg.K ( deg.R).
Vsb = Volume of gas as measured by the soap bubble meter, 
m\3\ (ft\3\).

    Vsb(std) = Volume of gas as measured by the soap bubble 
meter, corrected to standard conditions, scm (scf).
 = Soap bubble travel time, min.
s = Time, min.

    16.2  Critical Orifices for Volume and Rate Measurements. A 
critical orifice may be used in place of the DGM specified in Section 
6.1.1.10, provided that it is selected, calibrated, and used as 
follows:
    16.2.1  Preparation of Sampling Train. Assemble the sampling train 
as shown in Figure 6-2. The rate meter and surge tank are optional but 
are recommended in order to detect changes in the flow rate.


    Note: The critical orifices can be adapted to a Method 6 type 
sampling train as follows: Insert sleeve type, serum bottle stoppers 
into two reducing unions. Insert the needle into the stoppers as 
shown in Figure 6-3.

    16.2.2  Selection of Critical Orifices.
    16.2.2.1  The procedure that follows describes the use of 
hypodermic needles and stainless steel needle tubings, which have been 
found suitable for use as critical orifices. Other materials and 
critical orifice designs may be used provided the orifices act as true 
critical orifices, (i.e., a critical vacuum can be obtained) as 
described in this section. Select a critical orifice that is sized to 
operate at the desired flow rate. The needle sizes and tubing lengths 
shown in Table 6-1 give the following approximate flow rates.
    16.2.2.2  Determine the suitability and the appropriate operating 
vacuum of the critical orifice as follows: If applicable, temporarily 
attach a rate meter and surge tank to the outlet of the sampling train, 
if said equipment is not present (see Section 16.2.1). Turn on the pump 
and adjust the valve to give an outlet vacuum reading corresponding to 
about half of the atmospheric pressure. Observe the rate meter reading. 
Slowly increase the vacuum until a stable reading is obtained on the 
rate meter. Record the critical vacuum, which is the outlet vacuum when 
the rate meter first reaches a stable value. Orifices that do not reach 
a critical value must not be used.
    16.2.3  Field Procedures.
    16.2.3.1  Leak-Check Procedure. A leak-check before the sampling 
run is recommended, but not required. The leak-check procedure is as 
follows: Temporarily attach a suitable (e.g., 0-40 ml/min) rotameter 
and surge tank, or a soap bubble meter and surge tank to the outlet of 
the pump. Plug the probe inlet, pull an outlet vacuum of at least 250 
mm Hg (10 in. Hg), and note the flow rate as indicated by the rotameter 
or bubble meter. A leakage rate in excess of 2 percent of the average 
sampling rate (Qstd) is not acceptable. Carefully release 
the probe inlet plug before turning off the pump.
    16.2.3.2  Moisture Determination. At the sampling location, prior 
to testing, determine the percent moisture of the ambient air using the 
wet and dry bulb temperatures or, if appropriate, a relative humidity 
meter.
    16.2.3.3  Critical Orifice Calibration. At the sampling location, 
prior to testing, calibrate the entire sampling train (i.e., determine 
the flow rate of the sampling train when operated at critical 
conditions). Attach a 500-ml soap bubble meter to the inlet of the 
probe, and operate the sampling train at an outlet vacuum of 25 to 50 
mm Hg (1 to 2 in. Hg) above the critical vacuum. Record the information 
listed in Figure 6-4. Calculate the standard volume of air measured by 
the soap bubble meter and the volumetric flow rate using the equations 
below:
[GRAPHIC] [TIFF OMITTED] TR17OC00.184

[GRAPHIC] [TIFF OMITTED] TR17OC00.185

    16.2.3.4  Sampling.
    16.2.3.4.1  Operate the sampling train for sample collection at the 
same vacuum used during the calibration run. Start the watch and pump 
simultaneously. Take readings (temperature, rate meter, inlet vacuum, 
and outlet vacuum) at least every 5 minutes. At the end of the sampling 
run, stop the watch and pump simultaneously.
    16.2.3.4.2  Conduct a post-test calibration run using the 
calibration procedure outlined in Section 16.2.3.3. If the 
Qstd obtained before and after the test differ by more than 
5 percent, void the test run; if not, calculate the volume of the gas 
measured with the critical orifice using Equation 6-6 as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.186

    16.2.3.4.3  If the percent difference between the molecular weight 
of the ambient air at saturated conditions and the sample gas is more 
that  3 percent, then the molecular weight of the gas 
sample must be considered in the calculations using the following 
equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.187


    Note: A post-test leak-check is not necessary because the post-
test calibration run results will indicate whether there is any 
leakage.

    16.2.3.4.4  Drain the ice bath, and purge the sampling train using 
the procedure described in Section 8.3.4.
    16.3  Elimination of Ammonia Interference. The following 
alternative procedures must be used in addition to those specified in 
the method when

[[Page 61891]]

sampling at sources having ammonia emissions.
    16.3.1  Sampling. The probe shall be maintained at 275  deg.C (527 
deg.F) and equipped with a high-efficiency in-stack filter (glass 
fiber) to remove particulate matter. The filter material shall be 
unreactive to SO2. Whatman 934AH (formerly Reeve Angel 
934AH) filters treated as described in Reference 10 in Section 17.0 of 
Method 5 is an example of a filter that has been shown to work. Where 
alkaline particulate matter and condensed moisture are present in the 
gas stream, the filter shall be heated above the moisture dew point but 
below 225  deg.C (437  deg.F).
    16.3.2  Sample Recovery. Recover the sample according to Section 
8.4 except for discarding the contents of the midget bubbler. Add the 
bubbler contents, including the rinsings of the bubbler with water, to 
a separate polyethylene bottle from the rest of the sample. Under 
normal testing conditions where sulfur trioxide will not be present 
significantly, the tester may opt to delete the midget bubbler from the 
sampling train. If an approximation of the sulfur trioxide 
concentration is desired, transfer the contents of the midget bubbler 
to a separate polyethylene bottle.
    16.3.3  Sample Analysis. Follow the procedures in Sections 11.1 and 
11.2, except add 0.5 ml of 0.1 N HCl to the Erlenmeyer flask and mix 
before adding the indicator. The following analysis procedure may be 
used for an approximation of the sulfur trioxide concentration. The 
accuracy of the calculated concentration will depend upon the ammonia 
to SO2 ratio and the level of oxygen present in the gas 
stream. A fraction of the SO2 will be counted as sulfur 
trioxide as the ammonia to SO2 ratio and the sample oxygen 
content increases. Generally, when this ratio is 1 or less and the 
oxygen content is in the range of 5 percent, less than 10 percent of 
the SO2 will be counted as sulfur trioxide. Analyze the 
peroxide and isopropanol sample portions separately. Analyze the 
peroxide portion as described above. Sulfur trioxide is determined by 
difference using sequential titration of the isopropanol portion of the 
sample. Transfer the contents of the isopropanol storage container to a 
100-ml volumetric flask, and dilute to exactly 100 ml with water. 
Pipette a 20-ml aliquot of this solution into a 250-ml Erlenmeyer 
flask, add 0.5 ml of 0.1 N HCl, 80 ml of 100 percent isopropanol, and 
two to four drops of thorin indicator. Titrate to a pink endpoint using 
0.0100 N barium perchlorate. Repeat and average the titration volumes 
that agree within 1 percent or 0.2 ml, whichever is larger. Use this 
volume in Equation 6-2 to determine the sulfur trioxide concentration. 
From the flask containing the remainder of the isopropanol sample, 
determine the fraction of SO2 collected in the bubbler by 
pipetting 20-ml aliquots into 250-ml Erlenmeyer flasks. Add 5 ml of 3 
percent H2O2, 100 ml of 100 percent isopropanol, 
and two to four drips of thorin indicator, and titrate as before. From 
this titration volume, subtract the titrant volume determined for 
sulfur trioxide, and add the titrant volume determined for the peroxide 
portion. This final volume constitutes Vt, the volume of 
barium perchlorate used for the SO2 sample.

17.0  References

    1. Atmospheric Emissions from Sulfuric Acid Manufacturing 
Processes. U.S. DHEW, PHS, Division of Air Pollution. Public Health 
Service Publication No. 999-AP-13. Cincinnati, OH. 1965.
    2. Corbett, P.F. The Determination of SO2 and 
SO3 in Flue Gases. Journal of the Institute of Fuel. 
24:237-243. 1961.
    3. Matty, R.E., and E.K. Diehl. Measuring Flue-Gas 
SO2 and SO3. Power. 101:94-97. November 1957.
    4. Patton, W.F., and J.A. Brink, Jr. New Equipment and 
Techniques for Sampling Chemical Process Gases. J. Air Pollution 
Control Association. 13:162. 1963.
    5. Rom, J.J. Maintenance, Calibration, and Operation of 
Isokinetic Source Sampling Equipment. Office of Air Programs, U.S. 
Environmental Protection Agency. Research Triangle Park, NC. APTD-
0576. March 1972.
    6. Hamil, H.F., and D.E. Camann. Collaborative Study of Method 
for the Determination of Sulfur Dioxide Emissions from Stationary 
Sources (Fossil-Fuel Fired Steam Generators). U.S. Environmental 
Protection Agency, Research Triangle Park, NC. EPA-650/4-74-024. 
December 1973.
    7. Annual Book of ASTM Standards. Part 31; Water, Atmospheric 
Analysis. American Society for Testing and Materials. Philadelphia, 
PA. 1974. pp. 40-42.
    8. Knoll, J.E., and M.R. Midgett. The Application of EPA Method 
6 to High Sulfur Dioxide Concentrations. U.S. Environmental 
Protection Agency. Research Triangle Park, NC. EPA-600/4-76-038. 
July 1976.
    9. Westlin, P.R., and R.T. Shigehara. Procedure for Calibrating 
and Using Dry Gas Volume Meters as Calibration Standards. Source 
Evaluation Society Newsletter. 3(1):17-30. February 1978.
    10. Yu, K.K. Evaluation of Moisture Effect on Dry Gas Meter 
Calibration. Source Evaluation Society Newsletter. 5(1):24-28. 
February 1980.
    11. Lodge, J.P., Jr., et al. The Use of Hypodermic Needles as 
Critical Orifices in Air Sampling. J. Air Pollution Control 
Association. 16:197-200. 1966.
    12. Shigehara, R.T., and C.B. Sorrell. Using Critical Orifices 
as Method 5 CalibrationStandards. Source Evaluation Society 
Newsletter. 10:4-15. August 1985.
    13. Curtis, F., Analysis of Method 6 Samples in the Presence of 
Ammonia. Source Evaluation Society Newsletter. 13(1):9-15 February 
1988.

18.0  Tables, Diagrams, Flowcharts and Validation Data

       Table 6-1.--Approximate Flow Rates for Various Needle Sizes
------------------------------------------------------------------------
                                                   Needle
             Needle size  (gauge)                  length     Flow rate
                                                    (cm)       (ml/min)
------------------------------------------------------------------------
21............................................          7.6        1,100
22............................................          2.9        1,000
22............................................          3.8          900
23............................................          3.8          500
23............................................          5.1          450
24............................................          3.2          400
------------------------------------------------------------------------

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[[Page 61896]]

Method 6A--Determination of Sulfur Dioxide, Moisture, and Carbon 
Dioxide From Fossil Fuel Combustion Sources

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in this part. 
Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of at least the following 
additional test methods: Method 1, Method 2, Method 3, Method 5, 
Method 6, and Method 19.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
              Analyte                   CAS No.          Sensitivity
------------------------------------------------------------------------
SO2...............................      7449-09-05  3.4 mg SO2/m3
                                                    (2.12  x  10-7 lb/
                                                     ft3)
CO2...............................        124-38-9  N/A
H2O...............................       7732-18-5  N/A
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of sulfur dioxide (SO2) emissions from fossil fuel 
combustion sources in terms of concentration (mg/dscm or lb/dscf) and 
in terms of emission rate (ng/J or lb/106 Btu) and for the 
determination of carbon dioxide (CO2) concentration 
(percent). Moisture content (percent), if desired, may also be 
determined by this method.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  A gas sample is extracted from a sampling point in the stack. 
The SO2 and the sulfur trioxide, including those fractions 
in any sulfur acid mist, are separated. The SO2 fraction is 
measured by the barium-thorin titration method. Moisture and 
CO2 fractions are collected in the same sampling train, and 
are determined gravimetrically.

3.0  Definitions. [Reserved]

4.0  Interferences

    Same as Method 6, Section 4.0.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user to establish appropriate safety and health practices and 
determine the applicability of regulatory limitations prior to 
performing this test method.
    5.2  Corrosive reagents. Same as Method 6, Section 5.2.

6.0  Equipment and Supplies

    6.1  Sample Collection. Same as Method 6, Section 6.1, with the 
exception of the following:
    6.1.1  Sampling Train. A schematic of the sampling train used in 
this method is shown in Figure 6A-1.
    6.1.1.1  Impingers and Bubblers. Two 30=ml midget impingers with a 
1=mm restricted tip and two 30=ml midget bubblers with unrestricted 
tips. Other types of impingers and bubblers (e.g., Mae West for 
SO2 collection and rigid cylinders containing Drierite for 
moisture absorbers), may be used with proper attention to reagent 
volumes and levels, subject to the approval of the Administrator.
    6.1.1.2  CO2 Absorber. A sealable rigid cylinder or 
bottle with an inside diameter between 30 and 90 mm , a length between 
125 and 250 mm, and appropriate connections at both ends. The filter 
may be a separate heated unit or may be within the heated portion of 
the probe. If the filter is within the sampling probe, the filter 
should not be within 15 cm of the probe inlet or any unheated section 
of the probe, such as the connection to the first bubbler. The probe 
and filter should be heated to at least 20  deg.C (68  deg.F) above the 
source temperature, but not greater than 120  deg.C (248  deg.F). The 
filter temperature (i.e., the sample gas temperature) should be 
monitored to assure the desired temperature is maintained. A heated 
Teflon connector may be used to connect the filter holder or probe to 
the first impinger.


    Note: For applications downstream of wet scrubbers, a heated 
out-of-stack filter (either borosilicate glass wool or glass fiber 
mat) is necessary.


    6.2  Sample Recovery. Same as Method 6, Section 6.2.
    6.3  Sample Analysis. Same as Method 6, Section 6.3, with the 
addition of a balance to measure within 0.05 g.

7.0  Reagents and Standards

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


    7.1  Sample Collection. Same as Method 6, Section 7.1, with the 
addition of the following:
    7.1.1  Drierite. Anhydrous calcium sulfate (CaSO4) 
desiccant, 8 mesh, indicating type is recommended.


    Note: Do not use silica gel or similar desiccant in this 
application.


    7.1.2  CO2 Absorbing Material. Ascarite II. Sodium 
hydroxide-coated silica, 8- to 20-mesh.
    7.2  Sample Recovery and Analysis. Same as Method 6, Sections 7.2 
and 7.3, respectively.

8.0  Sample Collection, Preservation, Transport, and Storage

    8.1  Preparation of Sampling Train.
    8.1.1  Measure 15 ml of 80 percent isopropanol into the first 
midget bubbler and 15 ml of 3 percent hydrogen peroxide into each of 
the two midget impingers (the second and third vessels in the train) as 
described in Method 6, Section 8.1. Insert the glass wool into the top 
of the isopropanol bubbler as shown in Figure 6A-1. Place about 25 g of 
Drierite into the second midget bubbler (the fourth vessel in the 
train). Clean the outside of the bubblers and impingers and allow the 
vessels to reach room temperature. Weigh the four vessels 
simultaneously to the nearest 0.1 g, and record this initial weight 
(mwi).
    8.1.2  With one end of the CO2 absorber sealed, place 
glass wool into the cylinder to a depth of about 1 cm (0.5 in.). Place 
about 150 g of CO2 absorbing material in the cylinder on top 
of the glass wool, and fill the remaining space in the cylinder with 
glass wool. Assemble the cylinder as shown in Figure 6A-2. With the 
cylinder in a horizontal position, rotate it around the horizontal 
axis. The CO2 absorbing material should remain in position 
during the rotation, and no open spaces or channels should be formed. 
If necessary, pack more glass wool into the cylinder to make the 
CO2 absorbing material stable. Clean the outside of the 
cylinder of loose dirt and moisture and allow the cylinder to reach 
room temperature. Weigh the cylinder to the nearest 0.1 g, and record 
this initial weight (mai).

[[Page 61897]]

    8.1.3  Assemble the train as shown in Figure 6A-1. Adjust the probe 
heater to a temperature sufficient to prevent condensation (see Note in 
Section 6.1). Place crushed ice and water around the impingers and 
bubblers. Mount the CO2 absorber outside the water bath in a 
vertical flow position with the sample gas inlet at the bottom. 
Flexible tubing (e.g., Tygon) may be used to connect the last 
SO2 absorbing impinger to the moisture absorber and to 
connect the moisture absorber to the CO2 absorber. A second, 
smaller CO2 absorber containing Ascarite II may be added in-
line downstream of the primary CO2 absorber as a 
breakthrough indicator. Ascarite II turns white when CO2 is 
absorbed.
    8.2  Sampling Train Leak-Check Procedure and Sample Collection. 
Same as Method 6, Sections 8.2 and 8.3, respectively.
    8.3  Sample Recovery.
    8.3.1  Moisture Measurement. Disconnect the isopropanol bubbler, 
the SO2 impingers, and the moisture absorber from the sample 
train. Allow about 10 minutes for them to reach room temperature, clean 
the outside of loose dirt and moisture, and weigh them simultaneously 
in the same manner as in Section 8.1. Record this final weight 
(mwf).
    8.3.2  Peroxide Solution. Discard the contents of the isopropanol 
bubbler and pour the contents of the midget impingers into a leak-free 
polyethylene bottle for shipping. Rinse the two midget impingers and 
connecting tubes with water, and add the washing to the same storage 
container.
    8.3.3  CO2 Absorber. Allow the CO2 absorber 
to warm to room temperature (about 10 minutes), clean the outside of 
loose dirt and moisture, and weigh to the nearest 0.1 g in the same 
manner as in Section 8.1. Record this final weight (maf). 
Discard used Ascarite II material.

9.0  Quality Control

    Same as Method 6, Section 9.0.

10.0  Calibration and Standardization

    Same as Method 6, Section 10.0.

11.0  Analytical Procedure

    11.1 Sample Analysis. The sample analysis procedure for 
SO2 is the same as that specified in Method 6, Section 11.0.
    11.2  Quality Assurance (QA) Audit Samples. Analysis of QA audit 
samples is required only when this method is used for compliance 
determinations. Obtain an audit sample set as directed in Section 7.3.6 
of Method 6. Analyze the audit samples, and report the results as 
directed in Section 11.3 of Method 6. Acceptance criteria for the audit 
results are the same as those in Method 6.

12.0  Data Analysis and Calculations

    Same as Method 6, Section 12.0, with the addition of the following:
    12.1 Nomenclature.

Cw = Concentration of moisture, percent.
CCO2 = Concentration of CO2, dry basis, percent.
ESO2 = Emission rate of SO2, ng/J (lb/
106 Btu).
FC = Carbon F-factor from Method 19 for the fuel burned, 
dscm/J (dscf/106 Btu).
mwi = Initial weight of impingers, bubblers, and moisture 
absorber, g.
mwf = Final weight of impingers, bubblers, and moisture 
absorber, g.
mai = Initial weight of CO2 absorber, g.
maf = Final weight of CO2 absorber, g.
mSO2 = Mass of SO2 collected, mg.
VCO2(std) = Equivalent volume of CO2 collected at 
standard conditions, dscm (dscf).
Vw(std) = Equivalent volume of moisture collected at 
standard conditions, scm (scf).

    12.2  CO2 Volume Collected, Corrected to Standard 
Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.192

Where:

K3 = Equivalent volume of gaseous CO2 at standard 
conditions, 5.467  x  10-\4\ dscm/g (1.930  x  
10-\2\ dscf/g).

    12.3  Moisture Volume Collected, Corrected to Standard Conditions.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.193
    
Where:

K4 = Equivalent volume of water vapor at standard 
conditions, 1.336  x  10-\3\ scm/g (4.717  x  
10-\2\ scf/g).

    12.4  SO2 Concentration.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.194
    
Where:

K2 = 32.03 mg SO2/meq. SO2 (7.061  x  
10-\5\ lb SO2/meq. SO2)

    12.5  CO2 Concentration.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.195
    
    12.6  Moisture Concentration.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.196
    
13.0  Method Performance

    13.1  Range and Precision. The minimum detectable limit and the 
upper limit for the measurement of SO2 are the same as for 
Method 6. For a 20-liter sample, this method has a precision of 
0.5 percent CO2 for concentrations between 2.5 
and 25 percent CO2 and 1.0 percent moisture for 
moisture concentrations greater than 5 percent.

14.0  Pollution Prevention [Reserved]

15.0  Waste Management. [Reserved]

16.0  Alternative Methods

    If the only emission measurement desired is in terms of emission 
rate of SO2 (ng/J or lb/10\6\ Btu), an abbreviated

[[Page 61898]]

procedure may be used. The differences between the above procedure and 
the abbreviated procedure are described below.
    16.1  Sampling Train. The sampling train is the same as that shown 
in Figure 6A-1 and as described in Section 6.1, except that the dry gas 
meter is not needed.
    16.2  Preparation of the Sampling Train. Follow the same procedure 
as in Section 8.1, except do not weigh the isopropanol bubbler, the 
SO2 absorbing impingers, or the moisture absorber.
    16.3  Sampling Train Leak-Check Procedure and Sample Collection. 
Leak-check and operate the sampling train as described in Section 8.2, 
except that dry gas meter readings, barometric pressure, and dry gas 
meter temperatures need not be recorded during sampling.
    16.4  Sample Recovery. Follow the procedure in Section 8.3, except 
do not weigh the isopropanol bubbler, the SO2 absorbing 
impingers, or the moisture absorber.
    16.5  Sample Analysis. Analysis of the peroxide solution and QA 
audit samples is the same as that described in Sections 11.1 and 11.2, 
respectively.
    16.6  Calculations.
    16.6.1  SO2 Collected.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.197
    
Where:

K2 = 32.03 mg SO2/meq. SO2
K2 = 7.061  x  10-\5\ lb SO2/meq. 
SO2

    16.6.2  Sulfur Dioxide Emission Rate.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.198
    
Where:

K5 = 1.829  x  10\9\ mg/dscm
K2 = 0.1142 lb/dscf

17.0  References

    Same as Method 6, Section 17.0, References 1 through 8, with the 
addition of the following:

    1. Stanley, Jon and P.R. Westlin. An Alternate Method for Stack 
Gas Moisture Determination. Source Evaluation Society Newsletter. 
3(4). November 1978.
    2. Whittle, Richard N. and P.R. Westlin. Air Pollution Test 
Report: Development and Evaluation of an Intermittent Integrated 
SO2/CO2 Emission Sampling Procedure. 
Environmental Protection Agency, Emission Standard and Engineering 
Division, Emission Measurement Branch. Research Triangle Park, NC. 
December 1979. 14 pp.
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[[Page 61899]]

18.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.199


[[Page 61900]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.410

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[[Page 61901]]

Method 6B--Determination of Sulfur Dioxide and Carbon Dioxide Daily 
Average Emissions From Fossil Fuel Combustion Sources

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in this part. 
Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of at least the following 
additional test methods: Method 1, Method 2, Method 3, Method 5, 
Method 6, and Method 6A.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
              Analyte                   CAS No.          Sensitivity
------------------------------------------------------------------------
Sulfur dioxide (SO2)..............      7449-09-05  3.4 mg SO2/m\3\
                                                    (2.12  x  10-\7\ lb/
                                                     ft\3\)
Carbon dioxide (CO2)..............        124-38-9  N/A
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of SO2 emissions from combustion sources in terms of 
concentration (ng/dscm or lb/dscf) and emission rate (ng/J or lb/10\6\ 
Btu), and for the determination of CO2 concentration 
(percent) on a daily (24 hours) basis.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  A gas sample is extracted from the sampling point in the stack 
intermittently over a 24-hour or other specified time period. The 
SO2 fraction is measured by the barium-thorin titration 
method. Moisture and CO2 fractions are collected in the same 
sampling train, and are determined gravimetrically.

3.0  Definitions. [Reserved]

4.0  Interferences

    Same as Method 6, Section 4.0.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user to establish appropriate safety and health practices and 
determine the applicability of regulatory limitations prior to 
performing this test method.
    5.2  Corrosive Reagents. Same as Method 6, Section 5.2.

6.0  Equipment and Supplies

    Same as Method 6A, Section 6.0, with the following exceptions and 
additions:
    6.1  The isopropanol bubbler is not used. An empty bubbler for the 
collection of liquid droplets, that does not allow direct contact 
between the collected liquid and the gas sample, may be included in the 
sampling train.
    6.2  For intermittent operation, include an industrial timer-switch 
designed to operate in the ``on'' position at least 2 minutes 
continuously and ``off'' the remaining period over a repeating cycle. 
The cycle of operation is designated in the applicable regulation. At a 
minimum, the sampling operation should include at least 12, equal, 
evenly-spaced periods per 24 hours.
    6.3  Stainless steel sampling probes, type 316, are not recommended 
for use with Method 6B because of potential sample contamination due to 
corrosion. Glass probes or other types of stainless steel, e.g., 
Hasteloy or Carpenter 20, are recommended for long-term use.

    Note: For applications downstream of wet scrubbers, a heated 
out-of-stack filter (either borosilicate glass wool or glass fiber 
mat) is necessary. Probe and filter heating systems capable of 
maintaining a sample gas temperature of between 20 and 120  deg.C 
(68 and 248  deg.F) at the filter are also required in these cases. 
The electric supply for these heating systems should be continuous 
and separate from the timed operation of the sample pump.

7.0  Reagents and Standards

    Same as Method 6A, Section 7.0, with the following exceptions:
    7.1  Isopropanol is not used for sampling.
    7.2  The hydrogen peroxide absorbing solution shall be diluted to 
no less than 6 percent by volume, instead of 3 percent as specified in 
Methods 6 and 6A.
    7.3  If the Method 6B sampling train is to be operated in a low 
sample flow condition (less than 100 ml/min or 0.21 ft\3\/hr), 
molecular sieve material may be substituted for Ascarite II as the 
CO2 absorbing material. The recommended molecular sieve 
material is Union Carbide \1/16\ inch pellets, 5 A deg., or equivalent. 
Molecular sieve material need not be discarded following the sampling 
run, provided that it is regenerated as per the manufacturer's 
instruction. Use of molecular sieve material at flow rates higher than 
100 ml/min (0.21 ft\3\/hr) may cause erroneous CO2 results.

8.0  Sample Collection, Preservation, Transport, and Storage

    8.1  Preparation of Sampling Train. Same as Method 6A, Section 8.1, 
with the addition of the following:
    8.1.1  The sampling train is assembled as shown in Figure 6A-1 of 
Method 6A, except that the isopropanol bubbler is not included.
    8.1.2  Adjust the timer-switch to operate in the ``on'' position 
from 2 to 4 minutes on a 2-hour repeating cycle or other cycle 
specified in the applicable regulation. Other timer sequences may be 
used with the restriction that the total sample volume collected is 
between 25 and 60 liters (0.9 and 2.1 ft 3) for the amounts 
of sampling reagents prescribed in this method.
    8.1.3  Add cold water to the tank until the impingers and bubblers 
are covered at least two-thirds of their length. The impingers and 
bubbler tank must be covered and protected from intense heat and direct 
sunlight. If freezing conditions exist, the impinger solution and the 
water bath must be protected.


    Note: Sampling may be conducted continuously if a low flow-rate 
sample pump [20 to 40 ml/min (0.04 to 0.08 ft3/hr) for 
the reagent volumes described in this method] is used. If sampling 
is continuous, the timer-switch is not necessary. In addition, if 
the sample pump is designed for constant rate sampling, the rate 
meter may be deleted. The total gas volume collected should be 
between 25 and 60 liters (0.9 and 2.1 ft3) for the 
amounts of sampling reagents prescribed in this method.


    8.2  Sampling Train Leak-Check Procedure. Same as Method 6, Section 
8.2.
    8.3  Sample Collection.
    8.3.1  The probe and filter (either in-stack, out-of-stack, or 
both) must be heated to a temperature sufficient to prevent water 
condensation.
    8.3.2  Record the initial dry gas meter reading. To begin sampling, 
position the tip of the probe at the sampling point, connect the probe 
to the first impinger (or filter), and start the timer and the sample 
pump. Adjust the sample flow to

[[Page 61902]]

a constant rate of approximately 1.0 liter/min (0.035 cfm) as indicated 
by the rotameter. Observe the operation of the timer, and determine 
that it is operating as intended (i.e., the timer is in the ``on'' 
position for the desired period, and the cycle repeats as required).
    8.3.3  One time between 9 a.m. and 11 a.m. during the 24-hour 
sampling period, record the dry gas meter temperature (Tm) 
and the barometric pressure (P(bar)).
    8.3.4  At the conclusion of the run, turn off the timer and the 
sample pump, remove the probe from the stack, and record the final gas 
meter volume reading. Conduct a leak-check as described in Section 8.2. 
If a leak is found, void the test run or use procedures acceptable to 
the Administrator to adjust the sample volume for leakage. Repeat the 
steps in Sections 8.3.1 to 8.3.4 for successive runs.
    8.4  Sample Recovery. The procedures for sample recovery (moisture 
measurement, peroxide solution, and CO2 absorber) are the 
same as those in Method 6A, Section 8.3.

9.0  Quality Control

    Same as Method 6, Section 9.0., with the exception of the 
isopropanol-check.

10.0  Calibration and Standardization

    Same as Method 6, Section 10.0, with the addition of the following:
    10.1  Periodic Calibration Check. After 30 days of operation of the 
test train, conduct a calibration check according to the same 
procedures as the post-test calibration check (Method 6, Section 
10.1.2). If the deviation between initial and periodic calibration 
factors exceeds 5 percent, use the smaller of the two factors in 
calculations for the preceding 30 days of data, but use the most recent 
calibration factor for succeeding test runs.

11.0  Analytical Procedures

    11.1  Sample Loss Check and Analysis. Same as Method 6, Sections 
11.1 and 11.2, respectively.
    11.2  Quality Assurance (QA) Audit Samples. Analysis of QA audit 
samples is required only when this method is used for compliance 
determinations. Obtain an audit sample set as directed in Section 7.3.6 
of Method 6. Analyze the audit samples at least once for every 30 days 
of sample collection, and report the results as directed in Section 
11.3 of Method 6. The analyst performing the sample analyses shall 
perform the audit analyses. If more than one analyst performs the 
sample analyses during the 30-day sampling period, each analyst shall 
perform the audit analyses and all audit results shall be reported. 
Acceptance criteria for the audit results are the same as those in 
Method 6.

12.0  Data Analysis and Calculations

    Same as Method 6A, Section 12.0, except that Pbar and 
Tm correspond to the values recorded in Section 8.3.3 of 
this method. The values are as follows:

Pbar = Initial barometric pressure for the test period, mm 
Hg.
Tm = Absolute meter temperature for the test period,  deg.K.

13.0  Method Performance

    13.1  Range.
    13.1.1  Sulfur Dioxide. Same as Method 6.
    13.1.2  Carbon Dioxide. Not determined.
    13.2  Repeatability and Reproducibility. EPA-sponsored 
collaborative studies were undertaken to determine the magnitude of 
repeatability and reproducibility achievable by qualified testers 
following the procedures in this method. The results of the studies 
evolve from 145 field tests including comparisons with Methods 3 and 6. 
For measurements of emission rates from wet, flue gas desulfurization 
units in (ng/J), the repeatability (intra-laboratory precision) is 8.0 
percent and the reproducibility (inter-laboratory precision) is 11.1 
percent.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  Alternative Methods

    Same as Method 6A, Section 16.0, except that the timer is needed 
and is operated as outlined in this method.

17.0  References

    Same as Method 6A, Section 17.0, with the addition of the 
following:

    1. Butler, Frank E., et. al. The Collaborative Test of Method 
6B: Twenty-Four-Hour Analysis of SO2 and CO2. 
JAPCA. Vol. 33, No. 10. October 1983.

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

* * * * *

Method 7--Determination of Nitrogen Oxide Emissions From Stationary 
Sources

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

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
              Analyte                   CAS No.          Sensitivity
------------------------------------------------------------------------
Nitrogen oxides (NOX), as NO2,
 including:
    Nitric oxide (NO).............      10102-43-9
    Nitrogen dioxide (NO2)........      10102-44-0  2-400 mg/dscm
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the measurement 
of nitrogen oxides (NOX) emitted from stationary sources.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sample methods.

2.0  Summary of Method

    A grab sample is collected in an evacuated flask containing a 
dilute sulfuric acid-hydrogen peroxide absorbing solution, and the 
nitrogen oxides, except nitrous oxide, are measured colorimetrically 
using the phenoldisulfonic acid (PDS) procedure.

3.0  Definitions. [Reserved]

4.0  Interferences

    Biased results have been observed when sampling under conditions of 
high sulfur dioxide concentrations (above 2000 ppm).

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user to establish appropriate safety and health practices and to 
determine the applicability of regulatory limitations prior to 
performing this test method.
    5.2  Corrosive Reagents. The following reagents are hazardous.

[[Page 61903]]

Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water for at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burns as thermal 
burns.
    5.2.1  Hydrogen Peroxide (H2O2). Irritating 
to eyes, skin, nose, and lungs.
    5.2.2  Phenoldisulfonic Acid. Irritating to eyes and skin.
    5.2.3  Sodium Hydroxide (NaOH). Causes severe damage to eyes and 
skin. Inhalation causes irritation to nose, throat, and lungs. Reacts 
exothermically with limited amounts of water.
    5.2.4  Sulfuric Acid (H2SO4). Rapidly 
destructive to body tissue. Will cause third degree burns. Eye damage 
may result in blindness. Inhalation may be fatal from spasm of the 
larynx, usually within 30 minutes. May cause lung tissue damage with 
edema. 1 mg/m 3 for 8 hours will cause lung damage or, in 
higher concentrations, death. Provide ventilation to limit inhalation. 
Reacts violently with metals and organics.
    5.2.5  Phenol. Poisonous and caustic. Do not handle with bare hands 
as it is absorbed through the skin.

6.0  Equipment and Supplies

    6.1  Sample Collection. A schematic of the sampling train used in 
performing this method is shown in Figure 7-1. Other grab sampling 
systems or equipment, capable of measuring sample volume to within 2.0 
percent and collecting a sufficient sample volume to allow analytical 
reproducibility to within 5 percent, will be considered acceptable 
alternatives, subject to the approval of the Administrator. The 
following items are required for sample collection:
    6.1.1  Probe. Borosilicate glass tubing, sufficiently heated to 
prevent water condensation and equipped with an in-stack or heated out-
of-stack filter to remove particulate matter (a plug of glass wool is 
satisfactory for this purpose). Stainless steel or Teflon tubing may 
also be used for the probe. Heating is not necessary if the probe 
remains dry during the purging period.
    6.1.2  Collection Flask. Two-liter borosilicate, round bottom 
flask, with short neck and 24/40 standard taper opening, protected 
against implosion or breakage.
    6.1.3  Flask Valve. T-bore stopcock connected to a 24/40 standard 
taper joint.
    6.1.4  Temperature Gauge. Dial-type thermometer, or other 
temperature gauge, capable of measuring 1  deg.C (2  deg.F) intervals 
from -5 to 50  deg.C (23 to 122  deg.F).
    6.1.5  Vacuum Line. Tubing capable of withstanding a vacuum of 75 
mm (3 in.) Hg absolute pressure, with ``T'' connection and T-bore 
stopcock.
    6.1.6  Vacuum Gauge. U-tube manometer, 1 meter (39 in.), with 1 mm 
(0.04 in.) divisions, or other gauge capable of measuring pressure to 
within 2.5 mm (0.10 in.) Hg.
    6.1.7  Pump. Capable of evacuating the collection flask to a 
pressure equal to or less than 75 mm (3 in.) Hg absolute.
    6.1.8  Squeeze Bulb. One-way.
    6.1.9  Volumetric Pipette. 25-ml.
    6.1.10  Stopcock and Ground Joint Grease. A high-vacuum, high-
temperature chlorofluorocarbon grease is required. Halocarbon 25-5S has 
been found to be effective.
    6.1.11  Barometer. Mercury, aneroid, or other barometer capable of 
measuring atmospheric pressure to within 2.5 mm (0.1 in.) Hg. See NOTE 
in Method 5, Section 6.1.2.
    6.2  Sample Recovery. The following items are required for sample 
recovery:
    6.2.1  Graduated Cylinder. 50-ml with 1 ml divisions.
    6.2.2  Storage Containers. Leak-free polyethylene bottles.
    6.2.3  Wash Bottle. Polyethylene or glass.
    6.2.4  Glass Stirring Rod.
    6.2.5  Test Paper for Indicating pH. To cover the pH range of 7 to 
14.
    6.3  Analysis. The following items are required for analysis:
    6.3.1  Volumetric Pipettes. Two 1-ml, two 2-ml, one 3-ml, one 4-ml, 
two 10-ml, and one 25-ml for each sample and standard.
    6.3.2  Porcelain Evaporating Dishes. 175- to 250-ml capacity with 
lip for pouring, one for each sample and each standard. The Coors No. 
45006 (shallowform, 195-ml) has been found to be satisfactory. 
Alternatively, polymethyl pentene beakers (Nalge No. 1203, 150-ml), or 
glass beakers (150-ml) may be used. When glass beakers are used, 
etching of the beakers may cause solid matter to be present in the 
analytical step; the solids should be removed by filtration.
    6.3.3  Steam Bath. Low-temperature ovens or thermostatically 
controlled hot plates kept below 70  deg.C (160  deg.F) are acceptable 
alternatives.
    6.3.4  Dropping Pipette or Dropper. Three required.
    6.3.5  Polyethylene Policeman. One for each sample and each 
standard.
    6.3.6  Graduated Cylinder. 100-ml with 1-ml divisions.
    6.3.7  Volumetric Flasks. 50-ml (one for each sample and each 
standard), 100-ml (one for each sample and each standard, and one for 
the working standard KNO3 solution), and 1000-ml (one).
    6.3.8  Spectrophotometer. To measure at 410 nm.
    6.3.9  Graduated Pipette. 10-ml with 0.1-ml divisions.
    6.3.10  Test Paper for Indicating pH. To cover the pH range of 7 to 
14.
    6.3.11  Analytical Balance. To measure to within 0.1 mg.

7.0  Reagents and Standards

    Unless otherwise indicated, it is intended that all reagents 
conform to the specifications established by the Committee on 
Analytical Reagents of the American Chemical Society, where such 
specifications are available; otherwise, use the best available grade.
    7.1  Sample Collection. The following reagents are required for 
sampling:
    7.1.1  Water. Deionized distilled to conform to ASTM D 1193-77 or 
91 Type 3 (incorporated by reference--see Sec. 60.17). The 
KMnO4 test for oxidizable organic matter may be omitted when 
high concentrations of organic matter are not expected to be present.
    7.1.2  Absorbing Solution. Cautiously add 2.8 ml concentrated 
H2SO4 to a 1-liter flask partially filled with 
water. Mix well, and add 6 ml of 3 percent hydrogen peroxide, freshly 
prepared from 30 percent hydrogen peroxide solution. Dilute to 1 liter 
of water and mix well. The absorbing solution should be used within 1 
week of its preparation. Do not expose to extreme heat or direct 
sunlight.
    7.2  Sample Recovery. The following reagents are required for 
sample recovery:
    7.2.1  Water. Same as in 7.1.1.
    7.2.2  Sodium Hydroxide, 1 N. Dissolve 40 g NaOH in water, and 
dilute to 1 liter.
    7.3  Analysis. The following reagents and standards are required 
for analysis:
    7.3.1  Water. Same as in 7.1.1.
    7.3.2  Fuming Sulfuric Acid. 15 to 18 percent by weight free sulfur 
trioxide. HANDLE WITH CAUTION.
    7.3.3  Phenol. White solid.
    7.3.4  Sulfuric Acid. Concentrated, 95 percent minimum assay.
    7.3.5  Potassium Nitrate (KNO3). Dried at 105 to 110 
deg.C (221 to 230  deg.F) for a minimum of 2 hours just prior to 
preparation of standard solution.
    7.3.6  Standard KNO3 Solution. Dissolve exactly 2.198 g 
of dried KNO3 in water, and dilute to 1 liter with water in 
a 1000-ml volumetric flask.
    7.3.7  Working Standard KNO3 Solution. Dilute 10 ml of 
the standard solution to 100 ml with water. One ml of the working 
standard solution is equivalent to 100 g nitrogen dioxide 
(NO2).

[[Page 61904]]

    7.3.8  Phenoldisulfonic Acid Solution. Dissolve 25 g of pure white 
phenol solid in 150 ml concentrated sulfuric acid on a steam bath. 
Cool, add 75 ml fuming sulfuric acid (15 to 18 percent by weight free 
sulfur trioxide--HANDLE WITH CAUTION), and heat at 100  deg.C (212 
deg.F) for 2 hours. Store in a dark, stoppered bottle.
    7.3.9  Concentrated Ammonium Hydroxide.
    7.3.10  Quality Assurance Audit Samples. When making compliance 
determinations, and upon availability, audit samples may be obtained 
from the appropriate EPA Regional Office or from the responsible 
enforcement authority.


    Note: The responsible enforcement authority should be notified 
at least 30 days prior to the test date to allow sufficient time for 
sample delivery.

8.0  Sample Collection, Preservation, Storage and Transport

    8.1  Sample Collection.
    8.1.1  Flask Volume. The volume of the collection flask and flask 
valve combination must be known prior to sampling. Assemble the flask 
and flask valve, and fill with water to the stopcock. Measure the 
volume of water to 10 ml. Record this volume on the flask.
    8.1.2  Pipette 25 ml of absorbing solution into a sample flask, 
retaining a sufficient quantity for use in preparing the calibration 
standards. Insert the flask valve stopper into the flask with the valve 
in the ``purge'' position. Assemble the sampling train as shown in 
Figure 7-1, and place the probe at the sampling point. Make sure that 
all fittings are tight and leak-free, and that all ground glass joints 
have been greased properly with a high-vacuum, high temperature 
chlorofluorocarbon-based stopcock grease. Turn the flask valve and the 
pump valve to their ``evacuate'' positions. Evacuate the flask to 75 mm 
(3 in.) Hg absolute pressure, or less. Evacuation to a pressure 
approaching the vapor pressure of water at the existing temperature is 
desirable. Turn the pump valve to its ``vent'' position, and turn off 
the pump. Check for leakage by observing the manometer for any pressure 
fluctuation. (Any variation greater than 10 mm (0.4 in.) Hg over a 
period of 1 minute is not acceptable, and the flask is not to be used 
until the leakage problem is corrected. Pressure in the flask is not to 
exceed 75 mm (3 in.) Hg absolute at the time sampling is commenced.) 
Record the volume of the flask and valve (Vf), the flask 
temperature (Ti), and the barometric pressure. Turn the 
flask valve counterclockwise to its ``purge'' position, and do the same 
with the pump valve. Purge the probe and the vacuum tube using the 
squeeze bulb. If condensation occurs in the probe and the flask valve 
area, heat the probe, and purge until the condensation disappears. 
Next, turn the pump valve to its ``vent'' position. Turn the flask 
valve clockwise to its ``evacuate'' position, and record the difference 
in the mercury levels in the manometer. The absolute internal pressure 
in the flask (Pi) is equal to the barometric pressure less 
the manometer reading. Immediately turn the flask valve to the 
``sample'' position, and permit the gas to enter the flask until 
pressures in the flask and sample line (i.e., duct, stack) are equal. 
This will usually require about 15 seconds; a longer period indicates a 
plug in the probe, which must be corrected before sampling is 
continued. After collecting the sample, turn the flask valve to its 
``purge'' position, and disconnect the flask from the sampling train.
    8.1.3  Shake the flask for at least 5 minutes.
    8.1.4  If the gas being sampled contains insufficient oxygen for 
the conversion of NO to NO2 (e.g., an applicable subpart of 
the standards may require taking a sample of a calibration gas mixture 
of NO in N2), then introduce oxygen into the flask to permit 
this conversion. Oxygen may be introduced into the flask by one of 
three methods: (1) Before evacuating the sampling flask, flush with 
pure cylinder oxygen, then evacuate flask to 75 mm (3 in.) Hg absolute 
pressure or less; or (2) inject oxygen into the flask after sampling; 
or (3) terminate sampling with a minimum of 50 mm (2 in.) Hg vacuum 
remaining in the flask, record this final pressure, and then vent the 
flask to the atmosphere until the flask pressure is almost equal to 
atmospheric pressure.
    8.2  Sample Recovery. Let the flask sit for a minimum of 16 hours, 
and then shake the contents for 2 minutes.
    8.2.1  Connect the flask to a mercury filled U-tube manometer. Open 
the valve from the flask to the manometer, and record the flask 
temperature (Tf), the barometric pressure, and the 
difference between the mercury levels in the manometer. The absolute 
internal pressure in the flask (Pf) is the barometric 
pressure less the manometer reading. Transfer the contents of the flask 
to a leak-free polyethylene bottle. Rinse the flask twice with 5 ml 
portions of water, and add the rinse water to the bottle. Adjust the pH 
to between 9 and 12 by adding 1 N NaOH, dropwise (about 25 to 35 
drops). Check the pH by dipping a stirring rod into the solution and 
then touching the rod to the pH test paper. Remove as little material 
as possible during this step. Mark the height of the liquid level so 
that the container can be checked for leakage after transport. Label 
the container to identify clearly its contents. Seal the container for 
shipping.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
10.1..........................  Spectrophotometer  Ensure linearity of
                                 calibration.       spectrophotometer
                                                    response to
                                                    standards.
11.4..........................  Audit sample       Evaluate analytical
                                 analysis.          technique,
                                                    preparation of
                                                    standards.
------------------------------------------------------------------------

10.0  Calibration and Standardization

    10.1  Spectrophotometer.
    10.1.1  Optimum Wavelength Determination.
    10.1.1.1  Calibrate the wavelength scale of the spectrophotometer 
every 6 months. The calibration may be accomplished by using an energy 
source with an intense line emission such as a mercury lamp, or by 
using a series of glass filters spanning the measuring range of the 
spectrophotometer. Calibration materials are available commercially and 
from the National Institute of Standards and Technology. Specific 
details on the use of such materials should be supplied by the vendor; 
general information about calibration techniques can be obtained from 
general reference books on analytical chemistry. The wavelength scale 
of the spectrophotometer must read correctly within 5 nm at all 
calibration points; otherwise, repair and recalibrate the 
spectrophotometer. Once the wavelength scale of the spectrophotometer 
is in proper calibration, use 410 nm as the optimum wavelength for the 
measurement of the absorbance of the standards and samples.
    10.1.1.2  Alternatively, a scanning procedure may be employed to 
determine the proper measuring wavelength. If the instrument is a 
double-beam spectrophotometer, scan the spectrum between 400 and 415 nm

[[Page 61905]]

using a 200 g NO2 standard solution in the sample 
cell and a blank solution in the reference cell. If a peak does not 
occur, the spectrophotometer is probably malfunctioning and should be 
repaired. When a peak is obtained within the 400 to 415 nm range, the 
wavelength at which this peak occurs shall be the optimum wavelength 
for the measurement of absorbance of both the standards and the 
samples. For a single-beam spectrophotometer, follow the scanning 
procedure described above, except scan separately the blank and 
standard solutions. The optimum wavelength shall be the wavelength at 
which the maximum difference in absorbance between the standard and the 
blank occurs.
    10.1.2  Determination of Spectrophotometer Calibration Factor 
Kc. Add 0 ml, 2.0 ml, 4.0 ml, 6.0 ml, and 8.0 ml of the 
KNO3 working standard solution (1 ml = 100 g 
NO2) to a series of five 50-ml volumetric flasks. To each 
flask, add 25 ml of absorbing solution and 10 ml water. Add 1 N NaOH to 
each flask until the pH is between 9 and 12 (about 25 to 35 drops). 
Dilute to the mark with water. Mix thoroughly, and pipette a 25-ml 
aliquot of each solution into a separate porcelain evaporating dish. 
Beginning with the evaporation step, follow the analysis procedure of 
Section 11.2 until the solution has been transferred to the 100-ml 
volumetric flask and diluted to the mark. Measure the absorbance of 
each solution at the optimum wavelength as determined in Section 
10.2.1. This calibration procedure must be repeated on each day that 
samples are analyzed. Calculate the spectrophotometer calibration 
factor as shown in Section 12.2.
    10.1.3  Spectrophotometer Calibration Quality Control. Multiply the 
absorbance value obtained for each standard by the Kc factor 
(reciprocal of the least squares slope) to determine the distance each 
calibration point lies from the theoretical calibration line. The 
difference between the calculated concentration values and the actual 
concentrations (i.e., 100, 200, 300, and 400 g NO2) 
should be less than 7 percent for all standards.
    10.2  Barometer. Calibrate against a mercury barometer.
    10.3  Temperature Gauge. Calibrate dial thermometers against 
mercury-in-glass thermometers.
    10.4  Vacuum Gauge. Calibrate mechanical gauges, if used, against a 
mercury manometer such as that specified in Section 6.1.6.
    10.5  Analytical Balance. Calibrate against standard weights.

11.0  Analytical Procedures

    11.1  Sample Loss Check. Note the level of the liquid in the 
container, and confirm whether any sample was lost during shipment. 
Note this on the analytical data sheet. If a noticeable amount of 
leakage has occurred, either void the sample or use methods, subject to 
the approval of the Administrator, to correct the final results.
    11.2  Sample Preparation. Immediately prior to analysis, transfer 
the contents of the shipping container to a 50 ml volumetric flask, and 
rinse the container twice with 5 ml portions of water. Add the rinse 
water to the flask, and dilute to mark with water; mix thoroughly. 
Pipette a 25-ml aliquot into the porcelain evaporating dish. Return any 
unused portion of the sample to the polyethylene storage bottle. 
Evaporate the 25-ml aliquot to dryness on a steam bath, and allow to 
cool. Add 2 ml phenoldisulfonic acid solution to the dried residue, and 
triturate thoroughly with a polyethylene policeman. Make sure the 
solution contacts all the residue. Add 1 ml water and 4 drops of 
concentrated sulfuric acid. Heat the solution on a steam bath for 3 
minutes with occasional stirring. Allow the solution to cool, add 20 ml 
water, mix well by stirring, and add concentrated ammonium hydroxide, 
dropwise, with constant stirring, until the pH is 10 (as determined by 
pH paper). If the sample contains solids, these must be removed by 
filtration (centrifugation is an acceptable alternative, subject to the 
approval of the Administrator) as follows: Filter through Whatman No. 
41 filter paper into a 100-ml volumetric flask. Rinse the evaporating 
dish with three 5-ml portions of water. Filter these three rinses. Wash 
the filter with at least three 15-ml portions of water. Add the filter 
washings to the contents of the volumetric flask, and dilute to the 
mark with water. If solids are absent, the solution can be transferred 
directly to the 100-ml volumetric flask and diluted to the mark with 
water.
    11.3  Sample Analysis. Mix the contents of the flask thoroughly, 
and measure the absorbance at the optimum wavelength used for the 
standards (Section 10.2.1), using the blank solution as a zero 
reference. Dilute the sample and the blank with equal volumes of water 
if the absorbance exceeds A4, the absorbance of the 400-
g NO2 standard (see Section 10.2.2).
    11.4  Audit Sample Analysis.
    11.4.1  When the method is used to analyze samples to demonstrate 
compliance with a source emission regulation, an audit sample must be 
analyzed, subject to availability.
    11.4.2  Concurrently analyze the audit sample and the compliance 
samples in the same manner to evaluate the technique of the analyst and 
the standards preparation.
    11.4.3  The same analyst, analytical reagents, and analytical 
system must be used for the compliance samples and the audit sample. If 
this condition is met, duplicate auditing of subsequent compliance 
analyses for the same enforcement agency within a 30-day period is 
waived. An audit sample set may not be used to validate different sets 
of compliance samples under the jurisdiction of separate enforcement 
agencies, unless prior arrangements have been made with both 
enforcement agencies.
    11.5  Audit Sample Results.
    11.5.1  Calculate the audit sample concentrations and submit 
results using the instructions provided with the audit samples.
    11.5.2  Report the results of the audit samples and the compliance 
determination samples along with their identification numbers, and the 
analyst's name to the responsible enforcement authority. Include this 
information with reports of any subsequent compliance analyses for the 
same enforcement authority during the 30-day period.
    11.5.3  The concentrations of the audit samples obtained by the 
analyst must agree within 5 percent of the actual concentration. If the 
5 percent specification is not met, reanalyze the compliance and audit 
samples, and include initial and reanalysis values in the test report.
    11.5.4  Failure to meet the 5-percent specification may require 
retests until the audit problems are resolved. However, if the audit 
results do not affect the compliance or noncompliance status of the 
affected facility, the Administrator may waive the reanalysis 
requirement, further audits, or retests and accept the results of the 
compliance test. While steps are being taken to resolve audit analysis 
problems, the Administrator may also choose to use the data to 
determine the compliance or noncompliance status of the affected 
facility.

12.0  Data Analysis and Calculations

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

A = Absorbance of sample.
A1 = Absorbance of the 100-g NO2 
standard.
A2 = Absorbance of the 200-g NO2 
standard.

[[Page 61906]]

A3 = Absorbance of the 300-g NO2 
standard.
A4 = Absorbance of the 400-g NO2 
standard.
C = Concentration of NOX as NO2, dry basis, 
corrected to standard conditions, mg/dsm\3\ (lb/dscf).
Cd = Determined audit sample concentration, mg/dscm.
Ca = Actual audit sample concentration, mg/dscm.
F = Dilution factor (i.e., 25/5, 25/10, etc., required only if sample 
dilution was needed to reduce the absorbance into the range of the 
calibration).
Kc = Spectrophotometer calibration factor.
m = Mass of NOX as NO2 in gas sample, g.
Pf = Final absolute pressure of flask, mm Hg (in. Hg).
Pi = Initial absolute pressure of flask, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
RE = Relative error for QA audit samples, percent.
Tf = Final absolute temperature of flask,  deg.K ( deg.R).
Ti = Initial absolute temperature of flask,  deg.K ( deg.R).
Tstd = Standard absolute temperature, 293  deg.K (528 
deg.R).
Vsc = Sample volume at standard conditions (dry basis), ml.
Vf = Volume of flask and valve, ml.
Va = Volume of absorbing solution, 25 ml.

    12.2  Spectrophotometer Calibration Factor.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.200
    
    12.3  Sample Volume, Dry Basis, Corrected to Standard Conditions.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.201
    
Where:

K1 = 0.3858  deg.K/mm Hg for metric units,
K1 = 17.65  deg.R/in. Hg for English units.

    12.4  Total g NO2 per sample.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.202
    
Where:
2 = 50/25, the aliquot factor.


    Note: If other than a 25-ml aliquot is used for analysis, the 
factor 2 must be replaced by a corresponding factor.

    12.5  Sample Concentration, Dry Basis, Corrected to Standard 
Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.203

Where:
K2 = 10\3\ (mg/m\3\)/(g/ml) for metric units,
K2 = 6.242  x  10-\5\ (lb/scf)/(g/ml) 
for English units.
12.6  Relative Error for QA Audit Samples.
[GRAPHIC] [TIFF OMITTED] TR17OC00.204

13.0 Method Performance

    13.1 Range.  The analytical range of the method has been determined 
to be 2 to 400 milligrams NOX (as NO2) per dry 
standard cubic meter, without having to dilute the sample.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    1. Standard Methods of Chemical Analysis. 6th ed. New York, D. 
Van Nostrand Co., Inc. 1962. Vol. 1, pp. 329-330.
    2. Standard Method of Test for Oxides of Nitrogen in Gaseous 
Combustion Products (Phenoldisulfonic Acid Procedure). In: 1968 Book 
of ASTM Standards, Part 26. Philadelphia, PA. 1968. ASTM Designation 
D 1608-60, pp. 725-729.
    3. Jacob, M.B. The Chemical Analysis of Air Pollutants. New 
York. Interscience Publishers, Inc. 1960. Vol. 10, pp. 351-356.
    4. Beatty, R.L., L.B. Berger, and H.H. Schrenk. Determination of 
Oxides of Nitrogen by the Phenoldisulfonic Acid Method. Bureau of 
Mines, U.S. Dept. of Interior. R.I. 3687. February 1943.
    5. Hamil, H.F. and D.E. Camann. Collaborative Study of Method 
for the Determination of Nitrogen Oxide Emissions from Stationary 
Sources (Fossil Fuel-Fired Steam Generators). Southwest Research 
Institute Report for Environmental Protection Agency. Research 
Triangle Park, NC. October 5, 1973.
    6. Hamil, H.F. and R.E. Thomas. Collaborative Study of Method 
for the Determination of Nitrogen Oxide Emissions from Stationary 
Sources (Nitric Acid Plants). Southwest Research Institute Report 
for Environmental Protection Agency. Research Triangle Park, NC. May 
8, 1974.
    7. Stack Sampling Safety Manual (Draft). U.S. Environmental 
Protection Agency, Office of Air Quality Planning and Standards, 
Research Triangle Park, NC. September 1978.
BILLING CODE 6560-50-P

[[Page 61907]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.205

BILLING CODE 6560-50-C

[[Page 61908]]

Method 7A--Determination of Nitrogen Oxide Emissions From 
Stationary Sources (Ion Chromatographic Method)

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in this part. 
Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of at least the following 
additional test methods: Method 1, Method 3, Method 5, and Method 7.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
              Analyte                   CAS No.          Sensitivity
------------------------------------------------------------------------
Nitrogen oxides (NOX), as NO2,
 including:
    Nitric oxide (NO).............      10102-43-9  ....................
    Nitrogen dioxide (NO2)........      10102-44-0  65-655 ppmv
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of NOX emissions from stationary sources.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    A grab sample is collected in an evacuated flask containing a 
dilute sulfuric acid-hydrogen peroxide absorbing solution. The nitrogen 
oxides, excluding nitrous oxide (N2O), are oxidized to 
nitrate and measured by ion chromatography.

3.0  Definitions [Reserved]

4.0  Interferences

    Biased results have been observed when sampling under conditions of 
high sulfur dioxide concentrations (above 2000 ppm).

5.0  Safety

    5.1  This method may involve hazardous materials, operations, and 
equipment. This test method may not address all of the safety problems 
associated with its use. It is the responsibility of the user of this 
test method to establish appropriate safety and health practices and to 
determine the applicability of regulatory limitations prior to 
performing this test method.
    5.2  Corrosive reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burns as thermal 
burns.
    5.2.1  Hydrogen Peroxide (H2O2). Irritating 
to eyes, skin, nose, and lungs.
    5.2.2  Sulfuric Acid (H2SO4). Rapidly 
destructive to body tissue. Will cause third degree burns. Eye damage 
may result in blindness. Inhalation may be fatal from spasm of the 
larynx, usually within 30 minutes. May cause lung tissue damage with 
edema. 3 mg/m3 will cause lung damage in uninitiated. 1 mg/
m3 for 8 hours will cause lung damage or, in higher 
concentrations, death. Provide ventilation to limit inhalation. Reacts 
violently with metals and organics.

6.0  Equipment and Supplies

    6.1  Sample Collection. Same as in Method 7, Section 6.1.
    6.2  Sample Recovery. Same as in Method 7, Section 6.2, except the 
stirring rod and pH paper are not needed.
    6.3  Analysis. For the analysis, the following equipment and 
supplies are required. Alternative instrumentation and procedures will 
be allowed provided the calibration precision requirement in Section 
10.1.2 and audit accuracy requirement in Section 11.3 can be met.
    6.3.1  Volumetric Pipets. Class A;
1-, 2-, 4-, 5-ml (two for the set of standards and one per sample), 6-, 
10-, and graduated 5-ml sizes.
    6.3.2  Volumetric Flasks. 50-ml (two per sample and one per 
standard), 200-ml, and 1-liter sizes.
    6.3.3  Analytical Balance. To measure to within 0.1 mg.
    6.3.4  Ion Chromatograph. The ion chromatograph should have at 
least the following components:
    6.3.4.1  Columns. An anion separation or other column capable of 
resolving the nitrate ion from sulfate and other species present and a 
standard anion suppressor column (optional). Suppressor columns are 
produced as proprietary items; however, one can be produced in the 
laboratory using the resin available from BioRad Company, 32nd and 
Griffin Streets, Richmond, California. Peak resolution can be optimized 
by varying the eluent strength or column flow rate, or by experimenting 
with alternative columns that may offer more efficient separation. When 
using guard columns with the stronger reagent to protect the separation 
column, the analyst should allow rest periods between injection 
intervals to purge possible sulfate buildup in the guard column.
    6.3.4.2  Pump. Capable of maintaining a steady flow as required by 
the system.
    6.3.4.3  Flow Gauges. Capable of measuring the specified system 
flow rate.
    6.3.4.4  Conductivity Detector.
    6.3.4.5  Recorder. Compatible with the output voltage range of the 
detector.

7.0  Reagents and Standards

    Unless otherwise indicated, it is intended that all reagents 
conform to the specifications established by the Committee on 
Analytical Reagents of the American Chemical Society, where such 
specifications are available; otherwise, use the best available grade.
    7.1  Sample Collection. Same as Method 7, Section 7.1.
    7.2  Sample Recovery. Same as Method 7, Section 7.1.1.
    7.3  Analysis. The following reagents and standards are required 
for analysis:
    7.3.1  Water. Same as Method 7, Section 7.1.1.
    7.3.2  Stock Standard Solution, 1 mg NO2/ml. Dry an 
adequate amount of sodium nitrate (NaNO3) at 105 to 110 
deg.C (221 to 230  deg.F) for a minimum of 2 hours just before 
preparing the standard solution. Then dissolve exactly 1.847 g of dried 
NaNO3 in water, and dilute to l liter in a volumetric flask. 
Mix well. This solution is stable for 1 month and should not be used 
beyond this time.
    7.3.3  Working Standard Solution, 25 g/ml. Dilute 5 ml of 
the standard solution to 200 ml with water in a volumetric flask, and 
mix well.
    7.3.4  Eluent Solution. Weigh 1.018 g of sodium carbonate 
(Na2CO3) and 1.008 g of sodium bicarbonate 
(NaHCO3), and dissolve in 4 liters of water. This solution 
is 0.0024 M Na2CO3/0.003 M NaHCO3. 
Other eluents appropriate to the column type and capable of resolving 
nitrate ion from sulfate and other species present may be used.
    7.3.5  Quality Assurance Audit Samples. Same as Method 7, Section 
7.3.8.

[[Page 61909]]

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Sampling. Same as in Method 7, Section 8.1.
    8.2  Sample Recovery. Same as in Method 7, Section 8.2, except 
delete the steps on adjusting and checking the pH of the sample. Do not 
store the samples more than 4 days between collection and analysis.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
10.1..........................  Ion chromatograph  Ensure linearity of
                                 calibration.       ion chromatograph
                                                    response to
                                                    standards.
11.3..........................  Audit sample       Evaluate analytical
                                 analysis.          technique,
                                                    preparation of
                                                    standards.
------------------------------------------------------------------------

10.0  Calibration and Standardizations

    10.1  Ion Chromatograph.
    10.1.1  Determination of Ion Chromatograph Calibration Factor S. 
Prepare a series of five standards by adding 1.0, 2.0, 4.0, 6.0, and 
10.0 ml of working standard solution (25 g/ml) to a series of 
five 50-ml volumetric flasks. (The standard masses will equal 25, 50, 
100, 150, and 250 g.) Dilute each flask to the mark with 
water, and mix well. Analyze with the samples as described in Section 
11.2, and subtract the blank from each value. Prepare or calculate a 
linear regression plot of the standard masses in g (x-axis) 
versus their peak height responses in millimeters (y-axis). (Take peak 
height measurements with symmetrical peaks; in all other cases, 
calculate peak areas.) From this curve, or equation, determine the 
slope, and calculate its reciprocal to denote as the calibration 
factor, S.
    10.1.2  Ion Chromatograph Calibration Quality Control. If any point 
on the calibration curve deviates from the line by more than 7 percent 
of the concentration at that point, remake and reanalyze that standard. 
This deviation can be determined by multiplying S times the peak height 
response for each standard. The resultant concentrations must not 
differ by more than 7 percent from each known standard mass (i.e., 25, 
50, 100, 150, and 250 g).
    10.2  Conductivity Detector. Calibrate according to manufacturer's 
specifications prior to initial use.
    10.3  Barometer. Calibrate against a mercury barometer.
    10.4  Temperature Gauge. Calibrate dial thermometers against 
mercury-in-glass thermometers.
    10.5  Vacuum Gauge. Calibrate mechanical gauges, if used, against a 
mercury manometer such as that specified in Section 6.1.6 of Method 7.
    10.6  Analytical Balance. Calibrate against standard weights.

11.0  Analytical Procedures

    11.1  Sample Preparation.
    11.1.1  Note on the analytical data sheet, the level of the liquid 
in the container, and whether any sample was lost during shipment. If a 
noticeable amount of leakage has occurred, either void the sample or 
use methods, subject to the approval of the Administrator, to correct 
the final results. Immediately before analysis, transfer the contents 
of the shipping container to a 50-ml volumetric flask, and rinse the 
container twice with 5 ml portions of water. Add the rinse water to the 
flask, and dilute to the mark with water. Mix thoroughly.
    11.1.2  Pipet a 5-ml aliquot of the sample into a 50-ml volumetric 
flask, and dilute to the mark with water. Mix thoroughly. For each set 
of determinations, prepare a reagent blank by diluting 5 ml of 
absorbing solution to 50 ml with water. (Alternatively, eluent solution 
may be used instead of water in all sample, standard, and blank 
dilutions.)
    11.2  Analysis.
    11.2.1  Prepare a standard calibration curve according to Section 
10.1.1. Analyze the set of standards followed by the set of samples 
using the same injection volume for both standards and samples. Repeat 
this analysis sequence followed by a final analysis of the standard 
set. Average the results. The two sample values must agree within 5 
percent of their mean for the analysis to be valid. Perform this 
duplicate analysis sequence on the same day. Dilute any sample and the 
blank with equal volumes of water if the concentration exceeds that of 
the highest standard.
    11.2.2  Document each sample chromatogram by listing the following 
analytical parameters: injection point, injection volume, nitrate and 
sulfate retention times, flow rate, detector sensitivity setting, and 
recorder chart speed.
    11.3  Audit Sample Analysis. Same as Method 7, Section 11.4.

12.0  Data Analysis and Calculations

    Carry out the calculations, retaining at least one extra 
significant figure beyond that of the acquired data. Round off figures 
after final calculations.
    12.1  Sample Volume. Calculate the sample volume Vsc (in ml), on a 
dry basis, corrected to standard conditions, using Equation 7-2 of 
Method 7.
    12.2  Sample Concentration of NOX as NO2.
    12.2.1  Calculate the sample concentration C (in mg/dscm) as 
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.206

Where:

H = Sample peak height, mm.
S = Calibration factor, g/mm.
F = Dilution factor (required only if sample dilution was needed to 
reduce the concentration into the range of calibration), dimensionless.
104 = 1:10 dilution times conversion factor of: (mg/10\3\ 
g)(10\6\ ml/m\3\).

    12.2.2  If desired, the concentration of NO2 may be 
calculated as ppm NO2 at standard conditions as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.207

Where:

0.5228 = ml/mg NO2.

13.0  Method Performance

    13.1  Range. The analytical range of the method is from 125 to 1250 
mg NOX/m3 as NO2 (65 to 655 ppmv), and 
higher concentrations may be analyzed by diluting the sample. The lower 
detection limit is approximately 19 mg/m\3\ (10 ppmv), but may vary 
among instruments.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    1. Mulik, J.D., and E. Sawicki. Ion Chromatographic Analysis of 
Environmental Pollutants. Ann Arbor, Ann Arbor Science Publishers, 
Inc. Vol. 2, 1979.
    2. Sawicki, E., J.D. Mulik, and E. Wittgenstein. Ion 
Chromatographic Analysis of Environmental Pollutants. Ann Arbor, Ann 
Arbor Science Publishers, Inc. Vol. 1. 1978.
    3. Siemer, D.D. Separation of Chloride and Bromide from Complex 
Matrices Prior to Ion Chromatographic Determination. Anal. Chem. 
52(12):1874-1877. October 1980.
    4. Small, H., T.S. Stevens, and W.C. Bauman. Novel Ion Exchange 
Chromatographic Method Using Conductimetric Determination. Anal. 
Chem. 47(11):1801. 1975.

[[Page 61910]]

    5. Yu, K.K., and P.R. Westlin. Evaluation of Reference Method 7 
Flask Reaction Time. Source Evaluation Society Newsletter. 4(4). 
November 1979. 10 pp.
    6. Stack Sampling Safety Manual (Draft). U.S. Environmental 
Protection Agency, Office of Air Quality Planning and Standard, 
Research Triangle Park, NC. September 1978.

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

Method 7B--Determination of Nitrogen Oxide Emissions From 
Stationary Sources (Ultraviolet Spectrophotometric Method)

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in this part. 
Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of at least the following 
additional test methods: Method 1, Method 5, and Method 7.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
              Analyte                   CAS No.          Sensitivity
------------------------------------------------------------------------
Nitrogen oxides (NOX), as NO2,
 including:
    Nitric oxide (NO).............      10102-43-9
    Nitrogen dioxide (NO2)........      10102-44-0  30-786 ppmv
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of NOX emissions from nitric acid plants.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  A grab sample is collected in an evacuated flask containing a 
dilute sulfuric acid-hydrogen peroxide absorbing solution; the 
NOX, excluding nitrous oxide (N2O), are measured 
by ultraviolet spectrophotometry.

3.0  Definition. [Reserved]

4.0  Interferences. [Reserved]

5.0  Safety

    5.1  This method may involve hazardous materials, operations, and 
equipment. This test method may not address all of the safety problems 
associated with its use. It is the responsibility of the user of this 
test method to establish appropriate safety and health practices and to 
determine the applicability of regulatory limitations prior to 
performing this test method.
    5.2  Corrosive reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burn as thermal burn.
    5.2.1  Hydrogen Peroxide (H2O2). Irritating 
to eyes, skin, nose, and lungs.
    5.2.2  Sodium Hydroxide (NaOH). Causes severe damage to eyes and 
skin. Inhalation causes irritation to nose, throat, and lungs. Reacts 
exothermically with limited amounts of water.
    5.2.3  Sulfuric Acid (H2SO4). Rapidly 
destructive to body tissue. Will cause third degree burns. Eye damage 
may result in blindness. Inhalation may be fatal from spasm of the 
larynx, usually within 30 minutes. May cause lung tissue damage with 
edema. 3 mg/m \3\ will cause lung damage in uninitiated. 1 mg/m \3\ for 
8 hours will cause lung damage or, in higher concentrations, death. 
Provide ventilation to limit inhalation. Reacts violently with metals 
and organics.

6.0  Equipment and Supplies

    6.1  Sample Collection. Same as Method 7, Section 6.1.
    6.2  Sample Recovery. The following items are required for sample 
recovery:
    6.2.1  Wash Bottle. Polyethylene or glass.
    6.2.2  Volumetric Flasks. 100-ml (one for each sample).
    6.3  Analysis. The following items are required for analysis:
    6.3.1  Volumetric Pipettes. 5-, 10-, 15-, and 20-ml to make 
standards and sample dilutions.
    6.3.2  Volumetric Flasks. 1000- and 100-ml for preparing standards 
and dilution of samples.
    6.3.3  Spectrophotometer. To measure ultraviolet absorbance at 210 
nm.
    6.3.4  Analytical Balance. To measure to within 0.1 mg.

7.0  Reagents and Standards

    Note: Unless otherwise indicated, all reagents are to conform to 
the specifications established by the Committee on Analytical 
Reagents of the American Chemical Society, where such specifications 
are available. Otherwise, use the best available grade.


    7.1  Sample Collection. Same as Method 7, Section 7.1. It is 
important that the amount of hydrogen peroxide in the absorbing 
solution not be increased. Higher concentrations of peroxide may 
interfere with sample analysis.
    7.2  Sample Recovery. Same as Method 7, Section 7.2.
    7.3  Analysis. Same as Method 7, Sections 7.3.1, 7.3.3, and 7.3.4, 
with the addition of the following:
    7.3.1  Working Standard KNO3 Solution. Dilute 10 ml of 
the standard solution to 1000 ml with water. One milliliter of the 
working standard is equivalent to 10 g NO2.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Sample Collection. Same as Method 7, Section 8.1.
    8.2  Sample Recovery.
    8.2.1  Let the flask sit for a minimum of 16 hours, and then shake 
the contents for 2 minutes.
    8.2.2  Connect the flask to a mercury filled U-tube manometer. Open 
the valve from the flask to the manometer, and record the flask 
temperature (Tf), the barometric pressure, and the 
difference between the mercury levels in the manometer. The absolute 
internal pressure in the flask (Pf) is the barometric 
pressure less the manometer reading.
    8.2.3  Transfer the contents of the flask to a leak-free wash 
bottle. Rinse the flask three times with 10-ml portions of water, and 
add to the bottle. Mark the height of the liquid level so that the 
container can be checked for leakage after transport. Label the 
container to identify clearly its contents. Seal the container for 
shipping.

9.0  Quality Control

[[Page 61911]]



------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
10.1..........................  Spectrophometer    Ensures linearity of
                                 calibration.       spectrophotometer
                                                    response to
                                                    standards.
11.4..........................  Audit sample       Evaluates analytical
                                 analysis.          technique and
                                                    preparation of
                                                    standards.
------------------------------------------------------------------------

10.0  Calibration and Standardizations

    Same as Method 7, Sections 10.2 through 10.5, with the addition of 
the following:
    10.1  Determination of Spectrophotometer Standard Curve. Add 0 ml, 
5 ml, 10 ml, 15 ml, and 20 ml of the KNO3 working standard 
solution (1 ml = 10 g NO2) to a series of five 100-
ml volumetric flasks. To each flask, add 5 ml of absorbing solution. 
Dilute to the mark with water. The resulting solutions contain 0.0, 50, 
100, 150, and 200 g NO2, respectively. Measure the 
absorbance by ultraviolet spectrophotometry at 210 nm, using the blank 
as a zero reference. Prepare a standard curve plotting absorbance vs. 
g NO2.


    Note: If other than a 20-ml aliquot of sample is used for 
analysis, then the amount of absorbing solution in the blank and 
standards must be adjusted such that the same amount of absorbing 
solution is in the blank and standards as is in the aliquot of 
sample used.


    10.1.1  Calculate the spectrophotometer calibration factor as 
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.208

Where:

Mi = Mass of NO2 in standard i, g.
Ai = Absorbance of NO2 standard i.
n = Total number of calibration standards.

    10.1.2  For the set of calibration standards specified here, 
Equation 7B-1 simplifies to the following:
[GRAPHIC] [TIFF OMITTED] TR17OC00.209

    10.2  Spectrophotometer Calibration Quality Control. Multiply the 
absorbance value obtained for each standard by the Kc factor 
(reciprocal of the least squares slope) to determine the distance each 
calibration point lies from the theoretical calibration line. The 
difference between the calculated concentration values and the actual 
concentrations (i.e., 50, 100, 150, and 200 g NO2) 
should be less than 7 percent for all standards.

11.0  Analytical Procedures

    11.1  Sample Loss Check. Note the level of the liquid in the 
container, and confirm whether any sample was lost during shipment. 
Note this on the analytical data sheet. If a noticeable amount of 
leakage has occurred, either void the sample or use methods, subject to 
the approval of the Administrator, to correct the final results.
    11.2  Sample Preparation. Immediately prior to analysis, transfer 
the contents of the shipping container to a 100-ml volumetric flask, 
and rinse the container twice with 5-ml portions of water. Add the 
rinse water to the flask, and dilute to mark with water.
    11.3  Sample Analysis. Mix the contents of the flask thoroughly and 
pipette a 20 ml-aliquot of sample into a 100-ml volumetric flask. 
Dilute to the mark with water. Using the blank as zero reference, read 
the absorbance of the sample at 210 nm.
    11.4  Audit Sample Analysis. Same as Method 7, Section 11.4, except 
that a set of audit samples must be analyzed with each set of 
compliance samples or once per analysis day, or once per week when 
averaging continuous samples.

12.0  Data Analysis and Calculations

    Same as Method 7, Section 12.0, except replace Section 12.3 with 
the following:
    12.1 Total g NO2 Per Sample.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.211
    
Where:

5 = 100/20, the aliquot factor.


    Note: If other than a 20-ml aliquot is used for analysis, the 
factor 5 must be replaced by a corresponding factor.

13.0  Method Performance

    13.1  Range. The analytical range of the method as outlined has 
been determined to be 57 to 1500 milligrams NOX (as 
NO2) per dry standard cubic meter, or 30 to 786 parts per 
million by volume (ppmv) NOX.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    1. National Institute for Occupational Safety and Health. 
Recommendations for Occupational Exposure to Nitric Acid. In: 
Occupational Safety and Health Reporter. Washington, D.C. Bureau of 
National Affairs, Inc. 1976. p. 149.
    2. Rennie, P.J., A.M. Sumner, and F.B. Basketter. Determination 
of Nitrate in Raw, Potable, and Waste Waters by Ultraviolet 
Spectrophotometry. Analyst. 104:837. September 1979.

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

Method 7C--Determination of Nitrogen Oxide Emissions From 
Stationary Sources (Alkaline Permanganate/Colorimetric Method)

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in this part. 
Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of at least the following 
additional test methods: Method 1, Method 3, Method 6 and Method 7.

1.0  Scope and Application

    1.1  Analytes.

[[Page 61912]]



------------------------------------------------------------------------
              Analyte                   CAS no.          Sensitivity
------------------------------------------------------------------------
Nitrogen oxides (NOX), as NO2,
 including:
    Nitric oxide (NO).............      10102-43-9  ....................
    Nitrogen dioxide (NO2)........     10102-44-07  ppmv
------------------------------------------------------------------------

    1.2  Applicability. This method applies to the measurement of 
NOX emissions from fossil-fuel fired steam generators, 
electric utility plants, nitric acid plants, or other sources as 
specified in the regulations.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    An integrated gas sample is extracted from the stack and passed 
through impingers containing an alkaline potassium permanganate 
solution; NOX (NO + NO2) emissions are oxidized 
to NO2 and NO3. Then NO3-is 
reduced to NO2-with cadmium, and the 
NO2-is analyzed colorimetrically.

3.0  Definitions. [Reserved]

4.0  Interferences

    Possible interferents are sulfur dioxides (SO2) and 
ammonia (NH3).
    4.1  High concentrations of SO2 could interfere because 
SO2 consumes MnO4 (as does NOX) and, 
therefore, could reduce the NOX collection efficiency. 
However, when sampling emissions from a coal-fired electric utility 
plant burning 2.1 percent sulfur coal with no control of SO2 
emissions, collection efficiency was not reduced. In fact, calculations 
show that sampling 3000 ppm SO2 will reduce the 
MnO4 concentration by only 5 percent if all the 
SO2 is consumed in the first impinger.
    4.2  Ammonia (NH3) is slowly oxidized to 
NO3- by the absorbing solution. At 100 ppm 
NH3 in the gas stream, an interference of 6 ppm 
NOX (11 mg NO2/m\3\) was observed when the sample 
was analyzed 10 days after collection. Therefore, the method may not be 
applicable to plants using NH3 injection to control 
NOX emissions unless means are taken to correct the results. 
An equation has been developed to allow quantification of the 
interference and is discussed in Reference 5 of Section 16.0.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and to determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Corrosive Reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water for at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burns as thermal 
burns.
    5.2.1  Hydrochloric Acid (HCl). Highly toxic and corrosive. Causes 
severe damage to skin. Vapors are highly irritating to eyes, skin, 
nose, and lungs, causing severe damage. May cause bronchitis, 
pneumonia, or edema of lungs. Exposure to vapor concentrations of 0.13 
to 0.2 percent can be lethal in minutes. Will react with metals, 
producing hydrogen.
    5.2.2  Oxalic Acid (COOH)2. Poisonous. Irritating to 
eyes, skin, nose, and throat.
    5.2.3  Sodium Hydroxide (NaOH). Causes severe damage to eye tissues 
and to skin. Inhalation causes irritation to nose, throat, and lungs. 
Reacts exothermically with small amounts of water.
    5.2.4  Potassium Permanganate (KMnO4). Caustic, strong 
oxidizer. Avoid bodily contact with.

6.0  Equipment and Supplies

    6.1  Sample Collection and Sample Recovery. A schematic of the 
Method 7C sampling train is shown in Figure 7C-1, and component parts 
are discussed below. Alternative apparatus and procedures are allowed 
provided acceptable accuracy and precision can be demonstrated to the 
satisfaction of the Administrator.
    6.1.1  Probe. Borosilicate glass tubing, sufficiently heated to 
prevent water condensation and equipped with an in-stack or heated out-
of-stack filter to remove particulate matter (a plug of glass wool is 
satisfactory for this purpose). Stainless steel or Teflon tubing may 
also be used for the probe.
    6.1.2  Impingers. Three restricted-orifice glass impingers, having 
the specifications given in Figure 7C-2, are required for each sampling 
train. The impingers must be connected in series with leak-free glass 
connectors. Stopcock grease may be used, if necessary, to prevent 
leakage. (The impingers can be fabricated by a glass blower if not 
available commercially.)
    6.1.3  Glass Wool, Stopcock Grease, Drying Tube, Valve, Pump, 
Barometer, and Vacuum Gauge and Rotameter. Same as in Method 6, 
Sections 6.1.1.3, 6.1.1.4, 6.1.1.6, 6.1.1.7, 6.1.1.8, 6.1.2, and 6.1.3, 
respectively.
    6.1.4  Rate Meter. Rotameter, or equivalent, accurate to within 2 
percent at the selected flow rate of between 400 and 500 ml/min (0.014 
to 0.018 cfm). For rotameters, a range of 0 to 1 liter/min (0 to 0.035 
cfm) is recommended.
    6.1.5  Volume Meter. Dry gas meter (DGM) capable of measuring the 
sample volume under the sampling conditions of 400 to 500 ml/min (0.014 
to 0.018 cfm) for 60 minutes within an accuracy of 2 percent.
    6.1.6  Filter. To remove NOX from ambient air, prepared 
by adding 20 g of 5-angstrom molecular sieve to a cylindrical tube 
(e.g., a polyethylene drying tube).
    6.1.7  Polyethylene Bottles. 1-liter, for sample recovery.
    6.1.8  Funnel and Stirring Rods. For sample recovery.
    6.2  Sample Preparation and Analysis.
    6.2.1  Hot Plate. Stirring type with 50- by 10-mm Teflon-coated 
stirring bars.
    6.2.2  Beakers. 400-, 600-, and 1000-ml capacities.
    6.2.3  Filtering Flask. 500-ml capacity with side arm.
    6.2.4  Buchner Funnel. 75-mm ID, with spout equipped with a 13-mm 
ID by 90-mm long piece of Teflon tubing to minimize possibility of 
aspirating sample solution during filtration.
    6.2.5  Filter Paper. Whatman GF/C, 7.0-cm diameter.
    6.2.6  Stirring Rods.
    6.2.7  Volumetric Flasks. 100-, 200- or 250-, 500-, and 1000-ml 
capacity.
    6.2.8  Watch Glasses. To cover 600- and 1000-ml beakers.
    6.2.9  Graduated Cylinders. 50- and 250-ml capacities.
    6.2.10  Pipettes. Class A.
    6.2.11  pH Meter. To measure pH from 0.5 to 12.0.
    6.2.12  Burette. 50-ml with a micrometer type stopcock. (The 
stopcock is Catalog No. 8225-t-05, Ace Glass, Inc., Post Office Box 
996, Louisville, Kentucky 50201.) Place a glass wool plug in bottom of 
burette. Cut off burette at a height of 43 cm (17 in.)

[[Page 61913]]

from the top of plug, and have a blower attach a glass funnel to top of 
burette such that the diameter of the burette remains essentially 
unchanged. Other means of attaching the funnel are acceptable.
    6.2.13  Glass Funnel. 75-mm ID at the top.
    6.2.14  Spectrophotometer. Capable of measuring absorbance at 540 
nm; 1-cm cells are adequate.
    6.2.15  Metal Thermometers. Bimetallic thermometers, range 0 to 150 
 deg.C (32 to 300  deg.F).
    6.2.16  Culture Tubes. 20-by 150-mm, Kimax No. 45048.
    6.2.17  Parafilm ``M.'' Obtained from American Can Company, 
Greenwich, Connecticut 06830.
    6.2.18  CO2 Measurement Equipment. Same as in Method 3, 
Section 6.0.

7.0  Reagents and Standards

    Unless otherwise indicated, it is intended that all reagents 
conform to the specifications established by the Committee on 
Analytical Reagents of the American Chemical Society, where such 
specifications are available; otherwise, use the best available grade.
    7.1  Sample Collection.
    7.1.1  Water. Deionized distilled to conform to ASTM Specification 
D 1193-77 or 91 Type 3 (incorporated by reference--see Sec. 60.17).
    7.1.2  Potassium Permanganate, 4.0 Percent (w/w), Sodium Hydroxide, 
2.0 Percent (w/w) solution (KMnO4/NaOH solution). Dissolve 
40.0 g of KMnO4 and 20.0 g of NaOH in 940 ml of water.
    7.2  Sample Preparation and Analysis.
    7.2.1  Water. Same as in Section 7.1.1.
    7.2.2  Oxalic Acid Solution. Dissolve 48 g of oxalic acid 
[(COOH)22H2O] in water, and dilute to 
500 ml. Do not heat the solution.
    7.2.3  Sodium Hydroxide, 0.5 N. Dissolve 20 g of NaOH in water, and 
dilute to 1 liter.
    7.2.4  Sodium Hydroxide, 10 N. Dissolve 40 g of NaOH in water, and 
dilute to 100 ml.
    7.2.5  Ethylenediamine Tetraacetic Acid (EDTA) Solution, 6.5 
percent (w/v). Dissolve 6.5 g of EDTA (disodium salt) in water, and 
dilute to 100 ml. Dissolution is best accomplished by using a magnetic 
stirrer.
    7.2.6  Column Rinse Solution. Add 20 ml of 6.5 percent EDTA 
solution to 960 ml of water, and adjust the pH to between 11.7 and 12.0 
with 0.5 N NaOH.
    7.2.7  Hydrochloric Acid (HCl), 2 N. Add 86 ml of concentrated HCl 
to a 500 ml-volumetric flask containing water, dilute to volume, and 
mix well. Store in a glass-stoppered bottle.
    7.2.8  Sulfanilamide Solution. Add 20 g of sulfanilamide (melting 
point 165 to 167  deg.C (329 to 333  deg.F)) to 700 ml of water. Add, 
with mixing, 50 ml concentrated phosphoric acid (85 percent), and 
dilute to 1000 ml. This solution is stable for at least 1 month, if 
refrigerated.
    7.2.9  N-(1-Naphthyl)-Ethylenediamine Dihydrochloride (NEDA) 
Solution. Dissolve 0.5 g of NEDA in 500 ml of water. An aqueous 
solution should have one absorption peak at 320 nm over the range of 
260 to 400 nm. NEDA that shows more than one absorption peak over this 
range is impure and should not be used. This solution is stable for at 
least 1 month if protected from light and refrigerated.
    7.2.10  Cadmium. Obtained from Matheson Coleman and Bell, 2909 
Highland Avenue, Norwood, Ohio 45212, as EM Laboratories Catalog No. 
2001. Prepare by rinsing in 2 N HCl for 5 minutes until the color is 
silver-grey. Then rinse the cadmium with water until the rinsings are 
neutral when tested with pH paper. CAUTION: H2 is liberated 
during preparation. Prepare in an exhaust hood away from any flame or 
combustion source.
    7.2.11  Sodium Sulfite (NaNO2) Standard Solution, 
Nominal Concentration, 1000 g NO2-/ml. 
Desiccate NaNO2 overnight. Accurately weigh 1.4 to 1.6 g of 
NaNO2 (assay of 97 percent NaNO2 or greater), 
dissolve in water, and dilute to 1 liter. Calculate the exact 
NO2-concentration using Equation 7C-1 in Section 12.2. This 
solution is stable for at least 6 months under laboratory conditions.
    7.2.12  Potassium Nitrate (KNO3) Standard Solution. Dry 
KNO3 at 110  deg.C (230  deg.F) for 2 hours, and cool in a 
desiccator. Accurately weigh 9 to 10 g of KNO3 to within 0.1 
mg, dissolve in water, and dilute to 1 liter. Calculate the exact 
NO3- concentration using Equation 7C-2 in Section 
12.3. This solution is stable for 2 months without preservative under 
laboratory conditions.
    7.2.13  Spiking Solution. Pipette 7 ml of the KNO3 
standard into a 100-ml volumetric flask, and dilute to volume.
    7.2.14  Blank Solution. Dissolve 2.4 g of KMnO4 and 1.2 
g of NaOH in 96 ml of water. Alternatively, dilute 60 ml of 
KMnO4/NaOH solution to 100 ml.
    7.2.15  Quality Assurance Audit Samples. Same as in Method 7, 
Section 7.3.10. When requesting audit samples, specify that they be in 
the appropriate concentration range for Method 7C.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Preparation of Sampling Train. Add 200 ml of KMnO4/
NaOH solution (Section 7.1.2) to each of three impingers, and assemble 
the train as shown in Figure 7C-1. Adjust the probe heater to a 
temperature sufficient to prevent water condensation.
    8.2  Leak-Checks. Same as in Method 6, Section 8.2.
    8.3  Sample Collection.
    8.3.1  Record the initial DGM reading and barometric pressure. 
Determine the sampling point or points according to the appropriate 
regulations (e.g., Sec. 60.46(b)(5) of 40 CFR Part 60). Position the 
tip of the probe at the sampling point, connect the probe to the first 
impinger, and start the pump. Adjust the sample flow to a value between 
400 and 500 ml/min (0.014 and 0.018 cfm). CAUTION: DO NOT EXCEED THESE 
FLOW RATES. Once adjusted, maintain a constant flow rate during the 
entire sampling run. Sample for 60 minutes. For relative accuracy (RA) 
testing of continuous emission monitors, the minimum sampling time is 1 
hour, sampling 20 minutes at each traverse point.


    Note: When the SO2 concentration is greater than 1200 
ppm, the sampling time may have to be reduced to 30 minutes to 
eliminate plugging of the impinger orifice with MnO2. For 
RA tests with SO2 greater than 1200 ppm, sample for 30 
minutes (10 minutes at each point).


    8.3.2  Record the DGM temperature, and check the flow rate at least 
every 5 minutes. At the conclusion of each run, turn off the pump, 
remove the probe from the stack, and record the final readings. Divide 
the sample volume by the sampling time to determine the average flow 
rate. Conduct the mandatory post-test leak-check. If a leak is found, 
void the test run, or use procedures acceptable to the Administrator to 
adjust the sample volume for the leakage.
    8.4  CO2 Measurement. During sampling, measure the 
CO2 content of the stack gas near the sampling point using 
Method 3. The single-point grab sampling procedure is adequate, 
provided the measurements are made at least three times (near the 
start, midway, and before the end of a run), and the average 
CO2 concentration is computed. The Orsat or Fyrite analyzer 
may be used for this analysis.
    8.5  Sample Recovery. Disconnect the impingers. Pour the contents 
of the impingers into a 1-liter polyethylene bottle using a funnel and 
a stirring rod (or other means) to prevent spillage. Complete the 
quantitative transfer by

[[Page 61914]]

rinsing the impingers and connecting tubes with water until the 
rinsings are clear to light pink, and add the rinsings to the bottle. 
Mix the sample, and mark the solution level. Seal and identify the 
sample container.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.2, 10.1-10.3................  Sampling           Ensure accurate
                                 equipment leak-    measurement of
                                 check and          sample volume.
                                 calibration.
10.4..........................  Spectrophotometer  Ensure linearity of
                                 calibration.       spectrophotometer
                                                    response to
                                                    standards.
11.3..........................  Spiked sample      Ensure reduction
                                 analysis.          efficiency of
                                                    column.
11.6..........................  Audit sample       Evaluate analytical
                                 analysis.          technique,
                                                    preparation of
                                                    standards.
------------------------------------------------------------------------

10.0  Calibration and Standardizations

    10.1  Volume Metering System. Same as Method 6, Section 10.1. For 
detailed instructions on carrying out these calibrations, it is 
suggested that Section 3.5.2 of Reference 4 of Section 16.0 be 
consulted.
    10.2  Temperature Sensors and Barometer. Same as in Method 6, 
Sections 10.2 and 10.4, respectively.
    10.3  Check of Rate Meter Calibration Accuracy (Optional). 
Disconnect the probe from the first impinger, and connect the filter. 
Start the pump, and adjust the rate meter to read between 400 and 500 
ml/min (0.014 and 0.018 cfm). After the flow rate has stabilized, start 
measuring the volume sampled, as recorded by the dry gas meter and the 
sampling time. Collect enough volume to measure accurately the flow 
rate. Then calculate the flow rate. This average flow rate must be less 
than 500 ml/min (0.018 cfm) for the sample to be valid; therefore, it 
is recommended that the flow rate be checked as above prior to each 
test.
    10.4  Spectrophotometer.
    10.4.1  Dilute 5.0 ml of the NaNO2 standard solution to 
200 ml with water. This solution nominally contains 25 g 
NO2-/ml. Use this solution to prepare calibration 
standards to cover the range of 0.25 to 3.00 g 
NO2-/ml. Prepare a minimum of three standards 
each for the linear and slightly nonlinear (described below) range of 
the curve. Use pipettes for all additions.
    10.4.2  Measure the absorbance of the standards and a water blank 
as instructed in Section 11.5. Plot the net absorbance vs. g 
NO2-/ml. Draw a smooth curve through the points. 
The curve should be linear up to an absorbance of approximately 1.2 
with a slope of approximately 0.53 absorbance units/g 
NO2-/ml. The curve should pass through the 
origin. The curve is slightly nonlinear from an absorbance of 1.2 to 
1.6.

11.0  Analytical Procedures

    11.1  Sample Stability. Collected samples are stable for at least 
four weeks; thus, analysis must occur within 4 weeks of collection.
    11.2  Sample Preparation.
    11.2.1  Prepare a cadmium reduction column as follows: Fill the 
burette with water. Add freshly prepared cadmium slowly, with tapping, 
until no further settling occurs. The height of the cadmium column 
should be 39 cm (15 in). When not in use, store the column under rinse 
solution.


    Note: The column should not contain any bands of cadmium fines. 
This may occur if regenerated cadmium is used and will greatly 
reduce the column lifetime.


    11.2.2  Note the level of liquid in the sample container, and 
determine whether any sample was lost during shipment. If a noticeable 
amount of leakage has occurred, the volume lost can be determined from 
the difference between initial and final solution levels, and this 
value can then be used to correct the analytical result. Quantitatively 
transfer the contents to a 1-liter volumetric flask, and dilute to 
volume.
    11.2.3  Take a 100-ml aliquot of the sample and blank (unexposed 
KMnO4/NaOH) solutions, and transfer to 400-ml beakers 
containing magnetic stirring bars. Using a pH meter, add concentrated 
H2SO4 with stirring until a pH of 0.7 is 
obtained. Allow the solutions to stand for 15 minutes. Cover the 
beakers with watch glasses, and bring the temperature of the solutions 
to 50  deg.C (122  deg.F). Keep the temperature below 60  deg.C (140 
deg.F). Dissolve 4.8 g of oxalic acid in a minimum volume of water, 
approximately 50 ml, at room temperature. Do not heat the solution. Add 
this solution slowly, in increments, until the KMnO4 
solution becomes colorless. If the color is not completely removed, 
prepare some more of the above oxalic acid solution, and add until a 
colorless solution is obtained. Add an excess of oxalic acid by 
dissolving 1.6 g of oxalic acid in 50 ml of water, and add 6 ml of this 
solution to the colorless solution. If suspended matter is present, add 
concentrated H2SO4 until a clear solution is 
obtained.
    11.2.4  Allow the samples to cool to near room temperature, being 
sure that the samples are still clear. Adjust the pH to between 11.7 
and 12.0 with 10 N NaOH. Quantitatively transfer the mixture to a 
Buchner funnel containing GF/C filter paper, and filter the 
precipitate. Filter the mixture into a 500-ml filtering flask. Wash the 
solid material four times with water. When filtration is complete, wash 
the Teflon tubing, quantitatively transfer the filtrate to a 500-ml 
volumetric flask, and dilute to volume. The samples are now ready for 
cadmium reduction. Pipette a 50-ml aliquot of the sample into a 150-ml 
beaker, and add a magnetic stirring bar. Pipette in 1.0 ml of 6.5 
percent EDTA solution, and mix.
    11.3  Determine the correct stopcock setting to establish a flow 
rate of 7 to 9 ml/min of column rinse solution through the cadmium 
reduction column. Use a 50-ml graduated cylinder to collect and measure 
the solution volume. After the last of the rinse solution has passed 
from the funnel into the burette, but before air entrapment can occur, 
start adding the sample, and collect it in a 250-ml graduated cylinder. 
Complete the quantitative transfer of the sample to the column as the 
sample passes through the column. After the last of the sample has 
passed from the funnel into the burette, start adding 60 ml of column 
rinse solution, and collect the rinse solution until the solution just 
disappears from the funnel. Quantitatively transfer the sample to a 
200-ml volumetric flask (a 250-ml flask may be required), and dilute to 
volume. The samples are now ready for NO2-analysis.


    Note: Two spiked samples should be run with every group of 
samples passed through the column. To do this, prepare two 
additional 50-ml aliquots of the sample suspected to have the 
highest NO2-concentration, and add 1 ml of the spiking 
solution to these aliquots. If the spike recovery or column 
efficiency (see Section 12.2) is below 95 percent, prepare a new 
column, and repeat the cadmium reduction.


[[Page 61915]]


    11.4  Repeat the procedures outlined in Sections 11.2 and 11.3 for 
each sample and each blank.
    11.5  Sample Analysis. Pipette 10 ml of sample into a culture tube. 
Pipette in 10 ml of sulfanilamide solution and 1.4 ml of NEDA solution. 
Cover the culture tube with parafilm, and mix the solution. Prepare a 
blank in the same manner using the sample from treatment of the 
unexposed KMnO4/NaOH solution. Also, prepare a calibration 
standard to check the slope of the calibration curve. After a 10-minute 
color development interval, measure the absorbance at 540 nm against 
water. Read g NO2-/ml from the 
calibration curve. If the absorbance is greater than that of the 
highest calibration standard, use less than 10 ml of sample, and repeat 
the analysis. Determine the NO2-concentration 
using the calibration curve obtained in Section 10.4.

    Note: Some test tubes give a high blank 
NO2- value but culture tubes do not.


    11.6  Audit Sample Analysis. Same as in Method 7, Section 11.4.

12.0  Data Analysis and Calculations

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

B = Analysis of blank, g NO2-/ml.
C = Concentration of NOX as NO2, dry basis, mg/
dsm3.
E = Column efficiency, dimensionless
K2 = 10-3 mg/g.
m = Mass of NOX, as NO2, in sample, g.
Pbar = Barometric pressure, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
s = Concentration of spiking solution, g NO3/ml.
S = Analysis of sample, g NO2-/ml.
Tm = Average dry gas meter absolute temperature,  deg.K.
Tstd = Standard absolute temperature, 293  deg.K (528 
deg.R).
Vm(std) = Dry gas volume measured by the dry gas meter, 
corrected to standard conditions, dscm (dscf).
Vm = Dry gas volume as measured by the dry gas meter, scm 
(scf).
x = Analysis of spiked sample, g NO2-/
ml.
X = Correction factor for CO2 collection = 100/(100 - 
%CO2(V/V)).
y = Analysis of unspiked sample, g NO2-/
ml.
Y = Dry gas meter calibration factor.
1.0 ppm NO = 1.247 mg NO/m3 at STP.
1.0 ppm NO2 = 1.912 mg NO2/m3 at STP.
1 ft3 = 2.832  x  10-2 m3.

    12.2  NO2 Concentration. Calculate the NO2 
concentration of the solution (see Section 7.2.11) using the following 
equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.212

    12.3  NO3 Concentration. Calculate the NO3 
concentration of the KNO3 solution (see Section 7.2.12) 
using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.213

    12.4  Sample Volume, Dry Basis, Corrected to Standard Conditions.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.214
    
Where:

K1 = 0.3855  deg.K/mm Hg for metric units.
K1 = 17.65  deg.R/in. Hg for English units.

    12.5  Efficiency of Cadmium Reduction Column. Calculate this value 
as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.215

Where:

200 = Final volume of sample and blank after passing through the 
column, ml.
1.0 = Volume of spiking solution added, ml.
46.01 = g NO2-/mole.
62.01 = g NO3-/mole.


    12.6  Total g NO2.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.216
    
Where:

500 = Total volume of prepared sample, ml.
50 = Aliquot of prepared sample processed through cadmium column, ml.
100 = Aliquot of KMnO4/NaOH solution, ml.

[[Page 61916]]

1000 = Total volume of KMnO4/NaOH solution, ml.

    12.7  Sample Concentration.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.217
    
13.0  Method Performance

    13.1  Precision. The intra-laboratory relative standard deviation 
for a single measurement is 2.8 and 2.9 percent at 201 and 268 ppm 
NOX, respectively.
    13.2  Bias. The method does not exhibit any bias relative to Method 
7.
    13.3  Range. The lower detectable limit is 13 mg NOX/
m3, as NO2 (7 ppm NOX) when sampling 
at 500 ml/min for 1 hour. No upper limit has been established; however, 
when using the recommended sampling conditions, the method has been 
found to collect NOX emissions quantitatively up to 1782 mg 
NOX/m3, as NO2 (932 ppm 
NOX).

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    1. Margeson, J.H., W.J. Mitchell, J.C. Suggs, and M.R. Midgett. 
Integrated Sampling and Analysis Methods for Determining 
NOX Emissions at Electric Utility Plants. U.S. 
Environmental Protection Agency, Research Triangle Park, NC. Journal 
of the Air Pollution Control Association. 32:1210-1215. 1982.
    2. Memorandum and attachment from J.H. Margeson, Source Branch, 
Quality Assurance Division, Environmental Monitoring Systems 
Laboratory, to The Record, EPA. March 30, 1983. NH3 
Interference in Methods 7C and 7D.
    3. Margeson, J.H., J.C. Suggs, and M.R. Midgett. Reduction of 
Nitrate to Nitrite with Cadmium. Anal. Chem. 52:1955-57. 1980.
    4. Quality Assurance Handbook for Air Pollution Measurement 
Systems. Volume III--Stationary Source Specific Methods. U.S. 
Environmental Protection Agency. Research Triangle Park, NC. 
Publication No. EPA-600/4-77-027b. August 1977.
    5. Margeson, J.H., et al. An Integrated Method for Determining 
NOX Emissions at Nitric Acid Plants. Analytical 
Chemistry. 47 (11):1801. 1975.

BILLING CODE 6560-50-P

[[Page 61917]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.218


[[Page 61918]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.219


[[Page 61919]]


BILLING CODE 6560-50-C

Method 7D--Determination of Nitrogen Oxide Emissions From 
Stationary Sources (Alkaline-Permanganate/Ion Chromatographic 
Method)

    Note: This method is not inclusive with respect to 
specifications (e.g., equipment and supplies) and procedures (e.g., 
sampling and analytical) essential to its performance. Some material 
is incorporated by reference from other methods in this part. 
Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of at least the following 
additional test methods: Method 1, Method 3, Method 6, Method 7, and 
Method 7C.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
              Analyte                   CAS No.          Sensitivity
------------------------------------------------------------------------
Nitrogen oxides (NOX), as NO2,
 including:
    Nitric oxide (NO).............      10102-43-9
    Nitrogen dioxide (NO2)........      10102-44-0  7 ppmv
------------------------------------------------------------------------

    1.2  Applicability. This method applies to the measurement of 
NOX emissions from fossil-fuel fired steam generators, 
electric utility plants, nitric acid plants, or other sources as 
specified in the regulations.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    An integrated gas sample is extracted from the stack and passed 
through impingers containing an alkaline-potassium permanganate 
solution; NOX (NO + NO2) emissions are oxidized 
to NO3-. Then NO3- is 
analyzed by ion chromatography.

3.0  Definitions [Reserved]

4.0  Interferences

    Same as in Method 7C, Section 4.0.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and to determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Corrosive reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water for at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burns as thermal 
burns.
    5.2.1  Hydrogen Peroxide (H2O2). Irritating 
to eyes, skin, nose, and lungs. 30% H2O2 is a 
strong oxidizing agent; avoid contact with skin, eyes, and combustible 
material. Wear gloves when handling.
    5.2.2  Sodium Hydroxide (NaOH). Causes severe damage to eye tissues 
and to skin. Inhalation causes irritation to nose, throat, and lungs. 
Reacts exothermically with limited amounts of water.
    5.2.3  Potassium Permanganate (KMnO4). Caustic, strong 
oxidizer. Avoid bodily contact with.

6.0  Equipment and Supplies

    6.1  Sample Collection and Sample Recovery. Same as Method 7C, 
Section 6.1. A schematic of the sampling train used in performing this 
method is shown in Figure 7C-1 of Method 7C.
    6.2  Sample Preparation and Analysis.
    6.2.1  Magnetic Stirrer. With 25- by 10-mm Teflon-coated stirring 
bars.
    6.2.2  Filtering Flask. 500-ml capacity with sidearm.
    6.2.3  Buchner Funnel. 75-mm ID, with spout equipped with a 13-mm 
ID by 90-mm long piece of Teflon tubing to minimize possibility of 
aspirating sample solution during filtration.
    6.2.4  Filter Paper. Whatman GF/C, 7.0-cm diameter.
    6.2.5  Stirring Rods.
    6.2.6  Volumetric Flask. 250-ml.
    6.2.7  Pipettes. Class A.
    6.2.8  Erlenmeyer Flasks. 250-ml.
    6.2.9  Ion Chromatograph. Equipped with an anion separator column 
to separate NO3-, H3+ 
suppressor, and necessary auxiliary equipment. Nonsuppressed and other 
forms of ion chromatography may also be used provided that adequate 
resolution of NO3- is obtained. The system must 
also be able to resolve and detect NO2-.

7.0  Reagents and Standards

    Note: Unless otherwise indicated, it is intended that all 
reagents conform to the specifications established by the Committee 
on Analytical Reagents of the American Chemical Society, where such 
specifications are available; otherwise, use the best available 
grade.


    7.1  Sample Collection.
    7.1.1  Water. Deionized distilled to conform to ASTM specification 
D 1193-77 or 91 Type 3 (incorporated by reference--see Sec. 60.17).
    7.1.2  Potassium Permanganate, 4.0 Percent (w/w), Sodium Hydroxide, 
2.0 Percent (w/w). Dissolve 40.0 g of KMnO4 and 20.0 g of 
NaOH in 940 ml of water.
    7.2  Sample Preparation and Analysis.
    7.2.1  Water. Same as in Section 7.1.1.
    7.2.2  Hydrogen Peroxide (H2O2), 5 Percent. 
Dilute 30 percent H2O2 1:5 (v/v) with water.
    7.2.3  Blank Solution. Dissolve 2.4 g of KMnO4 and 1.2 g 
of NaOH in 96 ml of water. Alternatively, dilute 60 ml of 
KMnO4/NaOH solution to 100 ml.
    7.2.4  KNO3 Standard Solution. Dry KNO3 at 
110 deg.C for 2 hours, and cool in a desiccator. Accurately weigh 9 to 
10 g of KNO3 to within 0.1 mg, dissolve in water, and dilute 
to 1 liter. Calculate the exact NO3- 
concentration using Equation 7D-1 in Section 12.2. This solution is 
stable for 2 months without preservative under laboratory conditions.
    7.2.5  Eluent, 0.003 M NaHCO3/0.0024 M 
Na2CO3. Dissolve 1.008 g NaHCO3 and 
1.018 g Na2CO3 in water, and dilute to 4 liters. 
Other eluents capable of resolving nitrate ion from sulfate and other 
species present may be used.
    7.2.6  Quality Assurance Audit Samples. Same as Method 7, Section 
7.3.10. When requesting audit samples, specify that they be in the 
appropriate concentration range for Method 7D.
    8.0  Sample Collection, Preservation, Transport, and Storage.
    8.1  Sampling. Same as in Method 7C, Section 8.1.
    8.2  Sample Recovery. Same as in Method 7C, Section 8.2.
    8.3  Sample Preparation for Analysis.

    Note: Samples must be analyzed within 28 days of collection.


    8.3.1  Note the level of liquid in the sample container, and 
determine whether any sample was lost during shipment. If a noticeable 
amount of

[[Page 61920]]

leakage has occurred, the volume lost can be determined from the 
difference between initial and final solution levels, and this value 
can then be used to correct the analytical result. Quantitatively 
transfer the contents to a 1-liter volumetric flask, and dilute to 
volume.
    8.3.2  Sample preparation can be started 36 hours after collection. 
This time is necessary to ensure that all NO2- is 
converted to NO3- in the collection solution. 
Take a 50-ml aliquot of the sample and blank, and transfer to 250-ml 
Erlenmeyer flasks. Add a magnetic stirring bar. Adjust the stirring 
rate to as fast a rate as possible without loss of solution. Add 5 
percent H2O2 in increments of approximately 5 ml 
using a 5-ml pipette. When the KMnO4 color appears to have 
been removed, allow the precipitate to settle, and examine the 
supernatant liquid. If the liquid is clear, the H2O2 
addition is complete. If the KMnO4 color persists, add more 
H2O2, with stirring, until the supernatant liquid 
is clear.


    Note: The faster the stirring rate, the less volume of 
H2O2 that will be required to remove the 
KMnO4.) Quantitatively transfer the mixture to a Buchner 
funnel containing GF/C filter paper, and filter the precipitate. The 
spout of the Buchner funnel should be equipped with a 13-mm ID by 
90-mm long piece of Teflon tubing. This modification minimizes the 
possibility of aspirating sample solution during filtration. Filter 
the mixture into a 500-ml filtering flask. Wash the solid material 
four times with water. When filtration is complete, wash the Teflon 
tubing, quantitatively transfer the filtrate to a 250-ml volumetric 
flask, and dilute to volume. The sample and blank are now ready for 
NO3-analysis.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.2, 10.1-10.3................  Sampling           Ensure accurate
                                 equipment leak-    measurement of
                                 check and          sample volume.
                                 calibration.
10.4..........................  Spectrophotometer  Ensure linearity of
                                 calibration.       spectrophotometer
                                                    response to
                                                    standards.
11.3..........................  Spiked sample      Ensure reduction
                                 analysis.          efficiency of
                                                    column.
11.6..........................  Audit sample       Evaluate analytical
                                 analysis.          technique,
                                                    preparation of
                                                    standards.
------------------------------------------------------------------------

10.0  Calibration and Standardizations

    10.1  Dry Gas Meter (DGM) System.
    10.1.1  Initial Calibration. Same as in Method 6, Section 10.1.1. 
For detailed instructions on carrying out this calibration, it is 
suggested that Section 3.5.2 of Citation 4 in Section 16.0 of Method 7C 
be consulted.
    10.1.2  Post-Test Calibration Check. Same as in Method 6, Section 
10.1.2.
    10.2  Thermometers for DGM and Barometer. Same as in Method 6, 
Sections 10.2 and 10.4, respectively.
    10.3  Ion Chromatograph.
    10.3.1  Dilute a given volume (1.0 ml or greater) of the 
KNO3 standard solution to a convenient volume with water, 
and use this solution to prepare calibration standards. Prepare at 
least four standards to cover the range of the samples being analyzed. 
Use pipettes for all additions. Run standards as instructed in Section 
11.2. Determine peak height or area, and plot the individual values 
versus concentration in g NO3-/ml.
    10.3.2  Do not force the curve through zero. Draw a smooth curve 
through the points. The curve should be linear. With the linear curve, 
use linear regression to determine the calibration equation.

11.0  Analytical Procedures

    11.1  The following chromatographic conditions are recommended: 
0.003 M NaHCO3/0.0024 Na2CO3 eluent 
solution (Section 7.2.5), full scale range, 3 MHO; sample 
loop, 0.5 ml; flow rate, 2.5 ml/min. These conditions should give a 
NO3- retention time of approximately 15 minutes 
(Figure 7D-1).
    11.2  Establish a stable baseline. Inject a sample of water, and 
determine whether any NO3- appears in the 
chromatogram. If NO3- is present, repeat the 
water load/injection procedure approximately five times; then re-inject 
a water sample and observe the chromatogram. When no 
NO3- is present, the instrument is ready for use. 
Inject calibration standards. Then inject samples and a blank. Repeat 
the injection of the calibration standards (to compensate for any drift 
in response of the instrument). Measure the NO3- 
peak height or peak area, and determine the sample concentration from 
the calibration curve.

11.3  Audit Analysis. Same as in Method 7, Section 11.4

12.0  Data Analysis and Calculations

    Carry out calculations, retaining at least one extra significant 
figure beyond that of the acquired data. Round off figures after final 
calculation.
    12.1  Nomenclature. Same as in Method 7C, Section 12.1.
    12.2  NO3- concentration. Calculate the 
NO3- concentration in the KNO3 
standard solution (see Section 7.2.4) using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.220

    12.3  Sample Volume, Dry Basis, Corrected to Standard Conditions. 
Same as in Method 7C, Section 12.4.
    12.4  Total g NO2 Per Sample.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.221
    
Where:

250 = Volume of prepared sample, ml.
1000 = Total volume of KMnO4 solution, ml.
50 = Aliquot of KMnO4/NaOH solution, ml.
46.01 = Molecular weight of NO3-.
    62.01 = Molecular weight of NO3-.

    12.5  Sample Concentration. Same as in Method 7C, Section 12.7.

[[Page 61921]]

13.0  Method Performance

    13.1  Precision. The intra-laboratory relative standard deviation 
for a single measurement is approximately 6 percent at 200 to 270 ppm 
NOx.
    13.2  Bias. The method does not exhibit any bias relative to Method 
7.
    13.3  Range. The lower detectable limit is similar to that of 
Method 7C. No upper limit has been established; however, when using the 
recommended sampling conditions, the method has been found to collect 
NOX emissions quantitatively up to 1782 mg NOX/
m\3\, as NO2 (932 ppm NOx).

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    Same as Method 7C, Section 16.0, References 1, 2, 4, and 5.
BILLING CODE 6560-50-P

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.222

BILLING CODE 6560-50-C
* * * * *

Method 8--Determination of Sulfuric Acid and Sulfur Dioxide 
Emissions From Stationary Sources

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

[[Page 61922]]

of at least the following additional test methods: Method 1, Method 
2, Method 3, Method 5, and Method 6.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.            Sensitivity
------------------------------------------------------------------------
Sulfuric acid, including:       7664-93-9, 7449-   0.05 mg/m3 (0.03  x
 Sulfuric acid (H2SO4) mist,     11-9.              10-7 lb/ft3).
 Sulfur trioxide (SO3).
Sulfur dioxide (SO2)..........  7449-09-5........  1.2 mg/m3 (3  x  10-9
                                                    lb/ft3).
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of H2SO4 (including H2SO4 
mist and SO3) and gaseous SO2 emissions from 
stationary sources.


    Note: Filterable particulate matter may be determined along with 
H2SO4 and SO2 (subject to the 
approval of the Administrator) by inserting a heated glass fiber 
filter between the probe and isopropanol impinger (see Section 6.1.1 
of Method 6). If this option is chosen, particulate analysis is 
gravimetric only; sulfuric acid is not determined separately.


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

2.0  Summary of Method

    A gas sample is extracted isokinetically from the stack. The 
H2SO4 and the SO2 are separated, and 
both fractions are measured separately by the barium-thorin titration 
method.

3.0  Definitions. [Reserved]

4.0  Interferences

    4.1  Possible interfering agents of this method are fluorides, free 
ammonia, and dimethyl aniline. If any of these interfering agents is 
present (this can be determined by knowledge of the process), 
alternative methods, subject to the approval of the Administrator, are 
required.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Corrosive reagents. Same as Method 6, Section 5.2.

6.0  Equipment and Supplies

    6.1  Sample Collection. Same as Method 5, Section 6.1, with the 
following additions and exceptions:
    6.1.1  Sampling Train. A schematic of the sampling train used in 
this method is shown in Figure 8-1; it is similar to the Method 5 
sampling train, except that the filter position is different, and the 
filter holder does not have to be heated. See Method 5, Section 6.1.1, 
for details and guidelines on operation and maintenance.
    6.1.1.1  Probe Liner. Borosilicate or quartz glass, with a heating 
system to prevent visible condensation during sampling. Do not use 
metal probe liners.
    6.1.1.2  Filter Holder. Borosilicate glass, with a glass frit 
filter support and a silicone rubber gasket. Other gasket materials 
(e.g., Teflon or Viton) may be used, subject to the approval of the 
Administrator. The holder design shall provide a positive seal against 
leakage from the outside or around the filter. The filter holder shall 
be placed between the first and second impingers. Do not heat the 
filter holder.
    6.1.1.3  Impingers. Four, of the Greenburg-Smith design, as shown 
in Figure 8-1. The first and third impingers must have standard tips. 
The second and fourth impingers must be modified by replacing the 
insert with an approximately 13-mm (\1/2\-in.) ID glass tube, having an 
unconstricted tip located 13 mm (\1/2\ in.) from the bottom of the 
impinger. Similar collection systems, subject to the approval of the 
Administrator, may be used.
    6.1.1.4  Temperature Sensor. Thermometer, or equivalent, to measure 
the temperature of the gas leaving the impinger train to within 1 
deg.C (2  deg.F).
    6.2  Sample Recovery. The following items are required for sample 
recovery:
    6.2.1  Wash Bottles. Two polyethylene or glass bottles, 500-ml.
    6.2.2  Graduated Cylinders. Two graduated cylinders (volumetric 
flasks may be used), 250-ml, 1-liter.
    6.2.3  Storage Bottles. Leak-free polyethylene bottles, 1-liter 
size (two for each sampling run).
    6.2.4  Trip Balance. 500-g capacity, to measure to  0.5 
g (necessary only if a moisture content analysis is to be done).
    6.3  Analysis. The following items are required for sample 
analysis:
    6.3.1  Pipettes. Volumetric 10-ml, 100-ml.
    6.3.2  Burette. 50-ml.
    6.3.3  Erlenmeyer Flask. 250-ml (one for each sample, blank, and 
standard).
    6.3.4  Graduated Cylinder. 100-ml.
    6.3.5  Dropping Bottle. To add indicator solution, 125-ml size.

7.0  Reagents and Standards

    Note: Unless otherwise indicated, all reagents are to conform to 
the specifications established by the Committee on Analytical 
Reagents of the American Chemical Society, where such specifications 
are available. Otherwise, use the best available grade.


    7.1  Sample Collection. The following reagents are required for 
sample collection:
    7.1.1  Filters and Silica Gel. Same as in Method 5, Sections 7.1.1 
and 7.1.2, respectively.
    7.1.2  Water. Same as in Method 6, Section 7.1.1.
    7.1.3  Isopropanol, 80 Percent by Volume. Mix 800 ml of isopropanol 
with 200 ml of water.


    Note: Check for peroxide impurities using the procedure outlined 
in Method 6, Section 7.1.2.1.

    7.1.4  Hydrogen Peroxide (H\2\O\2\), 3 Percent by Volume. Dilute 
100 ml of 30 percent H2O2) to 1 liter with water. 
Prepare fresh daily.
    7.1.5  Crushed Ice.
    7.2  Sample Recovery. The reagents and standards required for 
sample recovery are:
    7.2.1  Water. Same as in Section 7.1.2.
    7.2.2  Isopropanol, 80 Percent. Same as in Section 7.1.3.
    7.3  Sample Analysis. Same as Method 6, Section 7.3.
    7.3.1  Quality Assurance Audit Samples. When making compliance 
determinations, and upon availability, audit samples may be obtained 
from the appropriate EPA Regional Office or from the responsible 
enforcement authority.


    Note: The responsible enforcement authority should be notified 
at least 30 days prior to the test date to allow sufficient time for 
sample delivery.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Pretest Preparation. Same as Method 5, Section 8.1, except 
that filters should be inspected but need not be desiccated, weighed, 
or identified. If the

[[Page 61923]]

effluent gas can be considered dry (i.e., moisture-free), the silica 
gel need not be weighed.
    8.2  Preliminary Determinations. Same as Method 5, Section 8.2.
    8.3  Preparation of Sampling Train. Same as Method 5, Section 8.3, 
with the following exceptions:
    8.3.1  Use Figure 8-1 instead of Figure 5-1.
    8.3.2  Replace the second sentence of Method 5, Section 8.3.1 with: 
Place 100 ml of 80 percent isopropanol in the first impinger, 100 ml of 
3 percent H2O2 in both the second and third 
impingers; retain a portion of each reagent for use as a blank 
solution. Place about 200 g of silica gel in the fourth impinger.
    8.3.3  Ignore any other statements in Section 8.3 of Method 5 that 
are obviously not applicable to the performance of Method 8.


    Note: If moisture content is to be determined by impinger 
analysis, weigh each of the first three impingers (plus absorbing 
solution) to the nearest 0.5 g, and record these weights. Weigh also 
the silica gel (or silica gel plus container) to the nearest 0.5 g, 
and record.)


    8.4  Metering System Leak-Check Procedure. Same as Method 5, 
Section 8.4.1.
    8.5  Pretest Leak-Check Procedure. Follow the basic procedure in 
Method 5, Section 8.4.2, noting that the probe heater shall be adjusted 
to the minimum temperature required to prevent condensation, and also 
that verbage such as ``* * * plugging the inlet to the filter holder * 
* * '' found in Section 8.4.2.2 of Method 5 shall be replaced by `` * * 
* plugging the inlet to the first impinger * * * ''. The pretest leak-
check is recommended, but is not required.
    8.6  Sampling Train Operation. Follow the basic procedures in 
Method 5, Section 8.5, in conjunction with the following special 
instructions:
    8.6.1  Record the data on a sheet similar to that shown in Figure 
8-2 (alternatively, Figure 5-2 in Method 5 may be used). The sampling 
rate shall not exceed 0.030 m\3\/min (1.0 cfm) during the run. 
Periodically during the test, observe the connecting line between the 
probe and first impinger for signs of condensation. If condensation 
does occur, adjust the probe heater setting upward to the minimum 
temperature required to prevent condensation. If component changes 
become necessary during a run, a leak-check shall be performed 
immediately before each change, according to the procedure outlined in 
Section 8.4.3 of Method 5 (with appropriate modifications, as mentioned 
in Section 8.5 of this method); record all leak rates. If the leakage 
rate(s) exceeds the specified rate, the tester shall either void the 
run or plan to correct the sample volume as outlined in Section 12.3 of 
Method 5. Leak-checks immediately after component changes are 
recommended, but not required. If these leak-checks are performed, the 
procedure in Section 8.4.2 of Method 5 (with appropriate modifications) 
shall be used.
    8.6.2  After turning off the pump and recording the final readings 
at the conclusion of each run, remove the probe from the stack. Conduct 
a post-test (mandatory) leak-check as outlined in Section 8.4.4 of 
Method 5 (with appropriate modifications), and record the leak rate. If 
the post-test leakage rate exceeds the specified acceptable rate, 
either correct the sample volume, as outlined in Section 12.3 of Method 
5, or void the run.
    8.6.3  Drain the ice bath and, with the probe disconnected, purge 
the remaining part of the train by drawing clean ambient air through 
the system for 15 minutes at the average flow rate used for sampling.


    Note: Clean ambient air can be provided by passing air through a 
charcoal filter. Alternatively, ambient air (without cleaning) may 
be used.

    8.7  Calculation of Percent Isokinetic. Same as Method 5, Section 
8.6.
    8.8  Sample Recovery. Proper cleanup procedure begins as soon as 
the probe is removed from the stack at the end of the sampling period. 
Allow the probe to cool. Treat the samples as follows:
    8.8.1  Container No. 1.
    8.8.1.1  If a moisture content analysis is to be performed, clean 
and weigh the first impinger (plus contents) to the nearest 0.5 g, and 
record this weight.
    8.8.1.2  Transfer the contents of the first impinger to a 250-ml 
graduated cylinder. Rinse the probe, first impinger, all connecting 
glassware before the filter, and the front half of the filter holder 
with 80 percent isopropanol. Add the isopropanol rinse solution to the 
cylinder. Dilute the contents of the cylinder to 225 ml with 80 percent 
isopropanol, and transfer the cylinder contents to the storage 
container. Rinse the cylinder with 25 ml of 80 percent isopropanol, and 
transfer the rinse to the storage container. Add the filter to the 
solution in the storage container and mix. Seal the container to 
protect the solution against evaporation. Mark the level of liquid on 
the container, and identify the sample container.
    8.8.2  Container No. 2.
    8.8.2.1  If a moisture content analysis is to be performed, clean 
and weigh the second and third impingers (plus contents) to the nearest 
0.5 g, and record the weights. Also, weigh the spent silica gel (or 
silica gel plus impinger) to the nearest 0.5 g, and record the weight.
    8.8.2.2  Transfer the solutions from the second and third impingers 
to a 1-liter graduated cylinder. Rinse all connecting glassware 
(including back half of filter holder) between the filter and silica 
gel impinger with water, and add this rinse water to the cylinder. 
Dilute the contents of the cylinder to 950 ml with water. Transfer the 
solution to a storage container. Rinse the cylinder with 50 ml of 
water, and transfer the rinse to the storage container. Mark the level 
of liquid on the container. Seal and identify the sample container.

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
7.1.3.........................  Isopropanol check  Ensure acceptable
                                                    level of peroxide
                                                    impurities in
                                                    isopropanol.
8.4, 8.5, 10.1................  Sampling           Ensure accurate
                                 equipment leak-    measurement of stack
                                 check and          gas flow rate,
                                 calibration.       sample volume.
10.2..........................  Barium standard    Ensure normality
                                 solution           determination.
                                 standardization.
11.2..........................  Replicate          Ensure precision of
                                 titrations.        titration
                                                    determinations.
11.3..........................  Audit sample       Evaluate analyst's
                                 analysis.          technique and
                                                    standards
                                                    preparation.
------------------------------------------------------------------------

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

10.0  Calibration and Standardization

    10.1  Sampling Equipment. Same as Method 5, Section 10.0.
    10.2  Barium Standard Solution. Same as Method 6, Section 10.5.

[[Page 61924]]

11.0  Analytical Procedure

    11.1.  Sample Loss. Same as Method 6, Section 11.1.
    11.2.  Sample Analysis.
    11.2.1  Container No. 1. Shake the container holding the 
isopropanol solution and the filter. If the filter breaks up, allow the 
fragments to settle for a few minutes before removing a sample aliquot. 
Pipette a 100-ml aliquot of this solution into a 250-ml Erlenmeyer 
flask, add 2 to 4 drops of thorin indicator, and titrate to a pink 
endpoint using 0.0100 N barium standard solution. Repeat the titration 
with a second aliquot of sample, and average the titration values. 
Replicate titrations must agree within 1 percent or 0.2 ml, whichever 
is greater.
    11.2.2  Container No. 2. Thoroughly mix the solution in the 
container holding the contents of the second and third impingers. 
Pipette a 10-ml aliquot of sample into a 250-ml Erlenmeyer flask. Add 
40 ml of isopropanol, 2 to 4 drops of thorin indicator, and titrate to 
a pink endpoint using 0.0100 N barium standard solution. Repeat the 
titration with a second aliquot of sample, and average the titration 
values. Replicate titrations must agree within 1 percent or 0.2 ml, 
whichever is greater.
    11.2.3  Blanks. Prepare blanks by adding 2 to 4 drops of thorin 
indicator to 100 ml of 80 percent isopropanol. Titrate the blanks in 
the same manner as the samples.
    11.3  Audit Sample Analysis.
    11.3.1  When the method is used to analyze samples to demonstrate 
compliance with a source emission regulation, EPA audit samples must be 
analyzed, subject to availability.
    11.3.2  Concurrently analyze audit samples and the compliance 
samples in the same manner to evaluate the technique of the analyst and 
the standards preparation.


    Note: It is recommended that known quality control samples be 
analyzed prior to the compliance and audit sample analyses to 
optimize the system accuracy and precision. These quality control 
samples may be obtained by contacting the appropriate EPA regional 
Office or the responsible enforcement authority.


    11.3.3  The same analyst, analytical reagents, and analytical 
system shall be used for the compliance samples and the EPA audit 
samples. If this condition is met, duplicate auditing of subsequent 
compliance analyses for the same enforcement agency within a 30-day 
period is waived. Audit samples may not be used to validate different 
compliance samples under the jurisdiction of separate enforcement 
agencies, unless prior arrangements have been made with both 
enforcement agencies.
    11.4  Audit Sample Results.
    11.4.1  Calculate the audit sample concentrations in mg/dscm and 
submit results using the instructions provided with the audit samples.
    11.4.2  Report the results of the audit samples and the compliance 
determination samples along with their identification numbers, and the 
analyst's name to the responsible enforcement authority. Include this 
information with reports of any subsequent compliance analyses for the 
same enforcement authority during the 30-day period.
    11.4.3  The concentrations of the audit samples obtained by the 
analyst shall agree within 5 percent of the actual concentrations. If 
the 5 percent specification is not met, reanalyze the compliance and 
audit samples, and include initial and reanalysis values in the test 
report.
    11.4.4  Failure to meet the 5 percent specification may require 
retests until the audit problems are resolved. However, if the audit 
results do not affect the compliance or noncompliance status of the 
affected facility, the Administrator may waive the reanalysis 
requirement, further audits, or retests and accept the results of the 
compliance test. While steps are being taken to resolve audit analysis 
problems, the Administrator may also choose to use the data to 
determine the compliance or noncompliance status of the affected 
facility.

12.0  Data Analysis and Calculations

    Carry out calculations retaining at least one extra significant 
figure beyond that of the acquired data. Round off figures after final 
calculation.
    12.1  Nomenclature. Same as Method 5, Section 12.1, with the 
following additions and exceptions:

Ca = Actual concentration of SO2 in audit sample, 
mg/dscm.
Cd = Determined concentration of SO2 in audit 
sample, mg/dscm.
CH2SO4 = Sulfuric acid (including SO3) 
concentration, g/dscm (lb/dscf).
CSO2 = Sulfur dioxide concentration, g/dscm (lb/dscf).
N = Normality of barium perchlorate titrant, meq/ml.
RE = Relative error of QA audit sample analysis, percent
Va = Volume of sample aliquot titrated, 100 ml for 
H2SO4 and 10 ml for SO2.
Vsoln = Total volume of solution in which the sample is 
contained, 250 ml for the SO2 sample and 1000 ml for the 
H2SO4 sample.
Vt = Volume of barium standard solution titrant used for the 
sample, ml.
Vtb = Volume of barium standard solution titrant used for 
the blank, ml.

    12.2  Average Dry Gas Meter Temperature and Average Orifice 
Pressure Drop. See data sheet (Figure 8-2).
    12.3  Dry Gas Volume. Same as Method 5, Section 12.3.
    12.4  Volume of Water Vapor Condensed and Moisture Content. 
Calculate the volume of water vapor using Equation 5-2 of Method 5; the 
weight of water collected in the impingers and silica gel can be 
converted directly to milliliters (the specific gravity of water is 1 
g/ml). Calculate the moisture content of the stack gas (Bws) 
using Equation 5-3 of Method 5. The Note in Section 12.5 of Method 5 
also applies to this method. Note that if the effluent gas stream can 
be considered dry, the volume of water vapor and moisture content need 
not be calculated.
    12.5  Sulfuric Acid Mist (Including SO3) Concentration.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.223
    
Where:

K3 = 0.04904 g/meq for metric units,
K3 = 1.081  x  10-4 lb/meq for English units.

    12.6  Sulfur Dioxide Concentration.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.224
    

[[Page 61925]]


Where:

K4 = 0.03203 g/meq for metric units,
K4 = 7.061  x  10-5 lb/meq for English units.

    12.7  Isokinetic Variation. Same as Method 5, Section 12.11.
    12.8  Stack Gas Velocity and Volumetric Flow Rate. Calculate the 
average stack gas velocity and volumetric flow rate, if needed, using 
data obtained in this method and the equations in Sections 12.6 and 
12.7 of Method 2.
    12.9  Relative Error (RE) for QA Audit Samples. Same as Method 6, 
Section 12.4.

13.0  Method Performance

    13.1  Analytical Range. Collaborative tests have shown that the 
minimum detectable limits of the method are 0.06 mg/m3 (4 
x  10-9 lb/ft3) for H2SO4 
and 1.2 mg/m3 (74  x  10-9 lb/ft3) for 
SO2. No upper limits have been established. Based on 
theoretical calculations for 200 ml of 3 percent 
H2O2 solution, the upper concentration limit for 
SO2 in a 1.0 m3 (35.3 ft3) gas sample 
is about 12,000 mg/m3 (7.7  x  10-4 lb/
ft3). The upper limit can be extended by increasing the 
quantity of peroxide solution in the impingers.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    Same as Section 17.0 of Methods 5 and 6.
BILLING CODE 6560-50-C

[[Page 61926]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.225


[[Page 61927]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.226

BILLING CODE 6560-50-C

[[Page 61928]]

Method 10A--Determination of Carbon Monoxide Emissions in 
Certifying Continuous Emission Monitoring Systems at Petroleum 
Refineries

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

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
              Analyte                   CAS No.          Sensitivity
------------------------------------------------------------------------
Carbon monoxide (CO)..............        630-08-0  3 ppmv
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of CO emissions at petroleum refineries. This method serves as the 
reference method in the relative accuracy test for nondispersive 
infrared (NDIR) CO continuous emission monitoring systems (CEMS) that 
are required to be installed in petroleum refineries on fluid catalytic 
cracking unit catalyst regenerators (Sec. 60.105(a)(2) of this part).
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    An integrated gas sample is extracted from the stack, passed 
through an alkaline permanganate solution to remove sulfur oxides and 
nitrogen oxides, and collected in a Tedlar bag. The CO concentration in 
the sample is measured spectrophotometrically using the reaction of CO 
with p-sulfaminobenzoic acid.

3.0  Definitions. [Reserved]

4.0  Interferences

    Sulfur oxides, nitric oxide, and other acid gases interfere with 
the colorimetric reaction. They are removed by passing the sampled gas 
through an alkaline potassium permanganate scrubbing solution. Carbon 
dioxide (CO2) does not interfere, but, because it is removed 
by the scrubbing solution, its concentration must be measured 
independently and an appropriate volume correction made to the sampled 
gas.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method. The analyzer users manual should 
be consulted for specific precautions to be taken with regard to the 
analytical procedure.
    5.2  Corrosive reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water for at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burns as thermal 
burns.
    5.2.1  Sodium Hydroxide (NaOH). Causes severe damage to eyes and 
skin. Inhalation causes irritation to nose, throat, and lungs. Reacts 
exothermically with limited amounts of water.

6.0  Equipment and Supplies

    6.1  Sample Collection. The sampling train shown in Figure 10A-1 is 
required for sample collection. Component parts are described below:
    6.1.1  Probe. Stainless steel, sheathed Pyrex glass, or equivalent, 
equipped with a glass wool plug to remove particulate matter.
    6.1.2  Sample Conditioning System. Three Greenburg-Smith impingers 
connected in series with leak-free connections.
    6.1.3  Pump. Leak-free pump with stainless steel and Teflon parts 
to transport sample at a flow rate of 300 ml/min (0.01 ft\3\/min) to 
the flexible bag.
    6.1.4  Surge Tank. Installed between the pump and the rate meter to 
eliminate the pulsation effect of the pump on the rate meter.
    6.1.5  Rate Meter. Rotameter, or equivalent, to measure flow rate 
at 300 ml/min (0.01 ft\3\/min). Calibrate according to Section 10.2.
    6.1.6  Flexible Bag. Tedlar, or equivalent, with a capacity of 10 
liters (0.35 ft\3\) and equipped with a sealing quick-connect plug. The 
bag must be leak-free according to Section 8.1. For protection, it is 
recommended that the bag be enclosed within a rigid container.
    6.1.7  Valves. Stainless-steel needle valve to adjust flow rate, 
and stainless-steel three-way valve, or equivalent.
    6.1.8  CO2 Analyzer. Fyrite, or equivalent, to measure 
CO2 concentration to within O.5 percent.
    6.1.9  Volume Meter. Dry gas meter, capable of measuring the sample 
volume under calibration conditions of 300 ml/min (0.01 ft\3\/min) for 
10 minutes.
    6.1.10  Pressure Gauge. A water filled U-tube manometer, or 
equivalent, of about 30 cm (12 in.) to leak-check the flexible bag.
    6.2  Sample Analysis.
    6.2.1  Spectrophotometer. Single- or double-beam to measure 
absorbance at 425 and 600 nm. Slit width should not exceed 20 nm.
    6.2.2  Spectrophotometer Cells. 1-cm pathlength.
    6.2.3  Vacuum Gauge. U-tube mercury manometer, 1 meter (39 in.), 
with 1-mm divisions, or other gauge capable of measuring pressure to 
within 1 mm Hg.
    6.2.4  Pump. Capable of evacuating the gas reaction bulb to a 
pressure equal to or less than 40 mm Hg absolute, equipped with coarse 
and fine flow control valves.
    6.2.5  Barometer. Mercury, aneroid, or other barometer capable of 
measuring atmospheric pressure to within 1 mm Hg.
    6.2.6  Reaction Bulbs. Pyrex glass, 100-ml with Teflon stopcock 
(Figure 10A-2), leak-free at 40 mm Hg, designed so that 10 ml of the 
colorimetric reagent can be added and removed easily and accurately. 
Commercially available gas sample bulbs such as Supelco Catalog No. 2-
2161 may also be used.
    6.2.7  Manifold. Stainless steel, with connections for three 
reaction bulbs and the appropriate connections for the manometer and 
sampling bag as shown in Figure 10A-3.
    6.2.8  Pipets. Class A, 10-ml size.
    6.2.9  Shaker Table. Reciprocating-stroke type such as Eberbach 
Corporation, Model 6015. A rocking arm or rotary-motion type shaker may 
also be used. The shaker must be large enough to accommodate at least 
six gas sample bulbs simultaneously. It may be necessary to construct a 
table top extension for most commercial shakers to provide sufficient 
space for the needed bulbs (Figure 10A-4).
    6.2.10  Valve. Stainless steel shut-off valve.

[[Page 61929]]

    6.2.11  Analytical Balance. Capable of weighing to 0.1 mg.

7.0  Reagents and Standards

    Unless otherwise indicated, all reagents shall conform to the 
specifications established by the Committee on Analytical Reagents of 
the American Chemical Society, where such specifications are available; 
otherwise, the best available grade shall be used.
    7.1  Sample Collection.
    7.1.1  Water. Deionized distilled, to conform to ASTM D 1193-77 or 
91, Type 3 (incorporated by reference--see Sec. 60.17). If high 
concentrations of organic matter are not expected to be present, the 
potassium permanganate test for oxidizable organic matter may be 
omitted.
    7.1.2  Alkaline Permanganate Solution, 0.25 M KMnO4/1.5 
M Sodium Hydroxide (NaOH). Dissolve 40 g KMnO4 and 60 g NaOH 
in approximately 900 ml water, cool, and dilute to 1 liter.
    7.2  Sample Analysis.
    7.2.1 Water. Same as in Section 7.1.1.
    7.2.2  1 M Sodium Hydroxide Solution. Dissolve 40 g NaOH in 
approximately 900 ml of water, cool, and dilute to 1 liter.
    7.2.3  0.1 M NaOH Solution. Dilute 50 ml of the 1 M NaOH solution 
prepared in Section 7.2.2 to 500 ml.
    7.2.4  0.1 M Silver Nitrate (AgNO3) Solution. Dissolve 
8.5 g AgNO3 in water, and dilute to 500 ml.
    7.2.5  0.1 M Para-Sulfaminobenzoic Acid (p-SABA) Solution. Dissolve 
10.0 g p-SABA in 0.1 M NaOH, and dilute to 500 ml with 0.1 M NaOH.
    7.2.6  Colorimetric Solution. To a flask, add 100 ml of 0.1 M p-
SABA solution and 100 ml of 0.1 M AgNO3 solution. Mix, and 
add 50 ml of 1 M NaOH with shaking. The resultant solution should be 
clear and colorless. This solution is acceptable for use for a period 
of 2 days.
    7.2.7  Standard Gas Mixtures. Traceable to National Institute of 
Standards and Technology (NIST) standards and containing between 50 and 
1000 ppm CO in nitrogen. At least two concentrations are needed to span 
each calibration range used (Section 10.3). The calibration gases must 
be certified by the manufacturer to be within 2 percent of the 
specified concentrations.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Sample Bag Leak-Checks. While a bag leak-check is required 
after bag use, it should also be done before the bag is used for sample 
collection. The bag should be leak-checked in the inflated and deflated 
condition according to the following procedure:
    8.1.1  Connect the bag to a water manometer, and pressurize the bag 
to 5 to 10 cm H2O (2 to 4 in H2O). Allow the bag 
to stand for 60 minutes. Any displacement in the water manometer 
indicates a leak.
    8.1.2  Evacuate the bag with a leakless pump that is connected to 
the downstream side of a flow indicating device such as a 0- to 100-ml/
min rotameter or an impinger containing water. When the bag is 
completely evacuated, no flow should be evident if the bag is leak-
free.
    8.2  Sample Collection.
    8.2.1  Evacuate the Tedlar bag completely using a vacuum pump. 
Assemble the apparatus as shown in Figure 10A-1. Loosely pack glass 
wool in the tip of the probe. Place 400 ml of alkaline permanganate 
solution in the first two impingers and 250 ml in the third. Connect 
the pump to the third impinger, and follow this with the surge tank, 
rate meter, and 3-way valve. Do not connect the Tedlar bag to the 
system at this time.
    8.2.2  Leak-check the sampling system by plugging the probe inlet, 
opening the 3-way valve, and pulling a vacuum of approximately 250 mm 
Hg on the system while observing the rate meter for flow. If flow is 
indicated on the rate meter, do not proceed further until the leak is 
found and corrected.
    8.2.3  Purge the system with sample gas by inserting the probe into 
the stack and drawing the sample gas through the system at 300 ml/min 
 10 percent for 5 minutes. Connect the evacuated Tedlar bag 
to the system, record the starting time, and sample at a rate of 300 
ml/min for 30 minutes, or until the Tedlar bag is nearly full. Record 
the sampling time, the barometric pressure, and the ambient 
temperature. Purge the system as described above immediately before 
each sample.
    8.2.4  The scrubbing solution is adequate for removing sulfur 
oxides and nitrogen oxides from 50 liters (1.8 ft\3\) of stack gas when 
the concentration of each is less than 1,000 ppm and the CO2 
concentration is less than 15 percent. Replace the scrubber solution 
after every fifth sample.
    8.3  Carbon Dioxide Measurement. Measure the CO2 content 
in the stack to the nearest 0.5 percent each time a CO sample is 
collected. A simultaneous grab sample analyzed by the Fyrite analyzer 
is acceptable.

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.1...........................  Sampling           Ensure accuracy and
                                 equipment leak-    precision of
                                 checks and         sampling
                                 calibration.       measurements.
10.3..........................  Spectrophotometer  Ensure linearity of
                                 calibration.       spectrophotometer
                                                    response to
                                                    standards.
------------------------------------------------------------------------

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

10.0  Calibration and Standardization

    Note: Maintain a laboratory log of all calibrations.

    10.1  Gas Bulb Calibration. Weigh the empty bulb to the nearest 0.1 
g. Fill the bulb to the stopcock with water, and again weigh to the 
nearest 0.1 g. Subtract the tare weight, and calculate the volume in 
liters to three significant figures using the density of water at the 
measurement temperature. Record the volume on the bulb. Alternatively, 
mark an identification number on the bulb, and record the volume in a 
notebook.
    10.2  Rate Meter Calibration. Assemble the system as shown in 
Figure 10A-1 (the impingers may be removed), and attach a volume meter 
to the probe inlet. Set the rotameter at 300 ml/min, record the volume 
meter reading, start the pump, and pull ambient air through the system 
for 10 minutes. Record the final volume meter reading. Repeat the 
procedure and average the results to determine the volume of gas that 
passed through the system.
    10.3  Spectrophotometer Calibration Curve.
    10.3.1  Collect the standards as described in Section 8.2. Prepare 
at least two sets of three bulbs as standards to span the 0 to 400 or 
400 to 1000 ppm range. If any samples span both concentration ranges, 
prepare a calibration curve for each range using separate reagent 
blanks. Prepare a set of three bulbs containing colorimetric reagent 
but no CO to serve as a reagent

[[Page 61930]]

blank. Analyze each standard and blank according to the sample analysis 
procedure of Section 11.0 Reject the standard set where any of the 
individual bulb absorbances differs from the set mean by more than 10 
percent.
    10.3.2  Calculate the average absorbance for each set (3 bulbs) of 
standards using Equation 10A-1 and Table 10A-1. Construct a graph of 
average absorbance for each standard against its corresponding 
concentration. Draw a smooth curve through the points. The curve should 
be linear over the two concentration ranges discussed in Section 13.3.

11.0  Analytical Procedure

    11.1  Assemble the system shown in Figure 10A-3, and record the 
information required in Table 10A-1 as it is obtained. Pipet 10.0 ml of 
the colorimetric reagent into each gas reaction bulb, and attach the 
bulbs to the system. Open the stopcocks to the reaction bulbs, but 
leave the valve to the Tedlar bag closed. Turn on the pump, fully open 
the coarse-adjust flow valve, and slowly open the fine-adjust valve 
until the pressure is reduced to at least 40 mm Hg. Now close the 
coarse adjust valve, and observe the manometer to be certain that the 
system is leak-free. Wait a minimum of 2 minutes. If the pressure has 
increased less than 1 mm Hg, proceed as described below. If a leak is 
present, find and correct it before proceeding further.
    11.2  Record the vacuum pressure (Pv) to the nearest 1 
mm Hg, and close the reaction bulb stopcocks. Open the Tedlar bag 
valve, and allow the system to come to atmospheric pressure. Close the 
bag valve, open the pump coarse adjust valve, and evacuate the system 
again. Repeat this fill/evacuation procedure at least twice to flush 
the manifold completely. Close the pump coarse adjust valve, open the 
Tedlar bag valve, and let the system fill to atmospheric pressure. Open 
the stopcocks to the reaction bulbs, and let the entire system come to 
atmospheric pressure. Close the bulb stopcocks, remove the bulbs, 
record the room temperature and barometric pressure (Pbar, 
to nearest mm Hg), and place the bulbs on the shaker table with their 
main axis either parallel to or perpendicular to the plane of the table 
top. Purge the bulb-filling system with ambient air for several minutes 
between samples. Shake the samples for exactly 2 hours.
    11.3  Immediately after shaking, measure the absorbance (A) of each 
bulb sample at 425 nm if the concentration is less than or equal to 400 
ppm CO or at 600 nm if the concentration is above 400 ppm.

    Note: This may be accomplished with multiple bulb sets by 
sequentially collecting sets and adding to the shaker at staggered 
intervals, followed by sequentially removing sets from the shaker 
for absorbance measurement after the two-hour designated intervals 
have elapsed.

    11.4  Use a small portion of the sample to rinse a 
spectrophotometer cell several times before taking an aliquot for 
analysis. If one cell is used to analyze multiple samples, rinse the 
cell with deionized distilled water several times between samples. 
Prepare and analyze standards and a reagent blank as described in 
Section 10.3. Use water as the reference. Reject the analysis if the 
blank absorbance is greater than 0.1. All conditions should be the same 
for analysis of samples and standards. Measure the absorbances as soon 
as possible after shaking is completed.
    11.5  Determine the CO concentration of each bag sample using the 
calibration curve for the appropriate concentration range as discussed 
in Section 10.3.

12.0  Calculations and Data Analysis

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

A = Sample absorbance, uncorrected for the reagent blank.
Ar = Absorbance of the reagent blank.
As = Average sample absorbance per liter, units/liter.
Bw = Moisture content in the bag sample.
C = CO concentration in the stack gas, dry basis, ppm.
Cb = CO concentration of the bag sample, dry basis, ppm.
Cg = CO concentration from the calibration curve, ppm.
F = Volume fraction of CO2 in the stack.
n = Number of reaction bulbs used per bag sample.
Pb = Barometric pressure, mm Hg.
Pv = Residual pressure in the sample bulb after evacuation, 
mm Hg.
Pw = Vapor pressure of H2O in the bag (from Table 
10A-2), mm Hg.
Vb = Volume of the sample bulb, liters.
Vr = Volume of reagent added to the sample bulb, 0.0100 
liter.

    12.2  Average Sample Absorbance per Liter. Calculate As 
for each gas bulb using Equation 10A-1, and record the value in Table 
10A-1. Calculate the average As for each bag sample, and 
compare the three values to the average. If any single value differs by 
more than 10 percent from the average, reject this value, and calculate 
a new average using the two remaining values.
[GRAPHIC] [TIFF OMITTED] TR17OC00.227


    Note: A and Ar must be at the same wavelength.

    12.3  CO Concentration in the Bag. Calculate Cb using 
Equations 10A-2 and 10A-3. If condensate is visible in the Tedlar bag, 
calculate Bw using Table 10A-2 and the temperature and 
barometric pressure in the analysis room. If condensate is not visible, 
calculate Bw using the temperature and barometric pressure 
at the sampling site.
[GRAPHIC] [TIFF OMITTED] TR17OC00.228

[GRAPHIC] [TIFF OMITTED] TR17OC00.229

    12.4  CO Concentration in the Stack.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.230
    
13.0  Method Performance

    13.1  Precision. The estimated intralaboratory standard deviation 
of the method is 3 percent of the mean for gas samples analyzed in 
duplicate in the concentration range of 39 to 412 ppm. The 
interlaboratory precision has not been established.
    13.2  Accuracy. The method contains no significant biases when 
compared to an NDIR analyzer calibrated with NIST standards.
    13.3  Range. Approximately 3 to 1800 ppm CO. Samples having 
concentrations below 400 ppm are analyzed at 425 nm, and samples having 
concentrations above 400 ppm are analyzed at 600 nm.
    13.4  Sensitivity. The detection limit is 3 ppmv based on a change 
in concentration equal to three times the standard deviation of the 
reagent blank solution.
    13.5  Stability. The individual components of the colorimetric 
reagent are stable for at least 1 month. The colorimetric reagent must 
be used within 2 days after preparation to avoid excessive blank 
correction. The samples in the Tedlar bag should be stable for at least 
1 week if the bags are leak-free.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    1. Butler, F.E., J.E. Knoll, and M.R. Midgett. Development and 
Evaluation of Methods for Determining Carbon Monoxide Emissions.

[[Page 61931]]

U.S. Environmental Protection Agency, Research Triangle Park, N.C. 
June 1985. 33 pp.
    2. Ferguson, B.B., R.E. Lester, and W.J. Mitchell. Field 
Evaluation of Carbon Monoxide and Hydrogen Sulfide Continuous 
Emission Monitors at an Oil Refinery. U.S. Environmental Protection 
Agency, Research Triangle Park, N.C. Publication No. EPA-600/4-82-
054. August 1982. 100 pp.
    3. Lambert, J.L., and R.E. Weins. Induced Colorimetric Method 
for Carbon Monoxide. Analytical Chemistry. 46(7):929-930. June 1974.
    4. Levaggi, D.A., and M. Feldstein. The Colorimetric 
Determination of Low Concentrations of Carbon Monoxide. Industrial 
Hygiene Journal. 25:64-66. January-February 1964.
    5. Repp, M. Evaluation of Continuous Monitors For Carbon 
Monoxide in Stationary Sources. U.S. Environmental Protection 
Agency. Research Triangle Park, N.C. Publication No. EPA-600/2-77-
063. March 1977. 155 pp.
    6. Smith, F., D.E. Wagoner, and R.P. Donovan. Guidelines for 
Development of a Quality Assurance Program: Volume VIII--
Determination of CO Emissions from Stationary Sources by NDIR 
Spectrometry. U.S. Environmental Protection Agency. Research 
Triangle Park, N.C. Publication No. EPA-650/4-74-005-h. February 
1975. 96 pp.

17.0  Tables, Diagrams, Flowcharts, and Validation Data

                                          Table 10A-1.--Data Recording Sheet for Samples Analyzed in Triplicate
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                                                                   Partial
                                Room                          Bulb     Reagent    pressure              Shaking      Abs
      Sample  No./type          temp      Stack     Bulb      vol.     vol. in   of  gas in   Pb,  mm    time,     versus     A-Ar       As      Avg As
                                deg.C     %CO2       No.     liters     bulb,     bulb,  mm     Hg        min       water
                                                                        liter        Hg
--------------------------------------------------------------------------------------------------------------------------------------------------------
blank
--------------------------------------------------------------------------------------------------------------------------------------------------------
 
                             ------------------------------------------------------------------------------------------------------------------
Std. 1
                             ------------------------------------------------------------------------------------------------------------------
 
--------------------------------------------------------------------------------------------------------------------------------------------------------
 
                             ------------------------------------------------------------------------------------------------------------------
Std. 2
                             ------------------------------------------------------------------------------------------------------------------
 
--------------------------------------------------------------------------------------------------------------------------------------------------------
 
                             ------------------------------------------------------------------------------------------------------------------
Sample 1
                             ------------------------------------------------------------------------------------------------------------------
 
--------------------------------------------------------------------------------------------------------------------------------------------------------
Sample 2
                             ------------------------------------------------------------------------------------------------------------------
 
--------------------------------------------------------------------------------------------------------------------------------------------------------
 
                             ------------------------------------------------------------------------------------------------------------------
 
                             ------------------------------------------------------------------------------------------------------------------
Sample 3
--------------------------------------------------------------------------------------------------------------------------------------------------------


                                        Table 10A-2.--Moisture Correction
----------------------------------------------------------------------------------------------------------------
                                                                       Vapor                           Vapor
                       Temperature  deg.C                           pressure of     Temperature     pressure of
                                                                    H2,O, mm Hg        deg.C         H2, mm Hg
----------------------------------------------------------------------------------------------------------------
4...............................................................             6.1              18            15.5
6...............................................................             7.0              20            17.5
8...............................................................             8.0              22            19.8
10..............................................................             9.2              24            22.4
12..............................................................            10.5              26            25.2
14..............................................................            12.0              28            28.3
16..............................................................            13.6              30            31.8
----------------------------------------------------------------------------------------------------------------

BILLING CODE 6560-50-P

[[Page 61932]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.231


[[Page 61933]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.232


[[Page 61934]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.233


[[Page 61935]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.234

BILLING CODE 6560-50-C

Method 10B--Determination of Carbon Monoxide Emissions From 
Stationary Sources

    Note: This method is not inclusive with respect to 
specifications (e.g., equipment and supplies) and procedures (e.g., 
sampling and analytical) essential to its performance. Some material 
is incorporated by reference from other methods in this part. 
Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of at least the following 
additional test methods: Method 1, Method 4, Method 10A, and Method 
25.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
             Analyte                   CAS No.           Sensitivity
------------------------------------------------------------------------
Carbon monoxide (CO).............        630-08-0   Not determined.
------------------------------------------------------------------------

    1.2  Applicability. This method applies to the measurement of CO 
emissions at petroleum refineries and from other sources when specified 
in an applicable subpart of the regulations.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  An integrated gas sample is extracted from the sampling point, 
passed through a conditioning system to remove interferences, and 
collected in a Tedlar bag. The CO is separated from the sample by gas 
chromatography (GC) and catalytically reduced to methane 
(CH4) which is determined by flame ionization detection 
(FID). The analytical portion of this method is identical to applicable 
sections in Method 25 detailing CO measurement.

3.0  Definitions. [Reserved]

4.0  Interferences

    4.1  Carbon dioxide (CO2) and organics potentially can 
interfere with the analysis. Most of the CO2 is removed from 
the sample by the alkaline permanganate conditioning system; any

[[Page 61936]]

residual CO2 and organics are separated from the CO by GC.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method. The analyzer users manual should 
be consulted for specific precautions concerning the analytical 
procedure.

6.0  Equipment and Supplies

    6.1  Sample Collection. Same as in Method 10A, Section 6.1.
    6.2  Sample Analysis. A GC/FID analyzer, capable of quantifying CO 
in the sample and consisting of at least the following major 
components, is required for sample analysis. [Alternatively, complete 
Method 25 analytical systems (Method 25, Section 6.3) are acceptable 
alternatives when calibrated for CO and operated in accordance with the 
Method 25 analytical procedures (Method 25, Section 11.0).]
    6.2.1  Separation Column. A column capable of separating CO from 
CO2 and organic compounds that may be present. A 3.2-mm (\1/
8\-in.) OD stainless steel column packed with 1.7 m (5.5 ft.) of 60/80 
mesh Carbosieve S-II (available from Supelco) has been used 
successfully for this purpose.
    6.2.2  Reduction Catalyst. Same as in Method 25, Section 6.3.1.2.
    6.2.3  Sample Injection System. Same as in Method 25, Section 
6.3.1.4, equipped to accept a sample line from the Tedlar bag.
    6.2.4  Flame Ionization Detector. Meeting the linearity 
specifications of Section 10.3 and having a minimal instrument range of 
10 to 1,000 ppm CO.
    6.2.5  Data Recording System. Analog strip chart recorder or 
digital integration system, compatible with the FID, for permanently 
recording the analytical results.

7.0  Reagents and Standards

    7.1  Sample Collection. Same as in Method 10A, Section 7.1.
    7.2  Sample Analysis.
    7.2.1  Carrier, Fuel, and Combustion Gases. Same as in Method 25, 
Sections 7.2.1, 7.2.2, and 7.2.3, respectively.
    7.2.2  Calibration Gases. Three standard gases with nominal CO 
concentrations of 20, 200, and 1,000 ppm CO in nitrogen. The 
calibration gases shall be certified by the manufacturer to be 
 2 percent of the specified concentrations.
    7.2.3  Reduction Catalyst Efficiency Check Calibration Gas. 
Standard CH4 gas with a nominal concentration of 1,000 ppm 
in air.

8.0  Sample Collection, Preservation, Storage, and Transport

    Same as in Method 10A, Section 8.0.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.0...........................  Sample bag/        Ensures that negative
                                 sampling system    bias introduced
                                 leak-checks.       through leakage is
                                                    minimized.
10.1..........................  Carrier gas blank  Ensures that positive
                                 check.             bias introduced by
                                                    contamination of
                                                    carrier gas is less
                                                    than 5 ppmv.
10.2..........................  Reduction          Ensures that negative
                                 catalyst           bias introduced by
                                 efficiency check.  inefficient
                                                    reduction catalyst
                                                    is less than 5
                                                    percent.
10.3..........................  Analyzer           Ensures linearity of
                                 calibration.       analyzer response to
                                                    standards.
11.2..........................  Triplicate sample  Ensures precision of
                                 analyses.          analytical results.
------------------------------------------------------------------------

10.0  Calibration and Standardization

    10.1  Carrier Gas Blank Check. Analyze each new tank of carrier gas 
with the GC analyzer according to Section 11.2 to check for 
contamination. The corresponding concentration must be less than 5 ppm 
for the tank to be acceptable for use.
    10.2  Reduction Catalyst Efficiency Check. Prior to initial use, 
the reduction catalyst shall be tested for reduction efficiency. With 
the heated reduction catalyst bypassed, make triplicate injections of 
the 1,000 ppm CH4 gas (Section 7.2.3) to calibrate the 
analyzer. Repeat the procedure using 1,000 ppm CO gas (Section 7.2.2) 
with the catalyst in operation. The reduction catalyst operation is 
acceptable if the CO response is within 5 percent of the certified gas 
value.
    10.3  Analyzer Calibration. Perform this test before the system is 
first placed into operation. With the reduction catalyst in operation, 
conduct a linearity check of the analyzer using the standards specified 
in Section 7.2.2. Make triplicate injections of each calibration gas, 
and then calculate the average response factor (area/ppm) for each gas, 
as well as the overall mean of the response factor values. The 
instrument linearity is acceptable if the average response factor of 
each calibration gas is within 2.5 percent of the overall mean value 
and if the relative standard deviation (calculated in Section 12.8 of 
Method 25) for each set of triplicate injections is less than 2 
percent. Record the overall mean of the response factor values as the 
calibration response factor (R).

11.0  Analytical Procedure

    11.1  Preparation for Analysis. Before putting the GC analyzer into 
routine operation, conduct the calibration procedures listed in Section 
10.0. Establish an appropriate carrier flow rate and detector 
temperature for the specific instrument used.
    11.2  Sample Analysis. Purge the sample loop with sample, and then 
inject the sample. Analyze each sample in triplicate, and calculate the 
average sample area (A). Determine the bag CO concentration according 
to Section 12.2.

12.0  Calculations and Data Analysis

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

A = Average sample area.
Bw = Moisture content in the bag sample, fraction.
C = CO concentration in the stack gas, dry basis, ppm.
Cb = CO concentration in the bag sample, dry basis, ppm.
F = Volume fraction of CO2 in the stack, fraction.
Pbar = Barometric pressure, mm Hg.
Pw = Vapor pressure of the H2O in the bag (from 
Table 10A-2, Method 10A), mm Hg.
R = Mean calibration response factor, area/ppm.

    12.2  CO Concentration in the Bag. Calculate Cb using 
Equations 10B-1 and 10B-2. If condensate is visible in the Tedlar bag, 
calculate Bw using Table 10A-2 of Method 10A and the 
temperature and barometric pressure in the analysis room. If condensate 
is not visible, calculate Bw using the

[[Page 61937]]

temperature and barometric pressure at the sampling site.
[GRAPHIC] [TIFF OMITTED] TR17OC00.235

[GRAPHIC] [TIFF OMITTED] TR17OC00.236

    12.3  CO Concentration in the Stack
    [GRAPHIC] [TIFF OMITTED] TR17OC00.237
    
13.0   Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    Same as in Method 25, Section 16.0, with the addition of the 
following:

    1. Butler, F.E, J.E. Knoll, and M.R. Midgett. Development and 
Evaluation of Methods for Determining Carbon Monoxide Emissions. 
Quality Assurance Division, Environmental Monitoring Systems 
Laboratory, U.S. Environmental Protection Agency, Research Triangle 
Park, NC. June 1985. 33 pp.

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

Method 11--Determination of Hydrogen Sulfide Content of Fuel Gas 
Streams in Petroleum Refineries

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
             Analyte                   CAS No.           Sensitivity
------------------------------------------------------------------------
Hydrogen sulfide (H2S)...........       7783-06-4   8 mg/m\3\--740 mg/
                                                     m\3\, (6 ppm--520
                                                     ppm).
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of the H2S content of fuel gas streams at petroleum 
refineries.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  A sample is extracted from a source and passed through a 
series of midget impingers containing a cadmium sulfate 
(CdSO4) solution; H2S is absorbed, forming 
cadmium sulfide (CdS). The latter compound is then measured 
iodometrically.

3.0  Definitions. [Reserved]

[[Page 61938]]

4.0  Interferences

    4.1  Any compound that reduces iodine (I2) or oxidizes 
the iodide ion will interfere in this procedure, provided it is 
collected in the CdSO4 impingers. Sulfur dioxide in 
concentrations of up to 2,600 mg/m\3\ is removed with an impinger 
containing a hydrogen peroxide (H2O2) solution. 
Thiols precipitate with H2S. In the absence of 
H2S, only traces of thiols are collected. When methane-and 
ethane-thiols at a total level of 300 mg/m\3\ are present in addition 
to H2S, the results vary from 2 percent low at an 
H2S concentration of 400 mg/m\3\ to 14 percent high at an 
H2S concentration of 100 mg/m\3\. Carbonyl sulfide at a 
concentration of 20 percent does not interfere. Certain carbonyl-
containing compounds react with iodine and produce recurring end 
points. However, acetaldehyde and acetone at concentrations of 1 and 3 
percent, respectively, do not interfere.
    4.2  Entrained H2O2 produces a negative 
interference equivalent to 100 percent of that of an equimolar quantity 
of H2S. Avoid the ejection of H2O2 
into the CdSO4 impingers.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Corrosive reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water for at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burns as thermal 
burns.
    5.2.1  Hydrogen Peroxide. Irritating to eyes, skin, nose, and 
lungs. 30% H2O2 is a strong oxidizing agent. 
Avoid contact with skin, eyes, and combustible material. Wear gloves 
when handling.
    5.2.2  Hydrochloric Acid. Highly toxic. Vapors are highly 
irritating to eyes, skin, nose, and lungs, causing severe damage. May 
cause bronchitis, pneumonia, or edema of lungs. Exposure to 
concentrations of 0.13 to 0.2 percent can be lethal in minutes. Will 
react with metals, producing hydrogen.

6.0  Equipment and Supplies

    6.1  Sample Collection. The following items are needed for sample 
collection:
    6.1.1  Sampling Line. Teflon tubing, 6- to 7- mm (\1/4\-in.) ID, to 
connect the sampling train to the sampling valve.
    6.1.2  Impingers. Five midget impingers, each with 30-ml capacity. 
The internal diameter of the impinger tip must be 1 mm  
0.05 mm. The impinger tip must be positioned 4 to 6 mm from the bottom 
of the impinger.
    6.1.3  Tubing. Glass or Teflon connecting tubing for the impingers.
    6.1.4  Ice Water Bath. To maintain absorbing solution at a low 
temperature.
    6.1.5  Drying Tube. Tube packed with 6- to 16- mesh indicating-type 
silica gel, or equivalent, to dry the gas sample and protect the meter 
and pump. If the silica gel has been used previously, dry at 175  deg.C 
(350  deg.F) for 2 hours. New silica gel may be used as received. 
Alternatively, other types of desiccants (equivalent or better) may be 
used, subject to approval of the Administrator.

    Note: Do not use more than 30 g of silica gel. Silica gel 
adsorbs gases such as propane from the fuel gas stream, and use of 
excessive amounts of silica gel could result in errors in the 
determination of sample volume.

    6.1.6  Sampling Valve. Needle valve, or equivalent, to adjust gas 
flow rate. Stainless steel or other corrosion-resistant material.
    6.1.7  Volume Meter. Dry gas meter (DGM), sufficiently accurate to 
measure the sample volume within 2 percent, calibrated at the selected 
flow rate (about 1.0 liter/min) and conditions actually encountered 
during sampling. The meter shall be equipped with a temperature sensor 
(dial thermometer or equivalent) capable of measuring temperature to 
within 3  deg.C (5.4  deg.F). The gas meter should have a petcock, or 
equivalent, on the outlet connector which can be closed during the 
leak-check. Gas volume for one revolution of the meter must not be more 
than 10 liters.
    6.1.8  Rate Meter. Rotameter, or equivalent, to measure flow rates 
in the range from 0.5 to 2 liters/min (1 to 4 ft\3\/hr).
    6.1.9  Graduated Cylinder. 25-ml size.
    6.1.10  Barometer. Mercury, aneroid, or other barometer capable of 
measuring

[[Page 61939]]

atmospheric pressure to within 2.5 mm Hg (0.1 in. Hg). In many cases, 
the barometric reading may be obtained from a nearby National Weather 
Service station, in which case, the station value (which is the 
absolute barometric pressure) shall be requested and an adjustment for 
elevation differences between the weather station and the sampling 
point shall be applied at a rate of minus 2.5 mm Hg (0.1 in Hg) per 30 
m (100 ft) elevation increase or vice-versa for elevation decrease.
    6.1.11  U-tube Manometer. 0-; to 30-cm water column, for leak-check 
procedure.
    6.1.12  Rubber Squeeze Bulb. To pressurize train for leak-check.
    6.1.13  Tee, Pinchclamp, and Connecting Tubing. For leak-check.
    6.1.14  Pump. Diaphragm pump, or equivalent. Insert a small surge 
tank between the pump and rate meter to minimize the pulsation effect 
of the diaphragm pump on the rate meter. The pump is used for the air 
purge at the end of the sample run; the pump is not ordinarily used 
during sampling, because fuel gas streams are usually sufficiently 
pressurized to force sample gas through the train at the required flow 
rate. The pump need not be leak-free unless it is used for sampling.
    6.1.15  Needle Valve or Critical Orifice. To set air purge flow to 
1 liter/min.
    6.1.16  Tube Packed with Active Carbon. To filter air during purge.
    6.1.17  Volumetric Flask. One 1000-ml.
    6.1.18  Volumetric Pipette. One 15-ml.
    6.1.19  Pressure-Reduction Regulator. Depending on the sampling 
stream pressure, a pressure-reduction regulator may be needed to reduce 
the pressure of the gas stream entering the Teflon sample line to a 
safe level.
    6.1.20  Cold Trap. If condensed water or amine is present in the 
sample stream, a corrosion-resistant cold trap shall be used 
immediately after the sample tap. The trap shall not be operated below 
0  deg.C (32  deg.F) to avoid condensation of C3 or 
C4 hydrocarbons.
    6.2  Sample Recovery. The following items are needed for sample 
recovery:
    6.2.1  Sample Container. Iodine flask, glass-stoppered, 500-ml 
size.
    6.2.2  Volumetric Pipette. One 50-ml.
    6.2.3  Graduated Cylinders. One each 25- and 250-ml.
    6.2.4  Erlenmeyer Flasks. 125-ml.
    6.2.5  Wash Bottle.
    6.2.6  Volumetric Flasks. Three 1000-ml.
    6.3  Sample Analysis. The following items are needed for sample 
analysis:
    6.3.1  Flask. Glass-stoppered iodine flask, 500-ml.
    6.3.2  Burette. 50-ml.
    6.3.3  Erlenmeyer Flask. 125-ml.
    6.3.4  Volumetric Pipettes. One 25-ml; two each 50- and 100-ml.
    6.3.5  Volumetric Flasks. One 1000-ml; two 500-ml.
    6.3.6  Graduated Cylinders. One each 10- and 100-ml.

7.0  Reagents and Standards

    Note: Unless otherwise indicated, it is intended that all 
reagents conform to the specifications established by the Committee 
on Analytical Reagents of the American Chemical Society, where such 
specifications are available. Otherwise, use the best available 
grade.

    7.1  Sample Collection. The following reagents are required for 
sample collection:
    7.1.1  CdSO4 Absorbing Solution. Dissolve 41 g of 
3CdSO48H2O and 15 ml of 0.1 M sulfuric acid in a 
1-liter volumetric flask that contains approximately \3/4\ liter of 
water. Dilute to volume with deionized, distilled water. Mix 
thoroughly. The pH should be 3  0.1. Add 10 drops of Dow-
Corning Antifoam B. Shake well before use. This solution is stable for 
at least one month. If Antifoam B is not used, a more labor-intensive 
sample recovery procedure is required (see Section 11.2).
    7.1.2  Hydrogen Peroxide, 3 Percent. Dilute 30 percent 
H2O2 to 3 percent as needed. Prepare fresh daily.
    7.1.3  Water. Deionized distilled to conform to ASTM D 1193-77 or 
91, Type 3 (incorporated by reference--see Sec. 60.17). The 
KMnO4 test for oxidizable organic matter may be omitted when 
high concentrations of organic matter are not expected to be present.
    7.2  Sample Recovery. The following reagents are needed for sample 
recovery:
    7.2.1  Water. Same as Section 7.1.3.
    7.2.2  Hydrochloric Acid (HCl) Solution, 3 M. Add 240 ml of 
concentrated HCl (specific gravity 1.19) to 500 ml of water in a 1-
liter volumetric flask. Dilute to 1 liter with water. Mix thoroughly.
    7.2.3  Iodine (I2) Solution, 0.1 N. Dissolve 24 g of 
potassium iodide (KI) in 30 ml of water. Add 12.7 g of resublimed 
iodine (I2) to the KI solution. Shake the mixture until the 
I2 is completely dissolved. If possible, let the solution 
stand overnight in the dark. Slowly dilute the solution to 1 liter with 
water, with swirling. Filter the solution if it is cloudy. Store 
solution in a brown-glass reagent bottle.
    7.2.4  Standard I2 Solution, 0.01 N. Pipette 100.0 ml of 
the 0.1 N iodine solution into a 1-liter volumetric flask, and dilute 
to volume with water. Standardize daily as in Section 10.2.1. This 
solution must be protected from light. Reagent bottles and flasks must 
be kept tightly stoppered.
    7.3  Sample Analysis. The following reagents and standards are 
needed for sample analysis:
    7.3.1  Water. Same as in Section 7.1.3.
    7.3.2  Standard Sodium Thiosulfate Solution, 0.1 N. Dissolve 24.8 g 
of sodium thiosulfate pentahydrate 
(Na2S2O35H2O) or 
15.8 g of anhydrous sodium thiosulfate 
(Na2S2O3) in 1 liter of water, and add 
0.01 g of anhydrous sodium carbonate (Na2CO3) and 
0.4 ml of chloroform (CHCl3) to stabilize. Mix thoroughly by 
shaking or by aerating with nitrogen for approximately 15 minutes, and 
store in a glass-stoppered, reagent bottle. Standardize as in Section 
10.2.2.
    7.3.3  Standard Sodium Thiosulfate Solution, 0.01 N. Pipette 50.0 
ml of the standard 0.1 N Na2S2O3 
solution into a volumetric flask, and dilute to 500 ml with water.

    Note: A 0.01 N phenylarsine oxide 
(C6H5AsO) solution may be prepared instead of 
0.01 N Na2S2O3 (see Section 7.3.4).

    7.3.4  Standard Phenylarsine Oxide Solution, 0.01 N. Dissolve 1.80 
g of (C6H5AsO) in 150 ml of 0.3 N sodium 
hydroxide. After settling, decant 140 ml of this solution into 800 ml 
of water. Bring the solution to pH 6-7 with 6 N HCl, and dilute to 1 
liter with water. Standardize as in Section 10.2.3.
    7.3.5  Starch Indicator Solution. Suspend 10 g of soluble starch in 
100 ml of water, and add 15 g of potassium hydroxide (KOH) pellets. 
Stir until dissolved, dilute with 900 ml of water, and let stand for 1 
hour. Neutralize the alkali with concentrated HCl, using an indicator 
paper similar to Alkacid test ribbon, then add 2 ml of glacial acetic 
acid as a preservative.

    Note: Test starch indicator solution for decomposition by 
titrating with 0.01 N I2 solution, 4 ml of starch 
solution in 200 ml of water that contains 1 g of KI. If more than 4 
drops of the 0.01 N I2 solution are required to obtain 
the blue color, a fresh solution must be prepared.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Sampling Train Preparation. Assemble the sampling train as 
shown in Figure 11-1, connecting the five midget impingers in series. 
Place 15 ml of 3 percent H2O2 solution in the 
first impinger. Leave the second impinger empty. Place 15 ml of the 
CdSO4 solution in the third, fourth, and fifth impingers. 
Place the impinger assembly in an ice water bath container, and place 
water and crushed ice around the impingers. Add more ice during the 
run, if needed.

[[Page 61940]]

    8.2  Leak-Check Procedure.
    8.2.1  Connect the rubber bulb and manometer to the first impinger, 
as shown in Figure 11-1. Close the petcock on the DGM outlet. 
Pressurize the train to 25 cm water with the bulb, and close off the 
tubing connected to the rubber bulb. The train must hold 25 cm water 
pressure with not more than a 1 cm drop in pressure in a 1-minute 
interval. Stopcock grease is acceptable for sealing ground glass 
joints.
    8.2.2  If the pump is used for sampling, it is recommended, but not 
required, that the pump be leak-checked separately, either prior to or 
after the sampling run. To leak-check the pump, proceed as follows: 
Disconnect the drying tube from the impinger assembly. Place a vacuum 
gauge at the inlet to either the drying tube or the pump, pull a vacuum 
of 250 mm Hg (10 in. Hg), plug or pinch off the outlet of the flow 
meter, and then turn off the pump. The vacuum should remain stable for 
at least 30 seconds. If performed prior to the sampling run, the pump 
leak-check should precede the leak-check of the sampling train 
described immediately above; if performed after the sampling run, the 
pump leak-check should follow the sampling train leak-check.
    8.3  Purge the connecting line between the sampling valve and the 
first impinger by disconnecting the line from the first impinger, 
opening the sampling valve, and allowing process gas to flow through 
the line for one to two minutes. Then, close the sampling valve, and 
reconnect the line to the impinger train. Open the petcock on the dry 
gas meter outlet. Record the initial DGM reading.
    8.4  Open the sampling valve, and then adjust the valve to obtain a 
rate of approximately 1 liter/min (0.035 cfm). Maintain a constant 
(10 percent) flow rate during the test. Record the DGM 
temperature.
    8.5  Sample for at least 10 minutes. At the end of the sampling 
time, close the sampling valve, and record the final volume and 
temperature readings. Conduct a leak-check as described in Section 8.2 
above.
    8.6  Disconnect the impinger train from the sampling line. Connect 
the charcoal tube and the pump as shown in Figure 11-1. Purge the train 
[at a rate of 1 liter/min (0.035 ft\3\/min)] with clean ambient air for 
15 minutes to ensure that all H2S is removed from the 
H2O2. For sample recovery, cap the open ends, and 
remove the impinger train to a clean area that is away from sources of 
heat. The area should be well lighted, but not exposed to direct 
sunlight.
    8.7  Sample Recovery.
    8.7.1  Discard the contents of the H2O2 
impinger. Carefully rinse with water the contents of the third, fourth, 
and fifth impingers into a 500-ml iodine flask.

    Note: The impingers normally have only a thin film of CdS 
remaining after a water rinse. If Antifoam B was not used or if 
significant quantities of yellow CdS remain in the impingers, the 
alternative recovery procedure in Section 11.2 must be used.

    8.7.2  Proceed to Section 11 for the analysis.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.2, 10.1.....................  Sampling           Ensure accurate
                                 equipment leak-    measurement of
                                 check and          sample volume.
                                 calibration.
11.2..........................  Replicate          Ensure precision of
                                 titrations of      titration
                                 blanks.            determinations.
------------------------------------------------------------------------

10.0  Calibration and Standardization

    Note: Maintain a log of all calibrations.

    10.1  Calibration. Calibrate the sample collection equipment as 
follows.
    10.1.1  Dry Gas Meter.
    10.1.1.1  Initial Calibration. The DGM shall be calibrated before 
its initial use in the field. Proceed as follows: First, assemble the 
following components in series: Drying tube, needle valve, pump, 
rotameter, and DGM. Then, leak-check the metering system as follows: 
Place a vacuum gauge (at least 760 mm Hg) at the inlet to the drying 
tube, and pull a vacuum of 250 mm Hg (10 in. Hg); plug or pinch off the 
outlet of the flow meter, and then turn off the pump. The vacuum shall 
remain stable for at least 30 seconds. Carefully release the vacuum 
gauge before releasing the flow meter end. Next, calibrate the DGM (at 
the sampling flow rate specified by the method) as follows: Connect an 
appropriately sized wet-test meter (e.g., 1 liter per revolution) to 
the inlet of the drying tube. Make three independent calibration runs, 
using at least five revolutions of the DGM per run. Calculate the 
calibration factor, Y (wet-test meter calibration volume divided by the 
DGM volume, both volumes adjusted to the same reference temperature and 
pressure), for each run, and average the results. If any Y value 
deviates by more than 2 percent from the average, the DGM is 
unacceptable for use. Otherwise, use the average as the calibration 
factor for subsequent test runs.
    10.1.1.2  Post-Test Calibration Check. After each field test 
series, conduct a calibration check as in Section 10.1.1.1, above, 
except for the following two variations: (a) three or more revolutions 
of the DGM may be used and (b) only two independent runs need be made. 
If the calibration factor does not deviate by more than 5 percent from 
the initial calibration factor (determined in Section 10.1.1.1), then 
the DGM volumes obtained during the test series are acceptable. If the 
calibration factor deviates by more than 5 percent, recalibrate the DGM 
as in Section 10.1.1.1, and for the calculations, use the calibration 
factor (initial or recalibration) that yields the lower gas volume for 
each test run.
    10.1.2  Temperature Sensors. Calibrate against mercury-in-glass 
thermometers.
    10.1.3  Rate Meter. The rate meter need not be calibrated, but 
should be cleaned and maintained according to the manufacturer's 
instructions.
    10.1.4  Barometer. Calibrate against a mercury barometer.
    10.2  Standardization.
    10.2.1  Iodine Solution Standardization. Standardize the 0.01 N 
I2 solution daily as follows: Pipette 25 ml of the 
I2 solution into a 125-ml Erlenmeyer flask. Add 2 ml of 3 M 
HCl. Titrate rapidly with standard 0.01 N 
Na2S2O3 solution or with 0.01 N 
C6H5AsO until the solution is light yellow, using 
gentle mixing. Add four drops of starch indicator solution, and 
continue titrating slowly until the blue color just disappears. Record 
the volume of Na2S2O3 solution used, 
VSI, or the volume of C6H5AsO solution 
used, VAI, in ml. Repeat until replicate values agree within 
0.05 ml. Average the replicate titration values which agree within 0.05 
ml, and calculate the exact normality of the I2 solution 
using Equation 11-3. Repeat the standardization daily.
    10.2.2  Sodium Thiosulfate Solution Standardization. Standardize 
the 0.1 N Na2S2O3 solution as follows: 
Oven-dry potassium dichromate 
(K2Cr2O7) at 180 to 200  deg.C (360 to 
390  deg.F). To the nearest milligram, weigh 2 g of the dichromate (W). 
Transfer the dichromate to a 500-ml volumetric flask, dissolve in 
water, and dilute to exactly 500 ml. In a 500-ml iodine flask, dissolve 
approximately 3 g of KI in 45 ml of water, then add 10 ml of 3 M HCl 
solution. Pipette 50

[[Page 61941]]

ml of the dichromate solution into this mixture. Gently swirl the 
contents of the flask once, and allow it to stand in the dark for 5 
minutes. Dilute the solution with 100 to 200 ml of water, washing down 
the sides of the flask with part of the water. Titrate with 0.1 N 
Na2S2O3 until the solution is light 
yellow. Add 4 ml of starch indicator and continue titrating slowly to a 
green end point. Record the volume of 
Na2S2O3 solution used, VS, 
in ml. Repeat until replicate values agree within 0.05 ml. Calculate 
the normality using Equation 11-1. Repeat the standardization each week 
or after each test series, whichever time is shorter.
    10.2.3  Phenylarsine Oxide Solution Standardization. Standardize 
the 0.01 N C6H5AsO (if applicable) as follows: 
Oven-dry K2Cr2O7 at 180 to 200  deg.C 
(360 to 390  deg.F). To the nearest milligram, weigh 2 g of the 
dichromate (W). Transfer the dichromate to a 500-ml volumetric flask, 
dissolve in water, and dilute to exactly 500 ml. In a 500-ml iodine 
flask, dissolve approximately 0.3 g of KI in 45 ml of water, then add 
10 ml of 3 M HCl. Pipette 5 ml of the dichromate solution into the 
iodine flask. Gently swirl the contents of the flask once, and allow it 
to stand in the dark for 5 minutes. Dilute the solution with 100 to 200 
ml of water, washing down the sides of the flask with part of the 
water. Titrate with 0.01 N C6H5AsO until the 
solution is light yellow. Add 4 ml of starch indicator, and continue 
titrating slowly to a green end point. Record the volume of 
C6H5AsO used, VA, in ml. Repeat until 
replicate analyses agree within 0.05 ml. Calculate the normality using 
Equation 11-2. Repeat the standardization each week or after each test 
series, whichever time is shorter.

11.0  Analytical Procedure

    Conduct the titration analyses in a clean area away from direct 
sunlight.
    11.1  Pipette exactly 50 ml of 0.01 N I2 solution into a 
125-ml Erlenmeyer flask. Add 10 ml of 3 M HCl to the solution. 
Quantitatively rinse the acidified I2 into the iodine flask. 
Stopper the flask immediately, and shake briefly.
    11.2  Use these alternative procedures if Antifoam B was not used 
or if significant quantities of yellow CdS remain in the impingers. 
Extract the remaining CdS from the third, fourth, and fifth impingers 
using the acidified I2 solution. Immediately after pouring 
the acidified I2 into an impinger, stopper it and shake for 
a few moments, then transfer the liquid to the iodine flask. Do not 
transfer any rinse portion from one impinger to another; transfer it 
directly to the iodine flask. Once the acidified I2 solution 
has been poured into any glassware containing CdS, the container must 
be tightly stoppered at all times except when adding more solution, and 
this must be done as quickly and carefully as possible. After adding 
any acidified I2 solution to the iodine flask, allow a few 
minutes for absorption of the H2S before adding any further 
rinses. Repeat the I2 extraction until all CdS is removed 
from the impingers. Extract that part of the connecting glassware that 
contains visible CdS. Quantitatively rinse all the I2 from 
the impingers, connectors, and the beaker into the iodine flask using 
water. Stopper the flask and shake briefly.
    11.3  Allow the iodine flask to stand about 30 minutes in the dark 
for absorption of the H2S into the I2, then 
complete the titration analysis as outlined in Sections 11.5 and 11.6.


    Note: Iodine evaporates from acidified I2 solutions. 
Samples to which acidified I2 has been added may not be 
stored, but must be analyzed in the time schedule stated above.


    11.4  Prepare a blank by adding 45 ml of CdSO4 absorbing 
solution to an iodine flask. Pipette exactly 50 ml of 0.01 N 
I2 solution into a 125-ml Erlenmeyer flask. Add 10 ml of 3 M 
HCl. Stopper the flask, shake briefly, let stand 30 minutes in the 
dark, and titrate with the samples.


    Note: The blank must be handled by exactly the same procedure as 
that used for the samples.


    11.5  Using 0.01 N Na2S2O3 
solution (or 0.01 N C6H5AsO, if applicable), 
rapidly titrate each sample in an iodine flask using gentle mixing, 
until solution is light yellow. Add 4 ml of starch indicator solution, 
and continue titrating slowly until the blue color just disappears. 
Record the volume of Na2S2O3 solution 
used, VTT, or the volume of C6H5AsO 
solution used, VAT, in ml.
    11.6  Titrate the blanks in the same manner as the samples. Run 
blanks each day until replicate values agree within 0.05 ml. Average 
the replicate titration values which agree within 0.05 ml.

12.0  Data Analysis and Calculations

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

CH2S = Concentration of H2S at standard 
conditions, mg/dscm.
NA = Normality of standard C6H5AsO 
solution, g-eq/liter.
NI = Normality of standard I2 solution, g-eq/
liter.
NS = Normality of standard (0.1 N) 
Na2S2O3 solution, g-eq/liter.
NT = Normality of standard (0.01 N) 
Na2S2O3 solution, assumed to be 0.1 
NS, g-eq/liter.
Pbar = Barometric pressure at the sampling site, mm Hg.
Pstd = Standard absolute pressure, 760 mm Hg.
Tm = Average DGM temperature,  deg.K.
Tstd = Standard absolute temperature, 293  deg.K.
VA = Volume of C6H5AsO solution used 
for standardization, ml.
VAI = Volume of standard C6H5AsO 
solution used for titration analysis, ml.
VI = Volume of standard I2 solution used for 
standardization, ml.
VIT = Volume of standard I2 solution used for 
titration analysis, normally 50 ml.
Vm = Volume of gas sample at meter conditions, liters.
Vm(std) = Volume of gas sample at standard conditions, 
liters.
VSI = Volume of ``0.1 N 
Na2S2O3 solution used for 
standardization, ml.
VT = Volume of standard (0.01 N) 
Na2S2O3 solution used in standardizing 
iodine solution (see Section 10.2.1), ml.
VTT = Volume of standard (0.01 N) 
Na2S2O3 solution used for titration 
analysis, ml.
W = Weight of K2Cr2O7 used to 
standardize Na2s2O3 or 
C6H5AsO solutions, as applicable (see Sections 
10.2.2 and 10.2.3), g.
Y = DGM calibration factor.

    12.2 Normality of the Standard (0.1 N) Sodium 
Thiosulfate Solution.
[GRAPHIC] [TIFF OMITTED] TR17OC00.238

Where:

2.039 = Conversion factor
= (6 g-eq I2/mole K2Cr2O7) 
(1,000 ml/liter)/(294.2 g K2Cr2O7/
mole) (10 aliquot factor)

    12.3  Normality of Standard Phenylarsine Oxide Solution (if 
applicable).
[GRAPHIC] [TIFF OMITTED] TR17OC00.239

Where:

0.2039 = Conversion factor.
= (6 g-eq I2/mole K2Cr2O7) 
(1,000 ml/liter)/(294.2 g K2Cr2O7/
mole) (100 aliquot factor)

    12.4  Normality of Standard Iodine Solution.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.240
    


[[Page 61942]]


    Note: If C6H5AsO is used instead of 
Na2S2O3, replace NT and 
VT in Equation 11-3 with NA and 
VAS, respectively (see Sections 10.2.1 and 10.2.3).


    12.5  Dry Gas Volume. Correct the sample volume measured by the DGM 
to standard conditions (20  deg.C and 760 mm Hg).
[GRAPHIC] [TIFF OMITTED] TR17OC00.241

    12.6  Concentration of H2S. Calculate the concentration 
of H2S in the gas stream at standard conditions using 
Equation 11-5:
[GRAPHIC] [TIFF OMITTED] TR17OC00.242

Where:

17.04  x  10\3\ = Conversion factor
= (34.07 g/mole H2S) (1,000 liters/m\3\) (1,000mg/g)/(1,000 
ml/liter) (2H2S eq/mole)


    Note: If C6H5AsO is used instead of 
NaS22O3, replace NA and 
VAT in Equation 11-5 with NA and 
VAT, respectively (see Sections 11.5 and 10.2.3).

13.0  Method Performance

    13.1  Precision. Collaborative testing has shown the intra-
laboratory precision to be 2.2 percent and the inter-laboratory 
precision to be 5 percent.
    13.2  Bias. The method bias was shown to be -4.8 percent when only 
H2S was present. In the presence of the interferences cited 
in Section 4.0, the bias was positive at low H2S 
concentration and negative at higher concentrations. At 230 mg 
H2S/m\3\, the level of the compliance standard, the bias was 
+2.7 percent. Thiols had no effect on the precision.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    1. Determination of Hydrogen Sulfide, Ammoniacal Cadmium 
Chloride Method. API Method 772-54. In: Manual on Disposal of 
Refinery Wastes, Vol. V: Sampling and Analysis of Waste Gases and 
Particulate Matter. American Petroleum Institute, Washington, D.C. 
1954.
    2. Tentative Method of Determination of Hydrogen Sulfide and 
Mercaptan Sulfur in Natural Gas. Natural Gas Processors Association, 
Tulsa, OK. NGPA Publication No. 2265-65. 1965.
    3. Knoll, J.D., and M.R. Midgett. Determination of Hydrogen 
Sulfide in Refinery Fuel Gases. Environmental Monitoring Series, 
Office of Research and Development, USEPA. Research Triangle Park, 
NC 27711. EPA 600/4-77-007.
    4. Scheil, G.W., and M.C. Sharp. Standardization of Method 11 at 
a Petroleum Refinery. Midwest Research Institute Draft Report for 
USEPA. Office of Research and Development. Research Triangle Park, 
NC 27711. EPA Contract No. 68-02-1098. August 1976. EPA 600/4-77-
088a (Volume 1) and EPA 600/4-77-088b (Volume 2).
BILLING CODE 6560-50-P

[[Page 61943]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.243

BILLING CODE 6560-50-C

[[Page 61944]]

Method 12--Determination of Inorganic Lead Emissions From 
Stationary Sources

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

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
             Analyte                   CAS No.           Sensitivity
------------------------------------------------------------------------
Inorganic Lead Compounds as lead        7439-92-1   see Section 13.3.
 (Pb).
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of inorganic lead emissions from stationary sources, only as specified 
in an applicable subpart of the regulations.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  Particulate and gaseous Pb emissions are withdrawn 
isokinetically from the source and are collected on a filter and in 
dilute nitric acid. The collected samples are digested in acid solution 
and are analyzed by atomic absorption spectrophotometry using an air/
acetylene flame.

3.0  Definitions. [Reserved]

4.0  Interferences

    4.1  Copper. High concentrations of copper may interfere with the 
analysis of Pb at 217.0 nm. This interference can be avoided by 
analyzing the samples at 283.3 nm.
    4.2  Matrix Effects. Analysis for Pb by flame atomic absorption 
spectrophotometry is sensitive to the chemical composition and to the 
physical properties (e.g., viscosity, pH) of the sample. The analytical 
procedure requires the use of the Method of Standard Additions to check 
for these matrix effects, and requires sample analysis using the Method 
of Standard Additions if significant matrix effects are found to be 
present.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and to determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Corrosive Reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burn as thermal burn.
    5.2.1  Hydrogen Peroxide (H2O2). Irritating 
to eyes, skin, nose, and lungs.
    5.2.2  Nitric Acid (HNO3). Highly corrosive to eyes, 
skin, nose, and lungs. Vapors cause bronchitis, pneumonia, or edema of 
lungs. Reaction to inhalation may be delayed as long as 30 hours and 
still be fatal. Provide ventilation to limit exposure. Strong oxidizer. 
Hazardous reaction may occur with organic materials such as solvents.

6.0  Equipment and Supplies

    6.1  Sample Collection. A schematic of the sampling train used in 
performing this method is shown in Figure 12-1 in Section 18.0; it is 
similar to the Method 5 train. The following items are needed for 
sample collection:
    6.1.1  Probe Nozzle, Probe Liner, Pitot Tube, Differential Pressure 
Gauge, Filter Holder, Filter Heating System, Temperature Sensor, 
Metering System, Barometer, and Gas Density Determination Equipment. 
Same as Method 5, Sections 6.1.1.1 through 6.1.1.7, 6.1.1.9, 6.1.2, and 
6.1.3, respectively.
    6.1.2  Impingers. Four impingers connected in series with leak-free 
ground glass fittings or any similar leak-free noncontaminating 
fittings are needed. For the first, third, and fourth impingers, use 
the Greenburg-Smith design, modified by replacing the tip with a 1.3 cm 
(\1/2\ in.) ID glass tube extending to about 1.3 cm (\1/2\ in.) from 
the bottom of the flask. For the second impinger, use the Greenburg-
Smith design with the standard tip.
    6.1.3  Temperature Sensor. Place a temperature sensor, capable of 
measuring temperature to within 1  deg.C (2  deg.F) at the outlet of 
the fourth impinger for monitoring purposes.
    6.2  Sample Recovery. The following items are needed for sample 
recovery:
    6.2.1  Probe-Liner and Probe-Nozzle Brushes, Petri Dishes, 
Graduated Cylinder and/or Balance, Plastic Storage Containers, and 
Funnel and Rubber Policeman. Same as Method 5, Sections 6.2.1 and 6.2.4 
through 6.2.7, respectively.
    6.2.2  Wash Bottles. Glass (2).
    6.2.3  Sample Storage Containers. Chemically resistant, 
borosilicate glass bottles, for 0.1 N nitric acid (HNO3) 
impinger and probe solutions and washes, 1000-ml. Use screw-cap liners 
that are either rubber-backed Teflon or leak-free and resistant to 
chemical attack by 0.1 N HNO3. (Narrow mouth glass bottles 
have been found to be less prone to leakage.)
    6.2.4  Funnel. Glass, to aid in sample recovery.
    6.3  Sample Analysis. The following items are needed for sample 
analysis:
    6.3.1  Atomic Absorption Spectrophotometer. With lead hollow 
cathode lamp and burner for air/acetylene flame.
    6.3.2  Hot Plate.
    6.3.3  Erlenmeyer Flasks. 125-ml, 24/40 standard taper.
    6.3.4  Membrane Filters. Millipore SCWPO 4700, or equivalent.
    6.3.5  Filtration Apparatus. Millipore vacuum filtration unit, or 
equivalent, for use with the above membrane filter.
    6.3.6  Volumetric Flasks. 100-ml, 250-ml, and 1000-ml.

7.0  Reagents and Standards

    Note: Unless otherwise indicated, it is intended that all 
reagents conform to the specifications established by the Committee 
on Analytical Reagents of the American Chemical Society, where such 
specifications are available; otherwise, use the best available 
grade.


    7.1  Sample Collection. The following reagents are needed for 
sample collection:
    7.1.1  Filter. Gelman Spectro Grade, Reeve Angel 934 AH, MSA 1106 
BH, all with lot assay for Pb, or other high-purity glass fiber 
filters, without organic binder, exhibiting at least 99.95 percent 
efficiency (0.05 percent penetration) on 0.3 micron dioctyl phthalate 
smoke particles. Conduct the filter efficiency test using ASTM D 2986-
71, 78, or 95a (incorporated by reference--see Sec. 60.17) or use test 
data from the supplier's quality control program.
    7.1.2  Silica Gel, Crushed Ice, and Stopcock Grease. Same as Method 
5,

[[Page 61945]]

Sections 7.1.2, 7.1.4, and 7.1.5, respectively.
    7.1.3  Water. Deionized distilled, to conform to ASTM D 1193-77 or 
91, Type 3 (incorporated by reference--see Sec. 60.17). If high 
concentrations of organic matter are not expected to be present, the 
potassium permanganate test for oxidizable organic matter may be 
omitted.
    7.1.4  Nitric Acid, 0.1 N. Dilute 6.5 ml of concentrated 
HNO3 to 1 liter with water. (It may be desirable to run 
blanks before field use to eliminate a high blank on test samples.)
    7.2  Sample Recovery. 0.1 N HNO3 (Same as in Section 
7.1.4 above).
    7.3  Sample Analysis. The following reagents and standards are 
needed for sample analysis:
    7.3.1  Water. Same as in Section 7.1.3.
    7.3.2  Nitric Acid, Concentrated.
    7.3.3  Nitric Acid, 50 Percent (v/v). Dilute 500 ml of concentrated 
HNO3 to 1 liter with water.
    7.3.4  Stock Lead Standard Solution, 1000 g Pb/ml. 
Dissolve 0.1598 g of lead nitrate [Pb(NO3)2] in 
about 60 ml water, add 2 ml concentrated HNO3, and dilute to 
100 ml with water.
    7.3.5  Working Lead Standards. Pipet 0.0, 1.0, 2.0, 3.0, 4.0, and 
5.0 ml of the stock lead standard solution (Section 7.3.4) into 250-ml 
volumetric flasks. Add 5 ml of concentrated HNO3 to each 
flask, and dilute to volume with water. These working standards contain 
0.0, 4.0, 8.0, 12.0, 16.0, and 20.0 g Pb/ml, respectively. 
Prepare, as needed, additional standards at other concentrations in a 
similar manner.
    7.3.6  Air. Suitable quality for atomic absorption 
spectrophotometry.
    7.3.7  Acetylene. Suitable quality for atomic absorption 
spectrophotometry.
    7.3.8  Hydrogen Peroxide, 3 Percent (v/v). Dilute 10 ml of 30 
percent H2O2 to 100 ml with water.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Pretest Preparation. Follow the same general procedure given 
in Method 5, Section 8.1, except that the filter need not be weighed.
    8.2  Preliminary Determinations. Follow the same general procedure 
given in Method 5, Section 8.2.
    8.3  Preparation of Sampling Train. Follow the same general 
procedure given in Method 5, Section 8.3, except place 100 ml of 0.1 N 
HNO3 (instead of water) in each of the first two impingers. 
As in Method 5, leave the third impinger empty and transfer 
approximately 200 to 300 g of preweighed silica gel from its container 
to the fourth impinger. Set up the train as shown in Figure 12-1.
    8.4  Leak-Check Procedures. Same as Method 5, Section 8.4.
    8.5  Sampling Train Operation. Same as Method 5, Section 8.5.
    8.6  Calculation of Percent Isokinetic. Same as Method 5, Section 
8.6.
    8.7  Sample Recovery. Same as Method 5, Sections 8.7.1 through 
8.7.6.1, with the addition of the following:
    8.7.1  Container No. 2 (Probe).
    8.7.1.1  Taking care that dust on the outside of the probe or other 
exterior surfaces does not get into the sample, quantitatively recover 
sample matter and any condensate from the probe nozzle, probe fitting, 
probe liner, and front half of the filter holder by washing these 
components with 0.1 N HNO3 and placing the wash into a glass 
sample storage container. Measure and record (to the nearest 2 ml) the 
total amount of 0.1 N HNO3 used for these rinses. Perform 
the 0.1 N HNO3 rinses as follows:
    8.7.1.2  Carefully remove the probe nozzle, and rinse the inside 
surfaces with 0.1 N HNO3 from a wash bottle while brushing 
with a stainless steel, Nylon-bristle brush. Brush until the 0.1 N 
HNO3 rinse shows no visible particles, then make a final 
rinse of the inside surface with 0.1 N HNO3.
    8.7.1.3  Brush and rinse with 0.1 N HNO3 the inside 
parts of the Swagelok fitting in a similar way until no visible 
particles remain.
    8.7.1.4  Rinse the probe liner with 0.1 N HNO3. While 
rotating the probe so that all inside surfaces will be rinsed with 0.1 
N HNO3, tilt the probe, and squirt 0.1 N HNO3 
into its upper end. Let the 0.1 N HNO3 drain from the lower 
end into the sample container. A glass funnel may be used to aid in 
transferring liquid washes to the container. Follow the rinse with a 
probe brush. Hold the probe in an inclined position, squirt 0.1 N 
HNO3 into the upper end of the probe as the probe brush is 
being pushed with a twisting action through the probe; hold the sample 
container underneath the lower end of the probe, and catch any 0.1 N 
HNO3 and sample matter that is brushed from the probe. Run 
the brush through the probe three times or more until no visible sample 
matter is carried out with the 0.1 N HNO3 and none remains 
on the probe liner on visual inspection. With stainless steel or other 
metal probes, run the brush through in the above prescribed manner at 
least six times, since metal probes have small crevices in which sample 
matter can be entrapped. Rinse the brush with 0.1 N HNO3, 
and quantitatively collect these washings in the sample container. 
After the brushing, make a final rinse of the probe as described above.
    8.7.1.5  It is recommended that two people clean the probe to 
minimize loss of sample. Between sampling runs, keep brushes clean and 
protected from contamination.
    8.7.1.6  After ensuring that all joints are wiped clean of silicone 
grease, brush and rinse with 0.1 N HNO3 the inside of the 
from half of the filter holder. Brush and rinse each surface three 
times or more, if needed, to remove visible sample matter. Make a final 
rinse of the brush and filter holder. After all 0.1 N HNO3 
washings and sample matter are collected in the sample container, 
tighten the lid on the sample container so that the fluid will not leak 
out when it is shipped to the laboratory. Mark the height of the fluid 
level to determine whether leakage occurs during transport. Label the 
container to identify its contents clearly.
    8.7.2  Container No. 3 (Silica Gel). Note the color of the 
indicating silica gel to determine if it has been completely spent, and 
make a notation of its condition. Transfer the silica gel from the 
fourth impinger to the original container, and seal. A funnel may be 
used to pour the silica gel from the impinger and a rubber policeman 
may be used to remove the silica gel from the impinger. It is not 
necessary to remove the small amount of particles that may adhere to 
the walls and are difficult to remove. Since the gain in weight is to 
be used for moisture calculations, do not use any water or other 
liquids to transfer the silica gel. If a balance is available in the 
field, follow the procedure for Container No. 3 in Section 11.4.2.
    8.7.3  Container No. 4 (Impingers). Due to the large quantity of 
liquid involved, the impinger solutions may be placed in several 
containers. Clean each of the first three impingers and connecting 
glassware in the following manner:
    8.7.3.1.  Wipe the impinger ball joints free of silicone grease, 
and cap the joints.
    8.7.3.2.  Rotate and agitate each impinger, so that the impinger 
contents might serve as a rinse solution.
    8.7.3.3.  Transfer the contents of the impingers to a 500-ml 
graduated cylinder. Remove the outlet ball joint cap, and drain the 
contents through this opening. Do not separate the impinger parts 
(inner and outer tubes) while transferring their contents to the 
cylinder. Measure the liquid volume to within 2 ml. Alternatively, 
determine the weight of the liquid to within 0.5 g. Record in the log 
the volume or weight of the liquid present, along with a

[[Page 61946]]

notation of any color or film observed in the impinger catch. The 
liquid volume or weight is needed, along with the silica gel data, to 
calculate the stack gas moisture content (see Method 5, Figure 5-6).
    8.7.3.4.  Transfer the contents to Container No. 4.


    Note: In Sections 8.7.3.5 and 8.7.3.6, measure and record the 
total amount of 0.1 N HNO3 used for rinsing.


    8.7.3.5.  Pour approximately 30 ml of 0.1 N HNO3 into 
each of the first three impingers and agitate the impingers. Drain the 
0.1 N HNO3 through the outlet arm of each impinger into 
Container No. 4. Repeat this operation a second time; inspect the 
impingers for any abnormal conditions.
    8.7.3.6.  Wipe the ball joints of the glassware connecting the 
impingers free of silicone grease and rinse each piece of glassware 
twice with 0.1 N HNO3; transfer this rinse into Container 
No. 4. Do not rinse or brush the glass-fritted filter support. Mark the 
height of the fluid level to determine whether leakage occurs during 
transport. Label the container to identify its contents clearly.
    8.8  Blanks.
    8.8.1  Nitric Acid. Save 200 ml of the 0.1 N HNO3 used 
for sampling and cleanup as a blank. Take the solution directly from 
the bottle being used and place into a glass sample container labeled 
``0.1 N HNO3 blank.''
    8.8.2  Filter. Save two filters from each lot of filters used in 
sampling. Place these filters in a container labeled ``filter blank.''

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.4, 10.1.....................  Sampling           Ensure accuracy and
                                 equipment leak-    precision of
                                 checks and         sampling
                                 calibration.       measurements.
10.2..........................  Spectrophotometer  Ensure linearity of
                                 calibration.       spectrophotometer
                                                    response to
                                                    standards.
11.5..........................  Check for matrix   Eliminate matrix
                                 effects.           effects.
------------------------------------------------------------------------

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

10.0  Calibration and Standardizations


    Note: Maintain a laboratory log of all calibrations.

    10.1  Sampling Equipment. Same as Method 5, Section 10.0.
    10.2  Spectrophotometer.
    10.2.1  Measure the absorbance of the standard solutions using the 
instrument settings recommended by the spectrophotometer manufacturer. 
Repeat until good agreement (3 percent) is obtained between 
two consecutive readings. Plot the absorbance (y-axis) versus 
concentration in g Pb/ml (x-axis). Draw or compute a straight 
line through the linear portion of the curve. Do not force the 
calibration curve through zero, but if the curve does not pass through 
the origin or at least lie closer to the origin than 0.003 
absorbance units, check for incorrectly prepared standards and for 
curvature in the calibration curve.
    10.2.2  To determine stability of the calibration curve, run a 
blank and a standard after every five samples, and recalibrate as 
necessary.

11.0  Analytical Procedures

    11.1  Sample Loss Check. Prior to analysis, check the liquid level 
in Containers Number 2 and Number 4. Note on the analytical data sheet 
whether leakage occurred during transport. If a noticeable amount of 
leakage occurred, either void the sample or take steps, subject to the 
approval of the Administrator, to adjust the final results.
    11.2  Sample Preparation.
    11.2.1  Container No. 1 (Filter). Cut the filter into strips and 
transfer the strips and all loose particulate matter into a 125-ml 
Erlenmeyer flask. Rinse the petri dish with 10 ml of 50 percent 
HNO3 to ensure a quantitative transfer, and add to the 
flask.


    Note: If the total volume required in Section 11.2.3 is expected 
to exceed 80 ml, use a 250-ml flask in place of the 125-ml flask.

    11.2.2  Containers No. 2 and No. 4 (Probe and Impingers). Combine 
the contents of Containers No. 2 and No. 4, and evaporate to dryness on 
a hot plate.
    11.2.3  Sample Extraction for Lead.
    11.2.3.1  Based on the approximate stack gas particulate 
concentration and the total volume of stack gas sampled, estimate the 
total weight of particulate sample collected. Next, transfer the 
residue from Containers No. 2 and No. 4 to the 125-ml Erlenmeyer flask 
that contains the sampling filter using a rubber policeman and 10 ml of 
50 percent HNO3 for every 100 mg of sample collected in the 
train or a minimum of 30 ml of 50 percent HNO3, whichever is 
larger.
    11.2.3.2  Place the Erlenmeyer flask on a hot plate, and heat with 
periodic stirring for 30 minutes at a temperature just below boiling. 
If the sample volume falls below 15 ml, add more 50 percent 
HNO3. Add 10 ml of 3 percent H2O2, and 
continue heating for 10 minutes. Add 50 ml of hot (80  deg.C, 176 
deg.F) water, and heat for 20 minutes. Remove the flask from the hot 
plate, and allow to cool. Filter the sample through a Millipore 
membrane filter, or equivalent, and transfer the filtrate to a 250-ml 
volumetric flask. Dilute to volume with water.
    11.2.4  Filter Blank. Cut each filter into strips, and place each 
filter in a separate 125-ml Erlenmeyer flask. Add 15 ml of 50 percent 
HNO3, and treat as described in Section 11.2.3 using 10 ml 
of 3 percent H2O2 and 50 ml of hot water. Filter 
and dilute to a total volume of 100 ml using water.
    11.2.5  Nitric Acid Blank, 0.1 N. Take the entire 200 ml of 0.1 N 
HNO3 to dryness on a steam bath, add 15 ml of 50 percent 
HNO3, and treat as described in Section 11.2.3 using 10 ml 
of 3 percent H202 and 50 ml of hot water. Dilute 
to a total volume of 100 ml using water.
    11.3  Spectrophotometer Preparation. Turn on the power; set the 
wavelength, slit width, and lamp current; and adjust the background 
corrector as instructed by the manufacturer's manual for the particular 
atomic absorption spectrophotometer. Adjust the burner and flame 
characteristics as necessary.
    11.4  Analysis.
    11.4.1  Lead Determination. Calibrate the spectrophotometer as 
outlined in Section 10.2, and determine the absorbance for each source 
sample, the filter blank, and 0.1 N HNO3 blank. Analyze each 
sample three times in this manner. Make appropriate dilutions, as 
needed, to bring all sample Pb concentrations into the linear 
absorbance range of the spectrophotometer. Because instruments vary 
between manufacturers, no detailed operating instructions will be given 
here. Instead, the instructions provided with the particular instrument 
should be followed. If the Pb concentration of a sample is at the low 
end of the calibration curve and high accuracy is required, the sample 
can be taken to dryness on a hot plate and the residue dissolved in the 
appropriate volume of water to bring it into the optimum range of the 
calibration curve.

[[Page 61947]]

    11.4.2  Container No. 3 (Silica Gel). This step may be conducted in 
the field. Weigh the spent silica gel (or silica gel plus impinger) to 
the nearest 0.5 g; record this weight.
    11.5  Check for Matrix Effects. Use the Method of Standard 
Additions as follows to check at least one sample from each source for 
matrix effects on the Pb results:
    11.5.1  Add or spike an equal volume of standard solution to an 
aliquot of the sample solution.
    11.5.2  Measure the absorbance of the resulting solution and the 
absorbance of an aliquot of unspiked sample.
    11.5.3  Calculate the Pb concentration Cm in g/
ml of the sample solution using Equation 12-1 in Section 12.5.
    Volume corrections will not be required if the solutions as 
analyzed have been made to the same final volume. Therefore, 
Cm and Ca represent Pb concentration before 
dilutions.
    Method of Standard Additions procedures described on pages 9-4 and 
9-5 of the section entitled ``General Information'' of the Perkin Elmer 
Corporation Atomic Absorption Spectrophotometry Manual, Number 303-0152 
(Reference 1 in Section 17.0) may also be used. In any event, if the 
results of the Method of Standard Additions procedure used on the 
single source sample do not agree to within 5 percent of 
the value obtained by the routine atomic absorption analysis, then 
reanalyze all samples from the source using the Method of Standard 
Additions procedure.

12.0  Data Analysis and Calculations

    12.1  Nomenclature.

Am = Absorbance of the sample solution.
An = Cross-sectional area of nozzle, m\2\ (ft\2\).
At = Absorbance of the spiked sample solution.
Bws = Water in the gas stream, proportion by volume.
Ca = Lead concentration in standard solution, g/ml.
Cm = Lead concentration in sample solution analyzed during 
check for matrix effects, g/ml.
Cs = Lead concentration in stack gas, dry basis, converted 
to standard conditions, mg/dscm (gr/dscf).
I = Percent of isokinetic sampling.
L1 = Individual leakage rate observed during the leak-check 
conducted prior to the first component change, m\3\/min (ft\3\/min)
La = Maximum acceptable leakage rate for either a pretest 
leak-check or for a leak-check following a component change; equal to 
0.00057 m\3\/min (0.020 cfm) or 4 percent of the average sampling rate, 
whichever is less.
Li = Individual leakage rate observed during the leak-check 
conducted prior to the ``ith'' component change (i = 1, 2, 3 * * * n), 
m\3\/min (cfm).
Lp = Leakage rate observed during the post-test leak-check, 
m\3\/min (cfm).
mt = Total weight of lead collected in the sample, 
g.
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 lb/lb-
mole).
Pbar = Barometric pressure at the sampling site, mm Hg (in. 
Hg).
Ps = Absolute stack gas pressure, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
R = Ideal gas constant, 0.06236 [(mm Hg) (m\3\)]/[( deg.K) (g-mole)] 
{21.85 [(in. Hg) (ft\3\)]/[( deg.R) (lb-mole)]}.
Tm = Absolute average dry gas meter temperature (see Figure 
5-3 of Method 5),  deg.K ( deg.R).
Tstd = Standard absolute temperature, 293  deg.K (528 
deg.R).
vs = Stack gas velocity, m/sec (ft/sec).
Vm = Volume of gas sample as measured by the dry gas meter, 
dry basis, m\3\ (ft\3\).
Vm(std) = Volume of gas sample as measured by the dry gas 
meter, corrected to standard conditions, m\3\ (ft\3\).
Vw(std) = Volume of water vapor collected in the sampling 
train, corrected to standard conditions, m\3\ (ft\3\).
Y = Dry gas meter calibration factor.
H = Average pressure differential across the orifice meter 
(see Figure 5-3 of Method 5), mm H2O (in. H2O).
 = Total sampling time, min.
l = Sampling time interval, from the beginning of 
a run until the first component change, min.
i = Sampling time interval, between two successive 
component changes, beginning with the interval between the first and 
second changes, min.
p = Sampling time interval, from the final (n\th\) 
component change until the end of the sampling run, min.
w = Density of water, 0.9982 g/ml (0.002201 lb/ml).
    12.2  Average Dry Gas Meter Temperatures (Tm) and 
Average Orifice Pressure Drop (H). See data sheet (Figure 5-3 
of Method 5).
    12.3  Dry Gas Volume, Volume of Water Vapor, and Moisture Content. 
Using data obtained in this test, calculate Vm(std), 
Vw(std), and Bws according to the procedures 
outlined in Method 5, Sections 12.3 through 12.5.
    12.4  Total Lead in Source Sample. For each source sample, correct 
the average absorbance for the contribution of the filter blank and the 
0.1 N HNO3 blank. Use the calibration curve and this 
corrected absorbance to determine the Pb concentration in the sample 
aspirated into the spectrophotometer. Calculate the total Pb content 
mt (in g) in the original source sample; correct 
for all the dilutions that were made to bring the Pb concentration of 
the sample into the linear range of the spectrophotometer.
    12.5  Sample Lead Concentration. Calculate the Pb concentration of 
the sample using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.244

    12.6  Lead Concentration. Calculate the stack gas Pb concentration 
Cs using Equation 12-2:
[GRAPHIC] [TIFF OMITTED] TR17OC00.245

Where:

K3 = 0.001 mg/g for metric units.
= 1.54  x  10-\5\ gr/g for English units

    12.7 Stack Gas Velocity and Volumetric Flow Rate. Calculate the 
average stack gas velocity and volumetric flow rate using data obtained 
in this method and the equations in Sections 12.2 and 12.3 of Method 2.
    12.8  Isokinetic Variation. Same as Method 5, Section 12.11.

13.0  Method Performance

    13.1  Precision. The within-laboratory precision, as measured by 
the coefficient of variation, ranges from 0.2 to 9.5 percent relative 
to a run-mean concentration. These values were based on tests conducted 
at a gray iron foundry, a lead storage battery manufacturing plant, a 
secondary lead smelter, and a lead recovery furnace of an alkyl lead 
manufacturing plant. The concentrations encountered during these tests 
ranged from 0.61 to 123.3 mg Pb/m\3\.
    13.2  Analytical Range. For a minimum analytical accuracy of 
10 percent, the lower limit of the range is 100 g. 
The upper limit can be extended considerably by dilution.
    13.3  Analytical Sensitivity. Typical sensitivities for a 1-percent 
change in absorption (0.0044 absorbance units) are 0.2 and 0.5 
g Pb/ml for the 217.0 and 283.3 nm lines, respectively.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  Alternative Procedures

    16.1  Simultaneous Determination of Particulate and Lead Emissions. 
Method

[[Page 61948]]

5 may be used to simultaneously determine Pb provided: (1) acetone is 
used to remove particulate from the probe and inside of the filter 
holder as specified by Method 5, (2) 0.1 N HNO3 is used in 
the impingers, (3) a glass fiber filter with a low Pb background is 
used, and (4) the entire train contents, including the impingers, are 
treated and analyzed for Pb as described in Sections 8.0 and 11.0 of 
this method.
    16.2  Filter Location. A filter may be used between the third and 
fourth impingers provided the filter is included in the analysis for 
Pb.
    16.3  In-Stack Filter. An in-stack filter may be used provided: (1) 
A glass-lined probe and at least two impingers, each containing 100 ml 
of 0.1 N HNO3 after the in-stack filter, are used and (2) 
the probe and impinger contents are recovered and analyzed for Pb. 
Recover sample from the nozzle with acetone if a particulate analysis 
is to be made.

17.0  References

    Same as Method 5, Section 17.0, References 2, 3, 4, 5, and 7, with 
the addition of the following:

    1. Perkin Elmer Corporation. Analytical Methods for Atomic 
Absorption Spectrophotometry. Norwalk, Connecticut. September 1976.
    2. American Society for Testing and Materials. Annual Book of 
ASTM Standards, Part 31: Water, Atmospheric Analysis. Philadelphia, 
PA 1974. p. 40-42.
    3. Kelin, R., and C. Hach. Standard Additions--Uses and 
Limitations in Spectrophotometric Analysis. Amer. Lab. 9:21-27. 
1977.
    4. Mitchell, W.J., and M.R. Midgett. Determining Inorganic and 
Alkyl Lead Emissions from Stationary Sources. U.S. Environmental 
Protection Agency. Emission Monitoring and Support Laboratory. 
Research Triangle Park, NC. (Presented at National APCA Meeting, 
Houston. June 26, 1978).
BILLING CODE 6560-50-P

[[Page 61949]]

18.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.246

BILLING CODE 6560-50-C

[[Page 61950]]

Method 13A--Determination of Total Fluoride Emissions From 
Stationary Sources (Spadns Zirconium Lake Method)

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

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.            Sensitivity
------------------------------------------------------------------------
Total fluorides as Fluorine....       7782-41-4   Not determined.
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of fluoride (F-) emissions from sources as specified in the 
regulations. It does not measure fluorocarbons, such as Freons.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary

    Gaseous and particulate F- are withdrawn isokinetically 
from the source and collected in water and on a filter. The total 
F- is then determined by the SPADNS Zirconium Lake 
Colorimetric method.

3.0  Definitions [Reserved]

4.0  Interferences

    4.1  Chloride. Large quantities of chloride will interfere with the 
analysis, but this interference can be prevented by adding silver 
sulfate into the distillation flask (see Section 11.3). If chloride ion 
is present, it may be easier to use the specific ion electrode method 
of analysis (Method 13B).
    4.2  Grease. Grease on sample-exposed surfaces may cause low 
F- results due to adsorption.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and to determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Corrosive Reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burn as thermal burn.
    5.2.1  Hydrochloric Acid (HCl). Highly toxic. Vapors are highly 
irritating to eyes, skin, nose, and lungs, causing severe damage. May 
cause bronchitis, pneumonia, or edema of lungs. Exposure to 
concentrations of 0.13 to 0.2 percent can be lethal in minutes. Will 
react with metals, producing hydrogen.
    5.2.2  Sodium Hydroxide (NaOH). Causes severe damage to eye tissues 
and to skin. Inhalation causes irritation to nose, throat, and lungs. 
Reacts exothermically with limited amounts of water.
    5.2.3  Sulfuric Acid (H2SO4). Rapidly 
destructive to body tissue. Will cause third degree burns. Eye damage 
may result in blindness. Inhalation may be fatal from spasm of the 
larynx, usually within 30 minutes. May cause lung tissue damage with 
edema. 1 mg/m\3\ for 8 hours will cause lung damage or, in higher 
concentrations, death. Provide ventilation to limit inhalation. Reacts 
violently with metals and organics.

6.0  Equipment and Supplies

    6.1  Sample Collection. A schematic of the sampling train used in 
performing this method is shown in Figure 13A-1; it is similar to the 
Method 5 sampling train except that the filter position is 
interchangeable. The sampling train consists of the following 
components:
    6.1.1  Probe Nozzle, Pitot Tube, Differential Pressure Gauge, 
Filter Heating System, Temperature Sensor, Metering System, Barometer, 
and Gas Density Determination Equipment. Same as Method 5, Sections 
6.1.1.1, 6.1.1.3 through 6.1.1.7, 6.1.1.9, 6.1.2, and 6.1.3, 
respectively. The filter heating system and temperature sensor are 
needed only when moisture condensation is a problem.
    6.1.2  Probe Liner. Borosilicate glass or 316 stainless steel. When 
the filter is located immediately after the probe, a probe heating 
system may be used to prevent filter plugging resulting from moisture 
condensation, but the temperature in the probe shall not be allowed to 
exceed 120  14  deg.C (248  25  deg.F).
    6.1.3  Filter Holder. With positive seal against leakage from the 
outside or around the filter. If the filter is located between the 
probe and first impinger, use borosilicate glass or stainless steel 
with a 20-mesh stainless steel screen filter support and a silicone 
rubber gasket; do not use a glass frit or a sintered metal filter 
support. If the filter is located between the third and fourth 
impingers, borosilicate glass with a glass frit filter support and a 
silicone rubber gasket may be used. Other materials of construction may 
be used, subject to the approval of the Administrator.
    6.1.4  Impingers. Four impingers connected as shown in Figure 13A-1 
with ground-glass (or equivalent), vacuum-tight fittings. For the 
first, third, and fourth impingers, use the Greenburg-Smith design, 
modified by replacing the tip with a 1.3-cm (\1/2\ in.) ID glass tube 
extending to 1.3 cm (\1/2\ in.) from the bottom of the flask. For the 
second impinger, use a Greenburg-Smith impinger with the standard tip. 
Modifications (e.g., flexible connections between the impingers or 
materials other than glass) may be used, subject to the approval of the 
Administrator. Place a temperature sensor, capable of measuring 
temperature to within 1  deg.C (2  deg.F), at the outlet of the fourth 
impinger for monitoring purposes.
    6.2  Sample Recovery. The following items are needed for sample 
recovery:
    6.2.1  Probe-liner and Probe-Nozzle Brushes, Wash Bottles, 
Graduated Cylinder and/or Balance, Plastic Storage Containers, Funnel 
and Rubber Policeman, and Funnel. Same as Method 5, Sections 6.2.1, 
6.2.2 and 6.2.5 to 6.2.8, respectively.
    6.2.2  Sample Storage Container. Wide-mouth, high-density 
polyethylene bottles for impinger water samples, 1 liter.
    6.3  Sample Preparation and Analysis. The following items are 
needed for sample preparation and analysis:
    6.3.1  Distillation Apparatus. Glass distillation apparatus 
assembled as shown in Figure 13A-2.
    6.3.2  Bunsen Burner.

[[Page 61951]]

    6.3.3  Electric Muffle Furnace. Capable of heating to 600  deg.C 
(1100  deg.F).
    6.3.4  Crucibles. Nickel, 75- to 100-ml.
    6.3.5  Beakers. 500-ml and 1500-ml.
    6.3.6  Volumetric Flasks. 50-ml.
    6.3.7  Erlenmeyer Flasks or Plastic Bottles. 500-ml.
    6.3.8  Constant Temperature Bath. Capable of maintaining a constant 
temperature of 1.0  deg.C at room temperature conditions.
    6.3.9  Balance. 300-g capacity, to measure to 0.5 g.
    6.3.10  Spectrophotometer. Instrument that measures absorbance at 
570 nm and provides at least a 1-cm light path.
    6.3.11  Spectrophotometer Cells. 1-cm path length.

7.0  Reagents and Standards

    Unless otherwise indicated, all reagents are to conform to the 
specifications established by the Committee on Analytical Reagents of 
the American Chemical Society, where such specifications are available. 
Otherwise, use the best available grade.
    7.1  Sample Collection. The following reagents are needed for 
sample collection:
    7.1.1  Filters.
    7.1.1.1  If the filter is located between the third and fourth 
impingers, use a Whatman No. 1 filter, or equivalent, sized to fit the 
filter holder.
    7.1.1.2  If the filter is located between the probe and first 
impinger, use any suitable medium (e.g., paper, organic membrane) that 
can withstand prolonged exposure to temperatures up to 135  deg.C (275 
deg.F), and has at least 95 percent collection efficiency (5 percent 
penetration) for 0.3 m dioctyl phthalate smoke particles. 
Conduct the filter efficiency test before the test series, using ASTM D 
2986-71, 78, or 95a (incorporated by reference--see Sec. 60.17), or use 
test data from the supplier's quality control program. The filter must 
also have a low F- blank value (0.015 mg F-/cm\2\ 
of filter area). Before the test series, determine the average 
F- blank value of at least three filters (from the lot to be 
used for sampling) using the applicable procedures described in 
Sections 8.3 and 8.4 of this method. In general, glass fiber filters 
have high and/or variable F- blank values, and will not be 
acceptable for use.
    7.1.2  Water. Deionized distilled, to conform to ASTM D 1193-77 or 
91, Type 3 (incorporated by reference--see Sec. 60.17). If high 
concentrations of organic matter are not expected to be present, the 
potassium permanganate test for oxidizable organic matter may be 
deleted.
    7.1.3  Silica Gel, Crushed Ice, and Stopcock Grease. Same as Method 
5, Sections 7.1.2, 7.1.4, and 7.1.5, respectively.
    7.2  Sample Recovery. Water, as described in Section 7.1.2, is 
needed for sample recovery.
    7.3  Sample Preparation and Analysis. The following reagents and 
standards are needed for sample preparation and analysis:
    7.3.1  Calcium Oxide (CaO). Certified grade containing 0.005 
percent F- or less.
    7.3.2  Phenolphthalein Indicator. Dissolve 0.1 g of phenolphthalein 
in a mixture of 50 ml of 90 percent ethanol and 50 ml of water.
    7.3.3  Silver Sulfate (Ag2SO4).
    7.3.4  Sodium Hydroxide (NaOH), Pellets.
    7.3.5  Sulfuric Acid (H2SO4), Concentrated.
    7.3.6  Sulfuric Acid, 25 Percent (v/v). Mix 1 part of concentrated 
H2SO4 with 3 parts of water.
    7.3.7  Filters. Whatman No. 541, or equivalent.
    7.3.8  Hydrochloric Acid (HCl), Concentrated.
    7.3.9  Water. Same as in Section 7.1.2.
    7.3.10  Fluoride Standard Solution, 0.01 mg F-/ml. Dry 
approximately 0.5 g of sodium fluoride (NaF) in an oven at 110  deg.C 
(230  deg.F) for at least 2 hours. Dissolve 0.2210 g of NaF in 1 liter 
of water. Dilute 100 ml of this solution to 1 liter with water.
    7.3.11  SPADNS Solution [4,5 Dihydroxyl-3-(p-Sulfophenylazo)-2,7-
Naphthalene-Disulfonic Acid Trisodium Salt]. Dissolve 0.960 
 0.010 g of SPADNS reagent in 500 ml water. If stored in a 
well-sealed bottle protected from the sunlight, this solution is stable 
for at least 1 month.
    7.3.12  Spectrophotometer Zero Reference Solution. Add 10 ml of 
SPADNS solution to 100 ml water, and acidify with a solution prepared 
by diluting 7 ml of concentrated HCl to 10 ml with deionized, distilled 
water. Prepare daily.
    7.3.13  SPADNS Mixed Reagent. Dissolve 0.135  0.005 g 
of zirconyl chloride octahydrate (ZrOCl2 8H2O) in 
25 ml of water. Add 350 ml of concentrated HCl, and dilute to 500 ml 
with deionized, distilled water. Mix equal volumes of this solution and 
SPADNS solution to form a single reagent. This reagent is stable for at 
least 2 months.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Pretest Preparation. Follow the general procedure given in 
Method 5, Section 8.1, except that the filter need not be weighed.
    8.2  Preliminary Determinations. Follow the general procedure given 
in Method 5, Section 8.2, except that the nozzle size must be selected 
such that isokinetic sampling rates below 28 liters/min (1.0 cfm) can 
be maintained.
    8.3  Preparation of Sampling Train. Follow the general procedure 
given in Method 5, Section 8.3, except for the following variation: 
Assemble the train as shown in Figure 13A-1 with the filter between the 
third and fourth impingers. Alternatively, if a 20-mesh stainless steel 
screen is used for the filter support, the filter may be placed between 
the probe and first impinger. A filter heating system to prevent 
moisture condensation may be used, but shall not allow the temperature 
to exceed 120  14  deg.C (248  25  deg.F). 
Record the filter location on the data sheet (see Section 8.5).
    8.4  Leak-Check Procedures. Follow the leak-check procedures given 
in Method 5, Section 8.4.
    8.5  Sampling Train Operation. Follow the general procedure given 
in Method 5, Section 8.5, keeping the filter and probe temperatures (if 
applicable) at 120  14  deg.C (248  25  deg.F) 
and isokinetic sampling rates below 28 liters/min (1.0 cfm). For each 
run, record the data required on a data sheet such as the one shown in 
Method 5, Figure 5-3.
    8.6  Sample Recovery. Proper cleanup procedure begins as soon as 
the probe is removed from the stack at the end of the sampling period. 
Allow the probe to cool.
    8.6.1  When the probe can be safely handled, wipe off all external 
particulate matter near the tip of the probe nozzle, and place a cap 
over it to keep from losing part of the sample. Do not cap off the 
probe tip tightly while the sampling train is cooling down as this 
would create a vacuum in the filter holder, thus drawing water from the 
impingers into the filter holder.
    8.6.2  Before moving the sample train to the cleanup site, remove 
the probe from the sample train, wipe off any silicone grease, and cap 
the open outlet of the probe. Be careful not to lose any condensate 
that might be present. Remove the filter assembly, wipe off any 
silicone grease from the filter holder inlet, and cap this inlet. 
Remove the umbilical cord from the last impinger, and cap the impinger. 
After wiping off any silicone grease, cap off the filter holder outlet 
and any open impinger inlets and outlets. Ground-glass stoppers, 
plastic caps, or serum caps may be used to close these openings.
    8.6.3  Transfer the probe and filter-impinger assembly to the 
cleanup area.

[[Page 61952]]

This area should be clean and protected from the wind so that the 
chances of contaminating or losing the sample will be minimized.
    8.6.4  Inspect the train prior to and during disassembly, and note 
any abnormal conditions. Treat the samples as follows:
    8.6.4.1  Container No. 1 (Probe, Filter, and Impinger Catches).
    8.6.4.1.1  Using a graduated cylinder, measure to the nearest ml, 
and record the volume of the water in the first three impingers; 
include any condensate in the probe in this determination. Transfer the 
impinger water from the graduated cylinder into a polyethylene 
container. Add the filter to this container. (The filter may be handled 
separately using procedures subject to the Administrator's approval.) 
Taking care that dust on the outside of the probe or other exterior 
surfaces does not get into the sample, clean all sample-exposed 
surfaces (including the probe nozzle, probe fitting, probe liner, first 
three impingers, impinger connectors, and filter holder) with water. 
Use less than 500 ml for the entire wash. Add the washings to the 
sample container. Perform the water rinses as follows:
    8.6.4.1.2  Carefully remove the probe nozzle and rinse the inside 
surface with water from a wash bottle. Brush with a Nylon bristle 
brush, and rinse until the rinse shows no visible particles, after 
which make a final rinse of the inside surface. Brush and rinse the 
inside parts of the Swagelok fitting with water in a similar way.
    8.6.4.1.3  Rinse the probe liner with water. While squirting the 
water into the upper end of the probe, tilt and rotate the probe so 
that all inside surfaces will be wetted with water. Let the water drain 
from the lower end into the sample container. A funnel (glass or 
polyethylene) may be used to aid in transferring the liquid washes to 
the container. Follow the rinse with a probe brush. Hold the probe in 
an inclined position, and squirt water into the upper end as the probe 
brush is being pushed with a twisting action through the probe. Hold 
the sample container underneath the lower end of the probe, and catch 
any water and particulate matter that is brushed from the probe. Run 
the brush through the probe three times or more. With stainless steel 
or other metal probes, run the brush through in the above prescribed 
manner at least six times since metal probes have small crevices in 
which particulate matter can be entrapped. Rinse the brush with water, 
and quantitatively collect these washings in the sample container. 
After the brushing, make a final rinse of the probe as described above.
    8.6.4.1.4  It is recommended that two people clean the probe to 
minimize sample losses. Between sampling runs, keep brushes clean and 
protected from contamination.
    8.6.4.1.5  Rinse the inside surface of each of the first three 
impingers (and connecting glassware) three separate times. Use a small 
portion of water for each rinse, and brush each sample-exposed surface 
with a Nylon bristle brush, to ensure recovery of fine particulate 
matter. Make a final rinse of each surface and of the brush.
    8.6.4.1.6  After ensuring that all joints have been wiped clean of 
the silicone grease, brush and rinse with water the inside of the 
filter holder (front-half only, if filter is positioned between the 
third and fourth impingers). Brush and rinse each surface three times 
or more if needed. Make a final rinse of the brush and filter holder.
    8.6.4.1.7  After all water washings and particulate matter have 
been collected in the sample container, tighten the lid so that water 
will not leak out when it is shipped to the laboratory. Mark the height 
of the fluid level to transport. Label the container clearly to 
identify its contents.
    8.6.4.2  Container No. 2 (Sample Blank). Prepare a blank by placing 
an unused filter in a polyethylene container and adding a volume of 
water equal to the total volume in Container No. 1. Process the blank 
in the same manner as for Container No. 1.
    8.6.4.3  Container No. 3 (Silica Gel). Note the color of the 
indicating silica gel to determine whether it has been completely 
spent, and make a notation of its condition. Transfer the silica gel 
from the fourth impinger to its original container, and seal. A funnel 
may be used to pour the silica gel and a rubber policeman to remove the 
silica gel from the impinger. It is not necessary to remove the small 
amount of dust particles that may adhere to the impinger wall and are 
difficult to remove. Since the gain in weight is to be used for 
moisture calculations, do not use any water or other liquids to 
transfer the silica gel. If a balance is available in the field, follow 
the analytical procedure for Container No. 3 in Section 11.4.2.

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.4, 10.1.....................  Sampling           Ensure accurate
                                 equipment leak-    measurement of stack
                                 check and          gas flow rate and
                                 calibration.       sample volume.
10.2..........................  Spectrophotometer  Evaluate analytical
                                 calibration.       technique,
                                                    preparation of
                                                    standards.
11.3.3........................  Interference/      Minimize negative
                                 recovery           effects of used
                                 efficiency check   acid.
                                 during
                                 distillation.
------------------------------------------------------------------------

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

10.0  Calibration and Standardization

    Note: Maintain a laboratory log of all calibrations.


    10.1  Sampling Equipment. Calibrate the probe nozzle, pitot tube, 
metering system, probe heater, temperature sensors, and barometer 
according to the procedures outlined in Method 5, Sections 10.1 through 
10.6. Conduct the leak-check of the metering system according to the 
procedures outlined in Method 5, Section 8.4.1.
    10.2  Spectrophotometer.
    10.2.1  Prepare the blank standard by adding 10 ml of SPADNS mixed 
reagent to 50 ml of water.
    10.2.2  Accurately prepare a series of standards from the 0.01 mg 
F-/ml standard fluoride solution (Section 7.3.10) by 
diluting 0, 2, 4, 6, 8, 10, 12, and 14 ml to 100 ml with deionized, 
distilled water. Pipet 50 ml from each solution, and transfer each to a 
separate 100-ml beaker. Then add 10 ml of SPADNS mixed reagent (Section 
7.3.13) to each. These standards will contain 0, 10, 20, 30, 40, 50, 
60, and 70 g F-(0 to 1.4 g/ml), 
respectively.
    10.2.3  After mixing, place the blank and calibration standards in 
a constant temperature bath for 30 minutes before reading the 
absorbance with the spectrophotometer. Adjust all samples to this same 
temperature before analyzing.
    10.2.4  With the spectrophotometer at 570 nm, use the blank 
standard to set

[[Page 61953]]

the absorbance to zero. Determine the absorbance of the standards.
    10.2.5  Prepare a calibration curve by plotting g 
F-/50 ml versus absorbance on linear graph paper. Prepare 
the standard curve initially and thereafter whenever the SPADNS mixed 
reagent is newly made. Also, run a calibration standard with each set 
of samples and, if it differs from the calibration curve by more than 
2 percent, prepare a new standard curve.

11.0  Analytical Procedures

    11.1  Sample Loss Check. Note the liquid levels in Containers No. 1 
and No. 2, determine whether leakage occurred during transport, and 
note this finding on the analytical data sheet. If noticeable leakage 
has occurred, either void the sample or use methods, subject to the 
approval of the Administrator, to correct the final results.
    11.2  Sample Preparation. Treat the contents of each sample 
container as described below:
    11.2.1  Container No. 1 (Probe, Filter, and Impinger Catches). 
Filter this container's contents, including the sampling filter, 
through Whatman No. 541 filter paper, or equivalent, into a 1500-ml 
beaker.
    11.2.1.1  If the filtrate volume exceeds 900 ml, make the filtrate 
basic (red to phenolphthalein) with NaOH, and evaporate to less than 
900 ml.
    11.2.1.2  Place the filtered material (including sampling filter) 
in a nickel crucible, add a few ml of water, and macerate the filters 
with a glass rod.
    11.2.1.2.1  Add 100 mg CaO to the crucible, and mix the contents 
thoroughly to form a slurry. Add two drops of phenolphthalein 
indicator. Place the crucible in a hood under infrared lamps or on a 
hot plate at low heat. Evaporate the water completely. During the 
evaporation of the water, keep the slurry basic (red to 
phenolphthalein) to avoid loss of F-. If the indicator turns 
colorless (acidic) during the evaporation, add CaO until the color 
turns red again.
    11.2.1.2.2  After evaporation of the water, place the crucible on a 
hot plate under a hood, and slowly increase the temperature until the 
Whatman No. 541 and sampling filters char. It may take several hours to 
char the filters completely.
    11.2.1.2.3  Place the crucible in a cold muffle furnace. Gradually 
(to prevent smoking) increase the temperature to 600  deg.C (1100 
deg.F), and maintain this temperature until the contents are reduced to 
an ash. Remove the crucible from the furnace, and allow to cool.
    11.2.1.2.4  Add approximately 4 g of crushed NaOH to the crucible, 
and mix. Return the crucible to the muffle furnace, and fuse the sample 
for 10 minutes at 600  deg.C.
    11.2.1.2.5  Remove the sample from the furnace, and cool to ambient 
temperature. Using several rinsings of warm water, transfer the 
contents of the crucible to the beaker containing the filtrate. To 
ensure complete sample removal, rinse finally with two 20-ml portions 
of 25 percent H2SO4, and carefully add to the 
beaker. Mix well, and transfer to a 1-liter volumetric flask. Dilute to 
volume with water, and mix thoroughly. Allow any undissolved solids to 
settle.
    11.2.2  Container No. 2 (Sample Blank). Treat in the same manner as 
described in Section 11.2.1 above.
    11.2.3  Adjustment of Acid/Water Ratio in Distillation Flask. Place 
400 ml of water in the distillation flask, and add 200 ml of 
concentrated H2SO4. Add some soft glass beads and 
several small pieces of broken glass tubing, and assemble the apparatus 
as shown in Figure 13A-2. Heat the flask until it reaches a temperature 
of 175  deg.C (347  deg.F) to adjust the acid/water ratio for 
subsequent distillations. Discard the distillate.

    Caution: Use a protective shield when carrying out this 
procedure. Observe standard precautions when mixing 
H2SO4 with water. Slowly add the acid to the 
flask with constant swirling.

    11.3  Distillation.
    11.3.1  Cool the contents of the distillation flask to below 80 
deg.C (180  deg.F). Pipet an aliquot of sample containing less than 
10.0 mg F- directly into the distillation flask, and add 
water to make a total volume of 220 ml added to the distillation flask. 
(To estimate the appropriate aliquot size, select an aliquot of the 
solution, and treat as described in Section 11.4.1. This will be an 
approximation of the F- content because of possible 
interfering ions.)


    Note: If the sample contains chloride, add 5 mg of 
Ag2SO4 to the flask for every mg of chloride.


    11.3.2  Place a 250-ml volumetric flask at the condenser exit. Heat 
the flask as rapidly as possible with a Bunsen burner, and collect all 
the distillate up to 175  deg.C (347  deg.F). During heatup, play the 
burner flame up and down the side of the flask to prevent bumping. 
Conduct the distillation as rapidly as possible (15 minutes or less). 
Slow distillations have been found to produce low F- 
recoveries. Be careful not to exceed 175  deg.C (347  deg.F) to avoid 
causing H2SO4 to distill over. If F- 
distillation in the mg range is to be followed by a distillation in the 
fractional mg range, add 220 ml of water and distill it over as in the 
acid adjustment step to remove residual F- from the 
distillation system.
    11.3.3  The acid in the distillation flask may be used until there 
is carry-over of interferences or poor F- recovery. Check 
for interference and for recovery efficiency every tenth distillation 
using a water blank and a standard solution. Change the acid whenever 
the F- recovery is less than 90 percent or the blank value 
exceeds 0.1 g/ml.
    11.4  Sample Analysis.
    11.4.1  Containers No. 1 and No. 2.
    11.4.1.1  After distilling suitable aliquots from Containers No. 1 
and No. 2 according to Section 11.3, dilute the distillate in the 
volumetric flasks to exactly 250 ml with water, and mix thoroughly. 
Pipet a suitable aliquot of each sample distillate (containing 10 to 40 
g F-/ml) into a beaker, and dilute to 50 ml with 
water. Use the same aliquot size for the blank. Add 10 ml of SPADNS 
mixed reagent (Section 7.3.13), and mix thoroughly.
    11.4.1.2  After mixing, place the sample in a constant-temperature 
bath containing the standard solutions for 30 minutes before reading 
the absorbance on the spectrophotometer.


    Note: After the sample and colorimetric reagent are mixed, the 
color formed is stable for approximately 2 hours. Also, a 3  deg.C 
(5.4  deg.F) temperature difference between the sample and standard 
solutions produces an error of approximately 0.005 mg F-/
liter. To avoid this error, the absorbencies of the sample and 
standard solutions must be measured at the same temperature.


    11.4.1.3  Set the spectrophotometer to zero absorbance at 570 nm 
with the zero reference solution (Section 7.3.12), and check the 
spectrophotometer calibration with the standard solution (Section 
7.3.10). Determine the absorbance of the samples, and determine the 
concentration from the calibration curve. If the concentration does not 
fall within the range of the calibration curve, repeat the procedure 
using a different size aliquot.
    11.4.2  Container No. 3 (Silica Gel). Weigh the spent silica gel 
(or silica gel plus impinger) to the nearest 0.5 g using a balance. 
This step may be conducted in the field.

12.0  Data Analysis and Calculations

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


[[Page 61954]]


Ad = Aliquot of distillate taken for color development, ml.
At = Aliquot of total sample added to still, ml.
Bws = Water vapor in the gas stream, portion by volume.
Cs = Concentration of F- in stack gas, mg/dscm 
(gr/dscf).
Fc = F- concentration from the calibration curve, 
g.
Ft = Total F- in sample, mg.
Tm = Absolute average dry gas meter (DGM) temperature (see 
Figure 5-3 of Method 5),  deg.K ( deg.R).
Ts = Absolute average stack gas temperature (see Figure 5-3 
of Method 5),  deg.K ( deg.R).
Vd = Volume of distillate as diluted, ml.
Vm(std) = Volume of gas sample as measured by DGM at 
standard conditions, dscm (dscf).
Vt = Total volume of F- sample, after final 
dilution, ml.
Vw(std) = Volume of water vapor in the gas sample at 
standard conditions, scm (scf)

    12.2  Average DGM Temperature and Average Orifice Pressure Drop 
(see Figure 5-3 of Method 5).
    12.3  Dry Gas Volume. Calculate Vm(std), and adjust for 
leakage, if necessary, using Equation 5-1 of Method 5.
    12.4  Volume of Water Vapor and Moisture Content. Calculate 
Vw(std) and Bws from the data obtained in this 
method. Use Equations 5-2 and 5-3 of Method 5.
    12.5  Total Fluoride in Sample. Calculate the amount of 
F- in the sample using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.247

Where:

K = 10-3 mg/g (metric units)
    = 1.54  x  10-5 gr/g (English units)

    12.6  Fluoride Concentration in Stack Gas. Determine the 
F- concentration in the stack gas using the following 
equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.248

    12.7  Isokinetic Variation. Same as Method 5, Section 12.11.

13.0  Method Performance

    The following estimates are based on a collaborative test done at a 
primary aluminum smelter. In the test, six laboratories each sampled 
the stack simultaneously using two sampling trains for a total of 12 
samples per sampling run. Fluoride concentrations encountered during 
the test ranged from 0.1 to 1.4 mg F-/m\3\.
    13.1  Precision. The intra- and inter-laboratory standard 
deviations, which include sampling and analysis errors, were 0.044 mg 
F-/m\3\ with 60 degrees of freedom and 0.064 mg 
F-/m\3\ with five degrees of freedom, respectively.
    13.2  Bias. The collaborative test did not find any bias in the 
analytical method.
    13.3  Range. The range of this method is 0 to 1.4 g 
F-/ml.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  Alternative Procedures

    16.1  Compliance with ASTM D 3270-73T, 80, 91, or 95 (incorporated 
by reference--see Sec. 60.17) ``Analysis of Fluoride Content of the 
Atmosphere and Plant Tissues (Semiautomated Method) is an acceptable 
alternative for the requirements specified in Sections 11.2, 11.3, and 
11.4.1 when applied to suitable aliquots of Containers 1 and 2 samples.

17.0  References

    1. Bellack, Ervin. Simplified Fluoride Distillation Method. J. 
of the American Water Works Association. 50:5306. 1958.
    2. Mitchell, W.J., J.C. Suggs, and F.J. Bergman. Collaborative 
Study of EPA Method 13A and Method 13B. Publication No. EPA-300/4-
77-050. U.S. Environmental Protection Agency, Research Triangle 
Park, NC. December 1977.
    3. Mitchell, W.J., and M.R. Midgett. Adequacy of Sampling Trains 
and Analytical Procedures Used for Fluoride. Atm. Environ. 10:865-
872. 1976.
BILLING CODE 6560-50-P

[[Page 61955]]

18.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.249


[[Page 61956]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.250

BILLING CODE 6560-50-C

Method 13B--Determination of Total Fluoride Emissions From 
Stationary Sources (Specific Ion Electrode Method)

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in this part. 
Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of at least the following 
additional test methods: Method 1, Method 2, Method 3, Method 5, and 
Method 13A.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.           Sensitivity
------------------------------------------------------------------------
Total fluorides as Fluorine....       7782-41-4  Not determined.
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of fluoride (F-) emissions from sources as specified in the 
regulations. It does not measure fluorocarbons, such as Freons.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary

    Gaseous and particulate F- are withdrawn isokinetically 
from the source and collected in water and on a filter. The total 
F- is then determined by the specific ion electrode method.

3.0  Definitions. [Reserved]

4.0  Interferences

    Grease on sample-exposed surfaces may cause low F- 
results because of adsorption.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method does not purport to address 
all of the safety problems associated with its use. It is the 
responsibility of the user of this test method to establish appropriate 
safety and health practices and to determine the applicability of 
regulatory limitations prior to performing this test method.
    5.2  Corrosive Reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water at least 15 minutes. Remove clothing under 
shower and

[[Page 61957]]

decontaminate. Treat residual chemical burn as thermal burn.
    5.2.1  Sodium Hydroxide (NaOH). Causes severe damage to eye tissues 
and to skin. Inhalation causes irritation to nose, throat, and lungs. 
Reacts exothermically with limited amounts of water.
    5.2.2  Sulfuric Acid (H2SO4). Rapidly 
destructive to body tissue. Will cause third degree burns. Eye damage 
may result in blindness. Inhalation may be fatal from spasm of the 
larynx, usually within 30 minutes. May cause lung tissue damage with 
edema. 1 mg/m\3\ for 8 hours will cause lung damage or, in higher 
concentrations, death. Provide ventilation to limit inhalation. Reacts 
violently with metals and organics.

6.0  Equipment and Supplies

    6.1  Sample Collection and Sample Recovery. Same as Method 13A, 
Sections 6.1 and 6.2, respectively.
    6.2  Sample Preparation and Analysis. The following items are 
required for sample preparation and analysis:
    6.2.1  Distillation Apparatus, Bunsen Burner, Electric Muffle 
Furnace, Crucibles, Beakers, Volumetric Flasks, Erlenmeyer Flasks or 
Plastic Bottles, Constant Temperature Bath, and Balance. Same as Method 
13A, Sections 6.3.1 to 6.3.9, respectively.
    6.2.2  Fluoride Ion Activity Sensing Electrode.
    6.2.3  Reference Electrode. Single junction, sleeve type.
    6.2.4  Electrometer. A pH meter with millivolt-scale capable of 
0.1-mv resolution, or a specific ion meter made 
specifically for specific ion electrode use.
    6.2.5  Magnetic Stirrer and Tetrafluoroethylene (TFE) Fluorocarbon-
Coated Stirring Bars.
    6.2.6  Beakers. Polyethylene, 100-ml.

7.0  Reagents and Standards

    Unless otherwise indicated, all reagents are to conform to the 
specifications established by the Committee on Analytical Reagents of 
the American Chemical Society, where such specifications are available. 
Otherwise, use the best available grade.
    7.1  Sample Collection and Sample Recovery. Same as Method 13A, 
Sections 7.1 and 7.2, respectively.
    7.2  Sample Preparation and Analysis. The following reagents and 
standards are required for sample analysis:
    7.2.1  Calcium Oxide (CaO). Certified grade containing 0.005 
percent F- or less.
    7.2.2  Phenolphthalein Indicator. Dissolve 0.1 g phenolphthalein in 
a mixture of 50 ml of 90 percent ethanol and 50 ml water.
    7.2.3  Sodium Hydroxide (NaOH), Pellets.
    7.2.4  Sulfuric Acid (H2SO4), Concentrated.
    7.2.5  Filters. Whatman No. 541, or equivalent.
    7.2.6  Water. Same as Section 7.1.2 of Method 13A.
    7.2.7  Sodium Hydroxide, 5 M. Dissolve 20 g of NaOH in 100 ml of 
water.
    7.2.8  Sulfuric Acid, 25 Percent (v/v). Mix 1 part of concentrated 
H2SO4 with 3 parts of water.
    7.2.9  Total Ionic Strength Adjustment Buffer (TISAB). Place 
approximately 500 ml of water in a 1-liter beaker. Add 57 ml of glacial 
acetic acid, 58 g of sodium chloride, and 4 g of cyclohexylene 
dinitrilo tetraacetic acid. Stir to dissolve. Place the beaker in a 
water bath and cool to 20  deg.C (68  deg.F). Slowly add 5 M NaOH to 
the solution, measuring the pH continuously with a calibrated pH/
reference electrode pair, until the pH is 5.3. Pour into a 1-liter 
volumetric flask, and dilute to volume with deionized, distilled water. 
Commercially prepared TISAB may be substituted for the above.
    7.2.10  Fluoride Standard Solution, 0.1 M. Oven dry approximately 
10 g of sodium fluoride (NaF) for a minimum of 2 hours at 110  deg.C 
(230  deg.F), and store in a desiccator. Then add 4.2 g of NaF to a 1-
liter volumetric flask, and add enough water to dissolve. Dilute to 
volume with water.

8.0  Sample Collection, Preservation, Storage, and Transport

    Same as Method 13A, Section 8.0.

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.0, 10.1.....................  Sampling           Ensure accurate
                                 equipment leak-    measurement of stack
                                 check and          gas flow rate and
                                 calibration.       sample volume.
10.2..........................  Fluoride           Evaluate analytical
                                 electrode.         technique,
                                                    preparation of
                                                    standards.
11.1..........................  Interference/      Minimize negative
                                 recovery           effects of used
                                 efficiency-check   acid.
                                 during
                                 distillation.
------------------------------------------------------------------------

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

10.0  Calibration and Standardizations

    Note: Maintain a laboratory log of all calibrations.


    10.1  Sampling Equipment. Same as Method 13A, Section 10.1.
    10.2  Fluoride Electrode. Prepare fluoride standardizing solutions 
by serial dilution of the 0.1 M fluoride standard solution. Pipet 10 ml 
of 0.1 M fluoride standard solution into a 100-ml volumetric flask, and 
make up to the mark with water for a 10-\2\ M standard 
solution. Use 10 ml of 10-\2\ M solution to make a 
10-\3\ M solution in the same manner. Repeat the dilution 
procedure, and make 10-\4\ and 10-\5\ M 
solutions.
    10.2.1  Pipet 50 ml of each standard into a separate beaker. Add 50 
ml of TISAB to each beaker. Place the electrode in the most dilute 
standard solution. When a steady millivolt reading is obtained, plot 
the value on the linear axis of semilog graph paper versus 
concentration on the log axis. Plot the nominal value for concentration 
of the standard on the log axis, (e.g., when 50 ml of 10-\2\ 
M standard is diluted with 50 ml of TISAB, the concentration is still 
designated ``10-\2\ M'').
    10.2.2  Between measurements, soak the fluoride sensing electrode 
in water for 30 seconds, and then remove and blot dry. Analyze the 
standards going from dilute to concentrated standards. A straight-line 
calibration curve will be obtained, with nominal concentrations of 
10-\4\, 10-\3\, 10-\2\, 
10-\1\ fluoride molarity on the log axis plotted versus 
electrode potential (in mv) on the linear scale. Some electrodes may be 
slightly nonlinear between 10-\5\ and 10-\4\ M. 
If this occurs, use additional standards between these two 
concentrations.
    10.2.3  Calibrate the fluoride electrode daily, and check it 
hourly. Prepare fresh fluoride standardizing solutions daily 
(10-\2\ M or less). Store fluoride standardizing solutions 
in polyethylene or polypropylene containers.

    Note: Certain specific ion meters have been designed 
specifically for fluoride electrode use and give a direct readout of 
fluoride ion concentration. These meters may be used in lieu of 
calibration curves for fluoride

[[Page 61958]]

measurements over a narrow concentration ranges. Calibrate the meter 
according to the manufacturer's instructions.

11.0  Analytical Procedures

    11.1  Sample Loss Check, Sample Preparation, and Distillation. Same 
as Method 13A, Sections 11.1 through 11.3, except that the Note 
following Section 11.3.1 is not applicable.
    11.2  Analysis.
    11.2.1  Containers No. 1 and No. 2. Distill suitable aliquots from 
Containers No. 1 and No. 2. Dilute the distillate in the volumetric 
flasks to exactly 250 ml with water, and mix thoroughly. Pipet a 25-ml 
aliquot from each of the distillate into separate beakers. Add an equal 
volume of TISAB, and mix. The sample should be at the same temperature 
as the calibration standards when measurements are made. If ambient 
laboratory temperature fluctuates more than 2  deg.C from 
the temperature at which the calibration standards were measured, 
condition samples and standards in a constant-temperature bath before 
measurement. Stir the sample with a magnetic stirrer during measurement 
to minimize electrode response time. If the stirrer generates enough 
heat to change solution temperature, place a piece of temperature 
insulating material, such as cork, between the stirrer and the beaker. 
Hold dilute samples (below 10-\4\ M fluoride ion content) in 
polyethylene beakers during measurement.
    11.2.2  Insert the fluoride and reference electrodes into the 
solution. When a steady millivolt reading is obtained, record it. This 
may take several minutes. Determine concentration from the calibration 
curve. Between electrode measurements, rinse the electrode with water.
    11.2.3  Container No. 3 (Silica Gel). Same as in Method 13A, 
Section 11.4.2.

12.0  Data Analysis and Calculations

    Carry out calculations, retaining at least one extra significant 
figure beyond that of the acquired data. Round off figures after final 
calculation.
    12.1  Nomenclature. Same as Method 13A, Section 12.1, with the 
addition of the following:

M = F- concentration from calibration curve, molarity.

    12.2  Average DGM Temperature and Average Orifice Pressure Drop, 
Dry Gas Volume, Volume of Water Vapor and Moisture Content, Fluoride 
Concentration in Stack Gas, and Isokinetic Variation. Same as Method 
13A, Sections 12.2 to 12.4, 12.6, and 12.7, respectively.
    12.3  Total Fluoride in Sample. Calculate the amount of 
F- in the sample using Equation 13B-1:
[GRAPHIC] [TIFF OMITTED] TR17OC00.251

Where:

K = 19 [(mgl)/(moleml)] (metric units)
    = 0.292 [(grl)/(moleml)] (English units)

13.0  Method Performance

    The following estimates are based on a collaborative test done at a 
primary aluminum smelter. In the test, six laboratories each sampled 
the stack simultaneously using two sampling trains for a total of 12 
samples per sampling run. Fluoride concentrations encountered during 
the test ranged from 0.1 to 1.4 mg F-/m\3\.
    13.1  Precision. The intra-laboratory and inter-laboratory standard 
deviations, which include sampling and analysis errors, are 0.037 mg 
F-/m\3\ with 60 degrees of freedom and 0.056 mg 
F-/m\3\ with five degrees of freedom, respectively.
    13.2  Bias. The collaborative test did not find any bias in the 
analytical method.
    13.3  Range. The range of this method is 0.02 to 2,000 g 
F-/ml; however, measurements of less than 0.1 g 
F-/ml require extra care.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  Alternative Procedures

    16.1  Compliance with ASTM D 3270-73T, 91, 95 ``Analysis for 
Fluoride Content of the Atmosphere and Plant Tissues (Semiautomated 
Method)'' is an acceptable alternative for the distillation and 
analysis requirements specified in Sections 11.1 and 11.2 when applied 
to suitable aliquots of Containers 1 and 2 samples.

17.0  References

    Same as Method 13A, Section 16.0, References 1 and 2, with the 
following addition:

    1. MacLeod, Kathryn E., and Howard L. Crist. Comparison of the 
SPADNS-Zirconium Lake and Specific Ion Electrode Methods of Fluoride 
Determination in Stack Emission Samples. Analytical Chemistry. 
45:1272-1273. 1973.

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

Method 14--Determination of Fluoride Emissions From Potroom Roof 
Monitors for Primary Aluminum Plants

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in this part. 
Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of at least the following 
additional test methods: Method 1, Method 2, Method 3, Method 5, 
Method 13A, and Method 13B.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
              Analyte                   CAS No.          Sensitivity
------------------------------------------------------------------------
Total fluorides as Fluorine.......       7782-41-4  Not determined.
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of fluoride emissions from roof monitors at primary aluminum reduction 
plant potroom groups.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  Gaseous and particulate fluoride roof monitor emissions are 
drawn into a permanent sampling manifold through several large nozzles. 
The sample is transported from the sampling manifold to ground level 
through a duct. The fluoride content of the gas in the duct is 
determined using either Method 13A or Method 13B. Effluent velocity and 
volumetric flow rate are determined using anemometers located in the 
roof monitor.

3.0  Definitions

    Potroom means a building unit which houses a group of electrolytic 
cells in which aluminum is produced.
    Potroom group means an uncontrolled potroom, a potroom which is 
controlled individually, or a group of potrooms or potroom segments 
ducted to a common control system.

[[Page 61959]]

    Roof monitor means that portion of the roof of a potroom where 
gases not captured at the cell exit from the potroom.

4.0  Interferences

    Same as Section 4.0 of either Method 13A or Method 13B, with the 
addition of the following:
    4.1  Magnetic Field Effects. Anemometer readings can be affected by 
potroom magnetic field effects. Section 6.1 provides for minimization 
of this interference through proper shielding or encasement of 
anemometer components.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and to determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Corrosive Reagents. Same as Section 5.2 of either Method 13A 
or Method 13B.

6.0  Equipment and Supplies

    Same as Section 6.0 of either Method 13A or Method 13B, as 
applicable, with the addition of the following:
    6.1  Velocity Measurement Apparatus.
    6.1.1  Anemometer Specifications. Propeller anemometers, or 
equivalent. Each anemometer shall meet the following specifications:
    6.1.1.1  Its propeller shall be made of polystyrene, or similar 
material of uniform density. To ensure uniformity of performance among 
propellers, it is desirable that all propellers be made from the same 
mold.
    6.1.1.2  The propeller shall be properly balanced, to optimize 
performance.
    6.1.1.3  When the anemometer is mounted horizontally, its threshold 
velocity shall not exceed 15 m/min (50 ft/min).
    6.1.1.4  The measurement range of the anemometer shall extend to at 
least 600 m/min (2,000 ft/min).
    6.1.1.5  The anemometer shall be able to withstand prolonged 
exposure to dusty and corrosive environments; one way of achieving this 
is to purge the bearings of the anemometer continuously with filtered 
air during operation.
    6.1.1.6  All anemometer components shall be properly shielded or 
encased, such that the performance of the anemometer is uninfluenced by 
potroom magnetic field effects.
    6.1.1.7  A known relationship shall exist between the electrical 
output signal from the anemometer generator and the propeller shaft rpm 
(see Section 10.2.1). Anemometers having other types of output signals 
(e.g., optical) may be used, subject to the approval of the 
Administrator. If other types of anemometers are used, there must be a 
known relationship between output signal and shaft rpm (see Section 
10.2.2).
    6.1.1.8  Each anemometer shall be equipped with a suitable readout 
system (see Section 6.1.3).
    6.1.2  Anemometer Installation Requirements.
    6.1.2.1  Single, Isolated Potroom. If the affected facility 
consists of a single, isolated potroom (or potroom segment), install at 
least one anemometer for every 85 m (280 ft) of roof monitor length. If 
the length of the roof monitor divided by 85 m (280 ft) is not a whole 
number, round the fraction to the nearest whole number to determine the 
number of anemometers needed. For monitors that are less than 130 m 
(430 ft) in length, use at least two anemometers. Divide the monitor 
cross-section into as many equal areas as anemometers, and locate an 
anemometer at the centroid of each equal area. See exception in Section 
6.1.2.3.
    6.1.2.2  Two or More Potrooms. If the affected facility consists of 
two or more potrooms (or potroom segments) ducted to a common control 
device, install anemometers in each potroom (or segment) that contains 
a sampling manifold. Install at least one anemometer for every 85 m 
(280 ft) of roof monitor length of the potroom (or segment). If the 
potroom (or segment) length divided by 85 m (280 ft) is not a whole 
number, round the fraction to the nearest whole number to determine the 
number of anemometers needed. If the potroom (or segment) length is 
less than 130 m (430 ft), use at least two anemometers. Divide the 
potroom (or segment) monitor cross-section into as many equal areas as 
anemometers, and locate an anemometer at the centroid of each equal 
area. See exception in Section 6.1.2.3.
    6.1.2.3  Placement of Anemometer at the Center of Manifold. At 
least one anemometer shall be installed in the immediate vicinity 
(i.e., within 10 m (33 ft)) of the center of the manifold (see Section 
6.2.1). For its placement in relation to the width of the monitor, 
there are two alternatives. The first is to make a velocity traverse of 
the width of the roof monitor where an anemometer is to be placed and 
install the anemometer at a point of average velocity along this 
traverse. The traverse may be made with any suitable low velocity 
measuring device, and shall be made during normal process operating 
conditions. The second alternative is to install the anemometer half-
way across the width of the roof monitor. In this latter case, the 
velocity traverse need not be conducted.
    6.1.3  Recorders. Recorders that are equipped with suitable 
auxiliary equipment (e.g., transducers) for converting the output 
signal from each anemometer to a continuous recording of air flow 
velocity or to an integrated measure of volumetric flowrate shall be 
used. A suitable recorder is one that allows the output signal from the 
propeller anemometer to be read to within 1 percent when the velocity 
is between 100 and 120 m/min (330 and 390 ft/min). For the purpose of 
recording velocity, ``continuous'' shall mean one readout per 15-minute 
or shorter time interval. A constant amount of time shall elapse 
between readings. Volumetric flow rate may be determined by an 
electrical count of anemometer revolutions. The recorders or counters 
shall permit identification of the velocities or flowrates measured by 
each individual anemometer.
    6.1.4  Pitot Tube. Standard-type pitot tube, as described in 
Section 6.7 of Method 2, and having a coefficient of 0.99  
0.01.
    6.1.5  Pitot Tube (Optional). Isolated, Type S pitot, as described 
in Section 6.1 of Method 2, and having a known coefficient, determined 
as outlined in Section 4.1 of Method 2.
    6.1.6  Differential Pressure Gauge. Inclined manometer, or 
equivalent, as described in Section 6.1.2 of Method 2.
    6.2  Roof Monitor Air Sampling System.
    6.2.1  Manifold System and Ductwork. A minimum of one manifold 
system shall be installed for each potroom group. The manifold system 
and ductwork shall meet the following specifications:
    6.2.1.1  The manifold system and connecting duct shall be 
permanently installed to draw an air sample from the roof monitor to 
ground level. A typical installation of a duct for drawing a sample 
from a roof monitor to ground level is shown in Figure 14-1 in Section 
17.0. A plan of a manifold system that is located in a roof monitor is 
shown in Figure 14-2. These drawings represent a typical installation 
for a generalized roof monitor. The dimensions on these figures may be 
altered slightly to make the manifold system fit into a particular roof 
monitor, but the general configuration shall be followed.

[[Page 61960]]

    6.2.1.2  There shall be eight nozzles, each having a diameter of 
0.40 to 0.50 m.
    6.2.1.3  The length of the manifold system from the first nozzle to 
the eighth shall be 35 m (115 ft) or eight percent of the length of the 
potroom (or potroom segment) roof monitor, whichever is greater. 
Deviation from this requirement is subject to the approval of the 
Administrator.
    6.2.1.4  The duct leading from the roof monitor manifold system 
shall be round with a diameter of 0.30 to 0.40 m (1.0 to 1.3 ft). All 
connections in the ductwork shall be leak-free.
    6.2.1.5  As shown in Figure 14-2, each of the sample legs of the 
manifold shall have a device, such as a blast gate or valve, to enable 
adjustment of the flow into each sample nozzle.
    6.2.1.6  The manifold system shall be located in the immediate 
vicinity of one of the propeller anemometers (see Section 8.1.1.4) and 
as close as possible to the midsection of the potroom (or potroom 
segment). Avoid locating the manifold system near the end of a potroom 
or in a section where the aluminum reduction pot arrangement is not 
typical of the rest of the potroom (or potroom segment). The sample 
nozzles shall be centered in the throat of the roof monitor (see Figure 
14-1).
    6.2.1.7  All sample-exposed surfaces within the nozzles, manifold, 
and sample duct shall be constructed with 316 stainless steel. 
Alternatively, aluminum may be used if a new ductwork is conditioned 
with fluoride-laden roof monitor air for a period of six weeks before 
initial testing. Other materials of construction may be used if it is 
demonstrated through comparative testing, to the satisfaction of the 
Administrator, that there is no loss of fluorides in the system.
    6.2.1.8  Two sample ports shall be located in a vertical section of 
the duct between the roof monitor and the exhaust fan (see Section 
6.2.2). The sample ports shall be at least 10 duct diameters downstream 
and three diameters upstream from any flow disturbance such as a bend 
or contraction. The two sample ports shall be situated 90 deg. apart. 
One of the sample ports shall be situated so that the duct can be 
traversed in the plane of the nearest upstream duct bend.
    6.2.2  Exhaust Fan. An industrial fan or blower shall be attached 
to the sample duct at ground level (see Figure 14-1). This exhaust fan 
shall have a capacity such that a large enough volume of air can be 
pulled through the ductwork to maintain an isokinetic sampling rate in 
all the sample nozzles for all flow rates normally encountered in the 
roof monitor. The exhaust fan volumetric flow rate shall be adjustable 
so that the roof monitor gases can be drawn isokinetically into the 
sample nozzles. This control of flow may be achieved by a damper on the 
inlet to the exhauster or by any other workable method.
    6.3  Temperature Measurement Apparatus. To monitor and record the 
temperature of the roof monitor effluent gas, and consisting of the 
following:
    6.3.1  Temperature Sensor. A temperature sensor shall be installed 
in the roof monitor near the sample duct. The temperature sensor shall 
conform to the specifications outlined in Method 2, Section 6.3.
    6.3.2  Signal Transducer. Transducer, to change the temperature 
sensor voltage output to a temperature readout.
    6.3.3  Thermocouple Wire. To reach from roof monitor to signal 
transducer and recorder.
    6.3.4  Recorder. Suitable recorder to monitor the output from the 
thermocouple signal transducer.

7.0  Reagents and Standards

    Same as Section 7.0 of either Method 13A or Method 13B, as 
applicable.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Roof Monitor Velocity Determination.
    8.1.1  Velocity Estimate(s) for Setting Isokinetic Flow. To assist 
in setting isokinetic flow in the manifold sample nozzles, the 
anticipated average velocity in the section of the roof monitor 
containing the sampling manifold shall be estimated before each test 
run. Any convenient means to make this estimate may be used (e.g., the 
velocity indicated by the anemometer in the section of the roof monitor 
containing the sampling manifold may be continuously monitored during 
the 24-hour period before the test run). If there is question as to 
whether a single estimate of average velocity is adequate for an entire 
test run (e.g., if velocities are anticipated to be significantly 
different during different potroom operations), the test run may be 
divided into two or more ``sub-runs,'' and a different estimated 
average velocity may be used for each sub-run (see Section 8.4.2).
    8.1.2  Velocity Determination During a Test Run. During the actual 
test run, record the velocity or volumetric flowrate readings of each 
propeller anemometer in the roof monitor. Readings shall be taken from 
each anemometer at equal time intervals of 15 minutes or less (or 
continuously).
    8.2  Temperature Recording. Record the temperature of the roof 
monitor effluent gases at least once every 2 hours during the test run.
    8.3  Pretest Ductwork Conditioning. During the 24-hour period 
immediately preceding the test run, turn on the exhaust fan, and draw 
roof monitor air through the manifold system and ductwork. Adjust the 
fan to draw a volumetric flow through the duct such that the velocity 
of gas entering the manifold nozzles approximates the average velocity 
of the air exiting the roof monitor in the vicinity of the sampling 
manifold.
    8.4  Manifold Isokinetic Sample Rate Adjustment(s).
    8.4.1  Initial Adjustment. Before the test run (or first sub-run, 
if applicable; see Sections 8.1.1 and 8.4.2), adjust the fan such that 
air enters the manifold sample nozzles at a velocity equal to the 
appropriate estimated average velocity determined under Section 8.1.1. 
Use Equation 14-1 (Section 12.2.2) to determine the correct stream 
velocity needed in the duct at the sampling location, in order for 
sample gas to be drawn isokinetically into the manifold nozzles. Next, 
verify that the correct stream velocity has been achieved, by 
performing a pitot tube traverse of the sample duct (using either a 
standard or Type S pitot tube); use the procedure outlined in Method 2.
    8.4.2  Adjustments During Run. If the test run is divided into two 
or more ``sub-runs'' (see Section 8.1.1), additional isokinetic rate 
adjustment(s) may become necessary during the run. Any such adjustment 
shall be made just before the start of a sub-run, using the procedure 
outlined in Section 8.4.1 above.


    Note: Isokinetic rate adjustments are not permissible during a 
sub-run.


    8.5  Pretest Preparation, Preliminary Determinations, Preparation 
of Sampling Train, Leak-Check Procedures, Sampling Train Operation, and 
Sample Recovery. Same as Method 13A, Sections 8.1 through 8.6, with the 
exception of the following:
    8.5.1  A single train shall be used for the entire sampling run. 
Alternatively, if two or more sub-runs are performed, a separate train 
may be used for each sub-run; note, however, that if this option is 
chosen, the area of the sampling nozzle shall be the same 
(2 percent) for each train. If the test run is divided into 
sub-runs, a complete traverse of the duct shall be performed during 
each sub-run.
    8.5.2 Time Per Run. Each test run shall last 8 hours or more; if 
more than one run is to be performed, all runs shall be of 
approximately the same (10 percent) length. If questions 
exist as to the representativeness of an 8-hour test,

[[Page 61961]]

a longer period should be selected. Conduct each run during a period 
when all normal operations are performed underneath the sampling 
manifold. For most recently-constructed plants, 24 hours are required 
for all potroom operations and events to occur in the area beneath the 
sampling manifold. During the test period, all pots in the potroom 
group shall be operated such that emissions are representative of 
normal operating conditions in the potroom group.

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
                                 Quality Control
            Section                  Measure               Effect
------------------------------------------------------------------------
8.0, 10.0.....................  Sampling           Ensure accurate
                                 equipment leak-    measurement of gas
                                 check and          flow rate in duct
                                 calibration.       and of sample
                                                    volume.
10.3, 10.4....................  Initial and        Ensure accurate and
                                 periodic           precise measurement
                                 performance        of roof monitor
                                 checks of roof     effluent gas
                                 monitor effluent   temperature and flow
                                 gas                rate.
                                 characterization
                                 apparatus.
11.0..........................  Interference/      Minimize negative
                                 recovery           effects of used
                                 efficiency check   acid.
                                 during
                                 distillation.
------------------------------------------------------------------------

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

10.0  Calibration and Standardization

    Same as Section 10.0 of either Method 13A or Method 13B, as 
applicable, with the addition of the following:
    10.1  Manifold Intake Nozzles. The manifold intake nozzles shall be 
calibrated when the manifold system is installed or, alternatively, the 
manifold may be preassembled and the nozzles calibrated on the ground 
prior to installation. The following procedures shall be observed:
    10.1.1  Adjust the exhaust fan to draw a volumetric flow rate 
(refer to Equation 14-1) such that the entrance velocity into each 
manifold nozzle approximates the average effluent velocity in the roof 
monitor.
    10.1.2  Measure the velocity of the air entering each nozzle by 
inserting a standard pitot tube into a 2.5 cm or less diameter hole 
(see Figure 14-2) located in the manifold between each blast gate (or 
valve) and nozzle. Note that a standard pitot tube is used, rather than 
a type S, to eliminate possible velocity measurement errors due to 
cross-section blockage in the small (0.13 m diameter) manifold leg 
ducts. The pitot tube tip shall be positioned at the center of each 
manifold leg duct. Take care to ensure that there is no leakage around 
the pitot tube, which could affect the indicated velocity in the 
manifold leg.
    10.1.3  If the velocity of air being drawn into each nozzle is not 
the same, open or close each blast gate (or valve) until the velocity 
in each nozzle is the same. Fasten each blast gate (or valve) so that 
it will remain in position, and close the pitot port holes.
    10.2  Initial Calibration of Propeller Anemometers.
    10.2.1  Anemometers that meet the specifications outlined in 
Section 6.1.1 need not be calibrated, provided that a reference 
performance curve relating anemometer signal output to air velocity 
(covering the velocity range of interest) is available from the 
manufacturer. If a reference performance curve is not available from 
the manufacturer, such a curve shall be generated.
    For the purpose of this method, a ``reference'' performance curve 
is defined as one that has been derived from primary standard 
calibration data, with the anemometer mounted vertically. ``Primary 
standard'' data are obtainable by: (a) direct calibration of one or 
more of the anemometers by the National Institute of Standards and 
Technology (NIST); (b) NIST-traceable calibration; or (c) Calibration 
by direct measurement of fundamental parameters such as length and time 
(e.g., by moving the anemometers through still air at measured rates of 
speed, and recording the output signals).
    10.2.2  Anemometers having output signals other than electrical 
(e.g., optical) may be used, subject to the approval of the 
Administrator. If other types of anemometers are used, a reference 
performance curve shall be generated, using procedures subject to the 
approval of the Administrator.
    10.2.3  The reference performance curve shall be derived from at 
least the following three points: 60  15, 900  
100, and 1800  100 rpm.
    10.3  Initial Performance Checks. Conduct these checks within 60 
days before the first performance test.
    10.3.1  Anemometers. A performance-check shall be conducted as 
outlined in Sections 10.3.1.1 through 10.3.1.3. Alternatively, any 
other suitable method that takes into account the signal output, 
propeller condition, and threshold velocity of the anemometer may be 
used, subject to the approval of the Administrator.
    10.3.1.1  Check the signal output of the anemometer by using an 
accurate rpm generator (see Figure 14-3) or synchronous motors to spin 
the propeller shaft at each of the three rpm settings described in 
Section 10.2.3, and measuring the output signal at each setting. If, at 
each setting, the output signal is within 5 percent of the 
manufacturer's value, the anemometer can be used. If the anemometer 
performance is unsatisfactory, the anemometer shall either be replaced 
or repaired.
    10.3.1.2  Check the propeller condition, by visually inspecting the 
propeller, making note of any significant damage or warpage; damaged or 
deformed propellers shall be replaced.
    10.3.1.3  Check the anemometer threshold velocity as follows: With 
the anemometer mounted as shown in Figure 14-4(A), fasten a known 
weight (a straight-pin will suffice) to the anemometer propeller at a 
fixed distance from the center of the propeller shaft. This will 
generate a known torque; for example, a 0.1-g weight, placed 10 cm from 
the center of the shaft, will generate a torque of 1.0 g-cm. If the 
known torque causes the propeller to rotate downward, approximately 
90 deg. [see Figure 14-4(B)], then the known torque is greater than or 
equal to the starting torque; if the propeller fails to rotate 
approximately 90 deg., the known torque is less than the starting 
torque. By trying different combinations of weight and distance, the 
starting torque of a particular anemometer can be satisfactorily 
estimated. Once an estimate of the starting torque has been obtained, 
the threshold velocity of the anemometer (for horizontal mounting) can 
be estimated from a graph such as Figure 14-5 (obtained from the 
manufacturer). If the horizontal threshold velocity is acceptable [15 
m/min (50 ft/min), when this technique is used], the anemometer can be 
used. If the threshold velocity of an anemometer is found to be 
unacceptably high, the anemometer shall either be replaced or repaired.
    10.3.2  Recorders and Counters. Check the calibration of each 
recorder and counter (see Section 6.1.2) at a minimum of three points, 
approximately spanning the expected range of velocities. Use the 
calibration

[[Page 61962]]

procedures recommended by the manufacturer, or other suitable 
procedures (subject to the approval of the Administrator). If a 
recorder or counter is found to be out of calibration by an average 
amount greater than 5 percent for the three calibration points, replace 
or repair the system; otherwise, the system can be used.
    10.3.3  Temperature Measurement Apparatus. Check the calibration of 
the Temperature Measurement Apparatus, using the procedures outlined in 
Section 10.3 of Method 2, at temperatures of 0, 100, and 150  deg.C 
(32, 212, and 302  deg.F). If the calibration is off by more than 5 
deg.C (9  deg.F) at any of the temperatures, repair or replace the 
apparatus; otherwise, the apparatus can be used.
    10.4  Periodic Performance Checks. Repeat the procedures outlined 
in Section 10.3 no more than 12 months after the initial performance 
checks. If the above systems pass the performance checks (i.e., if no 
repair or replacement of any component is necessary), continue with the 
performance checks on a 12-month interval basis. However, if any of the 
above systems fail the performance checks, repair or replace the 
system(s) that failed, and conduct the periodic performance checks on a 

3-month interval basis, until sufficient information (to the 
satisfaction of the Administrator) is obtained to establish a modified 
performance check schedule and calculation procedure.

    Note: If any of the above systems fails the 12-month periodic 
performance checks, the data for the past year need not be 
recalculated.

11.0  Analytical Procedures

    Same as Section 11.0 of either Method 13A or Method 13B.

12.0  Data Analysis and Calculations

    Same as Section 12.0 of either Method 13A or Method 13B, as 
applicable, with the following additions and exceptions:
    12.1  Nomenclature.

A = Roof monitor open area, m\2\ (ft\2\).
Bws = Water vapor in the gas stream, portion by volume.
Cs = Average fluoride concentration in roof monitor air, mg 
F/dscm (gr/dscf).
Dd = Diameter of duct at sampling location, m (ft).
Dn = Diameter of a roof monitor manifold nozzle, m (ft).
F = Emission Rate multiplication factor, dimensionless.
Ft = Total fluoride mass collected during a particular sub-
run (from Equation 13A-1 of Method 13A or Equation 13B-1 of Method 
13B), mg F- (gr F-).
Md = Mole fraction of dry gas, dimensionless.
Prm = Pressure in the roof monitor; equal to barometric 
pressure for this application.
Qsd = Average volumetric flow from roof monitor at standard 
conditions on a dry basis, m\3\/min.
Trm = Average roof monitor temperature (from Section 8.2), 
deg.C ( deg.F).
Vd = Desired velocity in duct at sampling location, m/sec.
Vm = Anticipated average velocity (from Section 8.1.1) in 
sampling duct, m/sec.
Vmt = Arithmetic mean roof monitor effluent gas velocity, m/
sec.
Vs = Actual average velocity in the sampling duct (from 
Equation 2-9 of Method 2 and data obtained from Method 13A or 13B), m/
sec.

    12.2  Isokinetic Sampling Check.
    12.2.1  Calculate the arithmetic mean of the roof monitor effluent 
gas velocity readings (vm) as measured by the anemometer in 
the section of the roof monitor containing the sampling manifold. If 
two or more sub-runs have been performed, the average velocity for each 
sub-run may be calculated separately.
    12.2.2  Calculate the expected average velocity (vd) in 
the duct, corresponding to each value of vm obtained under 
Section 12.2.1, using Equation 14-1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.252

Where:

8 = number of required manifold nozzles.
60 = sec/min.

    12.2.3  Calculate the actual average velocity (vs) in 
the sampling duct for each run or sub-run according to Equation 2-9 of 
Method 2, using data obtained during sampling (Section 8.0 of Method 
13A).
    12.2.4  Express each vs value from Section 12.2.3 as a percentage 
of the corresponding vd value from Section 12.2.2.
    12.2.4.1  If vs is less than or equal to 120 percent of 
vd, the results are acceptable (note that in cases where the 
above calculations have been performed for each sub-run, the results 
are acceptable if the average percentage for all sub-runs is less than 
or equal to 120 percent).
    12.2.4.2  If vs is more than 120 percent of 
vd, multiply the reported emission rate by the following 
factor:
[GRAPHIC] [TIFF OMITTED] TR17OC00.253

    12.3  Average Velocity of Roof Monitor Effluent Gas. Calculate the 
arithmetic mean roof monitor effluent gas velocity (vmt) 
using all the velocity or volumetric flow readings from Section 8.1.2.
    12.4  Average Temperature of Roof Monitor Effluent Gas. Calculate 
the arithmetic mean roof monitor effluent gas temperature 
(Tm) using all the temperature readings recorded in Section 
8.2.
    12.5  Concentration of Fluorides in Roof Monitor Effluent Gas.
    12.5.1  If a single sampling train was used throughout the run, 
calculate the average fluoride concentration for the roof monitor using 
Equation 13A-2 of Method 13A.
    12.5.2  If two or more sampling trains were used (i.e., one per 
sub-run), calculate the average fluoride concentration for the run 
using Equation 14-3:
[GRAPHIC] [TIFF OMITTED] TR17OC00.254

Where:

n = Total number of sub-runs.
    12.6  Mole Fraction of Dry Gas.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.255
    
    12.7  Average Volumetric Flow Rate of Roof Monitor Effluent Gas. 
Calculate the arithmetic mean volumetric flow rate of the roof monitor 
effluent gases using Equation 14-5.
[GRAPHIC] [TIFF OMITTED] TR17OC00.256

Where:

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

13.0 Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    Same as Section 16.0 of either Method 13A or Method 13B, as 
applicable, with the addition of the following:

    1. Shigehara, R.T. A Guideline for Evaluating Compliance Test 
Results (Isokinetic Sampling Rate Criterion). U.S. Environmental 
Protection Agency, Emission Measurement Branch, Research Triangle 
Park, NC. August 1977.
BILLING CODE 6560-50-P

[[Page 61963]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.257


[[Page 61964]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.258


[[Page 61965]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.259


[[Page 61966]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.260


[[Page 61967]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.261

BILLING CODE 6560-50-C

[[Page 61968]]

* * * * *

Method 15--Determination of Hydrogen Sulfide, Carbonyl Sulfide, and 
Carbon Disulfide Emissions From Stationary Sources

    Note: This method is not inclusive with respect to 
specifications (e.g., equipment and supplies) and procedures (e.g., 
sampling and analytical) essential to its performance. Some material 
is incorporated by reference from other methods in this part. 
Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of gas chromatography techniques.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
                                                  Sensitivity  (See Sec
            Analyte                  CAS No.              13.2)
------------------------------------------------------------------------
Carbon disulfide [CS2].........         75-15-0  0.5 ppmv
Carbonyl sulfide [COS].........        463-58-1  0.5 ppmv
Hydrogen sulfide [H2S].........       7783-06-4  0.5 ppmv
------------------------------------------------------------------------

    1.2  Applicability.
    1.2.1  This method applies to the determination of emissions of 
reduced sulfur compounds from tail gas control units of sulfur recovery 
plants, H2S in fuel gas for fuel gas combustion devices, and 
where specified in other applicable subparts of the regulations.
    1.2.2  The method described below uses the principle of gas 
chromatographic (GC) separation and flame photometric detection (FPD). 
Since there are many systems or sets of operating conditions that 
represent useable methods for determining sulfur emissions, all systems 
which employ this principle, but differ only in details of equipment 
and operation, may be used as alternative methods, provided that the 
calibration precision and sample-line loss criteria are met.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  A gas sample is extracted from the emission source and diluted 
with clean dry air (if necessary). An aliquot of the diluted sample is 
then analyzed for CS2, COS, and H2S by GC/FPD.

3.0  Definitions. [Reserved]

4.0  Interferences

    4.1  Moisture Condensation. Moisture condensation in the sample 
delivery system, the analytical column, or the FPD burner block can 
cause losses or interferences. This potential is eliminated by heating 
the probe, filter box, and connections, and by maintaining the 
SO2 scrubber in an ice water bath. Moisture is removed in 
the SO2 scrubber and heating the sample beyond this point is 
not necessary provided the ambient temperature is above 0  deg.C (32 
deg.F). Alternatively, moisture may be eliminated by heating the sample 
line, and by conditioning the sample with dry dilution air to lower its 
dew point below the operating temperature of the GC/FPD analytical 
system prior to analysis.
    4.2  Carbon Monoxide (CO) and Carbon Dioxide (CO2). CO 
and CO2 have substantial desensitizing effects on the FPD 
even after 9:1 dilution. (Acceptable systems must demonstrate that they 
have eliminated this interference by some procedure such as eluting CO 
and CO2 before any of the sulfur compounds to be measured.) 
Compliance with this requirement can be demonstrated by submitting 
chromatograms of calibration gases with and without CO2 in 
the diluent gas. The CO2 level should be approximately 10 
percent for the case with CO2 present. The two chromatograms 
should show agreement within the precision limits of Section 13.3.
    4.3  Elemental Sulfur. The condensation of sulfur vapor in the 
sampling system can lead to blockage of the particulate filter. This 
problem can be minimized by observing the filter for buildup and 
changing as needed.
    4.4  Sulfur Dioxide (SO2). SO2 is not a 
specific interferent but may be present in such large amounts that it 
cannot be effectively separated from the other compounds of interest. 
The SO2 scrubber described in Section 6.1.3 will effectively 
remove SO2 from the sample.
    4.5  Alkali Mist. Alkali mist in the emissions of some control 
devices may cause a rapid increase in the SO2 scrubber pH, 
resulting in low sample recoveries. Replacing the SO2 
scrubber contents after each run will minimize the chances of 
interference in these cases.

5.0  Safety

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

6.0  Equipment and Supplies

    6.1  Sample Collection. See Figure 15-1. The sampling train 
component parts are discussed in the following sections:
    6.1.1  Probe. The probe shall be made of Teflon or Teflon-lined 
stainless steel and heated to prevent moisture condensation. It shall 
be designed to allow calibration gas to enter the probe at or near the 
sample point entry. Any portion of the probe that contacts the stack 
gas must be heated to prevent moisture condensation. The probe 
described in Section 6.1.1 of Method 16A having a nozzle directed away 
from the gas stream is recommended for sources having particulate or 
mist emissions. Where very high stack temperatures prohibit the use of 
Teflon probe components, glass or quartz-lined probes may serve as 
substitutes.
    6.1.2  Particulate Filter. 50-mm Teflon filter holder and a 1- to 
2-micron porosity Teflon filter (available through Savillex 
Corporation, 5325 Highway 101, Minnetonka, Minnesota 55343). The filter 
holder must be maintained in a hot box at a temperature of at least 120 
 deg.C (248  deg.F).
    6.1.3  SO2 Scrubber. Three 300-ml Teflon segment 
impingers connected in series with flexible, thick-walled, Teflon 
tubing. (Impinger parts and tubing available through Savillex.) The 
first two impingers contain 100 ml of citrate buffer, and the third 
impinger is initially dry. The tip of the tube inserted into the 
solution should be constricted to less than 3-mm (\1/8\-in.) ID and 
should be immersed to a depth of at least 50 cm (2 in.). Immerse the 
impingers in an ice water bath and maintain near 0  deg.C. The scrubber 
solution will normally last for a 3-hour run before needing 
replacement. This will depend upon the effects of moisture and 
particulate matter on the solution strength and pH. Connections between 
the probe, particulate filter, and SO2 scrubber shall be 
made of Teflon and as short in length as possible. All portions of the 
probe, particulate filter, and connections prior

[[Page 61969]]

to the SO2 scrubber (or alternative point of moisture 
removal) shall be maintained at a temperature of at least 120  deg.C 
(248  deg.F).
    6.1.4  Sample Line. Teflon, no greater than 13-mm (\1/2\-in.) ID. 
Alternative materials, such as virgin Nylon, may be used provided the 
line-loss test is acceptable.
    6.1.5  Sample Pump. The sample pump shall be a leakless Teflon-
coated diaphragm type or equivalent.
    6.2  Analysis. The following items are needed for sample analysis:
    6.2.1  Dilution System. The dilution system must be constructed 
such that all sample contacts are made of Teflon, glass, or stainless 
steel. It must be capable of approximately a 9:1 dilution of the 
sample.
    6.2.2  Gas Chromatograph (see Figure 15-2). The gas chromatograph 
must have at least the following components:
    6.2.2.1  Oven. Capable of maintaining the separation column at the 
proper operating temperature  1  deg.C.
    6.2.2.2  Temperature Gauge. To monitor column oven, detector, and 
exhaust temperature  1  deg.C.
    6.2.2.3  Flow System. Gas metering system to measure sample, fuel, 
combustion gas, and carrier gas flows.
    6.2.2.4  Flame Photometric Detector.
    6.2.2.4.1  Electrometer. Capable of full scale amplification of 
linear ranges of 10-9 to 10-4 amperes full scale.
    6.2.2.4.2  Power Supply. Capable of delivering up to 750 volts.
    6.2.2.5  Recorder. Compatible with the output voltage range of the 
electrometer.
    6.2.2.6  Rotary Gas Valves. Multiport Teflon-lined valves equipped 
with sample loop. Sample loop volumes shall be chosen to provide the 
needed analytical range. Teflon tubing and fittings shall be used 
throughout to present an inert surface for sample gas. The GC shall be 
calibrated with the sample loop used for sample analysis.
    6.2.2.7  GC Columns. The column system must be demonstrated to be 
capable of resolving three major reduced sulfur compounds: 
H2S, COS, and CS2. To demonstrate that adequate 
resolution has been achieved, a chromatogram of a calibration gas 
containing all three reduced sulfur compounds in the concentration 
range of the applicable standard must be submitted. Adequate resolution 
will be defined as base line separation of adjacent peaks when the 
amplifier attenuation is set so that the smaller peak is at least 50 
percent of full scale. Base line separation is defined as a return to 
zero (5 percent) in the interval between peaks. Systems not 
meeting this criteria may be considered alternate methods subject to 
the approval of the Administrator.
    6.3  Calibration System (See Figure 15-3). The calibration system 
must contain the following components:
    6.3.1  Flow System. To measure air flow over permeation tubes 
within 2 percent. Each flowmeter shall be calibrated after each 
complete test series with a wet-test meter. If the flow measuring 
device differs from the wet-test meter by more than 5 percent, the 
completed test shall be discarded. Alternatively, use the flow data 
that will yield the lowest flow measurement. Calibration with a wet-
test meter before a test is optional. Flow over the permeation device 
may also be determined using a soap bubble flowmeter.
    6.3.2  Constant Temperature Bath. Device capable of maintaining the 
permeation tubes at the calibration temperature within 0.1  deg.C.
    6.3.3  Temperature Sensor. Thermometer or equivalent to monitor 
bath temperature within 0.1  deg.C.

7.0  Reagents and Standards

    7.1  Fuel. Hydrogen gas (H2). Prepurified grade or 
better.
    7.2  Combustion Gas. Oxygen (O2) or air, research purity 
or better.
    7.3  Carrier Gas. Prepurified grade or better.
    7.4  Diluent. Air containing less than 0.5 ppmv total sulfur 
compounds and less than 10 ppmv each of moisture and total 
hydrocarbons.
    7.5  Calibration Gases.
    7.5.1  Permeation Devices. One each of H2S, COS, and 
CS2, gravimetrically calibrated and certified at some 
convenient operating temperature. These tubes consist of hermetically 
sealed FEP Teflon tubing in which a liquified gaseous substance is 
enclosed. The enclosed gas permeates through the tubing wall at a 
constant rate. When the temperature is constant, calibration gases 
covering a wide range of known concentrations can be generated by 
varying and accurately measuring the flow rate of diluent gas passing 
over the tubes. These calibration gases are used to calibrate the GC/
FPD system and the dilution system.
    7.5.2  Cylinder Gases. Cylinder gases may be used as alternatives 
to permeation devices. The gases must be traceable to a primary 
standard (such as permeation tubes) and not used beyond the 
certification expiration date.
    7.6  Citrate Buffer. Dissolve 300 g of potassium citrate and 41 g 
of anhydrous citric acid in 1 liter of water. Alternatively, 284 g of 
sodium citrate may be substituted for the potassium citrate. Adjust the 
pH to between 5.4 and 5.6 with potassium citrate or citric acid, as 
required.
    8.0  Sample Collection, Preservation, Transport, and Storage
    8.1  Pretest Procedures. After the complete measurement system has 
been set up at the site and deemed to be operational, the following 
procedures should be completed before sampling is initiated. These 
procedures are not required, but would be helpful in preventing any 
problem which might occur later to invalidate the entire test.
    8.1.1  Leak-Check. Appropriate leak-check procedures should be 
employed to verify the integrity of all components, sample lines, and 
connections. The following procedure is suggested: For components 
upstream of the sample pump, attach the probe end of the sample line to 
a manometer or vacuum gauge, start the pump and pull a vacuum greater 
than 50 mm (2 in.) Hg, close off the pump outlet, and then stop the 
pump and ascertain that there is no leak for 1 minute. For components 
after the pump, apply a slight positive pressure and check for leaks by 
applying a liquid (detergent in water, for example) at each joint. 
Bubbling indicates the presence of a leak. As an alternative to the 
initial leak-test, the sample line loss test described in Section 8.3.1 
may be performed to verify the integrity of components.
    8.1.2  System Performance. Since the complete system is calibrated 
at the beginning and end of each day of testing, the precise 
calibration of each component is not critical. However, these 
components should be verified to operate properly. This verification 
can be performed by observing the response of flowmeters or of the GC 
output to changes in flow rates or calibration gas concentrations, 
respectively, and ascertaining the response to be within predicted 
limits. If any component or the complete system fails to respond in a 
normal and predictable manner, the source of the discrepancy should be 
identified and corrected before proceeding.

8.2  Sample Collection and Analysis

    8.2.1  After performing the calibration procedures outlined in 
Section 10.0, insert the sampling probe into the test port ensuring 
that no dilution air enters the stack through the port. Begin sampling 
and dilute the sample approximately 9:1 using the dilution system. Note 
that the precise dilution factor is the one determined in Section 10.4. 
Condition the entire system with sample for a minimum of 15 minutes 
before beginning the analysis. Inject aliquots of the sample into the 
GC/FPD analyzer for analysis.

[[Page 61970]]

Determine the concentration of each reduced sulfur compound directly 
from the calibration curves or from the equation for the least-squares 
line.
    8.2.2  If reductions in sample concentrations are observed during a 
sample run that cannot be explained by process conditions, the sampling 
must be interrupted to determine if the probe or filter is clogged with 
particulate matter. If either is found to be clogged, the test must be 
stopped and the results up to that point discarded. Testing may resume 
after cleaning or replacing the probe and filter. After each run, the 
probe and filter shall be inspected and, if necessary, replaced.
    8.2.3  A sample run is composed of 16 individual analyses (injects) 
performed over a period of not less than 3 hours or more than 6 hours.
    8.3  Post-Test Procedures.
    8.3.1  Sample Line Loss. A known concentration of H2S at 
the level of the applicable standard, 20 percent, must be 
introduced into the sampling system at the opening of the probe in 
sufficient quantities to ensure that there is an excess of sample which 
must be vented to the atmosphere. The sample must be transported 
through the entire sampling system to the measurement system in the 
same manner as the emission samples. The resulting measured 
concentration is compared to the known value to determine the sampling 
system loss. For sampling losses greater than 20 percent, the previous 
sample run is not valid. Sampling losses of 0-20 percent must be 
corrected by dividing the resulting sample concentration by the 
fraction of recovery. The known gas sample may be calibration gas as 
described in Section 7.5. Alternatively, cylinder gas containing 
H2S mixed in nitrogen and verified according to Section 
7.1.4 of Method 16A may be used. The optional pretest procedures 
provide a good guideline for determining if there are leaks in the 
sampling system.
    8.3.2  Determination of Calibration Drift. After each run, or after 
a series of runs made within a 24-hour period, perform a partial 
recalibration using the procedures in Section 10.0. Only H2S 
(or other permeant) need be used to recalibrate the GC/FPD analysis 
system and the dilution system. Compare the calibration curves obtained 
after the runs to the calibration curves obtained under Section 10.3. 
The calibration drift should not exceed the limits set forth in Section 
13.4. If the drift exceeds this limit, the intervening run or runs 
should be considered invalid. As an option, the calibration data set 
which gives the highest sample values may be chosen by the tester.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.3.1.........................  Sample line loss   Ensures that
                                 check.             uncorrected negative
                                                    bias introduced by
                                                    sample loss is no
                                                    greater than 20
                                                    percent, and
                                                    provides for
                                                    correction of bias
                                                    of 20 percent or
                                                    less.
8.3.2.........................  Calibration drift  Ensures that bias
                                 test.              introduced by drift
                                                    in the measurement
                                                    system output during
                                                    the run is no
                                                    greater than 5
                                                    percent.
10.0..........................  Analytical         Ensures precision of
                                 calibration.       analytical results
                                                    within 5 percent.
------------------------------------------------------------------------

10.0  Calibration and Standardization

    Prior to any sampling run, calibrate the system using the following 
procedures. (If more than one run is performed during any 24-hour 
period, a calibration need not be performed prior to the second and any 
subsequent runs. However, the calibration drift must be determined as 
prescribed in Section 8.3.2 after the last run is made within the 24-
hour period.)


    Note: This section outlines steps to be followed for use of the 
GC/FPD and the dilution system. The calibration procedure does not 
include detailed instructions because the operation of these systems 
is complex, and it requires an understanding of the individual 
system being used. Each system should include a written operating 
manual describing in detail the operating procedures associated with 
each component in the measurement system. In addition, the operator 
should be familiar with the operating principles of the components, 
particularly the GC/FPD. The references in Section 16.0 are 
recommended for review for this purpose.

    10.1  Calibration Gas Permeation Tube Preparation.
    10.1.1  Insert the permeation tubes into the tube chamber. Check 
the bath temperature to assure agreement with the calibration 
temperature of the tubes within 0.1  deg.C. Allow 24 hours for the 
tubes to equilibrate. Alternatively, equilibration may be verified by 
injecting samples of calibration gas at 1-hour intervals. The 
permeation tubes can be assumed to have reached equilibrium when 
consecutive hourly samples agree within 5 percent of their mean.
    10.1.2  Vary the amount of air flowing over the tubes to produce 
the desired concentrations for calibrating the analytical and dilution 
systems. The air flow across the tubes must at all times exceed the 
flow requirement of the analytical systems. The concentration in ppmv 
generated by a tube containing a specific permeant can be calculated 
using Equation 15-1 in Section 12.2.
    10.2  Calibration of Analytical System. Generate a series of three 
or more known concentrations spanning the linear range of the FPD 
(approximately 0.5 to 10 ppmv for a 1-ml sample) for each of the three 
major sulfur compounds. Bypassing the dilution system, inject these 
standards into the GC/FPD and monitor the responses until three 
consecutive injections for each concentration agree within 5 percent of 
their mean. Failure to attain this precision indicates a problem in the 
calibration or analytical system. Any such problem must be identified 
and corrected before proceeding.
    10.3  Calibration Curves. Plot the GC/FPD response in current 
(amperes) versus their causative concentrations in ppmv on log-log 
coordinate graph paper for each sulfur compound. Alternatively, a 
least-squares equation may be generated from the calibration data using 
concentrations versus the appropriate instrument response units.
    10.4  Calibration of Dilution System. Generate a known 
concentration of H2S using the permeation tube system. 
Adjust the flow rate of diluent air for the first dilution stage so 
that the desired level of dilution is approximated. Inject the diluted 
calibration gas into the GC/FPD system until the results of three 
consecutive injections for each dilution agree within 5 percent of 
their mean. Failure to attain this precision in this step is an 
indication of a problem in the dilution system. Any such problem must 
be identified and corrected before proceeding. Using the calibration 
data for H2S (developed under Section 10.3), determine the 
diluted calibration gas concentration in ppmv. Then calculate the 
dilution factor as the ratio of the calibration gas concentration 
before dilution to the diluted calibration gas concentration determined 
under this section. Repeat this procedure for each

[[Page 61971]]

stage of dilution required. Alternatively, the GC/FPD system may be 
calibrated by generating a series of three or more concentrations of 
each sulfur compound and diluting these samples before injecting them 
into the GC/FPD system. These data will then serve as the calibration 
data for the unknown samples and a separate determination of the 
dilution factor will not be necessary. However, the precision 
requirements are still applicable.

11.0  Analytical Procedure

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

12.0  Data Analysis and Calculations

    12.1  Nomenclature.

C = Concentration of permeant produced, ppmv.
COS = Carbonyl sulfide concentration, ppmv.
CS2 = Carbon disulfide concentration, ppmv.
d = Dilution factor, dimensionless.
H2S = Hydrogen sulfide concentration, ppmv.
K = 24.04 L/g mole. (Gas constant at 20 deg.C and 760 mm Hg)
L = Flow rate, L/min, of air over permeant 20 deg.C, 760 mm Hg.
M = Molecular weight of the permeant, g/g-mole.
N = Number of analyses performed.
Pr = Permeation rate of the tube, g/min.
    12.2  Permeant Concentration. Calculate the concentration generated 
by a tube containing a specific permeant (see Section 10.1) using the 
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.262

    12.3  Calculation of SO2 Equivalent. SO2 
equivalent will be determined for each analysis made by summing the 
concentrations of each reduced sulfur compound resolved during the 
given analysis. The SO2 equivalent is expressed as 
SO2 in ppmv.
[GRAPHIC] [TIFF OMITTED] TR17OC00.263

    12.4  Average SO2 Equivalent. This is determined using 
the following equation. Systems that do not remove moisture from the 
sample but condition the gas to prevent condensation must correct the 
average SO2 equivalent for the fraction of water vapor 
present. This is not done under applications where the emission 
standard is not specified on a dry basis.
[GRAPHIC] [TIFF OMITTED] TR17OC00.264

Where:

Avg SO2 equivalent = Average SO2 equivalent in 
ppmv, dry basis.
Average SO2 equivalent i = SO2 in ppmv 
as determined by Equation 15-2.

13.0  Method Performance

    13.1  Range. Coupled with a GC system using a 1-ml sample size, the 
maximum limit of the FPD for each sulfur compound is approximately 10 
ppmv. It may be necessary to dilute samples from sulfur recovery plants 
a hundredfold (99:1), resulting in an upper limit of about 1000 ppmv 
for each compound.
    13.2  Sensitivity. The minimum detectable concentration of the FPD 
is also dependent on sample size and would be about 0.5 ppmv for a 1-ml 
sample.
    13.3  Calibration Precision. A series of three consecutive 
injections of the same calibration gas, at any dilution, shall produce 
results which do not vary by more than 5 percent from the mean of the 
three injections.
    13.4  Calibration Drift. The calibration drift determined from the 
mean of three injections made at the beginning and end of any run or 
series of runs within a 24-hour period shall not exceed 5 percent.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References.

    1. O'Keeffe, A.E., and G.C. Ortman. ``Primary Standards for 
Trace Gas Analysis.'' Anal. Chem. 38,760. 1966.
    2. Stevens, R.K., A.E. O'Keeffe, and G.C. Ortman. ``Absolute 
Calibration of a Flame Photometric Detector to Volatile Sulfur 
Compounds at Sub-Part-Per-Million Levels.'' Environmental Science 
and Technology 3:7. July 1969.
    3. Mulik, J.D., R.K. Stevens, and R. Baumgardner. ``An 
Analytical System Designed to Measure Multiple Malodorous Compounds 
Related to Kraft Mill Activities.'' Presented at the 12th Conference 
on Methods in Air Pollution and Industrial Hygiene Studies, 
University of Southern California, Los Angeles, CA, April 6-8, 1971.
    4. Devonald, R.H., R.S. Serenius, and A.D. McIntyre. 
``Evaluation of the Flame Photometric Detector for Analysis of 
Sulfur Compounds.'' Pulp and Paper Magazine of Canada, 73,3. March 
1972.
    5. Grimley, K.W., W.S. Smith, and R.M. Martin. ``The Use of a 
Dynamic Dilution System in the Conditioning of Stack Gases for 
Automated Analysis by a Mobile Sampling Van.'' Presented at the 63rd 
Annual APCA Meeting in St. Louis, MO. June 14-19, 1970.
    6. General Reference. Standard Methods of Chemical Analysis 
Volume III-A and III-B: Instrumental Analysis. Sixth Edition. Van 
Nostrand Reinhold Co.

BILLING CODE 6560-50-P

[[Page 61972]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.265


[[Page 61973]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.266


[[Page 61974]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.267

BILLING CODE 6560-50-C

[[Page 61975]]

Method 15A--Determination of Total Reduced Sulfur Emissions From 
Sulfur Recovery Plants in Petroleum Refineries

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in this part. 
Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of at least the following 
additional test methods: Method 1, Method 6, Method 15, and Method 
16A.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.            Sensitivity
------------------------------------------------------------------------
Reduced sulfur compounds......  None assigned...  Not determined.
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of emissions of reduced sulfur compounds from sulfur recovery plants 
where the emissions are in a reducing atmosphere, such as in Stretford 
units.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  An integrated gas sample is extracted from the stack, and 
combustion air is added to the oxygen (O2)-deficient gas at 
a known rate. The reduced sulfur compounds [including carbon disulfide 
(CS2), carbonyl sulfide (COS), and hydrogen sulfide 
(H2S)] are thermally oxidized to sulfur dioxide 
(SO2), which is then collected in hydrogen peroxide as 
sulfate ion and analyzed according to the Method 6 barium-thorin 
titration procedure.

3.0  Definitions. [Reserved]

4.0  Interferences

    4.1  Reduced sulfur compounds, other than CS2, COS, and 
H2S, that are present in the emissions will also be oxidized 
to SO2, causing a positive bias relative to emission 
standards that limit only the three compounds listed above. For 
example, thiophene has been identified in emissions from a Stretford 
unit and produced a positive bias of 30 percent in the Method 15A 
result. However, these biases may not affect the outcome of the test at 
units where emissions are low relative to the standard.
    4.2  Calcium and aluminum have been shown to interfere in the 
Method 6 titration procedure. Since these metals have been identified 
in particulate matter emissions from Stretford units, a Teflon filter 
is required to minimize this interference.
    4.3  Dilution of the hydrogen peroxide (H2O2) 
absorbing solution can potentially reduce collection efficiency, 
causing a negative bias. When used to sample emissions containing 7 
percent moisture or less, the midget impingers have sufficient volume 
to contain the condensate collected during sampling. Dilution of the 
H2O2 does not affect the collection of 
SO2. At higher moisture contents, the potassium citrate-
citric acid buffer system used with Method 16A should be used to 
collect the condensate.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Corrosive reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water for at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burns as thermal 
burns.
    5.2.1  Hydrogen Peroxide (H2O2). Irritating 
to eyes, skin, nose, and lungs.
    5.2.2  Sodium Hydroxide (NaOH). Causes severe damage to eyes and 
skin. Inhalation causes irritation to nose, throat, and lungs. Reacts 
exothermically with limited amounts of water.
    5.2.3  Sulfuric Acid (H2SO4). Rapidly 
destructive to body tissue. Will cause third degree burns. Eye damage 
may result in blindness. Inhalation may be fatal from spasm of the 
larynx, usually within 30 minutes. May cause lung tissue damage with 
edema. 3 mg/m\3\ will cause lung damage in uninitiated. 1 mg/m\3\ for 8 
hours will cause lung damage or, in higher concentrations, death. 
Provide ventilation to limit inhalation. Reacts violently with metals 
and organics.

6.0  Equipment and Supplies

    6.1  Sample Collection. The sampling train used in performing this 
method is shown in Figure 15A-1, and component parts are discussed 
below. Modifications to this sampling train are acceptable provided 
that the system performance check is met.
    6.1.1  Probe. 6.4-mm (\1/4\-in.) OD Teflon tubing sequentially 
wrapped with heat-resistant fiber strips, a rubberized heating tape 
(with a plug at one end), and heat-resistant adhesive tape. A flexible 
thermocouple or some other suitable temperature-measuring device shall 
be placed between the Teflon tubing and the fiber strips so that the 
temperature can be monitored. The probe should be sheathed in stainless 
steel to provide in-stack rigidity. A series of bored-out stainless 
steel fittings placed at the front of the sheath will prevent flue gas 
from entering between the probe and sheath. The sampling probe is 
depicted in Figure 15A-2.
    6.1.2  Particulate Filter. A 50-mm Teflon filter holder and a 1- to 
2-mm porosity Teflon filter (available through Savillex Corporation, 
5325 Highway 101, Minnetonka, Minnesota 55345). The filter holder must 
be maintained in a hot box at a temperature high enough to prevent 
condensation.
    6.1.3  Combustion Air Delivery System. As shown in the schematic 
diagram in Figure 15A-3. The rate meter should be selected to measure 
an air flow rate of 0.5 liter/min (0.02 ft\3\/min).
    6.1.4  Combustion Tube. Quartz glass tubing with an expanded 
combustion chamber 2.54 cm (1 in.) in diameter and at least 30.5 cm (12 
in.) long. The tube ends should have an outside diameter of 0.6 cm (\1/
4\ in.) and be at least 15.3 cm (6 in.) long. This length is necessary 
to maintain the quartz-glass connector near ambient temperature and 
thereby avoid leaks. Alternatively, the outlet may be constructed with 
a 90 degree glass elbow and socket that would fit directly onto the 
inlet of the first peroxide impinger.
    6.1.5  Furnace. Of sufficient size to enclose the combustion tube. 
The furnace must have a temperature regulator capable of maintaining 
the temperature at 1100  50  deg.C (2,012  90 
deg.F). The furnace operating temperature must be checked with a 
thermocouple to ensure accuracy. Lindberg furnaces have been found to 
be satisfactory.

[[Page 61976]]

    6.1.6  Peroxide Impingers, Stopcock Grease, Temperature Sensor, 
Drying Tube, Valve, Pump, and Barometer. Same as in Method 6, Sections 
6.1.1.2, 6.1.1.4, 6.1.1.5, 6.1.1.6, 6.1.1.7, 6.1.1.8, and 6.1.2, 
respectively, except that the midget bubbler of Method 6, Section 
6.1.1.2 is not required.
    6.1.7  Vacuum Gauge and Rate Meter. At least 760 mm Hg (30 in. Hg) 
gauge and rotameter, or equivalent, capable of measuring flow rate to 
5 percent of the selected flow rate and calibrated as in 
Section 10.2.
    6.1.8  Volume Meter. Dry gas meter capable of measuring the sample 
volume under the particular sampling conditions with an accuracy of 2 
percent.
    6.1.9  U-tube manometer. To measure the pressure at the exit of the 
combustion gas dry gas meter.
    6.2  Sample Recovery and Analysis. Same as Method 6, Sections 6.2 
and 6.3, except a 10-ml buret with 0.05-ml graduations is required for 
titrant volumes of less than 10.0 ml, and the spectrophotometer is not 
needed.

7.0  Reagents and Standards

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


    7.1  Sample Collection. The following reagents and standards are 
required for sample analysis:
    7.1.1  Water. Same as Method 6, Section 7.1.1.
    7.1.2  Hydrogen Peroxide (H2O2), 3 Percent by 
Volume. Same as Method 6, Section 7.1.3 (40 ml is needed per sample).
    7.1.3  Recovery Check Gas. Carbonyl sulfide in nitrogen [100 parts 
per million by volume (ppmv) or greater, if necessary] in an aluminum 
cylinder. Concentration certified by the manufacturer with an accuracy 
of 2 percent or better, or verified by gas chromatography 
where the instrument is calibrated with a COS permeation tube.
    7.1.4  Combustion Gas. Air, contained in a gas cylinder equipped 
with a two-stage regulator. The gas shall contain less than 50 ppb of 
reduced sulfur compounds and less than 10 ppm total hydrocarbons.
    7.2  Sample Recovery and Analysis. Same as Method 6, Sections 7.2 
and 7.3.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Preparation of Sampling Train. For the Method 6 part of the 
train, measure 20 ml of 3 percent H2O2 into the 
first and second midget impingers. Leave the third midget impinger 
empty and add silica gel to the fourth impinger. Alternatively, a 
silica gel drying tube may be used in place of the fourth impinger. 
Place crushed ice and water around all impingers. Maintain the 
oxidation furnace at 1100  50  deg.C (2,012  90 
 deg.F) to ensure 100 percent oxidation of COS. Maintain the probe and 
filter temperatures at a high enough level (no visible condensation) to 
prevent moisture condensation and monitor the temperatures with a 
thermocouple.
    8.2  Leak-Check Procedure. Assemble the sampling train and leak-
check as described in Method 6, Section 8.2. Include the combustion air 
delivery system from the needle valve forward in the leak-check.
    8.3  Sample Collection. Adjust the pressure on the second stage of 
the regulator on the combustion air cylinder to 10 psig. Adjust the 
combustion air flow rate to 0.5  0.05 L/min (1.1 
 0.1 ft\3\/hr) before injecting combustion air into the 
sampling train. Then inject combustion air into the sampling train, 
start the sample pump, and open the stack sample gas valve. Carry out 
these three operations within 15 to 30 seconds to avoid pressurizing 
the sampling train. Adjust the total sample flow rate to 2.0 
 0.2 L/min (4.2  0.4 ft\3\/hr). These flow 
rates produce an O2 concentration of 5.0 percent in the 
stack gas, which must be maintained constantly to allow oxidation of 
reduced sulfur compounds to SO2. Adjust these flow rates 
during sampling as necessary. Monitor and record the combustion air 
manometer reading at regular intervals during the sampling period. 
Sample for 1 or 3 hours. At the end of sampling, turn off the sample 
pump and combustion air simultaneously (within 30 seconds of each 
other). All other procedures are the same as in Method 6, Section 8.3, 
except that the sampling train should not be purged. After collecting 
the sample, remove the probe from the stack and conduct a leak-check 
according to the procedures outlined in Section 8.2 of Method 6 
(mandatory). After each 3-hour test run (or after three 1-hour 
samples), conduct one system performance check (see Section 8.5). After 
this system performance check and before the next test run, it is 
recommended that the probe be rinsed and brushed and the filter 
replaced.


    Note: In Method 15, a test run is composed of 16 individual 
analyses (injects) performed over a period of not less than 3 hours 
or more than 6 hours. For Method 15A to be consistent with Method 
15, the following may be used to obtain a test run: (1) Collect 
three 60-minute samples or (2) collect one 3-hour sample. (Three 
test runs constitute a test.)


    8.4  Sample Recovery. Recover the hydrogen peroxide-containing 
impingers as detailed in Method 6, Section 8.4.
    8.5  System Performance Check.
    8.5.1  A system performance check is done (1) to validate the 
sampling train components and procedure (before testing, optional) and 
(2) to validate a test run (after a run, mandatory). Perform a check in 
the field before testing consisting of at least two samples (optional), 
and perform an additional check after each 3-hour run or after three 1-
hour samples (mandatory).
    8.5.2  The checks involve sampling a known concentration of COS and 
comparing the analyzed concentration with the known concentration. Mix 
the recovery gas with N2 as shown in Figure 15A-4 if 
dilution is required. Adjust the flow rates to generate a COS 
concentration in the range of the stack gas or within 20 percent of the 
applicable standard at a total flow rate of at least 2.5 L/min (5.3 
ft\3\/hr). Use Equation 15A-4 (see Section 12.5) to calculate the 
concentration of recovery gas generated. Calibrate the flow rate from 
both sources with a soap bubble flow tube so that the diluted 
concentration of COS can be accurately calculated. Collect 30-minute 
samples, and analyze in the same manner as the emission samples. 
Collect the samples through the probe of the sampling train using a 
manifold or some other suitable device that will ensure extraction of a 
representative sample.
    8.5.3  The recovery check must be performed in the field before 
replacing the particulate filter and before cleaning the probe. A 
sample recovery of 100  20 percent must be obtained for the 
data to be valid and should be reported with the emission data, but 
should not be used to correct the data. However, if the performance 
check results do not affect the compliance or noncompliance status of 
the affected facility, the Administrator may decide to accept the 
results of the compliance test. Use Equation 15A-5 (see Section 12.6) 
to calculate the recovery efficiency.

9.0  Quality Control

[[Page 61977]]



------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.5...........................  System             Ensures validity of
                                 performance        sampling train
                                 check.             components and
                                                    analytical
                                                    procedure.
8.2, 10.0.....................  Sampling           Ensures accurate
                                 equipment leak-    measurement of stack
                                 check and          gas flow rate,
                                 calibration.       sample volume
10.0..........................  Barium standard    Ensures precision of
                                 solution           normality
                                 standardization.   determination.
11.1..........................  Replicate          Ensures precision of
                                 titrations.        titration
                                                    determinations.
11.2..........................  Audit sample       Evaluates analyst's
                                 analysis.          technique and
                                                    standards
                                                    preparation.
------------------------------------------------------------------------

10.0  Calibration and Standardization

    10.1  Metering System, Temperature Sensors, Barometer, and Barium 
Perchlorate Solution. Same as Method 6, Sections 10.1, 10.2, 10.4, and 
10.5, respectively.
    10.2  Rate Meter. Calibrate with a bubble flow tube.

11.0  Analytical Procedure

    11.1  Sample Loss Check and Sample Analysis. Same as Method 6, 
Sections 11.1 and 11.2.
    11.2  Audit Sample Analysis. Same as Method 6, Section 11.3.

12.0  Data Analysis and Calculations

    In the calculations, retain at least one extra decimal figure 
beyond that of the acquired data. Round off figures after final 
calculations.
    12.1  Nomenclature.

CCOS = Concentration of COS recovery gas, ppm.
CRG(act) = Actual concentration of recovery check gas (after 
dilution), ppm.
CRG(m) = Measured concentration of recovery check gas 
generated, ppm.
CRS = Concentration of reduced sulfur compounds as 
SO2, dry basis, corrected to standard conditions, ppm.
N = Normality of barium perchlorate titrant, milliequivalents/ml.
Pbar = Barometric pressure at exit orifice of the dry gas 
meter, mm Hg.
Pstd = Standard absolute pressure, 760 mm Hg.
QCOS = Flow rate of COS recovery gas, liters/min.
QN = Flow rate of diluent N2, liters/min.
R = Recovery efficiency for the system performance check, percent.
Tm = Average dry gas meter absolute temperature,  deg.K.
Tstd = Standard absolute temperature, 293  deg.K.
Va = Volume of sample aliquot titrated, ml.
Vms = Dry gas volume as measured by the sample train dry gas 
meter, liters.
Vmc = Dry gas volume as measured by the combustion air dry 
gas meter, liters.
Vms(std) = Dry gas volume measured by the sample train dry 
gas meter, corrected to standard conditions, liters.
Vmc(std) = Dry gas volume measured by the combustion air dry 
gas meter, corrected to standard conditions, liters.
Vsoln = Total volume of solution in which the sulfur dioxide 
sample is contained, 100 ml.
Vt = Volume of barium perchlorate titrant used for the 
sample (average of replicate titrations), ml.
Vtb = Volume of barium perchlorate titrant used for the 
blank, ml.
Y = Calibration factor for sampling train dry gas meter.
Yc = Calibration factor for combustion air dry gas meter.
32.03 = Equivalent weight of sulfur dioxide, mg/meq.
[GRAPHIC] [TIFF OMITTED] TR17OC00.411

    12.2  Dry Sample Gas Volume, Corrected to Standard Conditions.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.268
    
Where:

K1 = 0.3855  deg.K/mm Hg for metric units,
= 17.65  deg.R/in. Hg for English units.

    12.3  Combustion Air Gas Volume, corrected to Standard Conditions.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.269
    
    Note: Correct Pbar for the average pressure of the 
manometer during the sampling period.
    12.4  Concentration of reduced sulfur compounds as ppm 
SO2.
[GRAPHIC] [TIFF OMITTED] TR17OC00.270


[[Page 61978]]


Where:
[GRAPHIC] [TIFF OMITTED] TR17OC00.271

    12.5  Concentration of Generated Recovery Gas.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.272
    
    12.6  Recovery Efficiency for the System Performance Check.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.273
    
13.0  Method Performance

    13.1  Analytical Range. The lower detectable limit is 0.1 ppmv when 
sampling at 2 lpm for 3 hours or 0.3 ppmv when sampling at 2 lpm for 1 
hour. The upper concentration limit of the method exceeds 
concentrations of reduced sulfur compounds generally encountered in 
sulfur recovery plants.
    13.2  Precision. Relative standard deviations of 2.8 and 6.9 
percent have been obtained when sampling a stream with a reduced sulfur 
compound concentration of 41 ppmv as SO2 for 1 and 3 hours, 
respectively.
    13.3  Bias. No analytical bias has been identified. However, 
results obtained with this method are likely to contain a positive bias 
relative to emission regulations due to the presence of nonregulated 
sulfur compounds (that are present in petroleum) in the emissions. The 
magnitude of this bias varies accordingly, and has not been quantified.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    1. American Society for Testing and Materials Annual Book of 
ASTM Standards. Part 31: Water, Atmospheric Analysis. Philadelphia, 
Pennsylvania. 1974. pp. 40-42.
    2. Blosser, R.O., H.S. Oglesby, and A.K. Jain. A Study of 
Alternate SO2 Scrubber Designs Used for TRS Monitoring. 
National Council of the Paper Industry for Air and Stream 
Improvement, Inc., New York, New York. Special Report 77-05. July 
1977.
    3. Curtis, F., and G.D. McAlister. Development and Evaluation of 
an Oxidation/Method 6 TRS Emission Sampling Procedure. Emission 
Measurement Branch, Emission Standards and Engineering Division, 
U.S. Environmental Protection Agency, Research Triangle Park, North 
Carolina. February 1980.
    4. Gellman, I. A Laboratory and Field Study of Reduced Sulfur 
Sampling and Monitoring Systems. National Council of the Paper 
Industry for Air and Stream Improvement, Inc., New York, New York. 
Atmospheric Quality Improvement Technical Bulletin No. 81. October 
1975.
    5. Margeson, J.H., et al. A Manual Method for TRS Determination. 
Journal of Air Pollution Control Association. 35:1280-1286. December 
1985.
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17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.274


[[Page 61980]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.275


[[Page 61981]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.276


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[GRAPHIC] [TIFF OMITTED] TR17OC00.277

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[[Page 61983]]

Method 16--Semicontinuous Determination of Sulfur Emissions From 
Stationary Sources

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in this part. 
Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of at least the following 
additional test methods: Method 1, Method 4, Method 15, and Method 
16A.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.           Sensitivity
------------------------------------------------------------------------
Dimethyl disulfide [(CH3)2S2]..        62-49-20  50 ppb.
Dimethyl sulfide [(CH3)2S].....         75-18-3  50 ppb.
Hydrogen sulfide [H2S].........       7783-06-4  50 ppb.
Methyl mercaptan [CH4S]........         74-93-1  50 ppb.
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of total reduced sulfur (TRS) compounds from recovery furnaces, lime 
kilns, and smelt dissolving tanks at kraft pulp mills and fuel gas 
combustion devices at petroleum refineries.


    Note: The method described below uses the principle of gas 
chromatographic (GC) separation and flame photometric detection 
(FPD). Since there are many systems or sets of operating conditions 
that represent useable methods of determining sulfur emissions, all 
systems which employ this principle, but differ only in details of 
equipment and operation, may be used as alternative methods, 
provided that the calibration precision and sample line loss 
criteria are met.


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

2.0  Summary of Method

    2.1  A gas sample is extracted from the emission source and an 
aliquot is analyzed for hydrogen sulfide (H2S), methyl 
mercaptan (MeSH), dimethyl sulfide (DMS), and dimethyl disulfide (DMDS) 
by GC/FPD. These four compounds are known collectively as TRS.

3.0  Definitions. [Reserved]

4.0  Interferences

    4.1  Moisture. Moisture condensation in the sample delivery system, 
the analytical column, or the FPD burner block can cause losses or 
interferences. This is prevented by maintaining the probe, filter box, 
and connections at a temperature of at least 120  deg.C (248  deg.F). 
Moisture is removed in the SO2 scrubber and heating the 
sample beyond this point is not necessary when the ambient temperature 
is above 0  deg.C (32  deg.F). Alternatively, moisture may be 
eliminated by heating the sample line, and by conditioning the sample 
with dry dilution air to lower its dew point below the operating 
temperature of the GC/FPD analytical system prior to analysis.
    4.2  Carbon Monoxide (CO) and Carbon Dioxide (CO2). CO 
and CO2 have a substantial desensitizing effect on the flame 
photometric detector even after dilution. Acceptable systems must 
demonstrate that they have eliminated this interference by some 
procedure such as eluting these compounds before any of the compounds 
to be measured. Compliance with this requirement can be demonstrated by 
submitting chromatograms of calibration gases with and without 
CO2 in the diluent gas. The CO2 level should be 
approximately 10 percent for the case with CO2 present. The 
two chromatograms should show agreement within the precision limits of 
Section 10.2.
    4.3  Particulate Matter. Particulate matter in gas samples can 
cause interference by eventual clogging of the analytical system. This 
interference is eliminated by using the Teflon filter after the probe.
    4.4  Sulfur Dioxide (SO2). Sulfur dioxide is not a 
specific interferant but may be present in such large amounts that it 
cannot effectively be separated from the other compounds of interest. 
The SO2 scrubber described in Section 6.1.3 will effectively 
remove SO2 from the sample.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Hydrogen Sulfide. A flammable, poisonous gas with the odor of 
rotten eggs. H2S is extremely hazardous and can cause 
collapse, coma, and death within a few seconds of one or two 
inhalations at sufficient concentrations. Low concentrations irritate 
the mucous membranes and may cause nausea, dizziness, and headache 
after exposure.

6.0  Equipment and Supplies

    6.1.  Sample Collection. The following items are needed for sample 
collection.
    6.1.1  Probe. Teflon or Teflon-lined stainless steel. The probe 
must be heated to prevent moisture condensation. It must be designed to 
allow calibration gas to enter the probe at or near the sample point 
entry. Any portion of the probe that contacts the stack gas must be 
heated to prevent moisture condensation. Figure 16-1 illustrates the 
probe used in lime kilns and other sources where significant amounts of 
particulate matter are present. The probe is designed with the 
deflector shield placed between the sample and the gas inlet holes to 
reduce clogging of the filter and possible adsorption of sample gas. As 
an alternative, the probe described in Section 6.1.1 of Method 16A 
having a nozzle directed away from the gas stream may be used at 
sources having significant amounts of particulate matter.
    6.1.2  Particulate Filter. 50-mm Teflon filter holder and a 1- to 
2-micron porosity Teflon filter (available through Savillex 
Corporation, 5325 Highway 101, Minnetonka, Minnesota 55343). The filter 
holder must be maintained in a hot box at a temperature of at least 120 
 deg.C (248  deg.F).
    6.1.3  SO2 Scrubber. Three 300-ml Teflon segmented 
impingers connected in series with flexible, thick-walled, Teflon 
tubing. (Impinger parts and tubing available through Savillex.) The 
first two impingers contain 100 ml of citrate buffer and the third 
impinger is initially dry. The tip of the tube inserted into the 
solution should be constricted to less than 3 mm (\1/8\ in.) ID and 
should be immersed to a depth of at least 5 cm (2 in.). Immerse the 
impingers in an ice water bath and maintain near 0  deg.C (32  deg.F). 
The scrubber solution will normally last for a 3-hour run before 
needing replacement. This will depend upon the

[[Page 61984]]

effects of moisture and particulate matter on the solution strength and 
pH. Connections between the probe, particulate filter, and 
SO2 scrubber must be made of Teflon and as short in length 
as possible. All portions of the probe, particulate filter, and 
connections prior to the SO2 scrubber (or alternative point 
of moisture removal) must be maintained at a temperature of at least 
120  deg.C (248  deg.F).
    6.1.4  Sample Line. Teflon, no greater than 1.3 cm (\1/2\ in.) ID. 
Alternative materials, such as virgin Nylon, may be used provided the 
line loss test is acceptable.
    6.1.5  Sample Pump. The sample pump must be a leakless Teflon-
coated diaphragm type or equivalent.
    6.2  Analysis. The following items are needed for sample analysis:
    6.2.1  Dilution System. Needed only for high sample concentrations. 
The dilution system must be constructed such that all sample contacts 
are made of Teflon, glass, or stainless steel.
    6.2.2  Gas Chromatograph. The gas chromatograph must have at least 
the following components:
    6.2.2.1  Oven. Capable of maintaining the separation column at the 
proper operating temperature  1  deg.C (2  deg.F).
    6.2.2.2  Temperature Gauge. To monitor column oven, detector, and 
exhaust temperature  1  deg.C (2  deg.F).
    6.2.2.3  Flow System. Gas metering system to measure sample, fuel, 
combustion gas, and carrier gas flows.
    6.2.2.4  Flame Photometric Detector.
    6.2.2.4.1  Electrometer. Capable of full scale amplification of 
linear ranges of 10-\9\ to 10-\4\ amperes full 
scale.
    6.2.2.4.2  Power Supply. Capable of delivering up to 750 volts.
    6.2.2.4.3  Recorder. Compatible with the output voltage range of 
the electrometer.
    6.2.2.4.4  Rotary Gas Valves. Multiport Teflon-lined valves 
equipped with sample loop. Sample loop volumes must be chosen to 
provide the needed analytical range. Teflon tubing and fittings must be 
used throughout to present an inert surface for sample gas. The gas 
chromatograph must be calibrated with the sample loop used for sample 
analysis.
    6.2.3  Gas Chromatogram Columns. The column system must be 
demonstrated to be capable of resolving the four major reduced sulfur 
compounds: H2S, MeSH, DMS, and DMDS. It must also 
demonstrate freedom from known interferences. To demonstrate that 
adequate resolution has been achieved, submit a chromatogram of a 
calibration gas containing all four of the TRS compounds in the 
concentration range of the applicable standard. Adequate resolution 
will be defined as base line separation of adjacent peaks when the 
amplifier attenuation is set so that the smaller peak is at least 50 
percent of full scale. Baseline separation is defined as a return to 
zero 5 percent in the interval between peaks. Systems not 
meeting this criteria may be considered alternate methods subject to 
the approval of the Administrator.
    6.3  Calibration. A calibration system, containing the following 
components, is required (see Figure 16-2).
    6.3.1  Tube Chamber. Chamber of glass or Teflon of sufficient 
dimensions to house permeation tubes.
    6.3.2  Flow System. To measure air flow over permeation tubes at 
2 percent. Flow over the permeation device may also be 
determined using a soap bubble flowmeter.
    6.3.3  Constant Temperature Bath. Device capable of maintaining the 
permeation tubes at the calibration temperature within 0.1  deg.C (0.2 
deg.F).
    6.3.4  Temperature Gauge. Thermometer or equivalent to monitor bath 
temperature within 1  deg.C (2  deg.F).

7.0  Reagents and Standards

    7.1  Fuel. Hydrogen (H2), prepurified grade or better.
    7.2  Combustion Gas. Oxygen (O2) or air, research purity 
or better.
    7.3  Carrier Gas. Prepurified grade or better.
    7.4  Diluent (if required). Air containing less than 50 ppb total 
sulfur compounds and less than 10 ppmv each of moisture and total 
hydrocarbons.

7.5  Calibration Gases

    7.5.1  Permeation tubes, one each of H2S, MeSH, DMS, and 
DMDS, gravimetrically calibrated and certified at some convenient 
operating temperature. These tubes consist of hermetically sealed FEP 
Teflon tubing in which a liquified gaseous substance is enclosed. The 
enclosed gas permeates through the tubing wall at a constant rate. When 
the temperature is constant, calibration gases covering a wide range of 
known concentrations can be generated by varying and accurately 
measuring the flow rate of diluent gas passing over the tubes. These 
calibration gases are used to calibrate the GC/FPD system and the 
dilution system.
    7.5.2  Cylinder Gases. Cylinder gases may be used as alternatives 
to permeation devices. The gases must be traceable to a primary 
standard (such as permeation tubes) and not used beyond the 
certification expiration date.
    7.6  Citrate Buffer and Sample Line Loss Gas. Same as Method 15, 
Sections 7.6 and 7.7.

8.0  Sample Collection, Preservation, Storage, and Transport

    Same as Method 15, Section 8.0, except that the references to the 
dilution system may not be applicable.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.0...........................  Sample line loss   Ensures that
                                 check.             uncorrected negative
                                                    bias introduced by
                                                    sample loss is no
                                                    greater than 20
                                                    percent, and
                                                    provides for
                                                    correction of bias
                                                    of 20 percent or
                                                    less.
8.0...........................  Calibration drift  Ensures that bias
                                 test.              introduced by drift
                                                    in the measurement
                                                    system output during
                                                    the run is no
                                                    greater than 5
                                                    percent.
10.0..........................  Analytical         Ensures precision of
                                 calibration.       analytical results
                                                    within 5 percent.
------------------------------------------------------------------------

10.0  Calibration and Standardization

    Same as Method 15, Section 10.0, with the following addition and 
exceptions:
    10.1  Use the four compounds that comprise TRS instead of the three 
reduced sulfur compounds measured by Method 15.
    10.2  Flow Meter. Calibration before each test run is recommended, 
but not required; calibration following each test series is mandatory. 
Calibrate each flow meter after each complete test series with a wet-
test meter. If the flow measuring device differs from the wet-test 
meter by 5 percent or more, the completed test runs must be voided. 
Alternatively, the flow data that yield the lower flow measurement may 
be used. Flow over the permeation device may also be determined using a 
soap bubble flowmeter.

[[Page 61985]]

11.0  Analytical Procedure

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

12.0  Data Analysis and Calculations

    12.1  Concentration of Reduced Sulfur Compounds. Calculate the 
average concentration of each of the four analytes (i.e., DMDS, DMS, 
H2S, and MeSH) over the sample run (specified in Section 8.2 
of Method 15 as 16 injections).
[GRAPHIC] [TIFF OMITTED] TR17OC00.278

Where:

Si = Concentration of any reduced sulfur compound from the 
ith sample injection, ppm.
C = Average concentration of any one of the reduced sulfur compounds 
for the entire run, ppm.
N = Number of injections in any run period.
    12.2  TRS Concentration. Using Equation 16-2, calculate the TRS 
concentration for each sample run.
[GRAPHIC] [TIFF OMITTED] TR17OC00.279

Where:

CTRS = TRS concentration, ppmv.
CH2S = Hydrogen sulfide concentration, ppmv.
CMeSH = Methyl mercaptan concentration, ppmv.
CDMS = Dimethyl sulfide concentration, ppmv.
CDMDS = Dimethyl disulfide concentration, ppmv.
d = Dilution factor, dimensionless.

    12.3  Average TRS Concentration. Calculate the average TRS 
concentration for all sample runs performed.
[GRAPHIC] [TIFF OMITTED] TR17OC00.280

Where:

Average TRS = Average total reduced sulfur in ppm.
TRSi = Total reduced sulfur in ppm as determined by Equation 
16-2.
N = Number of samples.
Bwo = Fraction of volume of water vapor in the gas stream as 
determined by Method 4--Determination of Moisture in Stack Gases.

13.0  Method Performance

    13.1  Analytical Range. The analytical range will vary with the 
sample loop size. Typically, the analytical range may extend from 0.1 
to 100 ppmv using 10- to 0.1-ml sample loop sizes. This eliminates the 
need for sample dilution in most cases.
    13.2  Sensitivity. Using the 10-ml sample size, the minimum 
detectable concentration is approximately 50 ppb.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    1. O'Keeffe, A.E., and G.C. Ortman. ``Primary Standards for 
Trace Gas Analysis.'' Analytical Chemical Journal, 38,76. 1966.
    2. Stevens, R.K., A.E. O'Keeffe, and G.C. Ortman. ``Absolute 
Calibration of a Flame Photometric Detector to Volatile Sulfur 
Compounds at Sub-Part-Per-Million Levels.'' Environmental Science 
and Technology, 3:7. July 1969.
    3. Mulik, J.D., R.K. Stevens, and R. Baumgardner. ``An 
Analytical System Designed to Measure Multiple Malodorous Compounds 
Related to Kraft Mill Activities.'' Presented at the 12th Conference 
on Methods in Air Pollution and Industrial Hygiene Studies, 
University of Southern California, Los Angeles, CA. April 6-8, 1971.
    4. Devonald, R.H., R.S. Serenius, and A.D. McIntyre. 
``Evaluation of the Flame Photometric Detector for Analysis of 
Sulfur Compounds.'' Pulp and Paper Magazine of Canada, 73,3. March 
1972.
    5. Grimley, K.W., W.S. Smith, and R.M. Martin. ``The Use of a 
Dynamic Dilution System in the Conditioning of Stack Gases for 
Automated Analysis by a Mobile Sampling Van.'' Presented at the 63rd 
Annual APCA Meeting, St. Louis, MO. June 14-19, 1970.
    6. General Reference. Standard Methods of Chemical Analysis, 
Volumes III-A and III-B Instrumental Methods. Sixth Edition. Van 
Nostrand Reinhold Co.
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17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.281


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[GRAPHIC] [TIFF OMITTED] TR17OC00.282

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[[Page 61988]]

Method 16A--Determination of Total Reduced Sulfur Emissions From 
Stationary Sources (Impinger Technique)

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in this part. 
Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of at least the following 
additional test methods: Method 1, Method 6, and Method 16.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
              Analyte                   CAS No.          Sensitivity
------------------------------------------------------------------------
Total reduced sulfur (TRS)                     N/A  See Section 13.1.
 including:
    Dimethyl disulfide [(CH3)2S2].        62-49-20
    Dimethyl sulfide [(CH3)2S]....         75-18-3
    Hydrogen sulfide [H2S]........       7783-06-4
    Methyl mercaptan [CH4S].......         74-93-1
Reduced sulfur (RS) including:                 N/A
    H2S...........................       7783-06-4
    Carbonyl sulfide [COS]........        463-58-1
    Carbon disulfide [CS2]........         75-15-0
Reported as: Sulfur dioxide (SO2).       7449-09-5
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of TRS emissions from recovery boilers, lime kilns, and smelt 
dissolving tanks at kraft pulp mills, reduced sulfur compounds 
(H2S, carbonyl sulfide, and carbon disulfide from sulfur 
recovery units at onshore natural gas processing facilities, and from 
other sources when specified in an applicable subpart of the 
regulations. The flue gas must contain at least 1 percent oxygen for 
complete oxidation of all TRS to SO2.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  An integrated gas sample is extracted from the stack. 
SO2 is removed selectively from the sample using a citrate 
buffer solution. TRS compounds are then thermally oxidized to 
SO2, collected in hydrogen peroxide as sulfate, and analyzed 
by the Method 6 barium-thorin titration procedure.

3.0  Definitions. [Reserved]

4.0  Interferences

    4.1  Reduced sulfur compounds other than those regulated by the 
emission standards, if present, may be measured by this method. 
Therefore, carbonyl sulfide, which is partially oxidized to 
SO2 and may be present in a lime kiln exit stack, would be a 
positive interferant.
    4.2  Particulate matter from the lime kiln stack gas (primarily 
calcium carbonate) can cause a negative bias if it is allowed to enter 
the citrate scrubber; the particulate matter will cause the pH to rise 
and H2S to be absorbed prior to oxidation. Furthermore, if 
the calcium carbonate enters the hydrogen peroxide impingers, the 
calcium will precipitate sulfate ion. Proper use of the particulate 
filter described in Section 6.1.3 will eliminate this interference.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Corrosive reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water for at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burns as thermal 
burns.
    5.2.1  Hydrogen Peroxide (H2O2). Irritating 
to eyes, skin, nose, and lungs.
    5.2.2  Sodium Hydroxide (NaOH). Causes severe damage to eyes and 
skin. Inhalation causes irritation to nose, throat, and lungs. Reacts 
exothermically with limited amounts of water.
    5.2.3  Sulfuric Acid (H2SO4). Rapidly 
destructive to body tissue. Will cause third degree burns. Eye damage 
may result in blindness. Inhalation may be fatal from spasm of the 
larynx, usually within 30 minutes. May cause lung tissue damage with 
edema. 3 mg/m\3\ will cause lung damage in uninitiated. 1 mg/m\3\ for 8 
hours will cause lung damage or, in higher concentrations, death. 
Provide ventilation to limit inhalation. Reacts violently with metals 
and organics.
    5.3  Hydrogen Sulfide (H2S). A flammable, poisonous gas 
with the odor of rotten eggs. H2S is extremely hazardous and 
can cause collapse, coma, and death within a few seconds of one or two 
inhalations at sufficient concentrations. Low concentrations irritate 
the mucous membranes and may cause nausea, dizziness, and headache 
after exposure.

6.0  Equipment and Supplies

    6.1  Sample Collection. The sampling train is shown in Figure 16A-1 
and component parts are discussed below. Modifications to this sampling 
train are acceptable provided the system performance check is met (see 
Section 8.5).
    6.1.1  Probe. Teflon tubing, 6.4-mm (\1/4\-in.) diameter, 
sequentially wrapped with heat-resistant fiber strips, a rubberized 
heat tape (plug at one end), and heat-resistant adhesive tape. A 
flexible thermocouple or other suitable temperature measuring device 
should be placed between the Teflon tubing and the fiber strips so that 
the temperature can be monitored to prevent softening of the probe. The 
probe should be sheathed in stainless steel to provide in-stack 
rigidity. A series of bored-out stainless steel fittings placed at the 
front of the sheath will prevent moisture and particulate from entering 
between the probe and sheath. A 6.4-mm (\1/4\-in.) Teflon elbow (bored 
out) should be attached to the inlet of the probe, and a 2.54 cm (1 
in.) piece of Teflon tubing should be attached at the open end of the 
elbow to permit the opening of the probe to be turned away from the 
particulate stream; this will reduce the amount of particulate drawn 
into the sampling train. The probe is depicted in Figure 16A-2.
    6.1.2  Probe Brush. Nylon bristle brush with handle inserted into a 
3.2-mm (\1/8\-in.) Teflon tubing. The Teflon tubing should be long 
enough to pass

[[Page 61989]]

the brush through the length of the probe.
    6.1.3  Particulate Filter. 50-mm Teflon filter holder and a 1- to 
2-m porosity, Teflon filter (available through Savillex 
Corporation, 5325 Highway 101, Minnetonka, Minnesota 55343). The filter 
holder must be maintained in a hot box at a temperature sufficient to 
prevent moisture condensation. A temperature of 121  deg.C (250  deg.F) 
was found to be sufficient when testing a lime kiln under sub-freezing 
ambient conditions.
    6.1.4  SO2 Scrubber. Three 300-ml Teflon segmented 
impingers connected in series with flexible, thick-walled, Teflon 
tubing. (Impinger parts and tubing available through Savillex.) The 
first two impingers contain 100 ml of citrate buffer and the third 
impinger is initially dry. The tip of the tube inserted into the 
solution should be constricted to less than 3 mm (\1/8\-in.) ID and 
should be immersed to a depth of at least 5 cm (2 in.).
    6.1.5  Combustion Tube. Quartz glass tubing with an expanded 
combustion chamber 2.54 cm (1 in.) in diameter and at least 30.5 cm (12 
in.) long. The tube ends should have an outside diameter of 0.6 cm (\1/
4\ in.) and be at least 15.3 cm (6 in.) long. This length is necessary 
to maintain the quartz-glass connector near ambient temperature and 
thereby avoid leaks. Alternatively, the outlet may be constructed with 
a 90-degree glass elbow and socket that would fit directly onto the 
inlet of the first peroxide impinger.
    6.1.6  Furnace. A furnace of sufficient size to enclose the 
combustion chamber of the combustion tube with a temperature regulator 
capable of maintaining the temperature at 800  100  deg.C 
(1472  180  deg.F). The furnace operating temperature 
should be checked with a thermocouple to ensure accuracy.
    6.1.7  Peroxide Impingers, Stopcock Grease, Temperature Sensor, 
Drying Tube, Valve, Pump, and Barometer. Same as Method 6, Sections 
6.1.1.2, 6.1.1.4, 6.1.1.5, 6.1.1.6, 6.1.1.7, 6.1.1.8, and 6.1.2, 
respectively, except that the midget bubbler of Method 6, Section 
6.1.1.2 is not required.
    6.1.8  Vacuum Gauge. At least 760 mm Hg (30 in. Hg) gauge.
    6.1.9  Rate Meter. Rotameter, or equivalent, accurate to within 5 
percent at the selected flow rate of approximately 2 liters/min (4.2 
ft\3\/hr).
    6.1.10  Volume Meter. Dry gas meter capable of measuring the sample 
volume under the sampling conditions of 2 liters/min (4.2 ft\3\/hr) 
with an accuracy of 2 percent.
    6.2  Sample Recovery. Polyethylene Bottles, 250-ml (one per 
sample).
    6.3  Sample Preparation and Analysis. Same as Method 6, Section 
6.3, except a 10-ml buret with 0.05-ml graduations is required, and the 
spectrophotometer is not needed.

7.0  Reagents and Standards

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

    7.1  Sample Collection. The following reagents are required for 
sample analysis:
    7.1.1  Water. Same as in Method 6, Section 7.1.1.
    7.1.2  Citrate Buffer. Dissolve 300 g of potassium citrate (or 284 
g of sodium citrate) and 41 g of anhydrous citric acid in 1 liter of 
water (200 ml is needed per test). Adjust the pH to between 5.4 and 5.6 
with potassium citrate or citric acid, as required.
    7.1.3  Hydrogen Peroxide, 3 percent. Same as in Method 6, Section 
7.1.3 (40 ml is needed per sample).
    7.1.4  Recovery Check Gas. Hydrogen sulfide (100 ppmv or less) in 
nitrogen, stored in aluminum cylinders. Verify the concentration by 
Method 11 or by gas chromatography where the instrument is calibrated 
with an H2S permeation tube as described below. For Method 
11, the relative standard deviation should not exceed 5 percent on at 
least three 20-minute runs.

    Note: Alternatively, hydrogen sulfide recovery gas generated 
from a permeation device gravimetrically calibrated and certified at 
some convenient operating temperature may be used. The permeation 
rate of the device must be such that at a dilution gas flow rate of 
3 liters/min (6.4 ft\3\/hr), an H2S concentration in the 
range of the stack gas or within 20 percent of the standard can be 
generated.

    7.1.5  Combustion Gas. Gas containing less than 50 ppb reduced 
sulfur compounds and less than 10 ppmv total hydrocarbons. The gas may 
be generated from a clean-air system that purifies ambient air and 
consists of the following components: Diaphragm pump, silica gel drying 
tube, activated charcoal tube, and flow rate measuring device. Flow 
from a compressed air cylinder is also acceptable.
    7.2  Sample Recovery and Analysis. Same as Method 6, Sections 7.2.1 
and 7.3, respectively.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Preparation of Sampling Train.
    8.1.1  For the SO2 scrubber, measure 100 ml of citrate 
buffer into the first and second impingers; leave the third impinger 
empty. Immerse the impingers in an ice bath, and locate them as close 
as possible to the filter heat box. The connecting tubing should be 
free of loops. Maintain the probe and filter temperatures sufficiently 
high to prevent moisture condensation, and monitor with a suitable 
temperature sensor.
    8.1.2  For the Method 6 part of the train, measure 20 ml of 3 
percent hydrogen peroxide into the first and second midget impingers. 
Leave the third midget impinger empty, and place silica gel in the 
fourth midget impinger. Alternatively, a silica gel drying tube may be 
used in place of the fourth impinger. Maintain the oxidation furnace at 
800  100  deg.C (1472  180  deg.F). Place 
crushed ice and water around all impingers.
    8.2  Citrate Scrubber Conditioning Procedure. Condition the citrate 
buffer scrubbing solution by pulling stack gas through the Teflon 
impingers and bypassing all other sampling train components. A purge 
rate of 2 liters/min for 10 minutes has been found to be sufficient to 
obtain equilibrium. After the citrate scrubber has been conditioned, 
assemble the sampling train, and conduct (optional) a leak-check as 
described in Method 6, Section 8.2.
    8.3  Sample Collection. Same as in Method 6, Section 8.3, except 
the sampling rate is 2 liters/min (10 percent) for 1 or 3 
hours. After the sample is collected, remove the probe from the stack, 
and conduct (mandatory) a post-test leak-check as described in Method 
6, Section 8.2. The 15-minute purge of the train following collection 
should not be performed. After each 3-hour test run (or after three 1-
hour samples), conduct one system performance check (see Section 8.5) 
to determine the reduced sulfur recovery efficiency through the 
sampling train. After this system performance check and before the next 
test run, rinse and brush the probe with water, replace the filter, and 
change the citrate scrubber (optional but recommended).


    Note: In Method 16, a test run is composed of 16 individual 
analyses (injects) performed over a period of not less than 3 hours 
or more than 6 hours. For Method 16A to be consistent with Method 
16, the following may be used to obtain a test run: (1) collect 
three 60-minute samples or (2) collect one 3-hour sample. (Three 
test runs constitute a test.)

    8.4  Sample Recovery. Disconnect the impingers. Quantitatively 
transfer the contents of the midget impingers of the Method 6 part of 
the train into a leak-free polyethylene bottle for

[[Page 61990]]

shipment. Rinse the three midget impingers and the connecting tubes 
with water and add the washings to the same storage container. Mark the 
fluid level. Seal and identify the sample container.
    8.5  System Performance Check.
    8.5.1  A system performance check is done (1) to validate the 
sampling train components and procedure (prior to testing; optional) 
and (2) to validate a test run (after a run). Perform a check in the 
field prior to testing consisting of at least two samples (optional), 
and perform an additional check after each 3 hour run or after three 1-
hour samples (mandatory).
    8.5.2  The checks involve sampling a known concentration of 
H2S and comparing the analyzed concentration with the known 
concentration. Mix the H2S recovery check gas (Section 
7.1.4) and combustion gas in a dilution system such as that shown in 
Figure 16A-3. Adjust the flow rates to generate an H2S 
concentration in the range of the stack gas or within 20 percent of the 
applicable standard and an oxygen concentration greater than 1 percent 
at a total flow rate of at least 2.5 liters/min (5.3 ft\3\/hr). Use 
Equation 16A-3 to calculate the concentration of recovery gas 
generated. Calibrate the flow rate from both sources with a soap bubble 
flow meter so that the diluted concentration of H2S can be 
accurately calculated.
    8.5.3  Collect 30-minute samples, and analyze in the same manner as 
the emission samples. Collect the sample through the probe of the 
sampling train using a manifold or some other suitable device that will 
ensure extraction of a representative sample.
    8.5.4  The recovery check must be performed in the field prior to 
replacing the SO2 scrubber and particulate filter and before 
the probe is cleaned. Use Equation 16A-4 (see Section 12.5) to 
calculate the recovery efficiency. Report the recovery efficiency with 
the emission data; do not correct the emission data for the recovery 
efficiency. A sample recovery of 100  20 percent must be 
obtained for the emission data to be valid. However, if the recovery 
efficiency is not in the 100  20 percent range but the 
results do not affect the compliance or noncompliance status of the 
affected facility, the Administrator may decide to accept the results 
of the compliance test.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.5...........................  System             Ensure validity of
                                 performance        sampling train
                                 check.             components and
                                                    analytical
                                                    procedure.
8.2, 10.0.....................  Sampling  equipme  Ensure accurate
                                 nt leak-check      measurement of stack
                                 and calibration.   gas flow rate,
                                                    sample volume.
10.0..........................  Barium standard    Ensure precision of
                                 solution           normality
                                 standardization.   determination.
11.1..........................  Replicate          Ensure precision of
                                 titrations.        titration
                                                    determinations.
11.2..........................  Audit sample       Evaluate analyst's
                                 analysis.          technique and
                                                    standards
                                                    preparation.
------------------------------------------------------------------------

10.0  Calibration

    Same as Method 6, Section 10.0.

11.0  Analytical Procedure

    11.1  Sample Loss Check and Sample Analysis. Same as Method 6, 
Sections 11.1 and 11.2, respectively, with the following exception: for 
1-hour sampling, take a 40-ml aliquot, add 160 ml of 100 percent 
isopropanol and four drops of thorin.
    11.2  Audit Sample Analysis. Same as Method 6, Section 11.3.

12.0  Data Analysis and Calculations

    In the calculations, at least one extra decimal figure should be 
retained beyond that of the acquired data. Figures should be rounded 
off after final calculations.
    12.1  Nomenclature.

CTRS = Concentration of TRS as SO2, dry basis 
corrected to standard conditions, ppmv.
CRG(act) = Actual concentration of recovery check gas (after 
dilution), ppm.
CRG(m) = Measured concentration of recovery check gas 
generated, ppm.
CH2S = Verified concentration of H2S recovery 
gas.
N = Normality of barium perchlorate titrant, milliequivalents/ml.
Pbar = Barometric pressure at exit orifice of the dry gas 
meter, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
QH2S = Calibrated flow rate of H2S recovery gas, 
liters/min.
QCG = Calibrated flow rate of combustion gas, liters/min.
R = Recovery efficiency for the system performance check, percent.
Tm = Average dry gas meter absolute temperature,  deg.K 
( deg.R).
Tstd = Standard absolute temperature, 293  deg.K (528 
deg.R).
Va = Volume of sample aliquot titrated, ml.
Vm = Dry gas volume as measured by the dry gas meter, liters 
(dcf).
Vm(std) = Dry gas volume measured by the dry gas meter, 
corrected to standard conditions, liters (dscf).
Vsoln = Total volume of solution in which the sulfur dioxide 
sample is contained, 100 ml.
Vt = Volume of barium perchlorate titrant used for the 
sample, ml (average of replicate titrations).
Vtb = Volume of barium perchlorate titrant used for the 
blank, ml.
Y = Dry gas meter calibration factor.
32.03 = Equivalent weight of sulfur dioxide, mg/meq.

    12.2  Dry Sample Gas Volume, Corrected to Standard Conditions.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.283
    
Where:

K1 = 0.3855  deg.K/mm Hg for metric units,
= 17.65  deg.R/in. Hg for English units.

    12.3  Concentration of TRS as ppm SO2.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.284
    

[[Page 61991]]


Where:
[GRAPHIC] [TIFF OMITTED] TR17OC00.285

    12.4  Concentration of Recovery Gas Generated in the System 
Performance Check.
[GRAPHIC] [TIFF OMITTED] TR17OC00.286

    12.5  Recovery Efficiency for the System Performance Check.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.287
    
13.0  Method Performance

    13.1  Analytical Range. The lower detectable limit is 0.1 ppmv 
SO2 when sampling at 2 liters/min (4.2 ft\3\/hr) for 3 hours 
or 0.3 ppmv when sampling at 2 liters/min (4.2 ft\3\/hr) for 1 hour. 
The upper concentration limit of the method exceeds the TRS levels 
generally encountered at kraft pulp mills.
    13.2  Precision. Relative standard deviations of 2.0 and 2.6 
percent were obtained when sampling a recovery boiler for 1 and 3 
hours, respectively.
    13.3  Bias.
    13.3.1  No bias was found in Method 16A relative to Method 16 in a 
separate study at a recovery boiler.
    13.3.2  Comparison of Method 16A with Method 16 at a lime kiln 
indicated that there was no bias in Method 16A. However, instability of 
the source emissions adversely affected the comparison. The precision 
of Method 16A at the lime kiln was similar to that obtained at the 
recovery boiler (Section 13.2.1).
    13.3.3  Relative standard deviations of 2.7 and 7.7 percent have 
been obtained for system performance checks.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  Alternative Procedures

    As an alternative to the procedures specified in Section 7.1.4, the 
following procedure may be used to verify the H2S 
concentration of the recovery check gas.
    16.1  Summary. The H2S is collected from the calibration 
gas cylinder and is absorbed in zinc acetate solution to form zinc 
sulfide. The latter compound is then measured iodometrically.
    16.2  Range. The procedure has been examined in the range of 5 to 
1500 ppmv.
    16.3  Interferences. There are no known interferences to this 
procedure when used to analyze cylinder gases containing H2S 
in nitrogen.
    16.4  Precision and Bias. Laboratory tests have shown a relative 
standard deviation of less than 3 percent. The procedure showed no bias 
when compared to a gas chromatographic method that used gravimetrically 
certified permeation tubes for calibration.
    16.5  Equipment and Supplies.
    16.5.1  Sampling Apparatus. The sampling train is shown in Figure 
16A-4. Its component parts are discussed in Sections 16.5.1.1 through 
16.5.2.
    16.5.1.1  Sampling Line. Teflon tubing (\1/4\-in.) to connect the 
cylinder regulator to the sampling valve.
    16.5.1.2  Needle Valve. Stainless steel or Teflon needle valve to 
control the flow rate of gases to the impingers.
    16.5.1.3  Impingers. Three impingers of approximately 100-ml 
capacity, constructed to permit the addition of reagents through the 
gas inlet stem. The impingers shall be connected in series with leak-
free glass or Teflon connectors. The impinger bottoms have a standard 
24/25 ground-glass fitting. The stems are from standard 6.4-mm (\1/4\-
in.) ball joint midget impingers, custom lengthened by about 1 in. When 
fitted together, the stem end should be approximately 1.27 cm (\1/2\ 
in.) from the bottom (Southern Scientific, Inc., Micanopy, Florida: Set 
Number S6962-048). The third in-line impinger acts as a drop-out 
bottle.
    16.5.1.4  Drying Tube, Rate Meter, and Barometer. Same as Method 
11, Sections 6.1.5, 6.1.8, and 6.1.10, respectively.
    16.5.1.5  Cylinder Gas Regulator. Stainless steel, to reduce the 
pressure of the gas stream entering the Teflon sampling line to a safe 
level.
    16.5.1.6  Soap Bubble Meter. Calibrated for 100 and 500 ml, or two 
separate bubble meters.
    16.5.1.7  Critical Orifice. For volume and rate measurements. The 
critical orifice may be fabricated according to Section 16.7.3 and must 
be calibrated as specified in Section 16.12.4.
    16.5.1.8  Graduated Cylinder. 50-ml size.
    16.5.1.9  Volumetric Flask. 1-liter size.
    16.5.1.10  Volumetric Pipette. 15-ml size.
    16.5.1.11  Vacuum Gauge. Minimum 20 in. Hg capacity.
    16.5.1.12  Stopwatch.
    16.5.2  Sample Recovery and Analysis.
    16.5.2.1  Erlenmeyer Flasks. 125- and 250-ml sizes.
    16.5.2.2  Pipettes. 2-, 10-, 20-, and 100-ml volumetric.
    16.5.2.3  Burette. 50-ml size.
    16.5.2.4  Volumetric Flask. 1-liter size.
    16.5.2.5  Graduated Cylinder. 50-ml size.
    16.5.2.6  Wash Bottle.
    16.5.2.7  Stirring Plate and Bars.
    16.6  Reagents and Standards. Unless otherwise indicated, all 
reagents must conform to the specifications established by the 
Committee on Analytical Reagents of the American Chemical Society, 
where such specifications are available. Otherwise, use the best 
available grade.
    16.6.1  Water. Same as Method 11, Section 7.1.3.
    16.6.2  Zinc Acetate Absorbing Solution. Dissolve 20 g zinc acetate 
in water, and dilute to 1 liter.
    16.6.3  Potassium Bi-iodate [KH(IO3)2] 
Solution, Standard 0.100 N. Dissolve 3.249 g anhydrous 
KH(IO3)2 in water, and dilute to 1 liter.
    16.6.4  Sodium Thiosulfate 
(Na2S2O3) Solution, Standard 0.1 N. 
Same as Method 11, Section 7.3.2. Standardize according to Section 
16.12.2.
    16.6.5  Na2S2O3 Solution, Standard 
0.01 N. Pipette 100.0 ml of 0.1 N 
Na2S2O3 solution into a 1-liter 
volumetric flask, and dilute to the mark with water.
    16.6.6  Iodine Solution, 0.1 N. Same as Method 11, Section 7.2.3.
    16.6.7  Standard Iodine Solution, 0.01 N. Same as in Method 11, 
Section 7.2.4. Standardize according to Section 16.12.3.
    16.6.8  Hydrochloric Acid (HCl) Solution, 10 Percent by Weight. Add 
230 ml concentrated HCl (specific gravity 1.19) to 770 ml water.
    16.6.9  Starch Indicator Solution. To 5 g starch (potato, 
arrowroot, or soluble), add a little cold water, and grind in a mortar 
to a thin paste. Pour into 1 liter of boiling water, stir, and let 
settle overnight. Use the clear supernatant. Preserve with 1.25 g 
salicylic acid, 4 g zinc chloride, or a combination of 4 g sodium 
propionate and 2 g sodium

[[Page 61992]]

azide per liter of starch solution. Some commercial starch substitutes 
are satisfactory.
    16.7  Pre-test Procedures.
    16.7.1  Selection of Gas Sample Volumes. This procedure has been 
validated for estimating the volume of cylinder gas sample needed when 
the H2S concentration is in the range of 5 to 1500 ppmv. The 
sample volume ranges were selected in order to ensure a 35 to 60 
percent consumption of the 20 ml of 0.01 N iodine (thus ensuring a 0.01 
N Na2S2O3 titer of approximately 7 to 
12 ml). The sample volumes for various H2S concentrations 
can be estimated by dividing the approximate ppm-liters desired for a 
given concentration range by the H2S concentration stated by 
the manufacturer. For example, for analyzing a cylinder gas containing 
approximately 10 ppmv H2S, the optimum sample volume is 65 
liters (650 ppm-liters/10 ppmv). For analyzing a cylinder gas 
containing approximately 1000 ppmv H2S, the optimum sample 
volume is 1 liter (1000 ppm-liters/1000 ppmv).

------------------------------------------------------------------------
                                                            Approximate
    Approximate cylinder gas H2S concentration (ppmv)       ppm-liters
                                                              desired
------------------------------------------------------------------------
5 to 30.................................................             650
30 to 500...............................................             800
500 to 1500.............................................            1000
------------------------------------------------------------------------

    16.7.2  Critical Orifice Flow Rate Selection. The following table 
shows the ranges of sample flow rates that are desirable in order to 
ensure capture of H2S in the impinger solution. Slight 
deviations from these ranges will not have an impact on measured 
concentrations.

------------------------------------------------------------------------
                                            Critical  orifice  flow rate
  Cylinder gas H2S concentration (ppmv)               (ml/min)
------------------------------------------------------------------------
5 to 50 ppmv.............................  1500  500
50 to 250 ppmv...........................  500  250
250 to 1000 ppmv.........................  200  50
>1000 ppmv...............................  75  25
------------------------------------------------------------------------

    16.7.3  Critical Orifice Fabrication. Critical orifice of desired 
flow rates may be fabricated by selecting an orifice tube of desired 
length and connecting \1/16\-in. x \1/4\-in. (0.16 cm x 0.64 cm) 
reducing fittings to both ends. The inside diameters and lengths of 
orifice tubes needed to obtain specific flow rates are shown below.

----------------------------------------------------------------------------------------------------------------
                                                                                  Flowrate  (ml/      Altech
                 Tube  (in. OD)                   Tube  (in. ID)   Length  (in.)       min)         Catalog No.
----------------------------------------------------------------------------------------------------------------
\1/16\..........................................           0.007             1.2              85          301430
\1/16\..........................................           0.01              3.2             215          300530
\1/16\..........................................           0.01              1.2             350          300530
\1/16\..........................................           0.02              1.2            1400          300230
----------------------------------------------------------------------------------------------------------------

    16.7.4  Determination of Critical Orifice Approximate Flow Rate. 
Connect the critical orifice to the sampling system as shown in Figure 
16A-4 but without the H2S cylinder. Connect a rotameter in 
the line to the first impinger. Turn on the pump, and adjust the valve 
to give a reading of about half atmospheric pressure. Observe the 
rotameter reading. Slowly increase the vacuum until a stable flow rate 
is reached, and record this as the critical vacuum. The measured flow 
rate indicates the expected critical flow rate of the orifice. If this 
flow rate is in the range shown in Section 16.7.2, proceed with the 
critical orifice calibration according to Section 16.12.4.
    16.7.5  Determination of Approximate Sampling Time. Determine the 
approximate sampling time for a cylinder of known concentration. Use 
the optimum sample volume obtained in Section 16.7.1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.288

    16.8  Sample Collection.
    16.8.1  Connect the Teflon tubing, Teflon tee, and rotameter to the 
flow control needle valve as shown in Figure 16A-4. Vent the rotameter 
to an exhaust hood. Plug the open end of the tee. Five to 10 minutes 
prior to sampling, open the cylinder valve while keeping the flow 
control needle valve closed. Adjust the delivery pressure to 20 psi. 
Open the needle valve slowly until the rotameter shows a flow rate 
approximately 50 to 100 ml above the flow rate of the critical orifice 
being used in the system.
    16.8.2  Place 50 ml of zinc acetate solution in two of the 
impingers, connect them and the empty third impinger (dropout bottle) 
and the rest of the equipment as shown in Figure 16A-4. Make sure the 
ground-glass fittings are tight. The impingers can be easily stabilized 
by using a small cardboard box in which three holes have been cut, to 
act as a holder. Connect the Teflon sample line to the first impinger. 
Cover the impingers with a dark cloth or piece of plastic to protect 
the absorbing solution from light during sampling.
    16.8.3  Record the temperature and barometric pressure. Note the 
gas flow rate through the rotameter. Open the closed end of the tee. 
Connect the sampling tube to the tee, ensuring a tight connection. 
Start the sampling pump and stopwatch simultaneously. Note the decrease 
in flow rate through the excess flow rotameter. This decrease should 
equal the known flow rate of the critical orifice being used. Continue 
sampling for the period determined in Section 16.7.5.
    16.8.4  When sampling is complete, turn off the pump and stopwatch. 
Disconnect the sampling line from the tee and plug it. Close the needle 
valve followed by the cylinder valve. Record the sampling time.
    16.9  Blank Analysis. While the sample is being collected, run a 
blank as follows: To a 250-ml Erlenmeyer flask, add 100 ml of zinc 
acetate solution, 20.0 ml of 0.01 N iodine solution, and 2 ml HCl 
solution. Titrate, while stirring, with 0.01 N 
Na2S2O3 until the solution is light 
yellow. Add starch, and continue titrating until the blue color 
disappears. Analyze a blank with each sample, as the blank titer has 
been observed to change over the course of a day.


    Note: Iodine titration of zinc acetate solutions is difficult to 
perform because the solution turns slightly white in color near the 
end point, and the disappearance of the blue color is hard to 
recognize. In addition, a blue color may reappear in the solution 
about 30 to 45 seconds after the titration endpoint is reached. This 
should not be taken to mean

[[Page 61993]]

the original endpoint was in error. It is recommended that persons 
conducting this test perform several titrations to be able to 
correctly identify the endpoint. The importance of this should be 
recognized because the results of this analytical procedure are 
extremely sensitive to errors in titration.


    16.10  Sample Analysis. Sample treatment is similar to the blank 
treatment. Before detaching the stems from the bottoms of the 
impingers, add 20.0 ml of 0.01 N iodine solution through the stems of 
the impingers holding the zinc acetate solution, dividing it between 
the two (add about 15 ml to the first impinger and the rest to the 
second). Add 2 ml HCl solution through the stems, dividing it as with 
the iodine. Disconnect the sampling line, and store the impingers for 
30 minutes. At the end of 30 minutes, rinse the impinger stems into the 
impinger bottoms. Titrate the impinger contents with 0.01 N 
Na2S2O3. Do not transfer the contents 
of the impinger to a flask because this may result in a loss of iodine 
and cause a positive bias.
    16.11  Post-test Orifice Calibration. Conduct a post-test critical 
orifice calibration run using the calibration procedures outlined in 
Section 16.12.4. If the Qstd obtained before and after the 
test differs by more than 5 percent, void the sample; if not, proceed 
to perform the calculations.
    16.12  Calibrations and Standardizations.
    16.12.1  Rotameter and Barometer. Same as Method 11, Sections 
10.1.3 and 10.1.4.
    16.12.2  Na2S2O3 Solution, 0.1 N. 
Standardize the 0.1 N Na2S2O3 solution 
as follows: To 80 ml water, stirring constantly, add 1 ml concentrated 
H2SO4, 10.0 ml of 0.100 N 
KH(IO3)2 and 1 g potassium iodide. Titrate 
immediately with 0.1 N Na2S2O3 until 
the solution is light yellow. Add 3 ml starch solution, and titrate 
until the blue color just disappears. Repeat the titration until 
replicate analyses agree within 0.05 ml. Take the average volume of 
Na2S2O3 consumed to calculate the 
normality to three decimal figures using Equation 16A-5.
    16.12.3  Iodine Solution, 0.01 N. Standardize the 0.01 N iodine 
solution as follows: Pipet 20.0 ml of 0.01 N iodine solution into a 
125-ml Erlenmeyer flask. Titrate with standard 0.01 N 
Na2S2O3 solution until the solution is 
light yellow. Add 3 ml starch solution, and continue titrating until 
the blue color just disappears. If the normality of the iodine tested 
is not 0.010, add a few ml of 0.1 N iodine solution if it is low, or a 
few ml of water if it is high, and standardize again. Repeat the 
titration until replicate values agree within 0.05 ml. Take the average 
volume to calculate the normality to three decimal figures using 
Equation 16A-6.
    16.12.4  Critical Orifice. Calibrate the critical orifice using the 
sampling train shown in Figure 16A-4 but without the H2S 
cylinder and vent rotameter. Connect the soap bubble meter to the 
Teflon line that is connected to the first impinger. Turn on the pump, 
and adjust the needle valve until the vacuum is higher than the 
critical vacuum determined in Section 16.7.4. Record the time required 
for gas flow to equal the soap bubble meter volume (use the 100-ml soap 
bubble meter for gas flow rates below 100 ml/min, otherwise use the 
500-ml soap bubble meter). Make three runs, and record the data listed 
in Table 16A-1. Use these data to calculate the volumetric flow rate of 
the orifice.
    16.13  Calculations.
    16.13.1  Nomenclature.

Bwa = Fraction of water vapor in ambient air during orifice 
calibration.
CH2S = H2S concentration in cylinder 
gas, ppmv.
[GRAPHIC] [TIFF OMITTED] TR17OC00.289

Ma = Molecular weight of ambient air saturated at impinger 
temperature, g/g-mole.
Ms = Molecular weight of sample gas (nitrogen) saturated at 
impinger temperature, g/g-mole.

    Note: (For tests carried out in a laboratory where the impinger 
temperature is 25  deg.C, Ma = 28.5 g/g-mole and 
Ms = 27.7 g/g-mole.)

NI = Normality of standard iodine solution (0.01 N), g-eq/
liter.
NT = Normality of standard 
Na2S2O3 solution (0.01 N), g-eq/liter.
Pbar = Barometric pressure, mm Hg.
Pstd = Standard absolute pressure, 760 mm Hg.
Qstd = Average volumetric flow rate through critical 
orifice, liters/min.
Tamb = Absolute ambient temperature,  deg.K.
Tstd = Standard absolute temperature, 293  deg.K.
s = Sampling time, min.
sb = Time for soap bubble meter flow rate 
measurement, min.
Vm(std) = Sample gas volume measured by the critical 
orifice, corrected to standard conditions, liters.
Vsb = Volume of gas as measured by the soap bubble meter, 
ml.
Vsb(std) = Volume of gas as measured by the soap bubble 
meter, corrected to standard conditions, liters.
VI = Volume of standard iodine solution (0.01 N) used, ml.
VT = Volume of standard 
Na2S2O3 solution (0.01 N) used, ml.
VTB = Volume of standard 
Na2S2O3 solution (0.01 N) used for the 
blank, ml.

    16.13.2  Normality of Standard 
Na2S2O3 Solution (0.1 N).
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    16.13.3  Normality of Standard Iodine Solution (0.01 N).
    [GRAPHIC] [TIFF OMITTED] TR17OC00.291
    
    16.13.4  Sample Gas Volume.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.292
    
    16.13.5  Concentration of H2S in the Gas Cylinder.

17.0  References
[GRAPHIC] [TIFF OMITTED] TR17OC00.293

    1. American Public Health Association, American Water Works 
Association, and Water Pollution Control Federation. Standard 
Methods for the Examination of Water and Wastewater. Washington, DC. 
American Public Health Association. 1975. pp. 316-317.
    2. American Society for Testing and Materials. Annual Book of 
ASTM Standards. Part 31: Water, Atmospheric Analysis. Philadelphia, 
PA. 1974. pp. 40-42.
    3. Blosser, R.O. A Study of TRS Measurement Methods. National 
Council of the Paper Industry for Air and Stream Improvement, Inc., 
New York, NY. Technical Bulletin No. 434. May 1984. 14 pp.
    4. Blosser, R.O., H.S. Oglesby, and A.K. Jain. A Study of 
Alternate SO2 Scrubber Designs Used for TRS Monitoring. A 
Special Report by the National Council of the Paper Industry for Air 
and Stream Improvement, Inc., New York, NY. July 1977.
    5. Curtis, F., and G.D. McAlister. Development and Evaluation of 
an Oxidation/Method 6 TRS Emission Sampling Procedure. Emission 
Measurement Branch, Emission Standards and Engineering Division, 
U.S. Environmental Protection Agency, Research Triangle Park, NC 
27711. February 1980.
    6. Gellman, I. A Laboratory and Field Study of Reduced Sulfur 
Sampling and Monitoring Systems. National Council of the Paper 
Industry for Air and Stream Improvement, Inc., New York, NY. 
Atmospheric Quality Improvement Technical Bulletin No. 81. October 
1975.
    7. Margeson, J.H., J.E. Knoll, and M.R. Midgett. A Manual Method 
for TRS Determination. Source Branch, Quality Assurance Division, 
U.S. Environmental Protection Agency, Research Triangle Park, NC 
27711.
    8. National Council of the Paper Industry for Air and Stream 
Improvement. An Investigation of H2S and SO2. 
Calibration Cylinder Gas Stability and Their Standardization Using 
Wet Chemical Techniques. Special Report 76-06. New York, NY. August 
1976.
    9. National Council of the Paper Industry for Air and Stream 
Improvement. Wet Chemical Method for Determining the H2S 
Concentration of Calibration Cylinder Gases. Technical Bulletin 
Number 450. New York, NY. January 1985. 23 pp.
    10. National Council of the Paper Industry for Air and Stream 
Improvement. Modified Wet Chemical Method for Determining the 
H2S Concentration of Calibration Cylinder Gases. Draft 
Report. New York, NY. March 1987. 29 pp.
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18.0  Tables, Diagrams, Flowcharts, and Validation Data
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Date------------------------------------------------------------------
Critical orifice ID---------------------------------------------------
Soap bubble meter volume, Vsb____ liters
Time, sb
Run no. 1 ____ min ____ sec
Run no. 2 ____ min ____ sec
Run no. 3 ____ min ____ sec
Average ____ min ____ sec
Covert the seconds to fraction of minute:
Time = ____ min + ____ Sec/60 = ____ min
Barometric pressure, Pbar = ____ mm Hg
Ambient temperature, t amb = 273 + ____  deg.C = ____ 
deg.K = ____ mm Hg. (This should be approximately 0.4 times 
barometric pressure.)
Pump vacuum,
[GRAPHIC] [TIFF OMITTED] TR17OC00.298

Table 16A-1. Critical Orifice Calibration Data

Method 16B--Determination of Total Reduced Sulfur Emissions From 
Stationary Sources

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

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
                         Analyte                              CAS No.
------------------------------------------------------------------------
Total reduced sulfur (TRS) including:                                N/A
    Dimethyl disulfide (DMDS), [(CH3)2S2]...............        62-49-20
    Dimethyl sulfide (DMS), [(CH3)2S]...................         75-18-3
    Hydrogen sulfide (H2S)..............................       7783-06-4
    Methyl mercaptan (MeSH), [CH4S].....................         74-93-1
Reported as: Sulfur dioxide (SO2).......................       7449-09-5
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for determining TRS 
emissions from recovery furnaces (boilers), lime kilns, and smelt 
dissolving tanks at kraft pulp mills, and from other sources when 
specified in an applicable subpart of the regulations. The flue gas 
must contain at least 1 percent oxygen for complete oxidation of all 
TRS to SO2.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  An integrated gas sample is extracted from the stack. The 
SO2 is removed selectively from the sample using a citrate 
buffer solution. The TRS compounds are then thermally oxidized to 
SO2 and analyzed as SO2 by gas chromatography 
(GC) using flame photometric detection (FPD).

3.0  Definitions. [Reserved]

4.0  Interferences

    4.1  Reduced sulfur compounds other than those regulated by the 
emission standards, if present, may be measured by this method. 
Therefore, carbonyl sulfide, which is partially oxidized to 
SO2 and may be present in a lime kiln exit stack, would be a 
positive interferant.
    4.2  Particulate matter from the lime kiln stack gas (primarily 
calcium carbonate) can cause a negative bias if it is allowed to enter 
the citrate scrubber; the particulate matter will cause the pH to rise 
and H2S to be absorbed before oxidation. Proper use of the 
particulate filter, described in Section 6.1.3 of Method 16A, will 
eliminate this interference.
    4.3  Carbon monoxide (CO) and carbon dioxide (CO2) have 
substantial desensitizing effects on the FPD even after dilution. 
Acceptable systems must demonstrate that they have eliminated this 
interference by some procedure such as eluting these compounds before 
the SO2. Compliance with this requirement can be 
demonstrated by submitting chromatograms of calibration gases with and 
without CO2 in diluent gas. The CO2 level should 
be approximately 10 percent for the case with CO2 present. 
The two chromatograms should show agreement within the precision limits 
of Section 13.0.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the

[[Page 62000]]

responsibility of the user of this test method to establish appropriate 
safety and health practices and determine the applicability of 
regulatory limitations prior to performing this test method.
    5.2  Hydrogen Sulfide (H2S). A flammable, poisonous gas 
with the odor of rotten eggs. H2S is extremely hazardous and 
can cause collapse, coma, and death within a few seconds of one or two 
inhalations at sufficient concentrations. Low concentrations irritate 
the mucous membranes and may cause nausea, dizziness, and headache 
after exposure.

6.0  Equipment and Supplies

    6.1  Sample Collection. The sampling train is shown in Figure 16B-
1. Modifications to the apparatus are accepted provided the system 
performance check in Section 8.4.1 is met.
    6.1.1  Probe, Probe Brush, Particulate Filter, SO2 
Scrubber, Combustion Tube, and Furnace. Same as in Method 16A, Sections 
6.1.1 to 6.1.6.
    6.1.2  Sampling Pump. Leakless Teflon-coated diaphragm type or 
equivalent.
    6.2  Analysis.
    6.2.1  Dilution System (optional), Gas Chromatograph, Oven, 
Temperature Gauges, Flow System, Flame Photometric Detector, 
Electrometer, Power Supply, Recorder, Calibration System, Tube Chamber, 
Flow System, and Constant Temperature Bath. Same as in Method 16, 
Sections 6.2.1, 6.2.2, and 6.3.
    6.2.2  Gas Chromatograph Columns. Same as in Method 16, Section 
6.2.3. Other columns with demonstrated ability to resolve 
SO2 and be free from known interferences are acceptable 
alternatives. Single column systems such as a 7-ft Carbsorb B HT 100 
column have been found satisfactory in resolving SO2 from 
CO2.

7.0  Reagents and Standards

    Same as in Method 16, Section 7.0, except for the following:
    7.1  Calibration Gas. SO2 permeation tube 
gravimetrically calibrated and certified at some convenient operating 
temperature. These tubes consist of hermetically sealed FEP Teflon 
tubing in which a liquefied gaseous substance is enclosed. The enclosed 
gas permeates through the tubing wall at a constant rate. When the 
temperature is constant, calibration gases covering a wide range of 
known concentrations can be generated by varying and accurately 
measuring the flow rate of diluent gas passing over the tubes. In place 
of SO2 permeation tubes, cylinder gases containing 
SO2 in nitrogen may be used for calibration. The cylinder 
gas concentration must be verified according to Section 8.2.1 of Method 
6C. The calibration gas is used to calibrate the GC/FPD system and the 
dilution system.
    7.2  Recovery Check Gas.
    7.2.1  Hydrogen sulfide [100 parts per million by volume (ppmv) or 
less] in nitrogen, stored in aluminum cylinders. Verify the 
concentration by Method 11, the procedure discussed in Section 16.0 of 
Method 16A, or gas chromatography where the instrument is calibrated 
with an H2S permeation tube as described below. For the wet-
chemical methods, the standard deviation should not exceed 5 percent on 
at least three 20-minute runs.
    7.2.2  Hydrogen sulfide recovery gas generated from a permeation 
device gravimetrically calibrated and certified at some convenient 
operation temperature may be used. The permeation rate of the device 
must be such that at a dilution gas flow rate of 3 liters/min (64 
ft\3\/hr), an H2S concentration in the range of the stack 
gas or within 20 percent of the emission standard can be generated.
    7.3  Combustion Gas. Gas containing less than 50 ppbv reduced 
sulfur compounds and less than 10 ppmv total hydrocarbons. The gas may 
be generated from a clean-air system that purifies ambient air and 
consists of the following components: diaphragm pump, silica gel drying 
tube, activated charcoal tube, and flow rate measuring device. Gas from 
a compressed air cylinder is also acceptable.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Pretest Procedures. Same as in Method 15, Section 8.1.
    8.2  Sample Collection. Before any source sampling is performed, 
conduct a system performance check as detailed in Section 8.4.1 to 
validate the sampling train components and procedures. Although this 
test is optional, it would significantly reduce the possibility of 
rejecting tests as a result of failing the post-test performance check. 
At the completion of the pretest system performance check, insert the 
sampling probe into the test port making certain that no dilution air 
enters the stack though the port. Condition the entire system with 
sample for a minimum of 15 minutes before beginning analysis. If the 
sample is diluted, determine the dilution factor as in Section 10.4 of 
Method 15.
    8.3  Analysis. Inject aliquots of the sample into the GC/FPD 
analyzer for analysis. Determine the concentration of SO2 
directly from the calibration curves or from the equation for the 
least-squares line.
    8.4.  Post-Test Procedures
    8.4.1  System Performance Check. Same as in Method 16A, Section 
8.5. A sufficient number of sample injections should be made so that 
the precision requirements of Section 13.2 are satisfied.
    8.4.2  Determination of Calibration Drift. Same as in Method 15, 
Section 8.3.2.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.2, 8.3......................  System             Ensure validity of
                                 performance        sampling train
                                 check.             components and
                                                    analytical
                                                    procedure.
8.1...........................  Sampling           Ensure accurate
                                 equipment leak-    measurement of stack
                                 check and          gas flow rate,
                                 calibration.       sample volume.
10.0..........................  Analytical         Ensure precision of
                                 calibration.       analytical results
                                                    within 5 percent.
------------------------------------------------------------------------

10.0  Calibration

    Same as in Method 16, Section 10, except SO2 is used 
instead of H2S.

11.0  Analytical Procedure

    11.1 Sample collection and analysis are concurrent for this method 
(see section 8.3).
    12.0  Data Analysis and Calculations
12.1  Nomenclature.

CSO2 = Sulfur dioxide concentration, 
ppmv.
CTRS = Total reduced sulfur 
concentration as determined by Equation 16B-1, ppmv.

[[Page 62001]]

d = Dilution factor, dimensionless.
N = Number of samples.

    12.2  SO2 Concentration. Determine the concentration of 
SO2, CSO2, directly from 
the calibration curves. Alternatively, the concentration may be 
calculated using the equation for the least-squares line.
    12.3  TRS Concentration.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.299
    
12.4  Average TRS Concentration
[GRAPHIC] [TIFF OMITTED] TR17OC00.300

13.0  Method Performance.

    13.1  Range and Sensitivity. Coupled with a GC using a 1-ml sample 
size, the maximum limit of the FPD for SO2 is approximately 
10 ppmv. This limit is extended by diluting the sample gas before 
analysis or by reducing the sample aliquot size. For sources with 
emission levels between 10 and 100 ppm, the measuring range can be best 
extended by reducing the sample size.
    13.2  GC/FPD Calibration and Precision. A series of three 
consecutive injections of the sample calibration gas, at any dilution, 
must produce results which do not vary by more than 5 percent from the 
mean of the three injections.
    13.3  Calibration Drift. The calibration drift determined from the 
mean of the three injections made at the beginning and end of any run 
or series of runs within a 24-hour period must not exceed 5 percent.
    13.4  System Calibration Accuracy. Losses through the sample 
transport system must be measured and a correction factor developed to 
adjust the calibration accuracy to 100 percent.
    13.5  Field tests between this method and Method 16A showed an 
average difference of less than 4.0 percent. This difference was not 
determined to be significant.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    1. Same as in Method 16, Section 16.0.
    2. National Council of the Paper Industry for Air and Stream 
Improvement, Inc, A Study of TRS Measurement Methods. Technical 
Bulletin No. 434. New York, NY. May 1984. 12p.
    3. Margeson, J.H., J.E. Knoll, and M.R. Midgett. A Manual Method 
for TRS Determination. Draft available from the authors. Source 
Branch, Quality Assurance Division, U.S. Environmental Protection 
Agency, Research Triangle Park, NC 27711.
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17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.301

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Method 17--Determination of Particulate Matter Emissions From 
Stationary Sources

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

1.0  Scope and Application

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

    Note: Particulate matter is not an absolute quantity. It is a 
function of temperature and pressure. Therefore, to prevent 
variability in PM emission regulations and/or associated test 
methods, the temperature and pressure at which PM is to be measured 
must be carefully defined. Of the two variables (i.e., temperature 
and pressure), temperature has the greater effect upon the amount of 
PM in an effluent gas stream; in most stationary source categories, 
the effect of pressure appears to be negligible. In Method 5, 120 
deg.C (248  deg.F) is established as a nominal reference 
temperature. Thus, where Method 5 is specified in an applicable 
subpart of the standard, PM is defined with respect to temperature. 
In order to maintain a collection temperature of 120  deg.C (248 
deg.F), Method 5 employs a heated glass sample probe and a heated 
filter holder. This equipment is somewhat cumbersome and requires 
care in its operation. Therefore, where PM concentrations (over the 
normal range of temperature associated with a specified source 
category) are known to be independent of temperature, it is 
desirable to eliminate the glass probe and the heating systems, and 
to sample at stack temperature.

    1.2  Applicability. This method is applicable for the determination 
of PM emissions, where PM concentrations are known to be independent of 
temperature over the normal range of temperatures characteristic of 
emissions from a specified source category. It is intended to be used 
only when specified by an applicable subpart of the standards, and only 
within the applicable temperature limits (if specified), or when 
otherwise approved by the Administrator. This method is not applicable 
to stacks that contain liquid droplets or are saturated with water 
vapor. In addition, this method shall not be used as written if the 
projected cross-sectional area of the probe extension-filter holder 
assembly covers more than 5 percent of the stack cross-sectional area 
(see Section 8.1.2).
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  Particulate matter is withdrawn isokinetically from the source 
and collected on a glass fiber filter maintained at stack temperature. 
The PM mass is determined gravimetrically after the removal of 
uncombined water.

3.0  Definitions

    Same as Method 5, Section 3.0.

4.0  Interferences. [Reserved]

5.0  Safety

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

6.0  Equipment and Supplies

    6.1  Sampling Train. A schematic of the sampling train used in this 
method is shown in Figure 17-1. The sampling train components and 
operation and maintenance are very similar to Method 5, which should be 
consulted for details.
    6.1.1  Probe Nozzle, Differential Pressure Gauge, Metering System, 
Barometer, Gas Density Determination Equipment. Same as in Method 5, 
Sections 6.1.1, 6.1.4, 6.1.8, 6.1.9, and 6.1.10, respectively.
    6.1.2  Filter Holder. The in-stack filter holder shall be 
constructed of borosilicate or quartz glass, or stainless steel. If a 
gasket is used, it shall be made of silicone rubber, Teflon, or 
stainless steel. Other holder and gasket materials may be used, subject 
to the approval of the Administrator. The filter holder shall be 
designed to provide a positive seal against leakage from the outside or 
around the filter.
    6.1.3  Probe Extension. Any suitable rigid probe extension may be 
used after the filter holder.
    6.1.4  Pitot Tube. Same as in Method 5, Section 6.1.3.
    6.1.4.1  It is recommended (1) that the pitot tube have a known 
baseline coefficient, determined as outlined in Section 10 of Method 2; 
and (2) that this known coefficient be preserved by placing the pitot 
tube in an interference-free arrangement with respect to the sampling 
nozzle, filter holder, and temperature sensor (see Figure 17-1). Note 
that the 1.9 cm (\3/4\-in.) free-space between the nozzle and pitot 
tube shown in Figure 17-1, is based on a 1.3 cm (\1/2\-in.) ID nozzle. 
If the sampling train is designed for sampling at higher flow rates 
than that described in APTD-0581, thus necessitating the use of larger 
sized nozzles, the free-space shall be 1.9 cm (\3/4\-in.) with the 
largest sized nozzle in place.
    6.1.4.2  Source-sampling assemblies that do not meet the minimum 
spacing requirements of Figure 17-1 (or the equivalent of these 
requirements, e.g., Figure 2-4 of Method 2) may be used; however, the 
pitot tube coefficients of such assemblies shall be determined by 
calibration, using methods subject to the approval of the 
Administrator.
    6.1.5  Condenser. It is recommended that the impinger system or 
alternatives described in Method 5 be used to determine the moisture 
content of the stack gas. Flexible tubing may be used between the probe 
extension and condenser. Long tubing lengths may affect the moisture 
determination.
    6.2  Sample Recovery. Probe-liner and probe-nozzle brushes, wash 
bottles, glass sample storage containers, petri dishes, graduated 
cylinder and/or balance, plastic storage containers, funnel and rubber 
policeman, funnel. Same as in Method 5, Sections 6.2.1 through 6.2.8, 
respectively.
    6.3  Sample Analysis. Glass weighing dishes, desiccator, analytical 
balance, balance, beakers, hygrometer, temperature sensor. Same as in 
Method 5, Sections 6.3.1 through 6.3.7, respectively.

7.0  Reagents and Standards

    7.1  Sampling. Filters, silica gel, water, crushed ice, stopcock 
grease. Same as in Method 5, Sections 7.1.1, 7.1.2, 7.1.3, 7.1.4, and 
7.1.5, respectively. Thimble glass fiber filters may also be used.
    7.2  Sample Recovery. Acetone (reagent grade). Same as in Method 5, 
Section 7.2.
    7.3  Sample Analysis. Acetone and Desiccant. Same as in Method 5, 
Sections 7.3.1 and 7.3.2, respectively.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Sampling.
    8.1.1  Pretest Preparation. Same as in Method 5, Section 8.1.1.
    8.1.2  Preliminary Determinations. Same as in Method 5, Section 
8.1.2, except as follows: Make a projected-area model of the probe 
extension-filter holder assembly, with the pitot tube face openings 
positioned along the centerline of the stack, as shown in Figure 17-2. 
Calculate the estimated cross-section blockage, as shown in Figure 17-
2. If the blockage exceeds 5 percent of the duct cross sectional area, 
the tester has the following options exist: (1) a suitable out-of-stack 
filtration

[[Page 62004]]

method may be used instead of in-stack filtration; or (2) a special in-
stack arrangement, in which the sampling and velocity measurement sites 
are separate, may be used; for details concerning this approach, 
consult with the Administrator (see also Reference 1 in Section 17.0). 
Select a probe extension length such that all traverse points can be 
sampled. For large stacks, consider sampling from opposite sides of the 
stack to reduce the length of probes.
    8.1.3  Preparation of Sampling Train. Same as in Method 5, Section 
8.1.3, except the following: Using a tweezer or clean disposable 
surgical gloves, place a labeled (identified) and weighed filter in the 
filter holder. Be sure that the filter is properly centered and the 
gasket properly placed so as not to allow the sample gas stream to 
circumvent the filter. Check filter for tears after assembly is 
completed. Mark the probe extension with heat resistant tape or by some 
other method to denote the proper distance into the stack or duct for 
each sampling point. Assemble the train as in Figure 17-1, using a very 
light coat of silicone grease on all ground glass joints and greasing 
only the outer portion (see APTD-0576) to avoid possibility of 
contamination by the silicone grease. Place crushed ice around the 
impingers.
    8.1.4  Leak-Check Procedures. Same as in Method 5, Section 8.1.4, 
except that the filter holder is inserted into the stack during the 
sampling train leak-check. To do this, plug the inlet to the probe 
nozzle with a material that will be able to withstand the stack 
temperature. Insert the filter holder into the stack and wait 
approximately 5 minutes (or longer, if necessary) to allow the system 
to come to equilibrium with the temperature of the stack gas stream.
    8.1.5  Sampling Train Operation. The operation is the same as in 
Method 5. Use a data sheet such as the one shown in Figure 5-3 of 
Method 5, except that the filter holder temperature is not recorded.
    8.1.6  Calculation of Percent Isokinetic. Same as in Method 5, 
Section 12.11.
    8.2  Sample Recovery.
    8.2.1  Proper cleanup procedure begins as soon as the probe 
extension assembly is removed from the stack at the end of the sampling 
period. Allow the assembly to cool.
    8.2.2  When the assembly can be safely handled, wipe off all 
external particulate matter near the tip of the probe nozzle and place 
a cap over it to prevent losing or gaining particulate matter. Do not 
cap off the probe tip tightly while the sampling train is cooling down 
as this would create a vacuum in the filter holder, forcing condenser 
water backward.
    8.2.3  Before moving the sample train to the cleanup site, 
disconnect the filter holder-probe nozzle assembly from the probe 
extension; cap the open inlet of the probe extension. Be careful not to 
lose any condensate, if present. Remove the umbilical cord from the 
condenser outlet and cap the outlet. If a flexible line is used between 
the first impinger (or condenser) and the probe extension, disconnect 
the line at the probe extension and let any condensed water or liquid 
drain into the impingers or condenser. Disconnect the probe extension 
from the condenser; cap the probe extension outlet. After wiping off 
the silicone grease, cap off the condenser inlet. Ground glass 
stoppers, plastic caps, or serum caps (whichever are appropriate) may 
be used to close these openings.
    8.2.4  Transfer both the filter holder-probe nozzle assembly and 
the condenser to the cleanup area. This area should be clean and 
protected from the wind so that the chances of contaminating or losing 
the sample will be minimized.
    8.2.5  Save a portion of the acetone used for cleanup as a blank. 
Take 200 ml of this acetone from the wash bottle being used and place 
it in a glass sample container labeled ``acetone blank.'' Inspect the 
train prior to and during disassembly and not any abnormal conditions. 
Treat the sample as discussed in Method 5, Section 8.2.

9.0  Quality Control. [Reserved]

10.0  Calibration and Standardization

    The calibrations of the probe nozzle, pitot tube, metering system, 
temperature sensors, and barometer are the same as in Method 5, 
Sections 10.1 through 10.3, 10.5, and 10.6, respectively.

11.0  Analytical Procedure

    Same as in Method 5, Section 11.0. Analytical data should be 
recorded on a form similar to that shown in Figure 5-6 of Method 5.

12.0  Data Analysis and Calculations.

    Same as in Method 5, Section 12.0.

13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  Alternative Procedures

    Same as in Method 5, Section 16.0.

17.0  References

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

    1. Vollaro, R.F. Recommended Procedure for Sample Traverses in 
Ducts Smaller than 12 Inches in Diameter. U.S. Environmental 
Protection Agency, Emission Measurement Branch. Research Triangle 
Park, NC. November 1976.
BILLING CODE 6560-50-P

[[Page 62005]]

18.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.302


[[Page 62006]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.303

BILLING CODE 6560-50-C

[[Page 62007]]

Method 18--Measurement of Gaseous Organic Compound Emissions By Gas 
Chromatography

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


    Note:
    This method should not be attempted by persons unfamiliar with 
the performance characteristics of gas chromatography, nor by those 
persons who are unfamiliar with source sampling. Particular care 
should be exercised in the area of safety concerning choice of 
equipment and operation in potentially explosive atmospheres.

1.0  Scope and Application

    1.1  Analyte. Total gaseous organic compounds.
    1.2  Applicability.
    1.2.1  This method is designed to measure gaseous organics emitted 
from an industrial source. While designed for ppm level sources, some 
detectors are quite capable of detecting compounds at ambient levels, 
e.g., ECD, ELCD, and helium ionization detectors. Some other types of 
detectors are evolving such that the sensitivity and applicability may 
well be in the ppb range in only a few years.
    1.2.2  This method will not determine compounds that (1) are 
polymeric (high molecular weight), (2) can polymerize before analysis, 
or (3) have very low vapor pressures at stack or instrument conditions.
    1.3  Range. The lower range of this method is determined by the 
sampling system; adsorbents may be used to concentrate the sample, thus 
lowering the limit of detection below the 1 part per million (ppm) 
typically achievable with direct interface or bag sampling. The upper 
limit is governed by GC detector saturation or column overloading; the 
upper range can be extended by dilution of sample with an inert gas or 
by using smaller volume gas sampling loops. The upper limit can also be 
governed by condensation of higher boiling compounds.
    1.4  Sensitivity. The sensitivity limit for a compound is defined 
as the minimum detectable concentration of that compound, or the 
concentration that produces a signal-to-noise ratio of three to one. 
The minimum detectable concentration is determined during the presurvey 
calibration for each compound.

2.0  Summary of Method

    The major organic components of a gas mixture are separated by gas 
chromatography (GC) and individually quantified by flame ionization, 
photoionization, electron capture, or other appropriate detection 
principles. The retention times of each separated component are 
compared with those of known compounds under identical conditions. 
Therefore, the analyst confirms the identity and approximate 
concentrations of the organic emission components beforehand. With this 
information, the analyst then prepares or purchases commercially 
available standard mixtures to calibrate the GC under conditions 
identical to those of the samples. The analyst also determines the need 
for sample dilution to avoid detector saturation, gas stream filtration 
to eliminate particulate matter, and prevention of moisture 
condensation.

3.0  Definitions. [Reserved]

4.0  Interferences

    4.1  Resolution interferences that may occur can be eliminated by 
appropriate GC column and detector choice or by shifting the retention 
times through changes in the column flow rate and the use of 
temperature programming.
    4.2  The analytical system is demonstrated to be essentially free 
from contaminants by periodically analyzing blanks that consist of 
hydrocarbon-free air or nitrogen.
    4.3  Sample cross-contamination that occurs when high-level and 
low-level samples or standards are analyzed alternately is best dealt 
with by thorough purging of the GC sample loop between samples.
    4.4  To assure consistent detector response, calibration gases are 
contained in dry air. To adjust gaseous organic concentrations when 
water vapor is present in the sample, water vapor concentrations are 
determined for those samples, and a correction factor is applied.
    4.5  The gas chromatograph run time must be sufficient to clear all 
eluting peaks from the column before proceeding to the next run (in 
order to prevent sample carryover).

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method. The analyzer users manual should 
be consulted for specific precautions to be taken with regard to the 
analytical procedure.

6.0  Equipment and Supplies

    6.1  Equipment needed for the presurvey sampling procedure can be 
found in Section 16.1.1.
    6.2  Equipment needed for the integrated bag sampling and analysis 
procedure can be found in Section 8.2.1.1.1.
    6.3  Equipment needed for direct interface sampling and analysis 
can be found in Section 8.2.2.1.
    6.4  Equipment needed for the dilution interface sampling and 
analysis can be found in Section 8.2.3.1.
    6.5  Equipment needed for adsorbent tube sampling and analysis can 
be found in Section 8.2.4.1.

7.0  Reagents and Standards

    7.1  Reagents needed for the presurvey sampling procedure can be 
found in Section 16.1.2.
    7.2  Quality Assurance Audit Samples. When making compliance 
determinations, and upon availability, an audit sample may be obtained 
from the appropriate EPA Regional Office or from the responsible 
enforcement authority.

    Note: The responsible enforcement autority should be notified at 
least 30 days prior to the test date to allow sufficient time for 
sample delivery.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.2  Final Sampling and Analysis Procedure. Considering safety 
(flame hazards) and the source conditions, select an appropriate 
sampling and analysis procedure (Section 8.2.1, 8.2.2, 8.2.3 or 8.2.4). 
In situations where a hydrogen flame is a hazard and no intrinsically 
safe GC is suitable, use the flexible bag collection technique or an 
adsorption technique.
    8.2.1  Integrated Bag Sampling and Analysis.
    8.2.1.1  Evacuated Container Sampling Procedure. In this procedure, 
the bags are filled by evacuating the rigid air-tight container holding 
the bags. Use a field sample data sheet as shown in Figure 18-10. 
Collect triplicate samples from each sample location.
    8.2.1.1.1  Apparatus.
    8.2.1.1.1.1  Probe. Stainless steel, Pyrex glass, or Teflon tubing 
probe, according to the duct temperature, with Teflon tubing of 
sufficient length to connect to the sample bag. Use stainless

[[Page 62008]]

steel or Teflon unions to connect probe and sample line.
    8.2.1.1.1.2  Quick Connects. Male (2) and female (2) of stainless 
steel construction.
    8.2.1.1.1.3  Needle Valve. To control gas flow.
    8.2.1.1.1.4  Pump. Leakless Teflon-coated diaphragm-type pump or 
equivalent. To deliver at least 1 liter/min.
    8.2.1.1.1.5  Charcoal Adsorption Tube. Tube filled with activated 
charcoal, with glass wool plugs at each end, to adsorb organic vapors.
    8.2.1.1.1.6  Flowmeter. 0 to 500-ml flow range; with manufacturer's 
calibration curve.
    8.2.1.1.2  Sampling Procedure. To obtain a sample, assemble the 
sample train as shown in Figure 18-9. Leak-check both the bag and the 
container. Connect the vacuum line from the needle valve to the Teflon 
sample line from the probe. Place the end of the probe at the centroid 
of the stack or at a point no closer to the walls than 1 m, and start 
the pump. Set the flow rate so that the final volume of the sample is 
approximately 80 percent of the bag capacity. After allowing sufficient 
time to purge the line several times, connect the vacuum line to the 
bag, and evacuate until the rotameter indicates no flow. Then position 
the sample and vacuum lines for sampling, and begin the actual 
sampling, keeping the rate proportional to the stack velocity. As a 
precaution, direct the gas exiting the rotameter away from sampling 
personnel. At the end of the sample period, shut off the pump, 
disconnect the sample line from the bag, and disconnect the vacuum line 
from the bag container. Record the source temperature, barometric 
pressure, ambient temperature, sampling flow rate, and initial and 
final sampling time on the data sheet shown in Figure 18-10. Protect 
the Tedlar bag and its container from sunlight. Record the time lapsed 
between sample collection and analysis, and then conduct the recovery 
procedure in Section 8.4.2.
    8.2.1.2  Direct Pump Sampling Procedure. Follow 8.2.1.1, except 
place the pump and needle valve between the probe and the bag. Use a 
pump and needle valve constructed of inert material not affected by the 
stack gas. Leak-check the system, and then purge with stack gas before 
connecting to the previously evacuated bag.
    8.2.1.3  Explosion Risk Area Bag Sampling Procedure. Follow 8.2.1.1 
except replace the pump with another evacuated can (see Figure 18-9a). 
Use this method whenever there is a possibility of an explosion due to 
pumps, heated probes, or other flame producing equipment.
    8.2.1.4  Other Modified Bag Sampling Procedures. In the event that 
condensation is observed in the bag while collecting the sample and a 
direct interface system cannot be used, heat the bag during collection, 
and maintain it at a suitably elevated temperature during all 
subsequent operations. (Note: Take care to leak-check the system prior 
to the dilutions so as not to create a potentially explosive 
atmosphere.) As an alternative, collect the sample gas, and 
simultaneously dilute it in the Tedlar bag.
    8.2.1.4.1  First Alternative Procedure. Heat the box containing the 
sample bag to 120  deg.C (5  deg.C). Then transport the bag 
as rapidly as possible to the analytical area while maintaining the 
heating, or cover the box with an insulating blanket. In the analytical 
area, keep the box heated to 120  deg.C (5  deg.C) until 
analysis. Be sure that the method of heating the box and the control 
for the heating circuit are compatible with the safety restrictions 
required in each area.
    8.2.1.4.2  Second Alternative Procedure. Prefill the Tedlar bag 
with a known quantity of inert gas. Meter the inert gas into the bag 
according to the procedure for the preparation of gas concentration 
standards of volatile liquid materials (Section 10.1.2.2), but 
eliminate the midget impinger section. Take the partly filled bag to 
the source, and meter the source gas into the bag through heated 
sampling lines and a heated flowmeter, or Teflon positive displacement 
pump. Verify the dilution factors before sampling each bag through 
dilution and analysis of gases of known concentration.
    8.2.1.5  Analysis of Bag Samples.
    8.2.1.5.1  Apparatus. Same as Section 8.1. A minimum of three gas 
standards are required.
    8.2.1.5.2  Procedure.
    8.2.1.5.2.1  Establish proper GC operating conditions as described 
in Section 10.2, and record all data listed in Figure 18-7. Prepare the 
GC so that gas can be drawn through the sample valve. Flush the sample 
loop with calibration gas mixture, and activate the valve (sample 
pressure at the inlet to the GC introduction valve should be similar 
during calibration as during actual sample analysis). Obtain at least 
three chromatograms for the mixture. The results are acceptable when 
the peak areas for the three injections agree to within 5 percent of 
their average. If they do not agree, run additional samples or correct 
the analytical techniques until this requirement is met. Then analyze 
the other two calibration mixtures in the same manner. Prepare a 
calibration curve as described in Section 10.2.
    8.2.1.5.2.2  Analyze the two field audit samples as described in 
Section 9.2 by connecting each Tedlar bag containing an audit gas 
mixture to the sampling valve. Calculate the results; record and report 
the data to the audit supervisor.
    8.2.1.5.2.3  Analyze the three source gas samples by connecting 
each bag to the sampling valve with a piece of Teflon tubing identified 
with that bag. Analyze each bag sample three times. Record the data in 
Figure 18-11. If certain items do not apply, use the notation ``N.A.'' 
If the bag has been maintained at an elevated temperature as described 
in Section 8.2.1.4, determine the stack gas water content by Method 4. 
After all samples have been analyzed, repeat the analysis of the mid-
level calibration gas for each compound. Compare the average response 
factor of the pre- and post-test analysis for each compound. If they 
differ by >5percent, analyze the other calibration gas levels for that 
compound, and prepare a calibration curve using all the pre- and post-
test calibration gas mixture values. If the two response factor 
averages (pre-and post-test) differ by less than 5 percent from their 
mean value, the tester has the option of using only the pre-test 
calibration curve to generate the concentration values.
    8.2.1.6  Determination of Bag Water Vapor Content. Measure the 
ambient temperature and barometric pressure near the bag. From a water 
saturation vapor pressure table, determine and record the water vapor 
content of the bag as a decimal figure. (Assume the relative humidity 
to be 100 percent unless a lesser value is known.) If the bag has been 
maintained at an elevated temperature as described in Section 8.2.1.4, 
determine the stack gas water content by Method 4.
    8.2.1.7  Audit Gas Analysis. Immediately prior to the analysis of 
the stack gas samples, perform audit analyses as described in Section 
9.2.
    8.2.1.8  Emission Calculations. From the calibration curve 
described in Section 8.2.1.5, select the value of Cs that 
corresponds to the peak area. Calculate the concentration Cc 
in ppm, dry basis, of each organic in the sample using Equation 18-5 in 
Section 12.6.
    8.2.2  Direct Interface Sampling and Analysis Procedure. The direct 
interface procedure can be used provided that the moisture content of 
the gas does not interfere with the analysis procedure, the physical 
requirements of the equipment can be met at the site, and the source 
gas concentration falls within the linear range of the detector. Adhere

[[Page 62009]]

to all safety requirements with this method.
    8.2.2.1  Apparatus.
    8.2.2.1.1  Probe. Constructed of stainless steel, Pyrex glass, or 
Teflon tubing as dictated by duct temperature and reactivity of target 
compounds. A filter or glass wool plug may be needed if particulate is 
present in the stack gas. If necessary, heat the probe with heating 
tape or a special heating unit capable of maintaining a temperature 
greater than 110  deg.C.
    8.2.2.1.2  Sample Lines. 6.4-mm OD (or other diameter as needed) 
Teflon lines, heat-traced to prevent condensation of material (greater 
than 110  deg.C).
    8.2.2.1.3  Quick Connects. To connect sample line to gas sampling 
valve on GC instrument and to pump unit used to withdraw source gas. 
Use a quick connect or equivalent on the cylinder or bag containing 
calibration gas to allow connection of the calibration gas to the gas 
sampling valve.
    8.2.2.1.4  Thermocouple Readout Device. Potentiometer or digital 
thermometer, to measure source temperature and probe temperature.
    8.2.2.1.5  Heated Gas Sampling Valve. Of two-position, six-port 
design, to allow sample loop to be purged with source gas or to direct 
source gas into the GC instrument.
    8.2.2.1.6  Needle Valve. To control gas sampling rate from the 
source.
    8.2.2.1.7  Pump. Leakless Teflon-coated diaphragm-type pump or 
equivalent, capable of at least 1 liter/minute sampling rate.
    8.2.2.1.8  Flowmeter. Of suitable range to measure sampling rate.
    8.2.2.1.9  Charcoal Adsorber. To adsorb organic vapor vented from 
the source to prevent exposure of personnel to source gas.
    8.2.2.1.10  Gas Cylinders. Carrier gas, oxygen and fuel as needed 
to run GC and detector.
    8.2.2.1.11  Gas Chromatograph. Capable of being moved into the 
field, with detector, heated gas sampling valve, column required to 
complete separation of desired components, and option for temperature 
programming.
    8.2.2.1.12  Recorder/Integrator. To record results.
    8.2.2.2  Procedure. Calibrate the GC using the procedures in 
Section 8.2.1.5.2.1. To obtain a stack gas sample, assemble the 
sampling system as shown in Figure 18-12. Make sure all connections are 
tight. Turn on the probe and sample line heaters. As the temperature of 
the probe and heated line approaches the target temperature as 
indicated on the thermocouple readout device, control the heating to 
maintain a temperature greater than 110  deg.C. Conduct a 3-point 
calibration of the GC by analyzing each gas mixture in triplicate. 
Generate a calibration curve. Place the inlet of the probe at the 
centroid of the duct, or at a point no closer to the walls than 1 m, 
and draw source gas into the probe, heated line, and sample loop. After 
thorough flushing, analyze the stack gas sample using the same 
conditions as for the calibration gas mixture. For each run, sample, 
analyze, and record five consecutive samples. A test consists of three 
runs (five samples per run times three runs, for a total of fifteen 
samples). After all samples have been analyzed, repeat the analysis of 
the mid-level calibration gas for each compound. For each calibration 
standard, compare the pre- and post-test average response factors (RF) 
for each compound. If the two calibration RF values (pre- and post-
analysis) differ by more than 5 percent from their mean value, then 
analyze the other calibration gas levels for that compound and 
determine the stack gas sample concentrations by comparison to both 
calibration curves (this is done by preparing a calibration curve using 
all the pre and post-test calibration gas mixture values). If the two 
calibration RF values differ by less than 5 percent from their mean 
value, the tester has the option of using only the pre-test calibration 
curve to generate the concentration values. Record this calibration 
data and the other required data on the data sheet shown in Figure 18-
11, deleting the dilution gas information.

    Note: Take care to draw all samples, calibration mixtures, and 
audits through the sample loop at the same pressure.

    8.2.2.3  Determination of Stack Gas Moisture Content. Use Method 4 
to measure the stack gas moisture content.
    8.2.2.4  Quality Assurance. Same as Section 8.2.1.7. Introduce the 
audit gases in the sample line immediately following the probe.
    8.2.2.5  Emission Calculations. Same as Section 8.2.1.8.
    8.2.3  Dilution Interface Sampling and Analysis Procedure. Source 
samples that contain a high concentration of organic materials may 
require dilution prior to analysis to prevent saturating the GC 
detector. The apparatus required for this direct interface procedure is 
basically the same as that described in the Section 8.2.2, except a 
dilution system is added between the heated sample line and the gas 
sampling valve. The apparatus is arranged so that either a 10:1 or 
100:1 dilution of the source gas can be directed to the chromatograph. 
A pump of larger capacity is also required, and this pump must be 
heated and placed in the system between the sample line and the 
dilution apparatus.
    8.2.3.1  Apparatus. The equipment required in addition to that 
specified for the direct interface system is as follows:
    8.2.3.1.1  Sample Pump. Leakless Teflon-coated diaphragm-type that 
can withstand being heated to 120 deg.C and deliver 1.5 liters/minute.
    8.2.3.1.2  Dilution Pumps. Two Model A-150 Komhyr Teflon positive 
displacement type delivering 150 cc/minute, or equivalent. As an 
option, calibrated flowmeters can be used in conjunction with Teflon-
coated diaphragm pumps.
    8.2.3.1.3  Valves. Two Teflon three-way valves, suitable for 
connecting to Teflon tubing.
    8.2.3.1.4  Flowmeters. Two, for measurement of diluent gas.
    8.2.3.1.5  Diluent Gas with Cylinders and Regulators. Gas can be 
nitrogen or clean dry air, depending on the nature of the source gases.
    8.2.3.1.6  Heated Box. Suitable for being heated to 120  deg.C, to 
contain the three pumps, three-way valves, and associated connections. 
The box should be equipped with quick connect fittings to facilitate 
connection of: (1) the heated sample line from the probe, (2) the gas 
sampling valve, (3) the calibration gas mixtures, and (4) diluent gas 
lines. A schematic diagram of the components and connections is shown 
in Figure 18-13. The heated box shown in Figure 18-13 is designed to 
receive a heated line from the probe. An optional design is to build a 
probe unit that attaches directly to the heated box. In this way, the 
heated box contains the controls for the probe heaters, or, if the box 
is placed against the duct being sampled, it may be possible to 
eliminate the probe heaters. In either case, a heated Teflon line is 
used to connect the heated box to the gas sampling valve on the 
chromatograph.

    Note: Care must be taken to leak-check the system prior to the 
dilutions so as not to create a potentially explosive atmosphere.

    8.2.3.2  Procedure.
    8.2.3.2.1  Assemble the apparatus by connecting the heated box, 
shown in Figure 18-13, between the heated sample line from the probe 
and the gas sampling valve on the chromatograph. Vent the source gas 
from the gas sampling valve directly to the charcoal filter, 
eliminating the pump and rotameter. Heat the sample probe, sample line, 
and heated box. Insert the probe and source thermocouple at the 
centroid of the duct, or to a point no closer to the walls than 1 m. 
Measure the source temperature, and adjust all

[[Page 62010]]

heating units to a temperature 0 to 3 deg.C above this temperature. If 
this temperature is above the safe operating temperature of the Teflon 
components, adjust the heating to maintain a temperature high enough to 
prevent condensation of water and organic compounds (greater than 110 
deg.C). Calibrate the GC through the dilution system by following the 
procedures in Section 8.2.1.5.2.1. Determine the concentration of the 
diluted calibration gas using the dilution factor and the certified 
concentration of the calibration gas. Record the pertinent data on the 
data sheet shown in Figure 18-11.
    8.2.3.2.2  Once the dilution system and GC operations are 
satisfactory, proceed with the analysis of source gas, maintaining the 
same dilution settings as used for the standards.
    8.2.3.2.3  Analyze the audit samples using either the dilution 
system, or directly connect to the gas sampling valve as required. 
Record all data and report the results to the audit supervisor.
    8.2.3.3  Determination of Stack Gas Moisture Content. Same as 
Section 8.2.2.3.
    8.2.3.4  Quality Assurance. Same as Section 8.2.2.4.
    8.2.3.5  Emission Calculations. Same as section 8.2.2.5, with the 
dilution factor applied.
    8.2.4  Adsorption Tube Procedure. Any commercially available 
adsorbent is allowed for the purposes of this method, as long as the 
recovery study criteria in Section 8.4.3 are met. Help in choosing the 
adsorbent may be found by calling the distributor, or the tester may 
refer to National Institute for Occupational Safety and Health (NIOSH) 
methods for the particular organics to be sampled. For some adsorbents, 
the principal interferent will be water vapor. If water vapor is 
thought to be a problem, the tester may place a midget impinger in an 
ice bath before the adsorbent tubes. If this option is chosen, the 
water catch in the midget impinger shall be analyzed for the target 
compounds. Also, the spike for the recovery study (in Section 8.4.3) 
shall be conducted in both the midget impinger and the adsorbent tubes. 
The combined recovery (add the recovered amount in the impinger and the 
adsorbent tubes to calculate R) shall then meet the criteria in Section 
8.4.3.

    Note: Post-test leak-checks are not allowed for this technique 
since this can result in sample contamination.

    8.2.4.1  Additional Apparatus. The following items (or equivalent) 
are suggested.
    8.2.4.1.1  Probe. Borosilicate glass or stainless steel, 
approximately 6-mm ID, with a heating system if water condensation is a 
problem, and a filter (either in-stack or out-of-stack, heated to stack 
temperature) to remove particulate matter. In most instances, a plug of 
glass wool is a satisfactory filter.
    8.2.4.1.2  Flexible Tubing. To connect probe to adsorption tubes. 
Use a material that exhibits minimal sample adsorption.
    8.2.4.1.3  Leakless Sample Pump. Flow controlled, constant rate 
pump, with a set of limiting (sonic) orifices.
    8.2.4.1.4  Bubble-Tube Flowmeter. Volume accuracy within 1 percent, 
to calibrate pump.
    8.2.4.1.5  Stopwatch. To time sampling and pump rate calibration.
    8.2.4.1.6  Adsorption Tubes. Precleaned adsorbent, with mass of 
adsorbent to be determined by calculating breakthrough volume and 
expected concentration in the stack.
    8.2.4.1.7  Barometer. Accurate to 5 mm Hg, to measure atmospheric 
pressure during sampling and pump calibration.
    8.2.4.1.8  Rotameter. O to 100 cc/min, to detect changes in flow 
rate during sampling.
    8.2.4.2  Sampling and Analysis.
    8.2.4.2.1  Calibrate the pump and limiting orifice flow rate 
through adsorption tubes with the bubble tube flowmeter before 
sampling. The sample system can be operated as a ``recirculating loop'' 
for this operation. Record the ambient temperature and barometric 
pressure. Then, during sampling, use the rotameter to verify that the 
pump and orifice sampling rate remains constant.
    8.2.4.2.2  Use a sample probe, if required, to obtain the sample at 
the centroid of the duct, or at a point no closer to the walls than 1 
m. Minimize the length of flexible tubing between the probe and 
adsorption tubes. Several adsorption tubes can be connected in series, 
if the extra adsorptive capacity is needed. Adsorption tubes should be 
maintained vertically during the test in order to prevent channeling. 
Provide the gas sample to the sample system at a pressure sufficient 
for the limiting orifice to function as a sonic orifice. Record the 
total time and sample flow rate (or the number of pump strokes), the 
barometric pressure, and ambient temperature. Obtain a total sample 
volume commensurate with the expected concentration(s) of the volatile 
organic(s) present, and recommended sample loading factors (weight 
sample per weight adsorption media). Laboratory tests prior to actual 
sampling may be necessary to predetermine this volume. If water vapor 
is present in the sample at concentrations above 2 to 3 percent, the 
adsorptive capacity may be severely reduced. Operate the gas 
chromatograph according to the manufacturer's instructions. After 
establishing optimum conditions, verify and document these conditions 
during all operations. Calibrate the instrument. Analyze the audit 
samples (see Section 16.1.4.3), then the emission samples.
    8.2.4.3  Standards and Calibration. If using thermal desorption, 
obtain calibration gases using the procedures in Section 10.1. If using 
solvent extraction, prepare liquid standards in the desorption solvent. 
Use a minimum of three different standards; select the concentrations 
to bracket the expected average sample concentration. Perform the 
calibration before and after each day's sample analyses using the 
procedures in Section 8.2.1.5.2.1.
    8.2.4.4  Quality Assurance.
    8.2.4.4.1  Determine the recovery efficiency of the pollutants of 
interest according to Section 8.4.3.
    8.2.4.4.2  Determination of Sample Collection Efficiency 
(Optional). If sample breakthrough is thought to be a problem, a 
routine procedure for determining breakthrough is to analyze the 
primary and backup portions of the adsorption tubes separately. If the 
backup portion exceeds 10 percent of the total amount (primary and 
back-up), it is usually a sign of sample breakthrough. For the purposes 
of this method, only the recovery efficiency value (Section 8.4.3) is 
used to determine the appropriateness of the sampling and analytical 
procedure.
    8.2.4.4.3  Volume Flow Rate Checks. Perform this check immediately 
after sampling with all sampling train components in place. Use the 
bubble-tube flowmeter to measure the pump volume flow rate with the 
orifice used in the test sampling, and record the result. If it has 
changed by more than 5 but less than 20 percent, calculate an average 
flow rate for the test. If the flow rate has changed by more than 20 
percent, recalibrate the pump and repeat the sampling.
    8.2.4.4.4  Calculations. Correct all sample volumes to standard 
conditions. If a sample dilution system has been used, multiply the 
results by the appropriate dilution ratio. Correct all results 
according to the applicable procedure in Section 8.4.3. Report results 
as ppm by volume, dry basis.
    8.3  Reporting of Results. At the completion of the field analysis 
portion of the study, ensure that the data sheets shown in Figure 18-11 
have been completed. Summarize this data on the data sheets shown in 
Figure 18-15.
    8.4  Recovery Study. After conducting the presurvey and

[[Page 62011]]

identifying all of the pollutants of interest, conduct the appropriate 
recovery study during the test based on the sampling system chosen for 
the compounds of interest.
    8.4.1  Recovery Study for Direct Interface or Dilution Interface 
Sampling. If the procedures in Section 8.2.2 or 8.2.3 are to be used to 
analyze the stack gas, conduct the calibration procedure as stated in 
Section 8.2.2.2 or 8.2.3.2, as appropriate. Upon successful completion 
of the appropriate calibration procedure, attach the mid-level 
calibration gas for at least one target compound to the inlet of the 
probe or as close as possible to the inlet of the probe, but before the 
filter. Repeat the calibration procedure by sampling and analyzing the 
mid-level calibration gas through the entire sampling and analytical 
system in triplicate. The mean of the calibration gas response sampled 
through the probe shall be within 10 percent of the analyzer response. 
If the difference in the two means is greater than 10 percent, check 
for leaks throughout the sampling system and repeat the analysis of the 
standard through the sampling system until this criterion is met.
    8.4.2  Recovery Study for Bag Sampling.
    8.4.2.1  Follow the procedures for the bag sampling and analysis in 
Section 8.2.1. After analyzing all three bag samples, choose one of the 
bag samples and tag this bag as the spiked bag. Spike the chosen bag 
sample with a known mixture (gaseous or liquid) of all of the target 
pollutants. The theoretical concentration, in ppm, of each spiked 
compound in the bag shall be 40 to 60 percent of the average 
concentration measured in the three bag samples. If a target compound 
was not detected in the bag samples, the concentration of that compound 
to be spiked shall be 5 times the limit of detection for that compound. 
Store the spiked bag for the same period of time as the bag samples 
collected in the field. After the appropriate storage time has passed, 
analyze the spiked bag three times. Calculate the average fraction 
recovered (R) of each spiked target compound with the equation in 
Section 12.7.
    8.4.2.2  For the bag sampling technique to be considered valid for 
a compound, 0.70  R  1.30. If the R value does 
not meet this criterion for a target compound, the sampling technique 
is not acceptable for that compound, and therefore another sampling 
technique shall be evaluated for acceptance (by repeating the recovery 
study with another sampling technique). Report the R value in the test 
report and correct all field measurements with the calculated R value 
for that compound by using the equation in Section 12.8.
    8.4.3  Recovery Study for Adsorption Tube Sampling. If following 
the adsorption tube procedure in Section 8.2.4, conduct a recovery 
study of the compounds of interest during the actual field test. Set up 
two identical sampling trains. Collocate the two sampling probes in the 
stack. The probes shall be placed in the same horizontal plane, where 
the first probe tip is 2.5 cm from the outside edge of the other. One 
of the sampling trains shall be designated the spiked train and the 
other the unspiked train. Spike all of the compounds of interest (in 
gaseous or liquid form) onto the adsorbent tube(s) in the spiked train 
before sampling. The mass of each spiked compound shall be 40 to 60 
percent of the mass expected to be collected with the unspiked train. 
Sample the stack gas into the two trains simultaneously. Analyze the 
adsorbents from the two trains utilizing identical analytical 
procedures and instrumentation. Determine the fraction of spiked 
compound recovered (R) using the equations in Section 12.9.
    8.4.3.1  Repeat the procedure in Section 8.4.3 twice more, for a 
total of three runs. In order for the adsorbent tube sampling and 
analytical procedure to be acceptable for a compound, 
0.70R1.30 (R in this case is the average of three 
runs). If the average R value does not meet this criterion for a target 
compound, the sampling technique is not acceptable for that compound, 
and therefore another sampling technique shall be evaluated for 
acceptance (by repeating the recovery study with another sampling 
technique). Report the R value in the test report and correct all field 
measurements with the calculated R value for that compound by using the 
equation in Section 12.8.

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.4.1.........................  Recovery study     Ensure that there are
                                 for direct         no significant leaks
                                 interface or       in the sampling
                                 dilution           system.
                                 interface
                                 sampling.
8.4.2.........................  Recovery study     Demonstrate that
                                 for bag sampling.  proper sampling/
                                                    analysis procedures
                                                    were selected.
8.4.3.........................  Recovery study     Demonstrate that
                                 for adsorption     proper sampling/
                                 tube sampling.     analysis procedures
                                                    were selected.
------------------------------------------------------------------------

    9.2  Quality Assurance for Laboratory Procedures. Immediately after 
the preparation of the calibration curves, the analysis audit described 
in 40 CFR Part 61, Appendix C, Procedure 2: ``Procedure for Field 
Auditing GC Analysis,'' should be performed if audit materials are 
available. The information required to document the analysis of the 
audit samples has been included on the example data sheets shown in 
Figures 18-3 and 18-7. The audit analyses should agree with the 
certified audit concentrations within 10 percent. Audit sample results 
shall be submitted according to directions provided with the audit 
samples.

10.0  Calibration and Standardization.

    10.1  Calibration Standards. Obtain calibration gas standards for 
each target compound to be analyzed. Commercial cylinder gases 
certified by the manufacturer to be accurate to within 1 percent of the 
certified label value are preferable, although cylinder gases certified 
by the manufacturer to 2 percent accuracy are allowed. Another option 
allowed by this method is for the tester to obtain high concentration 
certified cylinder gases and then use a dilution system meeting the 
requirements of Test Method 205, 40 CFR Part 51, Appendix M to make 
multi-level calibration gas standards. Prepare or obtain enough 
calibration standards so that there are three different concentrations 
of each organic compound expected to be measured in the source sample. 
For each organic compound, select those concentrations that bracket the 
concentrations expected in the source samples. A calibration standard 
may contain more than one organic compound. If samples are collected in 
adsorbent tubes and extracted using solvent extraction, prepare or 
obtain standards in the same solvent used for the sample extraction 
procedure. Verify the stability of all

[[Page 62012]]

standards for the time periods they are used.
    10.2  Preparation of Calibration Curves.
    10.2.1  Establish proper GC conditions, then flush the sampling 
loop for 30 seconds. Allow the sample loop pressure to equilibrate to 
atmospheric pressure, and activate the injection valve. Record the 
standard concentration, attenuator factor, injection time, chart speed, 
retention time, peak area, sample loop temperature, column temperature, 
and carrier gas flow rate. Analyze each standard in triplicate.
    10.2.2  Repeat this procedure for each standard. Prepare a 
graphical plot of concentration (Cs) versus the calibration 
area values. Perform a regression analysis, and draw the least square 
line.

11.0  Analytical Procedures

    11.1  Analysis Development
    11.1.1  Selection of GC Parameters
    11.1.1.1  Column Choice. Based on the initial contact with plant 
personnel concerning the plant process and the anticipated emissions, 
choose a column that provides good resolution and rapid analysis time. 
The choice of an appropriate column can be aided by a literature 
search, contact with manufacturers of GC columns, and discussion with 
personnel at the emission source.

    Note: Most column manufacturers keep excellent records on their 
products. Their technical service departments may be able to 
recommend appropriate columns and detector type for separating the 
anticipated compounds, and they may be able to provide information 
on interferences, optimum operating conditions, and column 
limitations. Plants with analytical laboratories may be able to 
provide information on their analytical procedures.

    11.1.1.2  Preliminary GC Adjustment. Using the standards and column 
obtained in Section 11.1.1.1, perform initial tests to determine 
appropriate GC conditions that provide good resolution and minimum 
analysis time for the compounds of interest.
    11.1.1.3  Preparation of Presurvey Samples. If the samples were 
collected on an adsorbent, extract the sample as recommended by the 
manufacturer for removal of the compounds with a solvent suitable to 
the type of GC analysis. Prepare other samples in an appropriate 
manner.
    11.1.1.4  Presurvey Sample Analysis.
    11.1.1.4.1  Before analysis, heat the presurvey sample to the duct 
temperature to vaporize any condensed material. Analyze the samples by 
the GC procedure, and compare the retention times against those of the 
calibration samples that contain the components expected to be in the 
stream. If any compounds cannot be identified with certainty by this 
procedure, identify them by other means such as GC/mass spectroscopy 
(GC/MS) or GC/infrared techniques. A GC/MS system is recommended.
    11.1.1.4.2  Use the GC conditions determined by the procedure of 
Section 11.1.1.2 for the first injection. Vary the GC parameters during 
subsequent injections to determine the optimum settings. Once the 
optimum settings have been determined, perform repeat injections of the 
sample to determine the retention time of each compound. To inject a 
sample, draw sample through the loop at a constant rate (100 ml/min for 
30 seconds). Be careful not to pressurize the gas in the loop. Turn off 
the pump and allow the gas in the sample loop to come to ambient 
pressure. Activate the sample valve, and record injection time, loop 
temperature, column temperature, carrier flow rate, chart speed, and 
attenuator setting. Calculate the retention time of each peak using the 
distance from injection to the peak maximum divided by the chart speed. 
Retention times should be repeatable within 0.5 seconds.
    11.1.1.4.3  If the concentrations are too high for appropriate 
detector response, a smaller sample loop or dilutions may be used for 
gas samples, and, for liquid samples, dilution with solvent is 
appropriate. Use the standard curves (Section 10.2) to obtain an 
estimate of the concentrations.
    11.1.1.4.4  Identify all peaks by comparing the known retention 
times of compounds expected to be in the retention times of peaks in 
the sample. Identify any remaining unidentified peaks which have areas 
larger than 5 percent of the total using a GC/MS, or estimation of 
possible compounds by their retention times compared to known 
compounds, with confirmation by further GC analysis.

12.0  Data Analysis and Calculations

    12.1  Nomenclature.

Bws = Water vapor content of the bag sample or stack gas, 
proportion by volume.
Cs = Concentration of the organic from the calibration 
curve, ppm.
Gv = Gas volume or organic compound injected, ml.
Lv = Liquid volume of organic injected, l.
M = Molecular weight of organic, g/g-mole.
ms = Total mass of compound measured on adsorbent with 
spiked train (g).
mu = Total mass of compound measured on adsorbent with 
unspiked train (g).
mv = Mass per volume of spiked compound measured 
(g/L).
Pi = Barometric or absolute sample loop pressure at time of 
sample analysis, mm Hg.
Pm = Absolute pressure of dry gas meter, mm Hg.
Pr = Reference pressure, the barometric pressure or absolute 
sample loop pressure recorded during calibration, mm Hg.
Ps = Absolute pressure of syringe before injection, mm Hg.
qc = Flow rate of the calibration gas to be diluted.
qc1 = Flow rate of the calibration gas to be diluted in 
stage 1.
qc2 = Flow rate of the calibration gas to be diluted in 
stage 2.
qd = Diluent gas flow rate.
qd1 = Flow rate of diluent gas in stage 1.
qd2 = Flow rate of diluent gas in stage 2.
s = Theoretical concentration (ppm) of spiked target compound in the 
bag.
S = Theoretical mass of compound spiked onto adsorbent in spiked train 
(g).
t = Measured average concentration (ppm) of target compound and source 
sample (analysis results subsequent to bag spiking)
Ti = Sample loop temperature at the time of sample analysis, 
 deg.K.
Tm = Absolute temperature of dry gas meter,  deg.K.
Ts = Absolute temperature of syringe before injection, 
deg.K.
u = Source sample average concentration (ppm) of target compound in the 
bag (analysis results before bag spiking).
Vm = Gas volume indicated by dry gas meter, liters.
vs = volume of stack gas sampled with spiked train (L).
vu = volume of stack gas sampled with unspiked train (L).
X = Mole or volume fraction of the organic in the calibration gas to be 
diluted.
Y = Dry gas meter calibration factor, dimensionless.
l = Liquid organic density as determined, g/ml.

24.055 = Ideal gas molar volume at 293  deg.K and 760 mm Hg, liters/g-
mole.

1000 = Conversion factor, ml/liter.
10\6\ = Conversion to ppm.

    12.2  Calculate the concentration, Cs, in ppm using the 
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.304


[[Page 62013]]


    12.3  Calculate the concentration, Cs, in ppm of the 
organic in the final gas mixture using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.305

    12.4  Calculate each organic standard concentration, Cs, 
in ppm using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.306

    12.5  Calculate each organic standard concentration, Cs, 
in ppm using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.307

    12.6  Calculate the concentration, Cc, in ppm, dry 
basis, of each organic is the sample using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.308

    12.7  Calculate the average fraction recovered (R) of each spiked 
target compound using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.309

    12.8  Correct all field measurements with the calculated R value 
for that compound using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.310

    12.9  Determine the mass per volume of spiked compound measured 
using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.311

    12.10  Calculate the fraction of spiked compound recovered, R, 
using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.312

13.0  Method Performance

    13.1  Since a potential sample may contain a variety of compounds 
from various sources, a specific precision limit for the analysis of 
field samples is impractical. Precision in the range of 5 to 10 percent 
relative standard deviation (RSD) is typical for gas chromatographic 
techniques, but an experienced GC operator with a reliable instrument 
can readily achieve 5 percent RSD. For this method, the following 
combined GC/operator values are required.
    (a)  Precision. Triplicate analyses of calibration standards fall 
within 5 percent of their mean value.
    (b)  Accuracy. Analysis results of prepared audit samples are 
within 10 percent of preparation values.
    (c)  Recovery. After developing an appropriate sampling and 
analytical system for the pollutants of interest, conduct the procedure 
in Section 8.4. Conduct the appropriate recovery study in Section 8.4 
at each sampling point where the method is being applied. Submit the 
data and results of the recovery procedure with the reporting of 
results under Section 8.3.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  Alternative Procedures

    16.1  Optional Presurvey and Presurvey Sampling.


[[Page 62014]]


    Note: Presurvey screening is optional. Presurvey sampling should 
be conducted for sources where the target pollutants are not known 
from previous tests and/or process knowledge.

    Perform a presurvey for each source to be tested. Refer to Figure 
18-1. Some of the information can be collected from literature surveys 
and source personnel. Collect gas samples that can be analyzed to 
confirm the identities and approximate concentrations of the organic 
emissions.
    16.1.1  Apparatus. This apparatus list also applies to Sections 8.2 
and 11.
    16.1.1.1  Teflon Tubing. (Mention of trade names or specific 
products does not constitute endorsement by the U.S. Environmental 
Protection Agency.) Diameter and length determined by connection 
requirements of cylinder regulators and the GC. Additional tubing is 
necessary to connect the GC sample loop to the sample.
    16.1.1.2  Gas Chromatograph. GC with suitable detector, columns, 
temperature-controlled sample loop and valve assembly, and temperature 
programmable oven, if necessary. The GC shall achieve sensitivity 
requirements for the compounds under study.
    16.1.1.3  Pump. Capable of pumping 100 ml/min. For flushing sample 
loop.
    16.1.1.4  Flow Meter. To measure flow rates.
    16.1.1.5  Regulators. Used on gas cylinders for GC and for cylinder 
standards.
    16.1.1.6  Recorder. Recorder with linear strip chart is minimum 
acceptable. Integrator (optional) is recommended.
    16.1.1.7  Syringes. 0.5-ml, 1.0- and 10-microliter size, 
calibrated, maximum accuracy (gas tight) for preparing calibration 
standards. Other appropriate sizes can be used.
    16.1.1.8  Tubing Fittings. To plumb GC and gas cylinders.
    16.1.1.9  Septa. For syringe injections.
    16.1.1.10  Glass Jars. If necessary, clean, colored glass jars with 
Teflon-lined lids for condensate sample collection. Size depends on 
volume of condensate.
    16.1.1.11  Soap Film Flowmeter. To determine flow rates.
    16.1.1.12  Tedlar Bags. 10- and 50-liter capacity, for preparation 
of standards.
    16.1.1.13  Dry Gas Meter with Temperature and Pressure Gauges. 
Accurate to 2 percent, for preparation of gas standards.
    16.1.1.14  Midget Impinger/Hot Plate Assembly. For preparation of 
gas standards.
    16.1.1.15  Sample Flasks. For presurvey samples, must have gas-
tight seals.
    16.1.1.16  Adsorption Tubes. If necessary, blank tubes filled with 
necessary adsorbent (charcoal, Tenax, XAD-2, etc.) for presurvey 
samples.
    16.1.1.17  Personnel Sampling Pump. Calibrated, for collecting 
adsorbent tube presurvey samples.
    16.1.1.18  Dilution System. Calibrated, the dilution system is to 
be constructed following the specifications of an acceptable method.
    16.1.1.19  Sample Probes. Pyrex or stainless steel, of sufficient 
length to reach centroid of stack, or a point no closer to the walls 
than 1 m.
    16.1.1.20  Barometer. To measure barometric pressure.
    16.1.2  Reagents.
    16.1.2.1  Water. Deionized distilled.
    16.1.2.2  Methylene chloride.
    16.1.2.3  Calibration Gases. A series of standards prepared for 
every compound of interest.
    16.1.2.4  Organic Compound Solutions. Pure (99.9 percent), or as 
pure as can reasonably be obtained, liquid samples of all the organic 
compounds needed to prepare calibration standards.
    16.1.2.5  Extraction Solvents. For extraction of adsorbent tube 
samples in preparation for analysis.
    16.1.2.6  Fuel. As recommended by the manufacturer for operation of 
the GC.
    16.1.2.7  Carrier Gas. Hydrocarbon free, as recommended by the 
manufacturer for operation of the detector and compatibility with the 
column.
    16.1.2.8  Zero Gas. Hydrocarbon free air or nitrogen, to be used 
for dilutions, blank preparation, and standard preparation.
    16.1.3  Sampling.
    16.1.3.1  Collection of Samples with Glass Sampling Flasks. 
Presurvey samples may be collected in precleaned 250-ml double-ended 
glass sampling flasks. Teflon stopcocks, without grease, are preferred. 
Flasks should be cleaned as follows: Remove the stopcocks from both 
ends of the flasks, and wipe the parts to remove any grease. Clean the 
stopcocks, barrels, and receivers with methylene chloride (or other 
non-target pollutant solvent, or heat and humidified air). Clean all 
glass ports with a soap solution, then rinse with tap and deionized 
distilled water. Place the flask in a cool glass annealing furnace, and 
apply heat up to 500  deg.C. Maintain at this temperature for 1 hour. 
After this time period, shut off and open the furnace to allow the 
flask to cool. Return the stopcocks to the flask receivers. Purge the 
assembly with high-purity nitrogen for 2 to 5 minutes. Close off the 
stopcocks after purging to maintain a slight positive nitrogen 
pressure. Secure the stopcocks with tape. Presurvey samples can be 
obtained either by drawing the gases into the previously evacuated 
flask or by drawing the gases into and purging the flask with a rubber 
suction bulb.
    16.1.3.1.1  Evacuated Flask Procedure. Use a high-vacuum pump to 
evacuate the flask to the capacity of the pump; then close off the 
stopcock leading to the pump. Attach a 6-mm outside diameter (OD) glass 
tee to the flask inlet with a short piece of Teflon tubing. Select a 6-
mm OD borosilicate sampling probe, enlarged at one end to a 12-mm OD 
and of sufficient length to reach the centroid of the duct to be 
sampled. Insert a glass wool plug in the enlarged end of the probe to 
remove particulate matter. Attach the other end of the probe to the tee 
with a short piece of Teflon tubing. Connect a rubber suction bulb to 
the third leg of the tee. Place the filter end of the probe at the 
centroid of the duct, and purge the probe with the rubber suction bulb. 
After the probe is completely purged and filled with duct gases, open 
the stopcock to the grab flask until the pressure in the flask reaches 
duct pressure. Close off the stopcock, and remove the probe from the 
duct. Remove the tee from the flask and tape the stopcocks to prevent 
leaks during shipment. Measure and record the duct temperature and 
pressure.
    16.1.3.1.2  Purged Flask Procedure. Attach one end of the sampling 
flask to a rubber suction bulb. Attach the other end to a 6-mm OD glass 
probe as described in Section 8.3.3.1.1. Place the filter end of the 
probe at the centroid of the duct, or at a point no closer to the walls 
than 1 m, and apply suction with the bulb to completely purge the probe 
and flask. After the flask has been purged, close off the stopcock near 
the suction bulb, and then close off the stopcock near the probe. 
Remove the probe from the duct, and disconnect both the probe and 
suction bulb. Tape the stopcocks to prevent leakage during shipment. 
Measure and record the duct temperature and pressure.
    16.1.3.2  Flexible Bag Procedure. Tedlar or aluminized Mylar bags 
can also be used to obtain the presurvey sample. Use new bags, and 
leak-check them before field use. In addition, check the bag before use 
for contamination by filling it with nitrogen or air, and analyzing the 
gas by GC at high sensitivity. Experience indicates that it is 
desirable to allow the inert gas to remain in the bag about 24 hours or

[[Page 62015]]

longer to check for desorption of organics from the bag. Follow the 
leak-check and sample collection procedures given in Section 8.2.1.
    16.1.3.3  Determination of Moisture Content. For combustion or 
water-controlled processes, obtain the moisture content from plant 
personnel or by measurement during the presurvey. If the source is 
below 59 deg.C, measure the wet bulb and dry bulb temperatures, and 
calculate the moisture content using a psychrometric chart. At higher 
temperatures, use Method 4 to determine the moisture content.
    16.1.4  Determination of Static Pressure. Obtain the static 
pressure from the plant personnel or measurement. If a type S pitot 
tube and an inclined manometer are used, take care to align the pitot 
tube 90 deg. from the direction of the flow. Disconnect one of the 
tubes to the manometer, and read the static pressure; note whether the 
reading is positive or negative.
    16.1.5  Collection of Presurvey Samples with Adsorption Tube. 
Follow Section 8.2.4 for presurvey sampling.

17.0  References

    1. American Society for Testing and Materials. C1 Through C5 
Hydrocarbons in the Atmosphere by Gas Chromatography. ASTM D 2820-
72, Part 23. Philadelphia, Pa. 23:950-958. 1973.
    2. Corazon, V.V. Methodology for Collecting and Analyzing 
Organic Air Pollutants. U.S. Environmental Protection Agency. 
Research Triangle Park, N.C. Publication No. EPA-600/2-79-042. 
February 1979.
    3. Dravnieks, A., B.K. Krotoszynski, J. Whitfield, A. O'Donnell, 
and T. Burgwald. Environmental Science and Technology. 5(12):1200-
1222. 1971.
    4. Eggertsen, F.T., and F.M. Nelsen. Gas Chromatographic 
Analysis of Engine Exhaust and Atmosphere. Analytical Chemistry. 
30(6): 1040-1043. 1958.
    5. Feairheller, W.R., P.J. Marn, D.H. Harris, and D.L. Harris. 
Technical Manual for Process Sampling Strategies for Organic 
Materials. U.S. Environmental Protection Agency. Research Triangle 
Park, N.C. Publication No. EPA 600/2-76-122. April 1976. 172 p.
    6. Federal Register, 39 FR 9319-9323. 1974.
    7. Federal Register, 39 FR 32857-32860. 1974.
    8. Federal Register, 23069-23072 and 23076-23090. 1976.
    9. Federal Register, 46569-46571. 1976.
    10. Federal Register, 41771-41776. 1977.
    11. Fishbein, L. Chromatography of Environmental Hazards, Volume 
II. Elesevier Scientific Publishing Company. New York, N.Y. 1973.
    12. Hamersma, J.W., S.L. Reynolds, and R.F. Maddalone. EPA/IERL-
RTP Procedures Manual: Level 1 Environmental Assessment. U.S. 
Environmental Protection Agency. Research Triangle Park, N.C. 
Publication No. EPA 600/276-160a. June 1976. 130 p.
    13. Harris, J.C., M.J. Hayes, P.L. Levins, and D.B. Lindsay. 
EPA/IERL-RTP Procedures for Level 2 Sampling and Analysis of Organic 
Materials. U.S. Environmental Protection Agency. Research Triangle 
Park, N.C. Publication No. EPA 600/7-79-033. February 1979. 154 p.
    14. Harris, W.E., H.W. Habgood. Programmed Temperature Gas 
Chromatography. John Wiley and Sons, Inc. New York. 1966.
    15. Intersociety Committee. Methods of Air Sampling and 
Analysis. American Health Association. Washington, D.C. 1972.
    16. Jones, P.W., R.D. Grammer, P.E. Strup, and T.B. Stanford. 
Environmental Science and Technology. 10:806-810. 1976.
    17. McNair Han Bunelli, E.J. Basic Gas Chromatography. 
Consolidated Printers. Berkeley. 1969.
    18. Nelson, G.O. Controlled Test Atmospheres, Principles and 
Techniques. Ann Arbor. Ann Arbor Science Publishers. 1971. 247 p.
    19. NIOSH Manual of Analytical Methods, Volumes 1, 2, 3, 4, 5, 
6, 7. U.S. Department of Health and Human Services, National 
Institute for Occupational Safety and Health. Center for Disease 
Control. 4676 Columbia Parkway, Cincinnati, Ohio 45226. April 1977--
August 1981. May be available from the Superintendent of Documents, 
Government Printing Office, Washington, D.C. 20402. Stock Number/
Price:

Volume 1--O17-033-00267-3/$13
Volume 2--O17-033-00260-6/$11
Volume 3--O17-033-00261-4/$14
Volume 4--O17-033-00317-3/$7.25
Volume 5--O17-033-00349-1/$10
Volume 6--O17-033-00369-6/$9
Volume 7--O17-033-00396-5/$7

Prices subject to change. Foreign orders add 25 percent.
    20. Schuetzle, D., T.J. Prater, and S.R. Ruddell. Sampling and 
Analysis of Emissions from Stationary Sources; I. Odor and Total 
Hydrocarbons. Journal of the Air Pollution Control Association. 
25(9): 925-932. 1975.
    21. Snyder, A.D., F.N. Hodgson, M.A. Kemmer and J.R. McKendree. 
Utility of Solid Sorbents for Sampling Organic Emissions from 
Stationary Sources. U.S. Environmental Protection Agency. Research 
Triangle Park, N.C. Publication No. EPA 600/2-76-201. July 1976. 71 
p.
    22. Tentative Method for Continuous Analysis of Total 
Hydrocarbons in the Atmosphere. Intersociety Committee, American 
Public Health Association. Washington, D.C. 1972. p. 184-186.
    23. Zwerg, G. CRC Handbook of Chromatography, Volumes I and II. 
Sherma, Joseph (ed.). CRC Press. Cleveland. 1972.

18.0  Tables, Diagrams, Flowcharts, and Validation Data

I. Name of company-----------------------------------------------------
Date-------------------------------------------------------------------
Address----------------------------------------------------------------
----------------------------------------------------------------------
Contracts--------------------------------------------------------------
Phone------------------------------------------------------------------
Process to be sampled--------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
Duct or vent to be sampled---------------------------------------------
----------------------------------------------------------------------
II. Process description------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
Raw material-----------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
Products---------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------

Operating cycle
Check: Batch ________ Continuous ________ Cyclic ________
Timing of batch or cycle-----------------------------------------------

[[Page 62016]]

Best time to test------------------------------------------------------

III. Sampling site-----------------------------------------------------
A. Description---------------------------------------------------------
Site decription--------------------------------------------------------
Duct shape and size----------------------------------------------------
Material---------------------------------------------------------------
Wall thickness ________ inches
Upstream distance ________ inches ________ diameter
Downstream distance ________ inches ________ diameter
Size of port-----------------------------------------------------------
Size of access area----------------------------------------------------
Hazards ________ Ambient temp. ________  deg.F

B. Properties of gas stream
Temperature ________  deg.C ________  deg.F, Data source ________
Velocity ________, Data source ________
Static pressure ________ inches H2O, Data source ________
Moisture content ________%, Data source ________
Particulate content ________, Data source________

Gaseous components
N2 ________ %  Hydrocarbons ________ ppm
O2   ________%  ________
CO ________ %  ________  ________
CO2 ________ %  ________  ________
SO2 ________ %  ________  ________

Hydrocarbon components
________  ________ ppm
________  ________ ppm
________  ________ ppm
________  ________ ppm
________  ________ ppm
________  ________ ppm

C. Sampling considerations
Location to set up GC--------------------------------------------------
----------------------------------------------------------------------
Special hazards to be considered---------------------------------------
----------------------------------------------------------------------
Power available at duct------------------------------------------------
Power available for GC-------------------------------------------------
Plant safety requirements----------------------------------------------
----------------------------------------------------------------------
Vehicle traffic rules--------------------------------------------------
----------------------------------------------------------------------
Plant entry requirements-----------------------------------------------
----------------------------------------------------------------------
Security agreements----------------------------------------------------
----------------------------------------------------------------------
Potential problems-----------------------------------------------------
----------------------------------------------------------------------

D. Site diagrams. (Attach additional sheets if required).
Figure 18-1. Preliminary Survey Data Sheet
Components to be analyzed and Expected concentration
----------------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
Suggested chromatographic column---------------------------------------
----------------------------------------------------------------------
Column flow rate __ ml/min
Head pressure ________ mm Hg

Column temperature: Isothermal ________  deg.C, Programmed from 
________  deg.C to ________  deg.C at ________  deg.C/min
Injection port/sample loop temperature ________  deg.C
Detector temperature ________  deg.C
Detector flow rates: Hydrogen ________ ml/min., head pressure ________ 
mm Hg, Air/Oxygen ________ ml/min., head pressure ________ mm Hg.
Chart speed ________ inches/minute

[[Page 62017]]

Compound data:
Compound and Retention time and Attenuation
----------------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
----------------------------------------------------------------------
Figure 18-2.  Chromatographic Conditions Data Sheet

                   Figure 18-3. Preparation of Standards in Tedlar Bags and Calibration Curve
----------------------------------------------------------------------------------------------------------------
                                                                                  Standards
                                                           -----------------------------------------------------
                                                               Mixture #1        Mixture #2        Mixture #3
----------------------------------------------------------------------------------------------------------------
Standards Preparation Data:
    Organic:
        Bag number or identification......................
        Dry gas meter calibration factor..................
        Final meter reading (liters)......................
        Initial meter reading (liters)....................
        Metered volume (liters)...........................
        Average meter temperature ( deg.K)................
        Average meter pressure, gauge (mm Hg).............
        Average atmospheric perssure (mm Hg)..............
        Average meter pressure, absolute (mm Hg)..........
        Syringe temperature ( deg.K) (see Section
         10.1.2.1)........................................
        Syringe pressure, absolute (mm Hg) (see Section
         10.1.2.1)........................................
        Volume of gas in syringe (ml) (Section 10.1.2.1)..
        Density of liquid organic (g/ml) (Section
         10.1.2.1)........................................
        Volume of liquid in syringe (ml) (Section
         10.1.2.1)........................................
GC Operating Conditions:
    Sample loop volume (ml)...............................
    Sample loop temperature ( deg.C)......................
    Carrier gas flow rate (ml/min)........................
Column temperature:
    Initial ( deg.C)......................................
    Rate change ( deg.C/min)..............................
    Final ( deg.C)........................................
Organic Peak Identification and Calculated Concentrations:
    Injection time (24 hour clock)........................
    Distance to peak (cm).................................
    Chart speed (cm/min)..................................
    Organic retention time (min)..........................
    Attenuation factor....................................
    Peak height (mm)......................................
    Peak area (mm2).......................................
    Peak area * attenuation factor (mm2)..................
    Calculated concentration (ppm) (Equation 18-3 or 18-4)
----------------------------------------------------------------------------------------------------------------
Plot peak area * attenuation factor against calculated concentration to obtain calibration curve.

Flowmeter number or identification-------------------------------------
Flowmeter Type---------------------------------------------------------
Method: Bubble meter____ Spirometer____ Wet test meter ____
Readings at laboratory conditions:
Laboratory temperature (Tlab) ____  deg.K
Laboratory barometric pressure (Plab)____ mm Hg
Flow data:

                                                    Flowmeter
----------------------------------------------------------------------------------------------------------------
         Reading (as marked)                     Temp. ( deg.K)                      Pressure (absolute)
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------


[[Page 62018]]


                                               Calibration Device
----------------------------------------------------------------------------------------------------------------
             Time (min)                           Gas volume a                           Flow rate b
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
a Vol. of gas may be measured in milliliters, liters or cubic feet.
b Convert to standard conditions (20  deg.C and 760 mm Hg). Plot flowmeter reading against flow rate (standard
  conditions), and draw a smooth curve. If the flowmeter being calibrated is a rotameter or other flow device
  that is viscosity dependent, it may be necessary to generate a ``family'' of calibration curves that cover the
  operating pressure and temperature ranges of the flowmeter. While the following technique should be verified
  before application, it may be possible to calculate flow rate reading for rotameters at standard conditions
  Qstd as follows:

  [GRAPHIC] [TIFF OMITTED] TR17OC00.313
  

------------------------------------------------------------------------
 Flow rate (laboratory conditions)        Flow rate (STD conditions)
------------------------------------------------------------------------
 
------------------------------------------------------------------------
 
------------------------------------------------------------------------
 
------------------------------------------------------------------------
 
------------------------------------------------------------------------
 
------------------------------------------------------------------------

Figure 18-4. Flowmeter Calibration
BILLING CODE 6560-50-P

[[Page 62019]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.314


[[Page 62020]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.315

BILLING CODE 6560-50-C

                            Preparation of Standards by Dilution of Cylinder Standard
                   [Cylinder Standard: Organic -------- Certified Concentration -------- ppm]
----------------------------------------------------------------------------------------------------------------
                                                                         Date:
     Standards preparation data:      --------------------------------------------------------------------------
                                              Mixture 1                Mixture 2                Mixture 3
----------------------------------------------------------------------------------------------------------------
Stage 1:
    Standard gas flowmeter reading...
    Diluent gas flowmeter reading
    Laboratory temperature ( deg.K)
    Barometric pressure (mm Hg)
    Flowmeter gage pressure (mm Hg)
    Flow rate cylinder gas at
     standard conditions (ml/min)
    Flow rate diluent gas at standard
     conditions (ml/min)
    Calculated concentration (ppm)
Stage 2 (if used):
    Standard gas flowmeter reading
    Diluent gas flowmeter reading
    Flow rate Stage 1 gas at standard
     conditions (ml/min)
    Flow rate diluent gas at standard
     conditions

[[Page 62021]]

 
    Calculated concentration (ppm)
GC Operating Conditions:
    Sample loop volume (ml)
    Sample loop temperature ( deg.C)
    Carrier gas flow rate (ml/min)
Column temperature:
    Initial ( deg.C)
    Program rate ( deg.C/min)
    Final ( deg.C)
Organic Peak Identification and
 Calculated Concentrations:
    Injection time (24-hour clock)
    Distance to peak (cm)
    Chart speed (cm/min)
    Retention time (min)
    Attenuation factor
    Peak area (mm \2\)
    Peak area *attenuation factor
----------------------------------------------------------------------------------------------------------------
Plot peak area *attenuation factor against calculated concentration to obtain calibration curve.

Figure 18-7. Standards Prepared by Dilution of Cylinder Standard
BILLING CODE 6560-50-P

[[Page 62022]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.316


[[Page 62023]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.317


[[Page 62024]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.318

BILLING CODE 6560-50-C

                                     Plant________ Date________ Site________
----------------------------------------------------------------------------------------------------------------
                                                                     Sample 1        Sample 2        Sample 3
----------------------------------------------------------------------------------------------------------------
Source temperature ( deg.C).....................................  ..............  ..............  ..............
Barometric pressure (mm Hg).....................................  ..............  ..............  ..............
Ambient temperature ( deg.C)....................................  ..............  ..............  ..............
Sample flow rate (appr.)........................................  ..............  ..............  ..............
Bag number......................................................  ..............  ..............  ..............
Start time......................................................  ..............  ..............  ..............
Finish time.....................................................  ..............  ..............  ..............
----------------------------------------------------------------------------------------------------------------

Figure 18-10. Field Sample Data Sheet--Tedlar Bag Collection Method

             Plant -------- Date -------- Location --------
 
                            m
1. General information:
    Source temperature ( deg.C).......................  ................
    Probe temperature ( deg.C)........................  ................
    Ambient temperature ( deg.C)......................  ................
    Atmospheric pressure (mm).........................  ................

[[Page 62025]]

 
    Source pressure ("Hg).............................  ................
    Absolute source pressure (mm).....................  ................
    Sampling rate (liter/min).........................  ................
    Sample loop volume (ml)...........................  ................
    Sample loop temperature ( deg.C)..................  ................
    Columnar temperature:
        Initial ( deg.C) time (min)...................  ................
        Program rate ( deg.C/min).....................  ................
        Final ( deg.C)/time (min).....................  ................
    Carrier gas flow rate (ml/min)....................  ................
    Detector temperature ( deg.C).....................  ................
    Injection time (24-hour basis)....................  ................
    Chart Speed (mm/min)..............................  ................
    Dilution gas flow rate (ml/min)...................  ................
    Dilution gas used (symbol)........................  ................
    Dilution ratio....................................  ................
 


                                                                             2. Field Analysis Data--Calibration Gas
                                                                                2. [Run No.________ Time________]
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                Components                           Area                          Attenuation                              A x A Factor                              Conc.__ (ppm)
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                                           .......................  ........................................  ........................................  ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                                           .......................  ........................................  ........................................  ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                                           .......................  ........................................  ........................................  ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                                           .......................  ........................................  ........................................  ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                                           .......................  ........................................  ........................................  ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                                           .......................  ........................................  ........................................  ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                                           .......................  ........................................  ........................................  ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                                           .......................  ........................................  ........................................  ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                                           .......................  ........................................  ........................................  ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                                           .......................  ........................................  ........................................  ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                                           .......................  ........................................  ........................................  ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                                           .......................  ........................................  ........................................  ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                                           .......................  ........................................  ........................................  ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                                           .......................  ........................................  ........................................  ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                                           .......................  ........................................  ........................................  ........................................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

Figure 18-11. Field Analysis Data Sheets
BILLING CODE 6560-50-P

[[Page 62026]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.319


[[Page 62027]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.320

BILLING CODE 6560-50-C

                                Gaseous Organic Sampling and Analysis Check List
                                [Respond with initials or number as appropriate]
 
                                                                                                Date
 
1. Presurvey data:
    A. Grab sample collected........................  {time}                        ______
        B. Grab sample analyzed for composition.....  {time}                        ______
        Method GC...................................  {time}                        ______
            GC/MS...................................  {time}                        ______
            Other...................................  {time}                        ______
    C. GC-FID analysis performed....................  {time}                        ______
2. Laboratory calibration data:
    A. Calibration curves prepared..................  {time}                        ______
        Number of components........................  {time}                        ______
        Number of concentrations/component (3         {time}                        ______
         required).
    B. Audit samples (optional):
    Analysis completed..............................  {time}                        ______
    Verified for concentration......................  {time}                        ______
    OK obtained for field work......................  {time}                        ______
3. Sampling procedures:
    A. Method:
        Bag sample..................................  {time}                        ______
        Direct interface............................  {time}                        ______
        Dilution interface..........................  {time}                        ______
    B. Number of samples collected..................  {time}                        ______
4. Field Analysis:
    A. Total hydrocarbon analysis performed.........  {time}                        ______

[[Page 62028]]

 
    B. Calibration curve prepared...................  {time}                        ______
        Number of components........................  {time}                        ______
        Number of concentrations per component (3     {time}                        ______
         required).
 

Gaseous Organic Sampling and Analysis Data
Plant------------------------------------------------------------------
Date-------------------------------------------------------------------
Location---------------------------------------------------------------

 
----------------------------------------------------------------------------------------------------------------
            Source sample 1                       Source sample 2                     Source sample 3
---------------------------------------------------------------------------------------------------------------
1. General information:
    Source temperature ( deg.C).......  ..................................  ..................................
    Probe temperature ( deg.C)........  ..................................  ..................................
    Ambient temperature ( deg.C)......  ..................................  ..................................
    Atmospheric pressure (mm Hg)......  ..................................  ..................................
    Source pressure (mm Hg)...........  ..................................  ..................................
    Sampling rate (ml/min)............  ..................................  ..................................
    Sample loop volume (ml)...........  ..................................  ..................................
    Sample loop temperature ( deg.C)..  ..................................  ..................................
    Sample collection time (24-hr       ..................................  ..................................
     basis).
    Column temperature:
        Initial ( deg.C)..............  ..................................  ..................................
        Program rate ( deg.C/min).....  ..................................  ..................................
        Final ( deg.C)................  ..................................  ..................................
    Carrier gas flow rate (ml/min)....  ..................................  ..................................
    Detector temperature ( deg.C).....  ..................................  ..................................
    Chart speed (cm/min)..............  ..................................  ..................................
    Dilution gas flow rate (ml/min)...  ..................................  ..................................
    Diluent gas used (symbol).........  ..................................  ..................................
    Dilution ratio....................  ..................................  ..................................
Performed by: (signature):________________________ Date:________________________
----------------------------------------------------------------------------------------------------------------

Figure 18-14. Sampling and Analysis Sheet

Method 19--Determination of Sulfur Dioxide Removal Efficiency and 
Particulate Matter, Sulfur Dioxide, and Nitrogen Oxide Emission 
Rates

1.0  Scope and Application

    1.1  Analytes. This method provides data reduction procedures 
relating to the following pollutants, but does not include any sample 
collection or analysis procedures.

------------------------------------------------------------------------
            Analyte                  CAS No.            Sensitivity
------------------------------------------------------------------------
Nitrogen oxides (NOX),
 including:
    Nitric oxide (NO).........  10102-43-9.......  N/A
    Nitrogen dioxide (NO2)....  10102-44-0.......
Particulate matter (PM).......  None assigned....  N/A
Sulfur dioxide (SO2)..........  7499-09-05.......  N/A
------------------------------------------------------------------------

    1.2  Applicability. Where specified by an applicable subpart of the 
regulations, this method is applicable for the determination of (a) PM, 
SO2, and NOX emission rates; (b) sulfur removal 
efficiencies of fuel pretreatment and SO2 control devices; 
and (c) overall reduction of potential SO2 emissions.

2.0  Summary of Method

    2.1  Emission Rates. Oxygen (O2) or carbon dioxide 
(CO2) concentrations and appropriate F factors (ratios of 
combustion gas volumes to heat inputs) are used to calculate pollutant 
emission rates from pollutant concentrations.
    2.2  Sulfur Reduction Efficiency and SO2 Removal 
Efficiency. An overall SO2 emission reduction efficiency is 
computed from the efficiency of fuel pretreatment systems, where 
applicable, and the efficiency of SO2 control devices.
    2.2.1  The sulfur removal efficiency of a fuel pretreatment system 
is determined by fuel sampling and analysis of the sulfur and heat 
contents of the fuel before and after the pretreatment system.
    2.2.2  The SO2 removal efficiency of a control device is 
determined by measuring the SO2 rates before and after the 
control device.
    2.2.2.1  The inlet rates to SO2 control systems (or, 
when SO2 control systems are not used, SO2 
emission rates to the atmosphere) are determined by fuel sampling and 
analysis.

[[Page 62029]]

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety [Reserved]

6.0  Equipment and Supplies [Reserved]

7.0  Reagents and Standards [Reserved]

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

9.0  Quality Control [Reserved]

10.0  Calibration and Standardization [Reserved]

11.0  Analytical Procedures [Reserved]

12.0  Data Analysis and Calculations

    12.1  Nomenclature

Bwa = Moisture fraction of ambient air, percent.
Bws = Moisture fraction of effluent gas, percent.
%C = Concentration of carbon from an ultimate analysis of fuel, weight 
percent.
Cd = Pollutant concentration, dry basis, ng/scm (lb/scf)
%CO2d,%CO2w = Concentration of carbon dioxide on 
a dry and wet basis, respectively, percent.
Cw = Pollutant concentration, wet basis, ng/scm (lb/scf).
D = Number of sampling periods during the performance test period.
E = Pollutant emission rate, ng/J (lb/million Btu).
Ea = Average pollutant rate for the specified performance 
test period, ng/J (lb/million Btu).
Eao, Eai = Average pollutant rate of the control 
device, outlet and inlet, respectively, for the performance test 
period, ng/J (lb/million Btu).
Ebi = Pollutant rate from the steam generating unit, ng/J 
(lb/million Btu)
Ebo = Pollutant emission rate from the steam generating 
unit, ng/J (lb/million Btu).
Eci = Pollutant rate in combined effluent, ng/J (lb/million 
Btu).
Eco = Pollutant emission rate in combined effluent, ng/J 
(lb/million Btu).
Ed = Average pollutant rate for each sampling period (e.g., 
24-hr Method 6B sample or 24-hr fuel sample) or for each fuel lot 
(e.g., amount of fuel bunkered), ng/J (lb/million Btu).
Edi = Average inlet SO2 rate for each sampling 
period d, ng/J (lb/million Btu)
Eg = Pollutant rate from gas turbine, ng/J (lb/million Btu).
Ega = Daily geometric average pollutant rate, ng/J (lbs/
million Btu) or ppm corrected to 7 percent O2.
Ejo,Eji = Matched pair hourly arithmetic average 
pollutant rate, outlet and inlet, respectively, ng/J (lb/million Btu) 
or ppm corrected to 7 percent O2.
Eh = Hourly average pollutant, ng/J (lb/million Btu).
Ehj = Hourly arithmetic average pollutant rate for hour 
``j,'' ng/J (lb/million Btu) or ppm corrected to 7 percent 
O2.
EXP = Natural logarithmic base (2.718) raised to the value enclosed by 
brackets.
Fd, Fw, Fc = Volumes of combustion 
components per unit of heat content, scm/J (scf/million Btu).
GCV = Gross calorific value of the fuel consistent with the ultimate 
analysis, kJ/kg (Btu/lb).
GCVp, GCVr = Gross calorific value for the 
product and raw fuel lots, respectively, dry basis, kJ/kg (Btu/lb).
%H = Concentration of hydrogen from an ultimate analysis of fuel, 
weight percent.
H = Total number of operating hours for which pollutant rates are 
determined in the performance test period.
Hb = Heat input rate to the steam generating unit from fuels 
fired in the steam generating unit, J/hr (million Btu/hr).
Hg = Heat input rate to gas turbine from all fuels fired in 
the gas turbine, J/hr (million Btu/hr).
%H2O = Concentration of water from an ultimate analysis of 
fuel, weight percent.
Hr = Total numbers of hours in the performance test period 
(e.g., 720 hours for 30-day performance test period).
K = Conversion factor, 10-\5\ (kJ/J)/(%) [106 
Btu/million Btu].
Kc = (9.57 scm/kg)/% [(1.53 scf/lb)/%].
Kcc = (2.0 scm/kg)/% [(0.321 scf/lb)/%].
Khd = (22.7 scm/kg)/% [(3.64 scf/lb)/%].
Khw = (34.74 scm/kg)/% [(5.57 scf/lb)/%].
Kn = (0.86 scm/kg)/% [(0.14 scf/lb)/%].
Ko = (2.85 scm/kg)/% [(0.46 scf/lb)/%].
Ks = (3.54 scm/kg)/% [(0.57 scf/lb)/%].
Kw = (1.30 scm/kg)/% [(0.21 scf/lb)/%].
ln = Natural log of indicated value.
Lp,Lr = Weight of the product and raw fuel lots, 
respectively, metric ton (ton).
%N = Concentration of nitrogen from an ultimate analysis of fuel, 
weight percent.
N = Number of fuel lots during the averaging period.
n = Number of fuels being burned in combination.
nd = Number of operating hours of the affected facility 
within the performance test period for each Ed determined.
nt = Total number of hourly averages for which paired inlet 
and outlet pollutant rates are available within the 24-hr midnight to 
midnight daily period.
%O = Concentration of oxygen from an ultimate analysis of fuel, weight 
percent.
%O2d, %O2w = Concentration of oxygen on a dry and 
wet basis, respectively, percent.
Ps = Potential SO2 emissions, percent.
%Rf = SO2 removal efficiency from fuel 
pretreatment, percent.
%Rg = SO2 removal efficiency of the control 
device, percent.
%Rga = Daily geometric average percent reduction.
%Ro = Overall SO2 reduction, percent.
%S = Sulfur content of as-fired fuel lot, dry basis, weight percent.
Se = Standard deviation of the hourly average pollutant 
rates for each performance test period, ng/J (lb/million Btu).
%Sf = Concentration of sulfur from an ultimate analysis of 
fuel, weight percent.
Si = Standard deviation of the hourly average inlet 
pollutant rates for each performance test period, ng/J (lb/million 
Btu).
So = Standard deviation of the hourly average emission rates 
for each performance test period, ng/J (lb/million Btu).
%Sp, %Sr = Sulfur content of the product and raw 
fuel lots respectively, dry basis, weight percent.
t0.95 = Values shown in Table 19-3 for the indicated number 
of data points n.
Xk = Fraction of total heat input from each type of fuel k.

    12.2  Emission Rates of PM, SO2, and NOx. 
Select from the following sections the applicable procedure to compute 
the PM, SO2, or NOx emission rate (E) in ng/J 
(lb/million Btu). The pollutant concentration must be in ng/scm (lb/
scf) and the F factor must be in scm/J (scf/million Btu). If the 
pollutant concentration (C) is not in the appropriate units, use Table 
19-1 in Section 17.0 to make the proper conversion. An F factor is the 
ratio of the gas volume of the products of combustion to the heat 
content of the fuel. The dry F factor (Fd) includes all 
components of combustion less water, the wet F factor (Fw) 
includes all components of combustion, and the carbon F factor 
(Fc) includes only carbon dioxide.

    Note: Since Fw factors include water resulting only 
from the combustion of

[[Page 62030]]

hydrogen in the fuel, the procedures using Fw factors are 
not applicable for computing E from steam generating units with wet 
scrubbers or with other processes that add water (e.g., steam 
injection).

    12.2.1  Oxygen-Based F Factor, Dry Basis. When measurements are on 
a dry basis for both O (%O2d) and pollutant (Cd) 
concentrations, use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.321

    12.2.2  Oxygen-Based F Factor, Wet Basis. When measurements are on 
a wet basis for both O2 (%O2w) and pollutant 
(Cw) concentrations, use either of the following:
    12.2.2.1  If the moisture fraction of ambient air (Bwa) 
is measured:
[GRAPHIC] [TIFF OMITTED] TR17OC00.322

    Instead of actual measurement, Bwa may be estimated 
according to the procedure below.
    Note: The estimates are selected to ensure that negative errors 
will not be larger than -1.5 percent. However, positive errors, or 
over-estimation of emissions by as much as 5 percent may be introduced 
depending upon the geographic location of the facility and the 
associated range of ambient moisture.
    12.2.2.1.1  Bwa = 0.027. This value may be used at any 
location at all times.
    12.2.2.1.2  Bwa = Highest monthly average of 
Bwa that occurred within the previous calendar year at the 
nearest Weather Service Station. This value shall be determined 
annually and may be used as an estimate for the entire current calendar 
year.
    12.2.2.1.3  Bwa = Highest daily average of Bwa that 
occurred within a calendar month at the nearest Weather Service 
Station, calculated from the data from the past 3 years. This value 
shall be computed for each month and may be used as an estimate for the 
current respective calendar month.
    12.2.2.2  If the moisture fraction (Bws) of the effluent 
gas is measured:
[GRAPHIC] [TIFF OMITTED] TR17OC00.323

    12.2.3  Oxygen-Based F Factor, Dry/Wet Basis.
    12.2.3.1  When the pollutant concentration is measured on a wet 
basis (Cw) and O2 concentration is measured on a 
dry basis (%O2d), use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.324

    12.2.3.2  When the pollutant concentration is measured on a dry 
basis (Cd) and the O2 concentration is measured 
on a wet basis (%O2w), use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.325

    12.2.4  Carbon Dioxide-Based F Factor, Dry Basis. When measurements 
are on a dry basis for both CO2 (%CO2d) and 
pollutant (Cd) concentrations, use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.326

    12.2.5  Carbon Dioxide-Based F Factor, Wet Basis. When measurements 
are on a wet basis for both CO2 (%CO2w) and 
pollutant (Cw) concentrations, use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.327

    12.2.6  Carbon Dioxide-Based F Factor, Dry/Wet Basis.
    12.2.6.1  When the pollutant concentration is measured on a wet 
basis (Cw) and CO2 concentration is measured on a 
dry basis (%CO2d), use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.328

    12.2.6.2  When the pollutant concentration is measured on a dry 
basis (Cd) and CO2 concentration is measured on a 
wet basis (%CO2w), use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.329

    12.2.7  Direct-Fired Reheat Fuel Burning. The effect of direct-
fired reheat fuel burning (for the purpose of raising the temperature 
of the exhaust effluent from wet scrubbers to above the moisture dew-
point) on emission rates will be less than 1.0 percent and, therefore, 
may be ignored.
    12.2.8  Combined Cycle-Gas Turbine Systems. For gas turbine-steam 
generator combined cycle systems, determine the emissions from the 
steam generating unit or the percent reduction in potential 
SO2 emissions as follows:
    12.2.8.1  Compute the emission rate from the steam generating unit 
using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.330

    12.2.8.1.1 Use the test methods and procedures section of 40 CFR 
Part 60, Subpart GG to obtain Eco and Eg. Do not 
use Fw factors for determining Eg or 
Eco. If an SO2 control device is used, measure 
Eco after the control device.
    12.2.8.1.2  Suitable methods shall be used to determine the heat 
input rates to the steam generating units (Hb) and the gas 
turbine (Hg).
    12.2.8.2  If a control device is used, compute the percent of 
potential SO2 emissions (Ps) using the following 
equations:
[GRAPHIC] [TIFF OMITTED] TR17OC00.331

[GRAPHIC] [TIFF OMITTED] TR17OC00.332


[[Page 62031]]


    Note: Use the test methods and procedures section of Subpart GG to 
obtain Eci and Eg. Do not use Fw 
factors for determining Eg or Eci.
    12.3  F Factors. Use an average F factor according to Section 
12.3.1 or determine an applicable F factor according to Section 12.3.2. 
If combined fuels are fired, prorate the applicable F factors using the 
procedure in Section 12.3.3.
    12.3.1  Average F Factors. Average F factors (Fd, 
Fw, or Fc) from Table 19-2 in Section 17.0 may be 
used.
    12.3.2  Determined F Factors. If the fuel burned is not listed in 
Table 19-2 or if the owner or operator chooses to determine an F factor 
rather than use the values in Table 19-2, use the procedure below:
    12.3.2.1  Equations. Use the equations below, as appropriate, to 
compute the F factors:
[GRAPHIC] [TIFF OMITTED] TR17OC00.333

[GRAPHIC] [TIFF OMITTED] TR17OC00.334

[GRAPHIC] [TIFF OMITTED] TR17OC00.335


    Note: Omit the %H2O term in the equations for 
Fw if %H and %O include the unavailable hydrogen and 
oxygen in the form of H2O.)

    12.3.2.2  Use applicable sampling procedures in Section 12.5.2.1 or 
12.5.2.2 to obtain samples for analyses.
    12.3.2.3  Use ASTM D 3176-74 or 89 (all cited ASTM standards are 
incorporated by reference--see Sec. 60.17) for ultimate analysis of the 
fuel.
    12.3.2.4  Use applicable methods in Section 12.5.2.1 or 12.5.2.2 to 
determine the heat content of solid or liquid fuels. For gaseous fuels, 
use ASTM D 1826-77 or 94 (incorporated by reference--see Sec. 60.17) to 
determine the heat content.
    12.3.3  F Factors for Combination of Fuels. If combinations of 
fuels are burned, use the following equations, as applicable unless 
otherwise specified in an applicable subpart:
[GRAPHIC] [TIFF OMITTED] TR17OC00.336

[GRAPHIC] [TIFF OMITTED] TR17OC00.337

[GRAPHIC] [TIFF OMITTED] TR17OC00.338

    12.4  Determination of Average Pollutant Rates.
    12.4.1  Average Pollutant Rates from Hourly Values. When hourly 
average pollutant rates (Eh), inlet or outlet, are obtained 
(e.g., CEMS values), compute the average pollutant rate (Ea) 
for the performance test period (e.g., 30 days) specified in the 
applicable regulation using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.339

    12.4.2  Average Pollutant Rates from Other than Hourly Averages. 
When pollutant rates are determined from measured values representing 
longer than 1-hour periods (e.g., daily fuel sampling and analyses or 
Method 6B values), or when pollutant rates are determined from 
combinations of 1-hour and longer than 1-hour periods (e.g., CEMS and 
Method 6B values), compute the average pollutant rate (Ea) 
for the performance test period (e.g., 30 days) specified in the 
applicable regulation using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.340

    12.4.3  Daily Geometric Average Pollutant Rates from Hourly Values. 
The geometric average pollutant rate (Ega) is computed using 
the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.341

    12.5  Determination of Overall Reduction in Potential Sulfur 
Dioxide Emission.
    12.5.1  Overall Percent Reduction. Compute the overall percent 
SO2 reduction (%Ro) using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.342

    12.5.2  Pretreatment Removal Efficiency (Optional). Compute the 
SO2 removal efficiency from fuel pretreatment 
(%Rf) for the averaging period (e.g., 90 days) as specified 
in the applicable regulation using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.343


    Note: In calculating %Rf, include %S and GCV values 
for all fuel lots that are not pretreated and are used during the 
averaging period.

    12.5.2.1  Solid Fossil (Including Waste) Fuel/Sampling and 
Analysis.


[[Page 62032]]


    Note: For the purposes of this method, raw fuel (coal or oil) is 
the fuel delivered to the desulfurization (pretreatment) facility. 
For oil, the input oil to the oil desulfurization process (e.g., 
hydrotreatment) is considered to be the raw fuel.

    12.5.2.1.1  Sample Increment Collection. Use ASTM D 2234-76, 96, 
97a, or 98 (incorporated by reference--see Sec. 60.17), Type I, 
Conditions A, B, or C, and systematic spacing. As used in this method, 
systematic spacing is intended to include evenly spaced increments in 
time or increments based on equal weights of coal passing the 
collection area. As a minimum, determine the number and weight of 
increments required per gross sample representing each coal lot 
according to Table 2 or Paragraph 7.1.5.2 of ASTM D 2234. Collect one 
gross sample for each lot of raw coal and one gross sample for each lot 
of product coal.
    12.5.2.1.2  ASTM Lot Size. For the purpose of Section 12.5.2 (fuel 
pretreatment), the lot size of product coal is the weight of product 
coal from one type of raw coal. The lot size of raw coal is the weight 
of raw coal used to produce one lot of product coal. Typically, the lot 
size is the weight of coal processed in a 1-day (24-hour) period. If 
more than one type of coal is treated and produced in 1 day, then gross 
samples must be collected and analyzed for each type of coal. A coal 
lot size equaling the 90-day quarterly fuel quantity for a steam 
generating unit may be used if representative sampling can be conducted 
for each raw coal and product coal.

    Note: Alternative definitions of lot sizes may be used, subject 
to prior approval of the Administrator.

    12.5.2.1.3  Gross Sample Analysis. Use ASTM D 2013-72 or 86 to 
prepare the sample, ASTM D 3177-75 or 89 or ASTM D 4239-85, 94, or 97 
to determine sulfur content (%S), ASTM D 3173-73 or 87 to determine 
moisture content, and ASTM D 2015-77 (Reapproved 1978) or 96, D 3286-85 
or 96, or D 5865-98 to determine gross calorific value (GCV) (all 
standards cited are incorporated by reference--see Sec. 60.17 for 
acceptable versions of the standards) on a dry basis for each gross 
sample.
    12.5.2.2  Liquid Fossil Fuel-Sampling and Analysis. See Note under 
Section 12.5.2.1.
    12.5.2.2.1  Sample Collection. Follow the procedures for continuous 
sampling in ASTM D 270 or D 4177-95 (incorporated by reference--see 
Sec. 60.17) for each gross sample from each fuel lot.
    12.5.2.2.2  Lot Size. For the purpose of Section 12.5.2 (fuel 
pretreatment), the lot size of a product oil is the weight of product 
oil from one pretreatment facility and intended as one shipment (ship 
load, barge load, etc.). The lot size of raw oil is the weight of each 
crude liquid fuel type used to produce a lot of product oil.

    Note: Alternative definitions of lot sizes may be used, subject 
to prior approval of the Administrator.

    12.5.2.2.3  Sample Analysis. Use ASTM D 129-64, 78, or 95, ASTM D 
1552-83 or 95, or ASTM D 4057-81 or 95 to determine the sulfur content 
(%S) and ASTM D 240-76 or 92 (all standards cited are incorporated by 
reference--see Sec. 60.17) to determine the GCV of each gross sample. 
These values may be assumed to be on a dry basis. The owner or operator 
of an affected facility may elect to determine the GCV by sampling the 
oil combusted on the first steam generating unit operating day of each 
calendar month and then using the lowest GCV value of the three GCV 
values per quarter for the GCV of all oil combusted in that calendar 
quarter.
    12.5.2.3  Use appropriate procedures, subject to the approval of 
the Administrator, to determine the fraction of total mass input 
derived from each type of fuel.
    12.5.3  Control Device Removal Efficiency. Compute the percent 
removal efficiency (%Rg) of the control device using the 
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.344

    12.5.3.1  Use continuous emission monitoring systems or test 
methods, as appropriate, to determine the outlet SO2 rates 
and, if appropriate, the inlet SO2 rates. The rates may be 
determined as hourly (Eh) or other sampling period averages 
(Ed). Then, compute the average pollutant rates for the 
performance test period (Eao and Eai) using the 
procedures in Section 12.4.
    12.5.3.2  As an alternative, as-fired fuel sampling and analysis 
may be used to determine inlet SO2 rates as follows:
    12.5.3.2.1  Compute the average inlet SO2 rate 
(Edi) for each sampling period using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.345

Where:
[GRAPHIC] [TIFF OMITTED] TR17OC00.346

After calculating Edi, use the procedures in Section 12.4 to 
determine the average inlet SO2 rate for the performance 
test period (Eai).
    12.5.3.2.2  Collect the fuel samples from a location in the fuel 
handling system that provides a sample representative of the fuel 
bunkered or consumed during a steam generating unit operating day. For 
the purpose of as-fired fuel sampling under Section 12.5.3.2 or Section 
12.6, the lot size for coal is the weight of coal bunkered or consumed 
during each steam generating unit operating day. The lot size for oil 
is the weight of oil supplied to the ``day'' tank or consumed during 
each steam generating unit operating day. For reporting and calculation 
purposes, the gross sample shall be identified with the calendar day on 
which sampling began. For steam generating unit operating days when a 
coal-fired steam generating unit is operated without coal being added 
to the bunkers, the coal analysis from the previous ``as bunkered'' 
coal sample shall be used until coal is bunkered again. For steam 
generating unit operating days when an oil-fired steam generating unit 
is operated without oil being added to the oil ``day'' tank, the oil 
analysis from the previous day shall be used until the ``day'' tank is 
filled again. Alternative definitions of fuel lot size may be used, 
subject to prior approval of the Administrator.
    12.5.3.2.3  Use ASTM procedures specified in Section 12.5.2.1 or 
12.5.2.2 to determine %S and GCV.
    12.5.4  Daily Geometric Average Percent Reduction from Hourly 
Values. The geometric average percent reduction (%Rga) is 
computed using the following equation:

[[Page 62033]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.347

    Note: The calculation includes only paired data sets (hourly 
average) for the inlet and outlet pollutant measurements.
    12.6  Sulfur Retention Credit for Compliance Fuel. If fuel sampling 
and analysis procedures in Section 12.5.2.1 are being used to determine 
average SO2 emission rates (Eas) to the 
atmosphere from a coal-fired steam generating unit when there is no 
SO2 control device, the following equation may be used to 
adjust the emission rate for sulfur retention credits (no credits are 
allowed for oil-fired systems) (Edi) for each sampling 
period using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.348

Where:
[GRAPHIC] [TIFF OMITTED] TR17OC00.349

    After calculating Edi, use the procedures in Section 
12.4.2 to determine the average SO2 emission rate to the 
atmosphere for the performance test period (Eao).
    12.7  Determination of Compliance When Minimum Data Requirement Is 
Not Met.
    12.7.1  Adjusted Emission Rates and Control Device Removal 
Efficiency. When the minimum data requirement is not met, the 
Administrator may use the following adjusted emission rates or control 
device removal efficiencies to determine compliance with the applicable 
standards.
    12.7.1.1  Emission Rate. Compliance with the emission rate standard 
may be determined by using the lower confidence limit of the emission 
rate (Eao*) as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.350

    12.7.1.2  Control Device Removal Efficiency. Compliance with the 
overall emission reduction (%Ro) may be determined by using 
the lower confidence limit of the emission rate (Eao*) and 
the upper confidence limit of the inlet pollutant rate 
(Eai*) in calculating the control device removal efficiency 
(%Rg) as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.351

[GRAPHIC] [TIFF OMITTED] TR17OC00.352

    12.7.2  Standard Deviation of Hourly Average Pollutant Rates. 
Compute the standard deviation (Se) of the hourly average 
pollutant rates using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.353

    Equation 19-19 through 19-31 may be used to compute the standard 
deviation for both the outlet (So) and, if applicable, inlet 
(Si) pollutant rates.

13.0  Method Performance [Reserved]

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References [Reserved]

17.0  Tables, Diagrams, Flowcharts, and Validation Data

                                Table 19-1.--Conversion Factors for Concentration
----------------------------------------------------------------------------------------------------------------
                  From                                   To                             Multiply by
----------------------------------------------------------------------------------------------------------------
g/scm...................................  ng/scm.........................  10\9\
mg/scm..................................  ng/scm.........................  10\6\
lb/scf..................................  ng/scm.........................  1.602  x  10\13\
ppm SO2.................................  ng/scm.........................  2.66  x  10\6\
ppm NOx.................................  ng/scm.........................  1.912  x  10\6\
ppm SO2.................................  lb/scf.........................  1.660  x  10-\7\
ppm NOx.................................  lb/scf.........................  1.194  x  10-7
----------------------------------------------------------------------------------------------------------------


[[Page 62034]]


                                                       Table 19-2.--F Factors for Various Fuels\1\
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                                                        Fd                              Fw                              Fc
                        Fuel Type                        -----------------------------------------------------------------------------------------------
                                                              dscm/J      dscf/10\6\ Btu      wscm/J      wscf/10\6\ Btu       scm/J       scf/10\6\ Btu
--------------------------------------------------------------------------------------------------------------------------------------------------------
Coal:
    Anthracite 2........................................     2.71 x 10-7          10,100     2.83 x 10-7          10,540    0.530 x 10-7           1,970
    Bituminus 2.........................................     2.63 x 10-7           9,780     2.86 x 10-7          10,640    0.484 x 10-7           1,800
    Lignite.............................................     2.65 x 10-7           9,860     3.21 x 10-7          11,950    0.513 x 10-7           1,910
    Oil \3\.............................................     2.47 x 10-7           9,190     2.77 x 10-7          10,320    0.383 x 10-7           1,420
Gas:....................................................
    Natural.............................................     2.34 x 10-7           8,710     2.85 x 10-7          10,610    0.287 x 10-7           1,040
    Propane.............................................     2.34 x 10-7           8,710     2.74 x 10-7          10,200    0.321 x 10-7           1,190
    Butane..............................................     2.34 x 10-7           8,710     2.79 x 10-7          10,390    0.337 x 10-7           1,250
Wood....................................................     2.48 x 10-7           9,240  ..............  ..............    0.492 x 10-7           1,830
Wood Bark...............................................     2.58 x 10-7           9,600  ..............  ..............    0.516 x 10-7           1,920
Municipal...............................................     2.57 x 10-7           9,570  ..............  ..............    0.488 x 10-7           1,820
Solid Waste.............................................  ..............  ..............  ..............  ..............  ..............  ..............
--------------------------------------------------------------------------------------------------------------------------------------------------------
\1\ Determined at standard conditions: 20  deg.C (68  deg.F) and 760 mm Hg (29.92 in Hg)
\2\ As classified according to ASTM D 388.
\3\ Crude, residual, or distillate.


                                         Table 19-3.--Values for T0.95*
----------------------------------------------------------------------------------------------------------------
                       n\1\                            t0.95       n\1\        t0.95        n\1\         t0.95
----------------------------------------------------------------------------------------------------------------
2.................................................        6.31           8        1.89         22-26        1.71
3.................................................        2.42           9        1.86         27-31        1.70
4.................................................        2.35          10        1.83         32-51        1.68
5.................................................        2.13          11        1.81         52-91        1.67
6.................................................        2.02       12-16        1.77        92-151        1.66
7.................................................        1.94       17-21        1.73   152 or more       1.65
----------------------------------------------------------------------------------------------------------------
\1\The values of this table are corrected for n-1 degrees of freedom. Use n equal to the number (H) of hourly
  average data points.

* * * * *

Method 21--Determination of Volatile Organic Compound Leaks

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
                  Analyte                              CAS No.
------------------------------------------------------------------------
Volatile Organic Compounds (VOC)..........  No CAS number assigned.
------------------------------------------------------------------------

    1.2 Scope. This method is applicable for the determination of VOC 
leaks from process equipment. These sources include, but are not 
limited to, valves, flanges and other connections, pumps and 
compressors, pressure relief devices, process drains, open-ended 
valves, pump and compressor seal system degassing vents, accumulator 
vessel vents, agitator seals, and access door seals.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  A portable instrument is used to detect VOC leaks from 
individual sources. The instrument detector type is not specified, but 
it must meet the specifications and performance criteria contained in 
Section 6.0. A leak definition concentration based on a reference 
compound is specified in each applicable regulation. This method is 
intended to locate and classify leaks only, and is not to be used as a 
direct measure of mass emission rate from individual sources.

3.0  Definitions

    3.1  Calibration gas means the VOC compound used to adjust the 
instrument meter reading to a known value. The calibration gas is 
usually the reference compound at a known concentration approximately 
equal to the leak definition concentration.
    3.2  Calibration precision means the degree of agreement between 
measurements of the same known value, expressed as the relative 
percentage of the average difference between the meter readings and the 
known concentration to the known concentration.
    3.3  Leak definition concentration means the local VOC 
concentration at the surface of a leak source that indicates that a VOC 
emission (leak) is present. The leak definition is an instrument meter 
reading based on a reference compound.
    3.4  No detectable emission means a local VOC concentration at the 
surface of a leak source, adjusted for local VOC ambient concentration, 
that is less than 2.5 percent of the specified leak definition 
concentration. that indicates that a VOC emission (leak) is not 
present.
    3.5  Reference compound means the VOC species selected as the 
instrument calibration basis for specification of the leak definition 
concentration. (For example, if a leak definition concentration is 
10,000 ppm as methane, then any source emission that results in a local 
concentration that yields a meter reading of 10,000 on an instrument 
meter calibrated with methane would be classified as a leak. In this 
example, the leak definition concentration is 10,000 ppm and the 
reference compound is methane.)
    3.6  Response factor means the ratio of the known concentration of 
a VOC compound to the observed meter reading when measured using an 
instrument calibrated with the reference compound specified in the 
applicable regulation.
    3.7  Response time means the time interval from a step change in 
VOC concentration at the input of the sampling system to the time at 
which 90 percent of the corresponding final value is reached as 
displayed on the instrument readout meter.

[[Page 62035]]

4.0  Interferences. [Reserved]

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Hazardous Pollutants. Several of the compounds, leaks of which 
may be determined by this method, may be irritating or corrosive to 
tissues (e.g., heptane) or may be toxic (e.g., benzene, methyl 
alcohol). Nearly all are fire hazards. Compounds in emissions should be 
determined through familiarity with the source. Appropriate precautions 
can be found in reference documents, such as reference No. 4 in Section 
16.0.

6.0  Equipment and Supplies

    A VOC monitoring instrument meeting the following specifications is 
required:
    6.1  The VOC instrument detector shall respond to the compounds 
being processed. Detector types that may meet this requirement include, 
but are not limited to, catalytic oxidation, flame ionization, infrared 
absorption, and photoionization.
    6.2  The instrument shall be capable of measuring the leak 
definition concentration specified in the regulation.
    6.3  The scale of the instrument meter shall be readable to 
2.5 percent of the specified leak definition concentration.
    6.4  The instrument shall be equipped with an electrically driven 
pump to ensure that a sample is provided to the detector at a constant 
flow rate. The nominal sample flow rate, as measured at the sample 
probe tip, shall be 0.10 to 3.0 l/min (0.004 to 0.1 ft\3\/min) when the 
probe is fitted with a glass wool plug or filter that may be used to 
prevent plugging of the instrument.
    6.5  The instrument shall be equipped with a probe or probe 
extension or sampling not to exceed 6.4 mm (\1/4\ in) in outside 
diameter, with a single end opening for admission of sample.
    6.6  The instrument shall be intrinsically safe for operation in 
explosive atmospheres as defined by the National Electrical Code by the 
National Fire Prevention Association or other applicable regulatory 
code for operation in any explosive atmospheres that may be encountered 
in its use. The instrument shall, at a minimum, be intrinsically safe 
for Class 1, Division 1 conditions, and/or Class 2, Division 1 
conditions, as appropriate, as defined by the example code. The 
instrument shall not be operated with any safety device, such as an 
exhaust flame arrestor, removed.

7.0  Reagents and Standards

    7.1  Two gas mixtures are required for instrument calibration and 
performance evaluation:
    7.1.1  Zero Gas. Air, less than 10 parts per million by volume 
(ppmv) VOC.
    7.1.2  Calibration Gas. For each organic species that is to be 
measured during individual source surveys, obtain or prepare a known 
standard in air at a concentration approximately equal to the 
applicable leak definition specified in the regulation.
    7.2  Cylinder Gases. If cylinder calibration gas mixtures are used, 
they must be analyzed and certified by the manufacturer to be within 2 
percent accuracy, and a shelf life must be specified. Cylinder 
standards must be either reanalyzed or replaced at the end of the 
specified shelf life.
    7.3  Prepared Gases. Calibration gases may be prepared by the user 
according to any accepted gaseous preparation procedure that will yield 
a mixture accurate to within 2 percent. Prepared standards must be 
replaced each day of use unless it is demonstrated that degradation 
does not occur during storage.
    7.4  Mixtures with non-Reference Compound Gases. Calibrations may 
be performed using a compound other than the reference compound. In 
this case, a conversion factor must be determined for the alternative 
compound such that the resulting meter readings during source surveys 
can be converted to reference compound results.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Instrument Performance Evaluation. Assemble and start up the 
instrument according to the manufacturer's instructions for recommended 
warmup period and preliminary adjustments.
    8.1.1  Response Factor. A response factor must be determined for 
each compound that is to be measured, either by testing or from 
reference sources. The response factor tests are required before 
placing the analyzer into service, but do not have to be repeated at 
subsequent intervals.
    8.1.1.1  Calibrate the instrument with the reference compound as 
specified in the applicable regulation. Introduce the calibration gas 
mixture to the analyzer and record the observed meter reading. 
Introduce zero gas until a stable reading is obtained. Make a total of 
three measurements by alternating between the calibration gas and zero 
gas. Calculate the response factor for each repetition and the average 
response factor.
    8.1.1.2  The instrument response factors for each of the individual 
VOC to be measured shall be less than 10 unless otherwise specified in 
the applicable regulation. When no instrument is available that meets 
this specification when calibrated with the reference VOC specified in 
the applicable regulation, the available instrument may be calibrated 
with one of the VOC to be measured, or any other VOC, so long as the 
instrument then has a response factor of less than 10 for each of the 
individual VOC to be measured.
    8.1.1.3  Alternatively, if response factors have been published for 
the compounds of interest for the instrument or detector type, the 
response factor determination is not required, and existing results may 
be referenced. Examples of published response factors for flame 
ionization and catalytic oxidation detectors are included in References 
1-3 of Section 17.0.
    8.1.2  Calibration Precision. The calibration precision test must 
be completed prior to placing the analyzer into service and at 
subsequent 3-month intervals or at the next use, whichever is later.
    8.1.2.1  Make a total of three measurements by alternately using 
zero gas and the specified calibration gas. Record the meter readings. 
Calculate the average algebraic difference between the meter readings 
and the known value. Divide this average difference by the known 
calibration value and multiply by 100 to express the resulting 
calibration precision as a percentage.
    8.1.2.2  The calibration precision shall be equal to or less than 
10 percent of the calibration gas value.
    8.1.3  Response Time. The response time test is required before 
placing the instrument into service. If a modification to the sample 
pumping system or flow configuration is made that would change the 
response time, a new test is required before further use.
    8.1.3.1  Introduce zero gas into the instrument sample probe. When 
the meter reading has stabilized, switch quickly to the specified 
calibration gas. After switching, measure the time required to attain 
90 percent of the final stable reading. Perform this test sequence 
three times and record the

[[Page 62036]]

results. Calculate the average response time.
    8.1.3.2  The instrument response time shall be equal to or less 
than 30 seconds. The instrument pump, dilution probe (if any), sample 
probe, and probe filter that will be used during testing shall all be 
in place during the response time determination.
    8.2  Instrument Calibration. Calibrate the VOC monitoring 
instrument according to Section 10.0.
    8.3  Individual Source Surveys.
    8.3.1  Type I--Leak Definition Based on Concentration. Place the 
probe inlet at the surface of the component interface where leakage 
could occur. Move the probe along the interface periphery while 
observing the instrument readout. If an increased meter reading is 
observed, slowly sample the interface where leakage is indicated until 
the maximum meter reading is obtained. Leave the probe inlet at this 
maximum reading location for approximately two times the instrument 
response time. If the maximum observed meter reading is greater than 
the leak definition in the applicable regulation, record and report the 
results as specified in the regulation reporting requirements. Examples 
of the application of this general technique to specific equipment 
types are:
    8.3.1.1  Valves. The most common source of leaks from valves is the 
seal between the stem and housing. Place the probe at the interface 
where the stem exits the packing gland and sample the stem 
circumference. Also, place the probe at the interface of the packing 
gland take-up flange seat and sample the periphery. In addition, survey 
valve housings of multipart assembly at the surface of all interfaces 
where a leak could occur.
    8.3.1.2  Flanges and Other Connections. For welded flanges, place 
the probe at the outer edge of the flange-gasket interface and sample 
the circumference of the flange. Sample other types of nonpermanent 
joints (such as threaded connections) with a similar traverse.
    8.3.1.3  Pumps and Compressors. Conduct a circumferential traverse 
at the outer surface of the pump or compressor shaft and seal 
interface. If the source is a rotating shaft, position the probe inlet 
within 1 cm of the shaft-seal interface for the survey. If the housing 
configuration prevents a complete traverse of the shaft periphery, 
sample all accessible portions. Sample all other joints on the pump or 
compressor housing where leakage could occur.
    8.3.1.4  Pressure Relief Devices. The configuration of most 
pressure relief devices prevents sampling at the sealing seat 
interface. For those devices equipped with an enclosed extension, or 
horn, place the probe inlet at approximately the center of the exhaust 
area to the atmosphere.
    8.3.1.5  Process Drains. For open drains, place the probe inlet at 
approximately the center of the area open to the atmosphere. For 
covered drains, place the probe at the surface of the cover interface 
and conduct a peripheral traverse.
    8.3.1.6  Open-ended Lines or Valves. Place the probe inlet at 
approximately the center of the opening to the atmosphere.
    8.3.1.7  Seal System Degassing Vents and Accumulator Vents. Place 
the probe inlet at approximately the center of the opening to the 
atmosphere.
    8.3.1.8  Access door seals. Place the probe inlet at the surface of 
the door seal interface and conduct a peripheral traverse.
    8.3.2  Type II--``No Detectable Emission''. Determine the local 
ambient VOC concentration around the source by moving the probe 
randomly upwind and downwind at a distance of one to two meters from 
the source. If an interference exists with this determination due to a 
nearby emission or leak, the local ambient concentration may be 
determined at distances closer to the source, but in no case shall the 
distance be less than 25 centimeters. Then move the probe inlet to the 
surface of the source and determine the concentration as outlined in 
Section 8.3.1. The difference between these concentrations determines 
whether there are no detectable emissions. Record and report the 
results as specified by the regulation. For those cases where the 
regulation requires a specific device installation, or that specified 
vents be ducted or piped to a control device, the existence of these 
conditions shall be visually confirmed. When the regulation also 
requires that no detectable emissions exist, visual observations and 
sampling surveys are required. Examples of this technique are:
    8.3.2.1  Pump or Compressor Seals. If applicable, determine the 
type of shaft seal. Perform a survey of the local area ambient VOC 
concentration and determine if detectable emissions exist as described 
in Section 8.3.2.
    8.3.2.2  Seal System Degassing Vents, Accumulator Vessel Vents, 
Pressure Relief Devices. If applicable, observe whether or not the 
applicable ducting or piping exists. Also, determine if any sources 
exist in the ducting or piping where emissions could occur upstream of 
the control device. If the required ducting or piping exists and there 
are no sources where the emissions could be vented to the atmosphere 
upstream of the control device, then it is presumed that no detectable 
emissions are present. If there are sources in the ducting or piping 
where emissions could be vented or sources where leaks could occur, the 
sampling surveys described in Section 8.3.2 shall be used to determine 
if detectable emissions exist.
    8.3.3  Alternative Screening Procedure.
    8.3.3.1  A screening procedure based on the formation of bubbles in 
a soap solution that is sprayed on a potential leak source may be used 
for those sources that do not have continuously moving parts, that do 
not have surface temperatures greater than the boiling point or less 
than the freezing point of the soap solution, that do not have open 
areas to the atmosphere that the soap solution cannot bridge, or that 
do not exhibit evidence of liquid leakage. Sources that have these 
conditions present must be surveyed using the instrument technique of 
Section 8.3.1 or 8.3.2.
    8.3.3.2  Spray a soap solution over all potential leak sources. The 
soap solution may be a commercially available leak detection solution 
or may be prepared using concentrated detergent and water. A pressure 
sprayer or squeeze bottle may be used to dispense the solution. Observe 
the potential leak sites to determine if any bubbles are formed. If no 
bubbles are observed, the source is presumed to have no detectable 
emissions or leaks as applicable. If any bubbles are observed, the 
instrument techniques of Section 8.3.1 or 8.3.2 shall be used to 
determine if a leak exists, or if the source has detectable emissions, 
as applicable.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.1.2.........................  Instrument         Ensure precision and
                                 calibration        accuracy,
                                 precision check.   respectively, of
                                                    instrument response
                                                    to standard.
10.0..........................  Instrument
                                 calibration.
------------------------------------------------------------------------


[[Page 62037]]

10.0 Calibration and Standardization

    10.1  Calibrate the VOC monitoring instrument as follows. After the 
appropriate warmup period and zero internal calibration procedure, 
introduce the calibration gas into the instrument sample probe. Adjust 
the instrument meter readout to correspond to the calibration gas 
value.

    Note: If the meter readout cannot be adjusted to the proper 
value, a malfunction of the analyzer is indicated and corrective 
actions are necessary before use.

11.0  Analytical Procedures. [Reserved]

12.0  Data Analyses and Calculations. [Reserved]

13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    1. Dubose, D.A., and G.E. Harris. Response Factors of VOC 
Analyzers at a Meter Reading of 10,000 ppmv for Selected Organic 
Compounds. U.S. Environmental Protection Agency, Research Triangle 
Park, NC. Publication No. EPA 600/2-81051. September 1981.
    2. Brown, G.E., et al. Response Factors of VOC Analyzers 
Calibrated with Methane for Selected Organic Compounds. U.S. 
Environmental Protection Agency, Research Triangle Park, NC. 
Publication No. EPA 600/2-81-022. May 1981.
    3. DuBose, D.A. et al. Response of Portable VOC Analyzers to 
Chemical Mixtures. U.S. Environmental Protection Agency, Research 
Triangle Park, NC. Publication No. EPA 600/2-81-110. September 1981.
    4. Handbook of Hazardous Materials: Fire, Safety, Health. 
Alliance of American Insurers. Schaumberg, IL. 1983.

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

Method 22--Visual Determination of Fugitive Emissions From Material 
Sources and Smoke Emissions From Flares

    Note: This method is not inclusive with respect to observer 
certification. Some material is incorporated by reference from 
Method 9.

1.0  Scope and Application

    This method is applicable for the determination of the frequency of 
fugitive emissions from stationary sources, only as specified in an 
applicable subpart of the regulations. This method also is applicable 
for the determination of the frequency of visible smoke emissions from 
flares.

2.0  Summary of Method

    2.1  Fugitive emissions produced during material processing, 
handling, and transfer operations or smoke emissions from flares are 
visually determined by an observer without the aid of instruments.
    2.2  This method is used also to determine visible smoke emissions 
from flares used for combustion of waste process materials.
    2.3  This method determines the amount of time that visible 
emissions occur during the observation period (i.e., the accumulated 
emission time). This method does not require that the opacity of 
emissions be determined. Since this procedure requires only the 
determination of whether visible emissions occur and does not require 
the determination of opacity levels, observer certification according 
to the procedures of Method 9 is not required. However, it is necessary 
that the observer is knowledgeable with respect to the general 
procedures for determining the presence of visible emissions. At a 
minimum, the observer must be trained and knowledgeable regarding the 
effects of background contrast, ambient lighting, observer position 
relative to lighting, wind, and the presence of uncombined water 
(condensing water vapor) on the visibility of emissions. This training 
is to be obtained from written materials found in References 1 and 2 or 
from the lecture portion of the Method 9 certification course.

3.0  Definitions

    3.1  Emission frequency means the percentage of time that emissions 
are visible during the observation period.
    3.2  Emission time means the accumulated amount of time that 
emissions are visible during the observation period.
    3.3  Fugitive emissions means emissions generated by an affected 
facility which is not collected by a capture system and is released to 
the atmosphere. This includes emissions that (1) escape capture by 
process equipment exhaust hoods; (2) are emitted during material 
transfer; (3) are emitted from buildings housing material processing or 
handling equipment; or (4) are emitted directly from process equipment.
    3.4  Observation period means the accumulated time period during 
which observations are conducted, not to be less than the period 
specified in the applicable regulation.
    3.5  Smoke emissions means a pollutant generated by combustion in a 
flare and occurring immediately downstream of the flame. Smoke 
occurring within the flame, but not downstream of the flame, is not 
considered a smoke emission.

4.0  Interferences

    4.1  Occasionally, fugitive emissions from sources other than the 
affected facility (e.g., road dust) may prevent a clear view of the 
affected facility. This may particularly be a problem during periods of 
high wind. If the view of the potential emission points is obscured to 
such a degree that the observer questions the validity of continuing 
observations, then the observations shall be terminated, and the 
observer shall clearly note this fact on the data form.

5.0  Safety

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

6.0  Equipment

    6.1  Stopwatches (two). Accumulative type with unit divisions of at 
least 0.5 seconds.
    6.2  Light Meter. Light meter capable of measuring illuminance in 
the 50 to 200 lux range, required for indoor observations only.

7.0  Reagents and Supplies. [Reserved]

8.0  Sample Collection, Preservation, Storage, and Transfer. [Reserved]

9.0  Quality Control. [Reserved]

10.0  Calibration and Standardization. [Reserved]

11.0  Analytical Procedure

    11.1  Selection of Observation Location. Survey the affected 
facility, or the building or structure housing the process to be 
observed, and determine the locations of potential emissions. If the 
affected facility is located inside a building, determine an 
observation location that is consistent with the requirements of the 
applicable regulation (i.e., outside observation of emissions escaping 
the building/structure or inside observation of emissions directly 
emitted from the affected facility process unit). Then select a 
position that enables a clear view of the potential emission point(s) 
of the affected facility or of the building or structure housing the 
affected facility, as appropriate for the applicable subpart. A 
position at least 4.6 m (15 feet), but not more than 400 m (0.25 
miles), from the emission source is recommended. For outdoor locations, 
select a position where the sunlight is

[[Page 62038]]

not shining directly in the observer's eyes.
    11.2  Field Records.
    11.2.1  Outdoor Location. Record the following information on the 
field data sheet (Figure 22-1): Company name, industry, process unit, 
observer's name, observer's affiliation, and date. Record also the 
estimated wind speed, wind direction, and sky condition. Sketch the 
process unit being observed, and note the observer location relative to 
the source and the sun. Indicate the potential and actual emission 
points on the sketch.
    11.2.2  Indoor Location. Record the following information on the 
field data sheet (Figure 22-2): Company name, industry, process unit, 
observer's name, observer's affiliation, and date. Record as 
appropriate the type, location, and intensity of lighting on the data 
sheet. Sketch the process unit being observed, and note the observer 
location relative to the source. Indicate the potential and actual 
fugitive emission points on the sketch.
    11.3  Indoor Lighting Requirements. For indoor locations, use a 
light meter to measure the level of illumination at a location as close 
to the emission source(s) as is feasible. An illumination of greater 
than 100 lux (10 foot candles) is considered necessary for proper 
application of this method.
    11.4  Observations.
    11.4.1  Procedure. Record the clock time when observations begin. 
Use one stopwatch to monitor the duration of the observation period. 
Start this stopwatch when the observation period begins. If the 
observation period is divided into two or more segments by process 
shutdowns or observer rest breaks (see Section 11.4.3), stop the 
stopwatch when a break begins and restart the stopwatch without 
resetting it when the break ends. Stop the stopwatch at the end of the 
observation period. The accumulated time indicated by this stopwatch is 
the duration of observation period. When the observation period is 
completed, record the clock time. During the observation period, 
continuously watch the emission source. Upon observing an emission 
(condensed water vapor is not considered an emission), start the second 
accumulative stopwatch; stop the watch when the emission stops. 
Continue this procedure for the entire observation period. The 
accumulated elapsed time on this stopwatch is the total time emissions 
were visible during the observation period (i.e., the emission time.)
    11.4.2  Observation Period. Choose an observation period of 
sufficient length to meet the requirements for determining compliance 
with the emission standard in the applicable subpart of the 
regulations. When the length of the observation period is specifically 
stated in the applicable subpart, it may not be necessary to observe 
the source for this entire period if the emission time required to 
indicate noncompliance (based on the specified observation period) is 
observed in a shorter time period. In other words, if the regulation 
prohibits emissions for more than 6 minutes in any hour, then 
observations may (optional) be stopped after an emission time of 6 
minutes is exceeded. Similarly, when the regulation is expressed as an 
emission frequency and the regulation prohibits emissions for greater 
than 10 percent of the time in any hour, then observations may 
(optional) be terminated after 6 minutes of emission are observed since 
6 minutes is 10 percent of an hour. In any case, the observation period 
shall not be less than 6 minutes in duration. In some cases, the 
process operation may be intermittent or cyclic. In such cases, it may 
be convenient for the observation period to coincide with the length of 
the process cycle.
    11.4.3  Observer Rest Breaks. Do not observe emissions continuously 
for a period of more than 15 to 20 minutes without taking a rest break. 
For sources requiring observation periods of greater than 20 minutes, 
the observer shall take a break of not less than 5 minutes and not more 
than 10 minutes after every 15 to 20 minutes of observation. If 
continuous observations are desired for extended time periods, two 
observers can alternate between making observations and taking breaks.
    11.5  Recording Observations. Record the accumulated time of the 
observation period on the data sheet as the observation period 
duration. Record the accumulated time emissions were observed on the 
data sheet as the emission time. Record the clock time the observation 
period began and ended, as well as the clock time any observer breaks 
began and ended.

12.0  Data Analysis and Calculations

    If the applicable subpart requires that the emission rate be 
expressed as an emission frequency (in percent), determine this value 
as follows: Divide the accumulated emission time (in seconds) by the 
duration of the observation period (in seconds) or by any minimum 
observation period required in the applicable subpart, if the actual 
observation period is less than the required period, and multiply this 
quotient by 100.

13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    1. Missan, R., and A. Stein. Guidelines for Evaluation of 
Visible Emissions Certification, Field Procedures, Legal Aspects, 
and Background Material. EPA Publication No. EPA-340/1-75-007. April 
1975.
    2. Wohlschlegel, P., and D.E. Wagoner. Guideline for Development 
of a Quality Assurance Program: Volume IX-- Visual Determination of 
Opacity Emissions from Stationary Sources. EPA Publication No. EPA-
650/4-74-005i. November 1975.
BILLING CODE 6560-50-P

[[Page 62039]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.354


[[Page 62040]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.355

BILLING CODE 6560-50-C

[[Page 62041]]

* * * * *

Method 24--Determination of Volatile Matter Content, Water Content, 
Density, Volume Solids, and Weight Solids of Surface Coatings

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
                  Analyte                              CAS No.
------------------------------------------------------------------------
Volatile organic compounds Water..........  No CAS Number assigned 7732-
                                             18-5
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of volatile matter content, water content, density, volume solids, and 
weight solids of paint, varnish, lacquer, or other related surface 
coatings.
    1.3  Precision and Bias. Intra-and inter-laboratory analytical 
precision statements are presented in Section 13.1. No bias has been 
identified.

2.0  Summary of Method

    2.1  Standard methods are used to determine the volatile matter 
content, water content, density, volume solids, and weight solids of 
paint, varnish, lacquer, or other related surface coatings.

3.0  Definitions

    3.1  Waterborne coating means any coating which contains more than 
5 percent water by weight in its volatile fraction.
    3.2  Multicomponent coatings are coatings that are packaged in two 
or more parts, which are combined before application. Upon combination 
a coreactant from one part of the coating chemically reacts, at ambient 
conditions, with a coreactant from another part of the coating.
    3.3  Ultraviolet (UV) radiation-cured coatings are coatings which 
contain unreacted monomers that are polymerized by exposure to 
ultraviolet light.

4.0  Interferences. [Reserved]

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and to determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Hazardous Components. Several of the compounds that may be 
contained in the coatings analyzed by this method may be irritating or 
corrosive to tissues (e.g., heptane) or may be toxic (e.g., benzene, 
methyl alcohol). Nearly all are fire hazards. Appropriate precautions 
can be found in reference documents, such as Reference 3 of Section 
16.0.

6.0  Equipment and Supplies

    The equipment and supplies specified in the ASTM methods listed in 
Sections 6.1 through 6.6 (incorporated by reference--see Sec. 60.17 for 
acceptable versions of the methods) are required:
    6.1  ASTM D 1475-60, 80, or 90, Standard Test Method for Density of 
Paint, Varnish, Lacquer, and Related Products.
    6.2  ASTM D 2369-81, 87, 90, 92, 93, or 95, Standard Test Method 
for Volatile Content of Coatings.
    6.3  ASTM D 3792-79 or 91, Standard Test Method for Water Content 
of Water Reducible Paints by Direct Injection into a Gas Chromatograph.
    6.4  ASTM D 4017-81, 90, or 96a, Standard Test Method for Water in 
Paints and Paint Materials by the Karl Fischer Titration Method.
    6.5  ASTM 4457-85 91, Standard Test Method for Determination of 
Dichloromethane and 1,1,1-Trichloroethane in Paints and Coatings by 
Direct Injection into a Gas Chromatograph.
    6.6  ASTM D 5403-93, Standard Test Methods for Volatile Content of 
Radiation Curable Materials.

7.0  Reagents and Standards

    7.1  The reagents and standards specified in the ASTM methods 
listed in Sections 6.1 through 6.6 are required.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Follow the sample collection, preservation, storage, and 
transport procedures described in Reference 1 of Section 16.0.

9.0  Quality Control

    9.1  Reproducibility

    Note:
    Not applicable to UV radiation-cured coatings). The variety of 
coatings that may be subject to analysis makes it necessary to 
verify the ability of the analyst and the analytical procedures to 
obtain reproducible results for the coatings tested. Verification is 
accomplished by running duplicate analyses on each sample tested 
(Sections 11.2 through 11.4) and comparing the results with the 
intra-laboratory precision statements (Section 13.1) for each 
parameter.


    9.2  Confidence Limits for Waterborne Coatings. Because of the 
inherent increased imprecision in the determination of the VOC content 
of waterborne coatings as the weight percent of water increases, 
measured parameters for waterborne coatings are replaced with 
appropriate confidence limits (Section 12.6). These confidence limits 
are based on measured parameters and inter-laboratory precision 
statements.

10.0  Calibration and Standardization

    10.1  Perform the calibration and standardization procedures 
specified in the ASTM methods listed in Sections 6.1 through 6.6.

11.0  Analytical Procedure

    Additional guidance can be found in Reference 2 of Section 16.0.
    11.1  Non Thin-film Ultraviolet Radiation-cured (UV radiation-
cured) Coatings.
    11.1.1  Volatile Content. Use the procedure in ASTM D 5403 to 
determine the volatile matter content of the coating except the curing 
test described in NOTE 2 of ASTM D 5403 is required.
    11.1.2  Water Content. To determine water content, follow Section 
11.3.2.
    11.1.3  Coating Density. To determine coating density, follow 
Section 11.3.3.
    11.1.4  Solids Content. To determine solids content, follow Section 
11.3.4.
    11.1.5  To determine if a coating or ink can be classified as a 
thin-film UV cured coating or ink, use the equation in Section 12.2. If 
C is less than 0.2 g and A is greater than or equal to 225 cm\2\ (35 
in\2\) then the coating or ink is considered a thin-film UV radiation-
cured coating and ASTM D 5403 is not applicable.

    Note: As noted in Section 1.4 of ASTM D 5403, this method may 
not be applicable to radiation curable materials wherein the 
volatile material is water.

    11.2  Multi-component Coatings.
    11.2.1  Sample Preparation.
    11.2.1.1  Prepare about 100 ml of sample by mixing the components 
in a storage container, such as a glass jar with a screw top or a metal 
can with a cap. The storage container should be just large enough to 
hold the mixture. Combine the components (by weight or volume) in the 
ratio recommended by the manufacturer. Tightly close the container 
between additions and during mixing to prevent loss of volatile 
materials. However, most manufacturers mixing instructions are by 
volume. Because of possible error caused by expansion of the liquid 
when measuring the volume, it is recommended that the components be 
combined by weight. When weight is used to combine the components and 
the manufacturer's recommended ratio is by volume, the density must be 
determined by Section 11.3.3.

[[Page 62042]]

    11.2.1.2  Immediately after mixing, take aliquots from this 100 ml 
sample for determination of the total volatile content, water content, 
and density.
    11.2.2  Volatile Content. To determine total volatile content, use 
the apparatus and reagents described in ASTM D2369 Sections 3 and 4 
(incorporated by reference--see Sec. 60.17 for the approved versions of 
the standard), respectively, and use the following procedures:
    11.2.2.1  Weigh and record the weight of an aluminum foil weighing 
dish. Add 3  1 ml of suitable solvent as specified in ASTM 
D2369 to the weighing dish. Using a syringe as specified in ASTM D2369, 
weigh to 1 mg, by difference, a sample of coating into the weighing 
dish. For coatings believed to have a volatile content less than 40 
weight percent, a suitable size is 0.3 + 0.10 g, but for coatings 
believed to have a volatile content greater than 40 weight percent, a 
suitable size is 0.5  0.1 g.

    Note: If the volatile content determined pursuant to Section 
12.4 is not in the range corresponding to the sample size chosen 
repeat the test with the appropriate sample size. Add the specimen 
dropwise, shaking (swirling) the dish to disperse the specimen 
completely in the solvent. If the material forms a lump that cannot 
be dispersed, discard the specimen and prepare a new one. Similarly, 
prepare a duplicate. The sample shall stand for a minimum of 1 hour, 
but no more than 24 hours prior to being oven cured at 110 
 5 deg.C (230  9 deg.F) for 1 hour.

    11.2.2.2  Heat the aluminum foil dishes containing the dispersed 
specimens in the forced draft oven for 60 min at 110  
5 deg.C (230  9 deg.F). Caution--provide adequate 
ventilation, consistent with accepted laboratory practice, to prevent 
solvent vapors from accumulating to a dangerous level.
    11.2.2.3  Remove the dishes from the oven, place immediately in a 
desiccator, cool to ambient temperature, and weigh to within 1 mg.
    11.2.2.4  Run analyses in pairs (duplicate sets) for each coating 
mixture until the criterion in Section 11.4 is met. Calculate 
WV following Equation 24-2 and record the arithmetic 
average.
    11.2.3  Water Content. To determine water content, follow Section 
11.3.2.
    11.2.4  Coating Density. To determine coating density, follow 
Section 11.3.3.
    11.2.5  Solids Content. To determine solids content, follow Section 
11.3.4.
    11.2.6  Exempt Solvent Content. To determine the exempt solvent 
content, follow Section 11.3.5.

    Note: For all other coatings (i.e., water-or solvent-borne 
coatings) not covered by multicomponent or UV radiation-cured 
coatings, analyze as shown below:

    11.3  Water-or Solvent-borne coatings.
    11.3.1  Volatile Content. Use the procedure in ASTM D 2369 to 
determine the volatile matter content (may include water) of the 
coating.
    11.3.1.1  Record the following information:

W1 = weight of dish and sample before heating, g
W2 = weight of dish and sample after heating, g
W3 = sample weight, g.

    11.3.1.2  Calculate the weight fraction of the volatile matter 
(Wv) for each analysis as shown in Section 12.3.
    11.3.1.3  Run duplicate analyses until the difference between the 
two values in a set is less than or equal to the intra-laboratory 
precision statement in Section 13.1.
    11.3.1.4  Record the arithmetic average (Wv).
    11.3.2  Water Content. For waterborne coatings only, determine the 
weight fraction of water (Ww) using either ASTM D 3792 or 
ASTM D 4017.
    11.3.2.1  Run duplicate analyses until the difference between the 
two values in a set is less than or equal to the intra-laboratory 
precision statement in Section 13.1.
    11.3.2.2  Record the arithmetic average (ww).
    11.3.3  Coating Density. Determine the density (Dc, kg/l) of the 
surface coating using the procedure in ASTM D 1475.
    11.3.3.1  Run duplicate analyses until each value in a set deviates 
from the mean of the set by no more than the intra-laboratory precision 
statement in Section 13.1.
    11.3.3.2  Record the arithmetic average (Dc).
    11.3.4  Solids Content. Determine the volume fraction 
(Vs) solids of the coating by calculation using the 
manufacturer's formulation.
    11.3.5  Exempt Solvent Content. Determine the weight fraction of 
exempt solvents (WE) by using ASTM Method D4457. Run a 
duplicate set of determinations and record the arithmetic average 
(WE).
    11.4  Sample Analysis Criteria. For Wv and 
Ww, run duplicate analyses until the difference between the 
two values in a set is less than or equal to the intra-laboratory 
precision statement for that parameter. For Dc, run 
duplicate analyses until each value in a set deviates from the mean of 
the set by no more than the intra-laboratory precision statement. If, 
after several attempts, it is concluded that the ASTM procedures cannot 
be used for the specific coating with the established intra-laboratory 
precision (excluding UV radiation-cured coatings), the U.S. 
Environmental Protection Agency (EPA) will assume responsibility for 
providing the necessary procedures for revising the method or precision 
statements upon written request to: Director, Emissions, Monitoring, 
and Analysis Division, MD-14, Office of Air Quality Planning and 
Standards, U.S. Environmental Protection Agency, Research Triangle 
Park, NC 27711.

12.0  Calculations and Data Analysis

    12.1  Nomenclature.

A = Area of substrate, cm2, (in2).
C = Amount of coating or ink added to the substrate, g.
Dc = Density of coating or ink, g/cm\3\ (g/in\3\).
F = Manufacturer's recommended film thickness, cm (in).
Wo = Weight fraction of nonaqueous volatile matter, g/g.
Ws = Weight fraction of solids, g/g.
Wv = Weight fraction of the volatile matter, g/g.
Ww = Weight fraction of the water, g/g.
    12.2  To determine if a coating or ink can be classified as a thin-
film UV cured coating or ink, use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.356

    12.3  Calculate Wv for each analysis as shown below:
    [GRAPHIC] [TIFF OMITTED] TR17OC00.357
    
    12.4  Nonaqueous Volatile Matter.
    12.4.1  Solvent-borne Coatings.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.358
    
    12.4.2  Waterborne Coatings.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.359
    
    12.4.3  Coatings Containing Exempt Solvents.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.360
    
    12.5  Weight Fraction Solids.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.361
    
    12.6  Confidence Limit Calculations for Waterborne Coatings. To 
calculate the lower confidence limit, subtract the appropriate inter-
laboratory precision value from the measured mean value for that 
parameter. To calculate the upper confidence limit, add the appropriate 
inter-laboratory precision value to the measured mean value for that 
parameter. For Wv and Dc, use the lower 
confidence limits; for Ww, use the upper confidence limit. 
Because Ws is calculated, there is no adjustment for this 
parameter.

[[Page 62043]]

13.0  Method Performance

    13.1  Analytical Precision Statements. The intra-and inter-
laboratory precision statements are given in Table 24-1 in Section 
17.0.

14.0  Pollution Prevention [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    Same as specified in Section 6.0, with the addition of the 
following:
    1. Standard Procedure for Collection of Coating and Ink Samples for 
Analysis by Reference Methods 24 and 24A. EPA-340/1-91-010. U.S. 
Environmental Protection Agency, Stationary Source Compliance Division, 
Washington, D.C. September 1991.
    2. Standard Operating Procedure for Analysis of Coating and Ink 
Samples by Reference Methods 24 and 24A.
    EPA-340/1-91-011. U.S. Environmental Protection Agency, Stationary 
Source Compliance Division, Washington, D.C. September 1991.
    3. Handbook of Hazardous Materials: Fire, Safety, Health. Alliance 
of American Insurers. Schaumberg, IL. 1983.

17.0  Tables, Diagrams, Flowcharts, and Validation Data

                                  Table 24-1.--Analytical Precision Statements
----------------------------------------------------------------------------------------------------------------
                                                   Intra-laboratory                    Inter-laboratory
----------------------------------------------------------------------------------------------------------------
Volatile matter content, Wv............   0.015 Wv..............   0.047 W8v
Water content, Ww......................   0.029 W8w.............   0.075 Ww
Density, Dc............................   0.001 kg/l............   0.002 kg/l
----------------------------------------------------------------------------------------------------------------

Method 24A--Determination of Volatile Matter Content and Density of 
Publication Rotogravure Inks and Related Publication Rotogravure 
Coatings

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
                  Analyte                              CAS No.
------------------------------------------------------------------------
Volatile organic compounds (VOC)..........  No CAS number assigned.
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of the VOC content and density of solvent-borne (solvent-reducible) 
publication rotogravure inks and related publication rotogravure 
coatings.

2.0  Summary of Method

    2.1  Separate procedures are used to determine the VOC weight 
fraction and density of the ink or related coating and the density of 
the solvent in the ink or related coating. The VOC weight fraction is 
determined by measuring the weight loss of a known sample quantity 
which has been heated for a specified length of time at a specified 
temperature. The density of both the ink or related coating and solvent 
are measured by a standard procedure. From this information, the VOC 
volume fraction is calculated.

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method does not purport to address 
all of the safety problems associated with its use. It is the 
responsibility of the user of this test method to establish appropriate 
safety and health practices and to determine the applicability of 
regulatory limitations prior to performing this test method.
    5.2  Hazardous Components. Some of the compounds that may be 
contained in the inks or related coatings analyzed by this method may 
be irritating or corrosive to tissues or may be toxic. Nearly all are 
fire hazards. Appropriate precautions can be found in reference 
documents, such as Reference 6 of Section 16.0.

6.0  Equipment and Supplies

    The following equipment and supplies are required for sample 
analysis:
    6.1  Weighing Dishes. Aluminum foil, 58 mm (2.3 in.) in diameter by 
18 mm (0.7 in.) high, with a flat bottom. There must be at least three 
weighing dishes per sample.
    6.2  Disposable Syringe. 5 ml.
    6.3  Analytical Balance. To measure to within 0.1 mg.
    6.4  Oven. Vacuum oven capable of maintaining a temperature of 120 
 2  deg.C (248  4  deg.F) and an absolute 
pressure of 510  51 mm Hg (20  2 in. Hg) for 4 
hours. Alternatively, a forced draft oven capable of maintaining a 
temperature of 120  2  deg.C (248  4  deg.F) 
for 24 hours.
    6.5  The equipment and supplies specified in ASTM D 1475-60, 80, or 
90 (incorporated by reference--see Sec. 60.17).

7.0  Reagents and Standards

    7.1  The reagents and standards specified in ASTM D 1475-60, 80, or 
90 are required.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Follow the sample collection, preservation, storage, and 
transport procedures described in Reference 4 of Section 16.0.

9.0  Quality Control [Reserved]

10.0  Calibration and Standardization [Reserved]

11.0  Analytical Procedure

    Additional guidance can be found in Reference 5 of Section 16.0.
    11.1  VOC Weight Fraction. Shake or mix the ink or related coating 
sample thoroughly to assure that all the solids are completely 
suspended. Label and weigh to the nearest 0.1 mg a weighing dish and 
record this weight (Mx1). Using a 5 ml syringe, without a 
needle, extract an aliquot from the ink or related coating sample. 
Weigh the syringe and aliquot to the nearest 0.1 mg and record this 
weight (Mcy1). Transfer 1 to 3 g of the aliquot to the tared 
weighing dish. Reweigh the syringe and remaining aliquot to the nearest 
0.1 mg and record this weight (Mcy2). Heat the weighing dish 
with the transferred aliquot in a vacuum oven at an absolute pressure 
of 510  51 mm Hg (20  2 in. Hg) and a 
temperature of 120  2  deg.C (248  4  deg.F) 
for 4 hours. Alternatively, heat the weighing dish with the transferred 
aliquot in a forced draft oven at a temperature of 120  2 
deg.C for 24 hours. After the weighing dish has cooled, reweigh it to 
the nearest 0.1 mg and record the weight (Mx2). Repeat this 
procedure two times for each ink or related coating sample, for a total 
of three samples.
    11.2  Ink or Related Coating Density. Determine the density of the 
ink or related coating (Dc) according to the procedure 
outlined in ASTM D 1475. Make a total of three determinations for each 
ink or related coating sample. Report the ink or related coating 
density as the arithmetic average (Dc) of the three 
determinations.
    11.3  Solvent Density. Determine the density of the solvent 
(Do) according to

[[Page 62044]]

the procedure outlined in ASTM D 1475. Make a total of three 
determinations for each ink or related coating sample. Report the 
solvent density as the arithmetic average (Do) of the three 
determinations.

12.0  Calculations and Data Analysis

    12.1  VOC Weight Fraction. For each determination, calculate the 
volatile organic content weight fraction (Wo) using the 
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.362

Make a total of three determinations. Report the VOC weight fraction as 
the arithmetic average (Wo) of the three determinations.
    12.2  VOC Volume Fraction. Calculate the volume fraction volatile 
organic content (Vo) using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.363

13.0  Method Performance [Reserved]

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

    1. Standard Test Method for Density of Paint, Varnish, Lacquer, 
and Related Products. ASTM Designation D 1475.
    2. Teleconversation. Wright, Chuck, Inmont Corporation with 
Reich, R., A., Radian Corporation. September 25, 1979, Gravure Ink 
Analysis.
    3. Teleconversation. Oppenheimer, Robert, Gravure Research 
Institute with Burt, Rick, Radian Corporation, November 5, 1979, 
Gravure Ink Analysis.
    4. Standard Procedure for Collection of Coating and Ink Samples 
for Analysis by Reference Methods 24 and 24A. EPA-340/1-91-010. U.S. 
Environmental Protection Agency, Stationary Source Compliance 
Division, Washington, D.C. September 1991.
    5. Standard Operating Procedure for Analysis of Coating and Ink 
Samples by Reference Methods 24 and 24A. EPA-340/1-91-011. U.S. 
Environmental Protection Agency, Stationary Source Compliance 
Division, Washington, D.C. September 1991.
    6. Handbook of Hazardous Materials: Fire, Safety, Health. 
Alliance of American Insurers. Schaumberg, IL. 1983.

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

Method 25--Determination of Total Gaseous Nonmethane Organic 
Emissions as Carbon

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
              Analyte                   CAS No.          Sensitivity
------------------------------------------------------------------------
Total gaseous nonmethane organic               N/A  Dependent upon
 compounds (TGNMO).                                  analytical
                                                     equipment.
------------------------------------------------------------------------

    1.2  Applicability.
    1.2.1  This method is applicable for the determination of volatile 
organic compounds (VOC) (measured as total gaseous nonmethane organics 
(TGNMO) and reported as carbon) in stationary source emissions. This 
method is not applicable for the determination of organic particulate 
matter.
    1.2.2  This method is not the only method that applies to the 
measurement of VOC. Costs, logistics, and other practicalities of 
source testing may make other test methods more desirable for measuring 
VOC contents of certain effluent streams. Proper judgment is required 
in determining the most applicable VOC test method. For example, 
depending upon the molecular composition of the organics in the 
effluent stream, a totally automated semicontinuous nonmethane organics 
(NMO) analyzer interfaced directly to the source may yield accurate 
results. This approach has the advantage of providing emission data 
semicontinuously over an extended time period.
    1.2.3  Direct measurement of an effluent with a flame ionization 
detector (FID) analyzer may be appropriate with prior characterization 
of the gas stream and knowledge that the detector responds predictably 
to the organic compounds in the stream. If present, methane 
(CH4) will, of course, also be measured. The FID can be used 
under any of the following limited conditions: (1) Where only one 
compound is known to exist; (2) when the organic compounds consist of 
only hydrogen and carbon; (3) where the relative percentages of the 
compounds are known or can be determined, and the FID responses to the 
compounds are known; (4) where a consistent mixture of the compounds 
exists before and after emission control and only the relative 
concentrations are to be assessed; or (5) where the FID can be 
calibrated against mass standards of the compounds emitted (solvent 
emissions, for example).
    1.2.4  Another example of the use of a direct FID is as a screening 
method. If there is enough information available to provide a rough 
estimate of the analyzer accuracy, the FID analyzer can be used to 
determine the VOC content of an uncharacterized gas stream. With a 
sufficient buffer to account for possible inaccuracies, the direct FID 
can be a useful tool to obtain the desired results without costly exact 
determination.
    1.2.5  In situations where a qualitative/quantitative analysis of 
an

[[Page 62045]]

effluent stream is desired or required, a gas chromatographic FID 
system may apply. However, for sources emitting numerous organics, the 
time and expense of this approach will be formidable.

2.0  Summary of Method

    2.1  An emission sample is withdrawn from the stack at a constant 
rate through a heated filter and a chilled condensate trap by means of 
an evacuated sample tank. After sampling is completed, the TGNMO are 
determined by independently analyzing the condensate trap and sample 
tank fractions and combining the analytical results. The organic 
content of the condensate trap fraction is determined by oxidizing the 
NMO to carbon dioxide (CO2) and quantitatively collecting in 
the effluent in an evacuated vessel; then a portion of the 
CO2 is reduced to CH4 and measured by an FID. The 
organic content of the sample tank fraction is measured by injecting a 
portion of the sample into a gas chromatographic column to separate the 
NMO from carbon monoxide (CO), CO2, and CH4; the 
NMO are oxidized to CO2, reduced to CH4, and 
measured by an FID. In this manner, the variable response of the FID 
associated with different types of organics is eliminated.

3.0  Definitions [Reserved]

4.0  Interferences

    4.1  Carbon Dioxide and Water Vapor. When carbon dioxide 
(CO2) and water vapor are present together in the stack, 
they can produce a positive bias in the sample. The magnitude of the 
bias depends on the concentrations of CO2 and water vapor. 
As a guideline, multiply the CO2 concentration, expressed as 
volume percent, times the water vapor concentration. If this product 
does not exceed 100, the bias can be considered insignificant. For 
example, the bias is not significant for a source having 10 percent 
CO2 and 10 percent water vapor, but it might be significant 
for a source having 10 percent CO2 and 20 percent water 
vapor.
    4.2.  Particulate Matter. Collection of organic particulate matter 
in the condensate trap would produce a positive bias. A filter is 
included in the sampling equipment to minimize this bias.

5.0  Safety

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

6.0  Equipment and Supplies

    6.1  Sample Collection. The sampling system consists of a heated 
probe, heated filter, condensate trap, flow control system, and sample 
tank (see Figure 25-1). The TGNMO sampling equipment can be constructed 
from commercially available components and components fabricated in a 
machine shop. The following equipment is required:
    6.1.1  Heated Probe. 6.4-mm (\1/4\-in.) OD stainless steel tubing 
with a heating system capable of maintaining a gas temperature at the 
exit end of at least 129  deg.C (265  deg.F). The probe shall be 
equipped with a temperature sensor at the exit end to monitor the gas 
temperature. A suitable probe is shown in Figure 25-1. The nozzle is an 
elbow fitting attached to the front end of the probe while the 
temperature sensor is inserted in the side arm of a tee fitting 
attached to the rear of the probe. The probe is wrapped with a suitable 
length of high temperature heating tape, and then covered with two 
layers of glass cloth insulation and one layer of aluminum foil or an 
equivalent wrapping.

    Note: If it is not possible to use a heating system for safety 
reasons, an unheated system with an in-stack filter is a suitable 
alternative.


    6.1.2  Filter Holder. 25-mm (\15/16\-in.) ID Gelman filter holder 
with 303 stainless steel body and 316 stainless steel support screen 
with the Viton O-ring replaced by a Teflon O-ring.
    6.1.3  Filter Heating System.
    6.1.3.1  A metal box consisting of an inner and an outer shell 
separated by insulating material with a heating element in the inner 
shell capable of maintaining a gas temperature at the filter of 121 
 3  deg.C (250  5  deg.F). The heating box 
shall include temperature sensors to monitor the gas temperature 
immediately upstream and immediately downstream of the filter.
    6.1.3.2  A suitable heating box is shown in Figure 25-2. The outer 
shell is a metal box that measures 102 mm x 280 mm x 292 mm (4 in. x 11 
in. x 11\1/2\ in.), while the inner shell is a metal box measuring 76 
mm x 229 mm x 241 mm (3 in. x 9 in. x 9\1/2\ in.). The inner box is 
supported by 13-mm (\1/2\-in.) phenolic rods. The void space between 
the boxes is filled with ceramic fiber insulation which is sealed in 
place by means of a silicon rubber bead around the upper sides of the 
box. A removable lid made in a similar manner, with a 25-mm (1-in.) gap 
between the parts is used to cover the heating chamber. The inner box 
is heated with a 250-watt cartridge heater, shielded by a stainless 
steel shroud. The heater is regulated by a thermostatic temperature 
controller which is set to maintain a gas temperature of 121  deg.C 
(250  deg.F) as measured by the temperature sensor upstream of the 
filter.

    Note: If it is not possible to use a heating system for safety 
reasons, an unheated system with an in-stack filter is a suitable 
alternative.

    6.1.4  Condensate Trap. 9.5-mm (\3/8\-in.) OD 316 stainless steel 
tubing bent into a U-shape. Exact dimensions are shown in Figure 25-3. 
The tubing shall be packed with coarse quartz wool, to a density of 
approximately 0.11 g/cm\3\ before bending. While the condensate trap is 
packed with dry ice in the Dewar, an ice bridge may form between the 
arms of the condensate trap making it difficult to remove the 
condensate trap. This problem can be prevented by attaching a steel 
plate between the arms of the condensate trap in the same plane as the 
arms to completely fill the intervening space.
    6.1.5  Valve. Stainless steel control valve for starting and 
stopping sample flow.
    6.1.6  Metering Valve. Stainless steel valve for regulating the 
sample flow rate through the sample train.
    6.1.7  Rate Meter. Rotameter, or equivalent, capable of measuring 
sample flow in the range of 60 to 100 cm\3\/min (0.13 to 0.21 ft\3\/
hr).
    6.1.8  Sample Tank. Stainless steel or aluminum tank with a minimum 
volume of 4 liters (0.14 ft\3\).

    Note: Sample volumes greater than 4 liters may be required for 
sources with low organic concentrations.

    6.1.9  Mercury Manometer. U-tube manometer or absolute pressure 
gauge capable of measuring pressure to within 1 mm Hg in the range of 0 
to 900 mm.
    6.1.10  Vacuum Pump. Capable of evacuating to an absolute pressure 
of 10 mm Hg.
    6.2  Condensate Recovery. The system for the recovery of the 
organics captured in the condensate trap consists of a heat source, an 
oxidation catalyst, a nondispersive infrared (NDIR) analyzer, and an 
intermediate collection vessel (ICV). Figure 25-4 is a schematic of a 
typical system. The system shall be capable of proper oxidation and 
recovery, as specified in Section 10.1.1. The following major 
components are required:
    6.2.1  Heat Source. Sufficient to heat the condensate trap 
(including probe) to a temperature of 200  deg.C (390  deg.F). A system 
using both a heat gun and an electric tube furnace is recommended.

[[Page 62046]]

    6.2.2  Heat Tape. Sufficient to heat the connecting tubing between 
the water trap and the oxidation catalyst to 100  deg.C (212  deg.F).
    6.2.3  Oxidation Catalyst. A suitable length of 9.5 mm (\3/8\-in.) 
OD Inconel 600 tubing packed with 15 cm (6 in.) of 3.2 mm (\3/8\-in.) 
diameter 19 percent chromia on alumina pellets. The catalyst material 
is packed in the center of the catalyst tube with quartz wool packed on 
either end to hold it in place.
    6.2.4  Water Trap. Leak-proof, capable of removing moisture from 
the gas stream.
    6.2.5  Syringe Port. A 6.4-mm (\1/4\-in.) OD stainless steel tee 
fitting with a rubber septum placed in the side arm.
    6.2.6  NDIR Detector. Capable of indicating CO2 
concentration in the range of zero to 5 percent, to monitor the 
progress of combustion of the organic compounds from the condensate 
trap.
    6.2.7  Flow-Control Valve. Stainless steel, to maintain the trap 
conditioning system near atmospheric pressure.
    6.2.8  Intermediate Collection Vessel. Stainless steel or aluminum, 
equipped with a female quick connect. Tanks with nominal volumes of at 
least 6 liters (0.2 ft\3\) are recommended.
    6.2.9  Mercury Manometer. Same as described in Section 6.1.9.
    6.2.10  Syringe. 10-ml gas-tight glass syringe equipped with an 
appropriate needle.
    6.2.11  Syringes. 10-l and 50-l liquid injection 
syringes.
    6.2.12  Liquid Sample Injection Unit. 316 Stainless steel U-tube 
fitted with an injection septum (see Figure 25-7).
    6.3  Analysis.
    6.3.1  NMO Analyzer. The NMO analyzer is a gas chromatograph (GC) 
with backflush capability for NMO analysis and is equipped with an 
oxidation catalyst, reduction catalyst, and FID. Figures 25-5 and 25-6 
are schematics of a typical NMO analyzer. This semicontinuous GC/FID 
analyzer shall be capable of: (1) Separating CO, CO2, and 
CH4 from NMO, (2) reducing the CO2 to 
CH4 and quantifying as CH4, and (3) oxidizing the 
NMO to CO2, reducing the CO2 to CH4 
and quantifying as CH4, according to Section 10.1.2. The 
analyzer consists of the following major components:
    6.3.1.1  Oxidation Catalyst. A suitable length of 9.5-mm (\3/8\-
in.) OD Inconel 600 tubing packed with 5.1 cm (2 in.) of 19 percent 
chromia on 3.2-mm (\1/8\-in.) alumina pellets. The catalyst material is 
packed in the center of the tube supported on either side by quartz 
wool. The catalyst tube must be mounted vertically in a 650  deg.C 
(1200  deg.F) furnace. Longer catalysts mounted horizontally may be 
used, provided they can meet the specifications of Section 10.1.2.1.
    6.3.1.2  Reduction Catalyst. A 7.6-cm (3-in.) length of 6.4-mm (\1/
4\-in.) OD Inconel tubing fully packed with 100-mesh pure nickel 
powder. The catalyst tube must be mounted vertically in a 400  deg.C 
(750  deg.F) furnace.
    6.3.1.3  Separation Column(s). A 30-cm (1-ft) length of 3.2-mm (\1/
8\-in.) OD stainless steel tubing packed with 60/80 mesh Unibeads 1S 
followed by a 61-cm (2-ft) length of 3.2-mm (\1/8\-in.) OD stainless 
steel tubing packed with 60/80 mesh Carbosieve G. The Carbosieve and 
Unibeads columns must be baked separately at 200  deg.C (390  deg.F) 
with carrier gas flowing through them for 24 hours before initial use.
    6.3.1.4  Sample Injection System. A single 10-port GC sample 
injection valve or a group of valves with sufficient ports fitted with 
a sample loop properly sized to interface with the NMO analyzer (1-cc 
loop recommended).
    6.3.1.5  FID. An FID meeting the following specifications is 
required:
    6.3.1.5.1  Linearity. A linear response (5 percent) 
over the operating range as demonstrated by the procedures established 
in Section 10.1.2.3.
    6.3.1.5.2  Range. A full scale range of 10 to 50,000 ppm 
CH4. Signal attenuators shall be available to produce a 
minimum signal response of 10 percent of full scale.
    6.3.1.6  Data Recording System. Analog strip chart recorder or 
digital integration system compatible with the FID for permanently 
recording the analytical results.
    6.3.2  Barometer. Mercury, aneroid, or other barometer capable of 
measuring atmospheric pressure to within 1 mm Hg.
    6.3.3  Temperature Sensor. Capable of measuring the laboratory 
temperature within 1  deg.C (2  deg.F).
    6.3.4  Vacuum Pump. Capable of evacuating to an absolute pressure 
of 10 mm Hg.

7.0  Reagents and Standards

    7.1  Sample Collection. The following reagents are required for 
sample collection:
    7.1.1  Dry Ice. Solid CO2, crushed.
    7.1.2  Coarse Quartz Wool. 8 to 15 um.
    7.1.3  Filters. Glass fiber filters, without organic binder.
    7.2  NMO Analysis. The following gases are required for NMO 
analysis:
    7.2.1  Carrier Gases. Helium (He) and oxygen (O2) 
containing less than 1 ppm CO2 and less than 0.1 ppm 
hydrocarbon.
    7.2.2  Fuel Gas. Hydrogen (H2), at least 99.999 percent 
pure.
    7.2.3  Combustion Gas. Either air (less than 0.1 ppm total 
hydrocarbon content) or O2 (purity 99.99 percent or 
greater), as required by the detector.
    7.3  Condensate Analysis. The following are required for condensate 
analysis:
    7.3.1  Gases. Containing less than 1 ppm carbon.
    7.3.1.1  Air.
    7.3.1.2  Oxygen.
    7.3.2  Liquids. To conform to the specifications established by the 
Committee on Analytical Reagents of the American Chemical Society.
    7.3.2.1  Hexane.
    7.3.2.2  Decane.
    7.4  Calibration. For all calibration gases, the manufacturer must 
recommend a maximum shelf life for each cylinder (i.e., the length of 
time the gas concentration is not expected to change more than 
5 percent from its certified value). The date of gas 
cylinder preparation, certified organic concentration, and recommended 
maximum shelf life must be affixed to each cylinder before shipment 
from the gas manufacturer to the buyer. The following calibration gases 
are required:
    7.4.1  Oxidation Catalyst Efficiency Check Calibration Gas. Gas 
mixture standard with nominal concentration of 1 percent methane in 
air.
    7.4.2  FID Linearity and NMO Calibration Gases. Three gas mixture 
standards with nominal propane concentrations of 20 ppm, 200 ppm, and 
3000 ppm, in air.
    7.4.3  CO2 Calibration Gases. Three gas mixture 
standards with nominal CO2 concentrations of 50 ppm, 500 
ppm, and 1 percent, in air.


    Note:
    Total NMO less than 1 ppm required for 1 percent mixture.


    7.4.4  NMO Analyzer System Check Calibration Gases. Four 
calibration gases are needed as follows:
    7.4.4.1  Propane Mixture. Gas mixture standard containing (nominal) 
50 ppm CO, 50 ppm CH4, 1 percent CO2, and 20 ppm 
C3H8, prepared in air.
    7.4.4.2  Hexane. Gas mixture standard containing (nominal) 50 ppm 
hexane in air.
    7.4.4.3  Toluene. Gas mixture standard containing (nominal) 20 ppm 
toluene in air.
    7.4.4.4  Methanol. Gas mixture standard containing (nominal) 100 
ppm methanol in air.
    7.5  Quality Assurance Audit Samples.
    7.5.1  It is recommended, but not required, that a performance 
audit sample be analyzed in conjunction with the field samples. The 
audit sample should be in a suitable sample matrix at

[[Page 62047]]

a concentration similar to the actual field samples.
    7.5.2  When making compliance determinations, and upon 
availability, audit samples may be obtained from the appropriate EPA 
Regional Office or from the responsible enforcement authority and 
analyzed in conjunction with the field samples.


    Note:
    The responsible enforcement authority should be notified at 
least 30 days prior to the test date to allow sufficient time for 
sample delivery.

8.0  Sample Collection, Preservation, Transport, and Storage

    8.1  Sampling Equipment Preparation.
    8.1.1  Condensate Trap Cleaning. Before its initial use and after 
each use, a condensate trap should be thoroughly cleaned and checked to 
ensure that it is not contaminated. Both cleaning and checking can be 
accomplished by installing the trap in the condensate recovery system 
and treating it as if it were a sample. The trap should be heated as 
described in Section 11.1.3. A trap may be considered clean when the 
CO2 concentration in its effluent gas drops below 10 ppm. 
This check is optional for traps that most recently have been used to 
collect samples which were then recovered according to the procedure in 
Section 11.1.3.
    8.1.2  Sample Tank Evacuation and Leak-Check. Evacuate the sample 
tank to 10 mm Hg absolute pressure or less. Then close the sample tank 
valve, and allow the tank to sit for 60 minutes. The tank is acceptable 
if a change in tank vacuum of less than 1 mm Hg is noted. The 
evacuation and leak-check may be conducted either in the laboratory or 
the field.
    8.1.3  Sampling Train Assembly. Just before assembly, measure the 
tank vacuum using a mercury manometer. Record this vacuum, the ambient 
temperature, and the barometric pressure at this time. Close the sample 
tank valve and assemble the sampling system as shown in Figure 25-1. 
Immerse the condensate trap body in dry ice at least 30 minutes before 
commencing sampling to improve collection efficiency. The point where 
the inlet tube joins the trap body should be 2.5 to 5 cm (1 to 2 in.) 
above the top of the dry ice.
    8.1.4  Pretest Leak-Check. A pretest leak-check is required. 
Calculate or measure the approximate volume of the sampling train from 
the probe tip to the sample tank valve. After assembling the sampling 
train, plug the probe tip, and make certain that the sample tank valve 
is closed. Turn on the vacuum pump, and evacuate the sampling system 
from the probe tip to the sample tank valve to an absolute pressure of 
10 mm Hg or less. Close the purge valve, turn off the pump, wait a 
minimum period of 10 minutes, and recheck the indicated vacuum. 
Calculate the maximum allowable pressure change based on a leak rate of 
1 percent of the sampling rate using Equation 25-1, Section 12.2. If 
the measured pressure change exceeds the allowable, correct the problem 
and repeat the leak-check before beginning sampling.
    8.2  Sample Collection.
    8.2.1  Unplug the probe tip, and place the probe into the stack 
such that the probe is perpendicular to the duct or stack axis; locate 
the probe tip at a single preselected point of average velocity facing 
away from the direction of gas flow. For stacks having a negative 
static pressure, seal the sample port sufficiently to prevent air in-
leakage around the probe. Set the probe temperature controller to 129 
deg.C (265  deg.F) and the filter temperature controller to 121  deg.C 
(250  deg.F). Allow the probe and filter to heat for about 30 minutes 
before purging the sample train.
    8.2.2  Close the sample valve, open the purge valve, and start the 
vacuum pump. Set the flow rate between 60 and 100 cm3/min 
(0.13 and 0.21 ft3/hr), and purge the train with stack gas 
for at least 10 minutes.
    8.2.3  When the temperatures at the exit ends of the probe and 
filter are within the corresponding specified ranges, check the dry ice 
level around the condensate trap, and add dry ice if necessary. Record 
the clock time. To begin sampling, close the purge valve and stop the 
pump. Open the sample valve and the sample tank valve. Using the flow 
control valve, set the flow through the sample train to the proper 
rate. Adjust the flow rate as necessary to maintain a constant rate 
(10 percent) throughout the duration of the sampling 
period. Record the sample tank vacuum and flowmeter setting at 5-minute 
intervals. (See Figure 25-8.) Select a total sample time greater than 
or equal to the minimum sampling time specified in the applicable 
subpart of the regulations; end the sampling when this time period is 
reached or when a constant flow rate can no longer be maintained 
because of reduced sample tank vacuum.


    Note: If sampling had to be stopped before obtaining the minimum 
sampling time (specified in the applicable subpart) because a 
constant flow rate could not be maintained, proceed as follows: 
After closing the sample tank valve, remove the used sample tank 
from the sampling train (without disconnecting other portions of the 
sampling train). Take another evacuated and leak-checked sample 
tank, measure and record the tank vacuum, and attach the new tank to 
the sampling train. After the new tank is attached to the sample 
train, proceed with the sampling until the required minimum sampling 
time has been exceeded.


    8.3  Sample Recovery. After sampling is completed, close the flow 
control valve, and record the final tank vacuum; then record the tank 
temperature and barometric pressure. Close the sample tank valve, and 
disconnect the sample tank from the sample system. Disconnect the 
condensate trap at the inlet to the rate meter, and tightly seal both 
ends of the condensate trap. Do not include the probe from the stack to 
the filter as part of the condensate sample.
    8.4  Sample Storage and Transport. Keep the trap packed in dry ice 
until the samples are returned to the laboratory for analysis. Ensure 
that run numbers are identified on the condensate trap and the sample 
tank(s).

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
10.1.1........................  Initial            Ensure acceptable
                                 performance        condensate recovery
                                 check of           efficiency.
                                 condensate
                                 recovery
                                 apparatus.
10.1.2, 10.2..................  NMO analyzer       Ensure precision of
                                 initial and        analytical results.
                                 daily
                                 performance
                                 checks.
11.3..........................  Audit Sample       Evaluate analytical
                                 Analyses.          technique and
                                                    instrument
                                                    calibration.
------------------------------------------------------------------------

10.0  Calibration and Standardization

    Note: Maintain a record of performance of each item.


    10.1  Initial Performance Checks.
    10.1.1  Condensate Recovery Apparatus. Perform these tests before 
the system is first placed in operation, after any shutdown of 6 months 
or more, and after any major modification of the system, or at the 
frequency recommended by the manufacturer.

[[Page 62048]]

    10.1.1.1  Carrier Gas and Auxiliary O2 Blank Check. 
Analyze each new tank of carrier gas or auxiliary O2 with 
the NMO analyzer to check for contamination. Treat the gas cylinders as 
noncondensible gas samples, and analyze according to the procedure in 
Section 11.2.3. Add together any measured CH4, CO, 
CO2, or NMO. The total concentration must be less than 5 
ppm.
    10.1.1.2  Oxidation Catalyst Efficiency Check.
    10.1.1.2.1  With a clean condensate trap installed in the recovery 
system or a \1/8\" stainless steel connector tube, replace the carrier 
gas cylinder with the high level methane standard gas cylinder (Section 
7.4.1). Set the four-port valve to the recovery position, and attach an 
ICV to the recovery system. With the sample recovery valve in vent 
position and the flow-control and ICV valves fully open, evacuate the 
manometer or gauge, the connecting tubing, and the ICV to 10 mm Hg 
absolute pressure. Close the flow-control and vacuum pump valves.
    10.1.1.2.2  After the NDIR response has stabilized, switch the 
sample recovery valve from vent to collect. When the manometer or 
pressure gauge begins to register a slight positive pressure, open the 
flow-control valve. Keep the flow adjusted such that the pressure in 
the system is maintained within 10 percent of atmospheric pressure. 
Continue collecting the sample in a normal manner until the ICV is 
filled to a nominal gauge pressure of 300 mm Hg. Close the ICV valve, 
and remove the ICV from the system. Place the sample recovery valve in 
the vent position, and return the recovery system to its normal carrier 
gas and normal operating conditions. Analyze the ICV for CO2 
using the NMO analyzer; the catalyst efficiency is acceptable if the 
CO2 concentration is within 2 percent of the methane 
standard concentration.
    10.1.1.3  System Performance Check. Construct a liquid sample 
injection unit similar in design to the unit shown in Figure 25-7. 
Insert this unit into the condensate recovery and conditioning system 
in place of a condensate trap, and set the carrier gas and auxiliary 
O2 flow rates to normal operating levels. Attach an 
evacuated ICV to the system, and switch from system vent to collect. 
With the carrier gas routed through the injection unit and the 
oxidation catalyst, inject a liquid sample (see Sections 10.1.1.3.1 to 
10.1.1.3.4) into the injection port. Operate the trap recovery system 
as described in Section 11.1.3. Measure the final ICV pressure, and 
then analyze the vessel to determine the CO2 concentration. 
For each injection, calculate the percent recovery according to Section 
12.7. Calculate the relative standard deviation for each set of 
triplicate injections according to Section 12.8. The performance test 
is acceptable if the average percent recovery is 100  5 
percent and the relative standard deviation is less than 2 percent for 
each set of triplicate injections.
    10.1.1.3.1  50 l hexane.
    10.1.1.3.2  10 l hexane.
    10.1.1.3.3  50 l decane.
    10.1.1.3.4  10 l decane.
    10.1.2  NMO Analyzer. Perform these tests before the system is 
first placed in operation, after any shutdown longer than 6 months, and 
after any major modification of the system.
    10.1.2.1  Oxidation Catalyst Efficiency Check. Turn off or bypass 
the NMO analyzer reduction catalyst. Make triplicate injections of the 
high level methane standard (Section 7.4.1). The oxidation catalyst 
operation is acceptable if the FID response is less than 1 percent of 
the injected methane concentration.
    10.1.2.2  Reduction Catalyst Efficiency Check. With the oxidation 
catalyst unheated or bypassed and the heated reduction catalyst 
bypassed, make triplicate injections of the high level methane standard 
(Section 7.4.1). Repeat this procedure with both catalysts operative. 
The reduction catalyst operation is acceptable if the responses under 
both conditions agree within 5 percent of their average.
    10.1.2.3  NMO Analyzer Linearity Check Calibration. While operating 
both the oxidation and reduction catalysts, conduct a linearity check 
of the analyzer using the propane standards specified in Section 7.4.2. 
Make triplicate injections of each calibration gas. For each gas (i.e., 
each set of triplicate injections), calculate the average response 
factor (area/ppm C) for each gas, as well as and the relative standard 
deviation (according to Section 12.8). Then calculate the overall mean 
of the response factor values. The instrument linearity is acceptable 
if the average response factor of each calibration gas is within 2.5 
percent of the overall mean value and if the relative standard 
deviation gas is less than 2 percent of the overall mean value. Record 
the overall mean of the propane response factor values as the NMO 
calibration response factor (RFNMO). Repeat the linearity 
check using the CO2 standards specified in Section 7.4.3. 
Make triplicate injections of each gas, and then calculate the average 
response factor (area/ppm C) for each gas, as well as the overall mean 
of the response factor values. Record the overall mean of the response 
factor values as the CO2 calibration response factor 
(RFCO2). The RFCO2 must be within 10 percent of 
the RFNMO.
    10.1.2.4  System Performance Check. Check the column separation and 
overall performance of the analyzer by making triplicate injections of 
the calibration gases listed in Section 7.4.4. The analyzer performance 
is acceptable if the measured NMO value for each gas (average of 
triplicate injections) is within 5 percent of the expected value.
    10.2  NMO Analyzer Daily Calibration. The following calibration 
procedures shall be performed before and immediately after the analysis 
of each set of samples, or on a daily basis, whichever is more 
stringent:
    10.2.1  CO2 Response Factor. Inject triplicate samples 
of the high level CO2 calibration gas (Section 7.4.3), and 
calculate the average response factor. The system operation is adequate 
if the calculated response factor is within 5 percent of the 
RFCO2 calculated during the initial performance test 
(Section 10.1.2.3). Use the daily response factor (DRFCO2) 
for analyzer calibration and the calculation of measured CO2 
concentrations in the ICV samples.
    10.2.2  NMO Response Factors. Inject triplicate samples of the 
mixed propane calibration cylinder gas (Section 7.4.4.1), and calculate 
the average NMO response factor. The system operation is adequate if 
the calculated response factor is within 10 percent of the 
RFNMO calculated during the initial performance test 
(Section 10.1.2.4). Use the daily response factor (DRFNMO) 
for analyzer calibration and calculation of NMO concentrations in the 
sample tanks.
    10.3  Sample Tank and ICV Volume. The volume of the gas sampling 
tanks used must be determined. Determine the tank and ICV volumes by 
weighing them empty and then filled with deionized distilled water; 
weigh to the nearest 5 g, and record the results. Alternatively, 
measure the volume of water used to fill them to the nearest 5 ml.

11.0  Analytical Procedure

    11.1  Condensate Recovery. See Figure 25-9. Set the carrier gas 
flow rate, and heat the catalyst to its operating temperature to 
condition the apparatus.
    11.1.1  Daily Performance Checks. Each day before analyzing any 
samples, perform the following tests:
    11.1.1.1  Leak-Check. With the carrier gas inlets and the sample 
recovery valve closed, install a clean condensate trap in the system, 
and evacuate the system to 10 mm Hg absolute pressure or less. Monitor 
the system pressure for 10 minutes. The

[[Page 62049]]

system is acceptable if the pressure change is less than 2 mm Hg.
    11.1.1.2  System Background Test. Adjust the carrier gas and 
auxiliary oxygen flow rate to their normal values of 100 cc/min and 150 
cc/min, respectively, with the sample recovery valve in vent position. 
Using a 10-ml syringe, withdraw a sample from the system effluent 
through the syringe port. Inject this sample into the NMO analyzer, and 
measure the CO2 content. The system background is acceptable 
if the CO2 concentration is less than 10 ppm.
    11.1.1.3  Oxidation Catalyst Efficiency Check. Conduct a catalyst 
efficiency test as specified in Section 10.1.1.2. If the criterion of 
this test cannot be met, make the necessary repairs to the system 
before proceeding.
    11.1.2  Condensate Trap CO2 Purge and Sample Tank 
Pressurization.
    11.1.2.1  After sampling is completed, the condensate trap will 
contain condensed water and organics and a small volume of sampled gas. 
This gas from the stack may contain a significant amount of 
CO2 which must be removed from the condensate trap before 
the sample is recovered. This is accomplished by purging the condensate 
trap with zero air and collecting the purged gas in the original sample 
tank.
    11.1.2.2  Begin with the sample tank and condensate trap from the 
test run to be analyzed. Set the four-port valve of the condensate 
recovery system in the CO2 purge position as shown in Figure 
25-9. With the sample tank valve closed, attach the sample tank to the 
sample recovery system. With the sample recovery valve in the vent 
position and the flow control valve fully open, evacuate the manometer 
or pressure gauge to the vacuum of the sample tank. Next, close the 
vacuum pump valve, open the sample tank valve, and record the tank 
pressure.
    11.1.2.3  Attach the dry ice-cooled condensate trap to the recovery 
system, and initiate the purge by switching the sample recovery valve 
from vent to collect position. Adjust the flow control valve to 
maintain atmospheric pressure in the recovery system. Continue the 
purge until the CO2 concentration of the trap effluent is 
less than 5 ppm. CO2 concentration in the trap effluent 
should be measured by extracting syringe samples from the recovery 
system and analyzing the samples with the NMO analyzer. This procedure 
should be used only after the NDIR response has reached a minimum 
level. Using a 10-ml syringe, extract a sample from the syringe port 
prior to the NDIR, and inject this sample into the NMO analyzer.
    11.1.2.4  After the completion of the CO2 purge, use the 
carrier gas bypass valve to pressurize the sample tank to approximately 
1,060 mm Hg absolute pressure with zero air.
    11.1.3  Recovery of the Condensate Trap Sample (See Figure 25-10).
    11.1.3.1  Attach the ICV to the sample recovery system. With the 
sample recovery valve in a closed position, between vent and collect, 
and the flow control and ICV valves fully open, evacuate the manometer 
or gauge, the connecting tubing, and the ICV to 10 mm Hg absolute 
pressure. Close the flow-control and vacuum pump valves.
    11.1.3.2  Begin auxiliary oxygen flow to the oxidation catalyst at 
a rate of 150 cc/min, then switch the four-way valve to the trap 
recovery position and the sample recovery valve to collect position. 
The system should now be set up to operate as indicated in Figure 25-
10. After the manometer or pressure gauge begins to register a slight 
positive pressure, open the flow control valve. Adjust the flow-control 
valve to maintain atmospheric pressure in the system within 10 percent.
    11.1.3.3  Remove the condensate trap from the dry ice, and allow it 
to warm to ambient temperature while monitoring the NDIR response. If, 
after 5 minutes, the CO2 concentration of the catalyst 
effluent is below 10,000 ppm, discontinue the auxiliary oxygen flow to 
the oxidation catalyst. Begin heating the trap by placing it in a 
furnace preheated to 200  deg.C (390  deg.F). Once heating has begun, 
carefully monitor the NDIR response to ensure that the catalyst 
effluent concentration does not exceed 50,000 ppm. Whenever the 
CO2 concentration exceeds 50,000 ppm, supply auxiliary 
oxygen to the catalyst at the rate of 150 cc/min. Begin heating the 
tubing that connected the heated sample box to the condensate trap only 
after the CO2 concentration falls below 10,000 ppm. This 
tubing may be heated in the same oven as the condensate trap or with an 
auxiliary heat source such as a heat gun. Heating temperature must not 
exceed 200  deg.C (390  deg.F). If a heat gun is used, heat the tubing 
slowly along its entire length from the upstream end to the downstream 
end, and repeat the pattern for a total of three times. Continue the 
recovery until the CO2 concentration drops to less than 10 
ppm as determined by syringe injection as described under the 
condensate trap CO2 purge procedure (Section 11.1.2).
    11.1.3.4  After the sample recovery is completed, use the carrier 
gas bypass valve to pressurize the ICV to approximately 1060 mm Hg 
absolute pressure with zero air.
    11.2  Analysis. Once the initial performance test of the NMO 
analyzer has been successfully completed (see Section 10.1.2) and the 
daily CO2 and NMO response factors have been determined (see 
Section 10.2), proceed with sample analysis as follows:
    11.2.1  Operating Conditions. The carrier gas flow rate is 29.5 cc/
min He and 2.2 cc/min O2. The column oven is heated to 85 
deg.C (185  deg.F). The order of elution for the sample from the column 
is CO, CH4, CO2, and NMO.
    11.2.2  Analysis of Recovered Condensate Sample. Purge the sample 
loop with sample, and then inject the sample. Under the specified 
operating conditions, the CO2 in the sample will elute in 
approximately 100 seconds. As soon as the detector response returns to 
baseline following the CO2 peak, switch the carrier gas flow 
to backflush, and raise the column oven temperature to 195  deg.C (380 
deg.F) as rapidly as possible. A rate of 30  deg.C/min (90  deg.F) has 
been shown to be adequate. Record the value obtained for the 
condensible organic material (Ccm) measured as 
CO2 and any measured NMO. Return the column oven temperature 
to 85  deg.C (185  deg.F) in preparation for the next analysis. Analyze 
each sample in triplicate, and report the average Ccm.
    11.2.3  Analysis of Sample Tank. Perform the analysis as described 
in Section 11.2.2, but record only the value measured for NMO 
(Ctm).
    11.3  Audit Sample Analysis.
    11.3.1  When the method is used to analyze samples to demonstrate 
compliance with a source emission regulation, an audit sample, if 
available, must be analyzed.
    11.3.2  Concurrently analyze the audit sample and the compliance 
samples in the same manner to evaluate the technique of the analyst and 
the standards preparation.
    11.3.3  The same analyst, analytical reagents, and analytical 
system must be used for the compliance samples and the audit sample. If 
this condition is met, duplicate auditing of subsequent compliance 
analyses for the same enforcement agency within a 30-day period is 
waived. An audit sample set may not be used to validate different sets 
of compliance samples under the jurisdiction of separate enforcement 
agencies, unless prior arrangements have been made with both 
enforcement agencies.
    11.4  Audit Sample Results.
    11.4.1  Calculate the audit sample concentrations and submit 
results using the instructions provided with the audit samples.

[[Page 62050]]

    11.4.2  Report the results of the audit samples and the compliance 
determination samples along with their identification numbers, and the 
analyst's name to the responsible enforcement authority. Include this 
information with reports of any subsequent compliance analyses for the 
same enforcement authority during the 30-day period.
    11.4.3  The concentrations of the audit samples obtained by the 
analyst must agree within 20 percent of the actual concentration. If 
the 20-percent specification is not met, reanalyze the compliance and 
audit samples, and include initial and reanalysis values in the test 
report.
    11.4.4  Failure to meet the 20-percent specification may require 
retests until the audit problems are resolved. However, if the audit 
results do not affect the compliance or noncompliance status of the 
affected facility, the Administrator may waive the reanalysis 
requirement, further audits, or retests and accept the results of the 
compliance test. While steps are being taken to resolve audit analysis 
problems, the Administrator may also choose to use the data to 
determine the compliance or noncompliance status of the affected 
facility.

12.0  Data Analysis and Calculations

    Carry out the calculations, retaining at least one extra 
significant figure beyond that of the acquired data. Round off figures 
after final calculations. All equations are written using absolute 
pressure; absolute pressures are determined by adding the measured 
barometric pressure to the measured gauge or manometer pressure.
    12.1  Nomenclature.

C = TGNMO concentration of the effluent, ppm C equivalent.
Cc = Calculated condensible organic (condensate trap) 
concentration of the effluent, ppm C equivalent.
Ccm = Measured concentration (NMO analyzer) for the 
condensate trap ICV, ppm CO2.
Ct = Calculated noncondensible organic concentration (sample 
tank) of the effluent, ppm C equivalent.
Ctm = Measured concentration (NMO analyzer) for the sample 
tank, ppm NMO.
F = Sampling flow rate, cc/min.
L = Volume of liquid injected, l.
M = Molecular weight of the liquid injected, g/g-mole.
Mc = TGNMO mass concentration of the effluent, mg C/dsm\3\.
N = Carbon number of the liquid compound injected (N = 12 for decane, N 
= 6 for hexane).
n = Number of data points.
Pf = Final pressure of the intermediate collection vessel, 
mm Hg absolute.
Pb = Barometric pressure, cm Hg.
Pti = Gas sample tank pressure before sampling, mm Hg 
absolute.
Pt = Gas sample tank pressure after sampling, but before 
pressurizing, mm Hg absolute.
Ptf = Final gas sample tank pressure after pressurizing, mm 
Hg absolute.
q = Total number of analyzer injections of intermediate collection 
vessel during analysis (where k = injection number, 1 *  *  * q).
r = Total number of analyzer injections of sample tank during analysis 
(where j = injection number, 
1 *  *  * r).
r = Density of liquid injected, g/cc.
Tf = Final temperature of intermediate collection vessel, 
deg.K.
Tti = Sample tank temperature before sampling,  deg.K.
Tt = Sample tank temperature at completion of sampling, 
deg.K.
Ttf = Sample tank temperature after pressurizing,  deg.K.
V = Sample tank volume, m\3\.
Vt = Sample train volume, cc.
Vv = Intermediate collection vessel volume, m\3\.
Vs = Gas volume sampled, dsm\3\.
xi = Individual measurements.
x= Mean value.
P = Allowable pressure change, cm Hg.
 = Leak-check period, min.

    12.2  Allowable Pressure Change. For the pretest leak-check, 
calculate the allowable pressure change using Equation 25-1:
[GRAPHIC] [TIFF OMITTED] TR17OC00.364

    12.3  Sample Volume. For each test run, calculate the gas volume 
sampled using Equation 25-2:
[GRAPHIC] [TIFF OMITTED] TR17OC00.365

    12.4  Noncondensible Organics. For each sample tank, determine the 
concentration of nonmethane organics (ppm C) using Equation 25-3:
[GRAPHIC] [TIFF OMITTED] TR17OC00.366

    12.5  Condensible Organics. For each condensate trap determine the 
concentration of organics (ppm C) using Equation 25-4:
[GRAPHIC] [TIFF OMITTED] TR17OC00.367

    12.6  TGNMO Mass Concentration. Determine the TGNMO mass 
concentration as carbon for each test run, using Equation 25-5:
[GRAPHIC] [TIFF OMITTED] TR17OC00.368

    12.7 Percent Recovery. Calculate the percent recovery for the 
liquid injections to the condensate recovery and conditioning system 
using Equation 25-6:
[GRAPHIC] [TIFF OMITTED] TR17OC00.369

where K = 1.604 ( deg.K)(g-mole)(%)/(mm Hg)(ml)(m\3\)(ppm).
    12.8  Relative Standard Deviation. Use Equation 25-7 to calculate 
the relative standard deviation (RSD) of percent recovery and analyzer 
linearity.

[[Page 62051]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.370

13.0  Method Performance

    13.1  Range. The minimum detectable limit of the method has been 
determined to be 50 parts per million by volume (ppm). No upper limit 
has been established.

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

    1. Salo, A.E., S. Witz, and R.D. MacPhee. Determination of Solvent 
Vapor Concentrations by Total Combustion Analysis: A Comparison of 
Infrared with Flame Ionization Detectors. Paper No. 75-33.2. (Presented 
at the 68th Annual Meeting of the Air Pollution Control Association. 
Boston, MA. June 15-20, 1975.) 14 p.
    2. Salo, A.E., W.L. Oaks, and R.D. MacPhee. Measuring the Organic 
Carbon Content of Source Emissions for Air Pollution Control. Paper No. 
74-190. (Presented at the 67th Annual Meeting of the Air Pollution 
Control Association. Denver, CO. June 9-13, 1974.) 25 p.
BILLING CODE 6560-50-P

[[Page 62052]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.371


[[Page 62053]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.372


[[Page 62054]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.373


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[GRAPHIC] [TIFF OMITTED] TR17OC00.374


[[Page 62056]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.375


[[Page 62057]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.376


[[Page 62058]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.377


[[Page 62059]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.378


[[Page 62060]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.379


[[Page 62061]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.380

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[[Page 62062]]

Method 25A--Determination of Total Gaseous Organic Concentration 
Using a Flame Ionization Analyzer

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.           Sensitivity
------------------------------------------------------------------------
Total Organic Compounds........             N/A   2% of span.
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of total gaseous organic concentration of vapors consisting primarily 
of alkanes, alkenes, and/or arenes (aromatic hydrocarbons). The 
concentration is expressed in terms of propane (or other appropriate 
organic calibration gas) or in terms of carbon.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  A gas sample is extracted from the source through a heated 
sample line and glass fiber filter to a flame ionization analyzer 
(FIA). Results are reported as volume concentration equivalents of the 
calibration gas or as carbon equivalents.

3.0  Definitions

    3.1  Calibration drift means the difference in the measurement 
system response to a mid-level calibration gas before and after a 
stated period of operation during which no unscheduled maintenance, 
repair, or adjustment took place.
    3.2  Calibration error means the difference between the gas 
concentration indicated by the measurement system and the know 
concentration of the calibration gas.
    3.3  Calibration gas means a known concentration of a gas in an 
appropriate diluent gas.
    3.4  Measurement system means the total equipment required for the 
determination of the gas concentration. The system consists of the 
following major subsystems:
    3.4.1  Sample interface means that portion of a system used for one 
or more of the following: sample acquisition, sample transportation, 
sample conditioning, or protection of the analyzer(s) from the effects 
of the stack effluent.
    3.4.2  Organic analyzer means that portion of the measurement 
system that senses the gas to be measured and generates an output 
proportional to its concentration.
    3.5  Response time means the time interval from a step change in 
pollutant concentration at the inlet to the emission measurement system 
to the time at which 95 percent of the corresponding final value is 
reached as displayed on the recorder.
    3.6  Span Value means the upper limit of a gas concentration 
measurement range that is specified for affected source categories in 
the applicable part of the regulations. The span value is established 
in the applicable regulation and is usually 1.5 to 2.5 times the 
applicable emission limit. If no span value is provided, use a span 
value equivalent to 1.5 to 2.5 times the expected concentration. For 
convenience, the span value should correspond to 100 percent of the 
recorder scale.
    3.7  Zero drift means the difference in the measurement system 
response to a zero level calibration gas before or after a stated 
period of operation during which no unscheduled maintenance, repair, or 
adjustment took place.

4.0  Interferences [Reserved]

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method. The analyzer users manual should 
be consulted for specific precautions to be taken with regard to the 
analytical procedure.
    5.2  Explosive Atmosphere. This method is often applied in highly 
explosive areas. Caution and care should be exercised in choice of 
equipment and installation.

6.0  Equipment and Supplies

    6.1  Measurement System. Any measurement system for total organic 
concentration that meets the specifications of this method. A schematic 
of an acceptable measurement system is shown in Figure 25A-1. All 
sampling components leading to the analyzer shall be heated  
110  deg.C (220  deg.F) throughout the sampling period, unless safety 
reasons are cited (Section 5.2) The essential components of the 
measurement system are described below:
    6.1.1  Organic Concentration Analyzer. A flame ionization analyzer 
(FIA) capable of meeting or exceeding the specifications of this 
method. The flame ionization detector block shall be heated >120  deg.C 
(250  deg.F).
    6.1.2  Sample Probe. Stainless steel, or equivalent, three-hole 
rake type. Sample holes shall be 4 mm (0.16-in.) in diameter or smaller 
and located at 16.7, 50, and 83.3 percent of the equivalent stack 
diameter. Alternatively, a single opening probe may be used so that a 
gas sample is collected from the centrally located 10 percent area of 
the stack cross-section.
    6.1.3  Heated Sample Line. Stainless steel or Teflon'' tubing to 
transport the sample gas to the analyzer. The sample line should be 
heated (110  deg.C) to prevent any condensation.
    6.1.4  Calibration Valve Assembly. A three-way valve assembly to 
direct the zero and calibration gases to the analyzers is recommended. 
Other methods, such as quick-connect lines, to route calibration gas to 
the analyzers are applicable.
    6.1.5  Particulate Filter. An in-stack or an out-of-stack glass 
fiber filter is recommended if exhaust gas particulate loading is 
significant. An out-of-stack filter should be heated to prevent any 
condensation.
    6.1.6  Recorder. A strip-chart recorder, analog computer, or 
digital recorder for recording measurement data. The minimum data 
recording requirement is one measurement value per minute.

7.0  Reagents and Standards

    7.1  Calibration Gases. The calibration gases for the gas analyzer 
shall be propane in air or propane in nitrogen. Alternatively, organic 
compounds other than propane can be used; the appropriate corrections 
for response factor must be made. Calibration gases shall be prepared 
in accordance with the procedure listed in Citation 2 of Section 16. 
Additionally, the manufacturer of the cylinder should provide a 
recommended shelf life for each calibration gas cylinder over which the 
concentration does not change more than  2 percent from the 
certified

[[Page 62063]]

value. For calibration gas values not generally available (i.e., 
organics between 1 and 10 percent by volume), alternative methods for 
preparing calibration gas mixtures, such as dilution systems (Test 
Method 205, 40 CFR Part 51, Appendix M), may be used with prior 
approval of the Administrator.
    7.1.1  Fuel. A 40 percent H2/60 percent N2 
gas mixture is recommended to avoid an oxygen synergism effect that 
reportedly occurs when oxygen concentration varies significantly from a 
mean value.
    7.1.2  Zero Gas. High purity air with less than 0.1 part per 
million by volume (ppmv) of organic material (propane or carbon 
equivalent) or less than 0.1 percent of the span value, whichever is 
greater.
    7.1.3  Low-level Calibration Gas. An organic calibration gas with a 
concentration equivalent to 25 to 35 percent of the applicable span 
value.
    7.1.4  Mid-level Calibration Gas. An organic calibration gas with a 
concentration equivalent to 45 to 55 percent of the applicable span 
value.
    7.1.5  High-level Calibration Gas. An organic calibration gas with 
a concentration equivalent to 80 to 90 percent of the applicable span 
value.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Selection of Sampling Site. The location of the sampling site 
is generally specified by the applicable regulation or purpose of the 
test (i.e., exhaust stack, inlet line, etc.). The sample port shall be 
located to meet the testing requirements of Method 1.
    8.2  Location of Sample Probe. Install the sample probe so that the 
probe is centrally located in the stack, pipe, or duct and is sealed 
tightly at the stack port connection.
    8.3  Measurement System Preparation. Prior to the emission test, 
assemble the measurement system by following the manufacturer's written 
instructions for preparing sample interface and the organic analyzer. 
Make the system operable (Section 10.1).
    8.4  Calibration Error Test. Immediately prior to the test series 
(within 2 hours of the start of the test), introduce zero gas and high-
level calibration gas at the calibration valve assembly. Adjust the 
analyzer output to the appropriate levels, if necessary. Calculate the 
predicted response for the low-level and mid-level gases based on a 
linear response line between the zero and high-level response. Then 
introduce low-level and mid-level calibration gases successively to the 
measurement system. Record the analyzer responses for low-level and 
mid-level calibration gases and determine the differences between the 
measurement system responses and the predicted responses. These 
differences must be less than 5 percent of the respective calibration 
gas value. If not, the measurement system is not acceptable and must be 
replaced or repaired prior to testing. No adjustments to the 
measurement system shall be conducted after the calibration and before 
the drift check (Section 8.6.2). If adjustments are necessary before 
the completion of the test series, perform the drift checks prior to 
the required adjustments and repeat the calibration following the 
adjustments. If multiple electronic ranges are to be used, each 
additional range must be checked with a mid-level calibration gas to 
verify the multiplication factor.
    8.5  Response Time Test. Introduce zero gas into the measurement 
system at the calibration valve assembly. When the system output has 
stabilized, switch quickly to the high-level calibration gas. Record 
the time from the concentration change to the measurement system 
response equivalent to 95 percent of the step change. Repeat the test 
three times and average the results.
    8.6  Emission Measurement Test Procedure.
    8.6.1  Organic Measurement. Begin sampling at the start of the test 
period, recording time and any required process information as 
appropriate. In particulate, note on the recording chart, periods of 
process interruption or cyclic operation.
    8.6.2  Drift Determination. Immediately following the completion of 
the test period and hourly during the test period, reintroduce the zero 
and mid-level calibration gases, one at a time, to the measurement 
system at the calibration valve assembly. (Make no adjustments to the 
measurement system until both the zero and calibration drift checks are 
made.) Record the analyzer response. If the drift values exceed the 
specified limits, invalidate the test results preceding the check and 
repeat the test following corrections to the measurement system. 
Alternatively, recalibrate the test measurement system as in Section 
8.4 and report the results using both sets of calibration data (i.e., 
data determined prior to the test period and data determined following 
the test period).


    Note: Note on the recording chart periods of process 
interruption or cyclic operation.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
        Method section               measure               Effect
------------------------------------------------------------------------
8.4...........................  Zero and           Ensures that bias
                                 calibration        introduced by drift
                                 drift tests.       in the measurement
                                                    system output during
                                                    the run is no
                                                    greater than 3
                                                    percent of span.
------------------------------------------------------------------------

10.0  Calibration and Standardization

    10.1  FIA equipment can be calibrated for almost any range of total 
organic concentrations. For high concentrations of organics (> 1.0 
percent by volume as propane), modifications to most commonly available 
analyzers are necessary. One accepted method of equipment modification 
is to decrease the size of the sample to the analyzer through the use 
of a smaller diameter sample capillary. Direct and continuous 
measurement of organic concentration is a necessary consideration when 
determining any modification design.

11.0  Analytical Procedure

    The sample collection and analysis are concurrent for this method 
(see Section 8.0).

12.0  Calculations and Data Analysis

    12.1  Determine the average organic concentration in terms of ppmv 
as propane or other calibration gas. The average shall be determined by 
integration of the output recording over the period specified in the 
applicable regulation. If results are required in terms of ppmv as 
carbon, adjust measured concentrations using Equation 25A-1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.381

Where:
Cc = Organic concentration as carbon, ppmv.
Cmeas = Organic concentration as measured, ppmv.
K = Carbon equivalent correction factor.
    = 2 for ethane.
    = 3 for propane.
    = 4 for butane.
    = Appropriate response factor for other organic calibration gases.

[[Page 62064]]

13.0  Method Performance

    13.1  Measurement System Performance Specifications.
    13.1.1  Zero Drift. Less than 3 percent of the span 
value.
    13.1.2  Calibration Drift. Less than 3 percent of span 
value.
    13.1.3  Calibration Error. Less than 5 percent of the 
calibration gas value.

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

    1. Measurement of Volatile Organic Compounds--Guideline Series. 
U.S. Environmental Protection Agency. Research Triangle Park, NC. 
Publication No. EPA-450/2-78-041. June 1978. p. 46-54.
    2. EPA Traceability Protocol for Assay and Certification of 
Gaseous Calibration Standards. U.S. Environmental Protection Agency, 
Quality Assurance and Technical Support Division. Research Triangle 
Park, N.C. September 1993.
    3. Gasoline Vapor Emission Laboratory Evaluation--Part 2. U.S. 
Environmental Protection Agency, Office of Air Quality Planning and 
Standards. Research Triangle Park, NC. EMB Report No. 75-GAS-6. 
August 1975.
BILLING CODE 6560--50--P

[[Page 62065]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.382

BILLING CODE 6560--50--C

[[Page 62066]]

Method 25B--Determination of Total Gaseous Organic Concentration 
Using a Nondispersive Infrared Analyzer

    Note: This method does not include all of the specifications (e.g., 
equipment and supplies) and procedures (e.g., sampling) essential to 
its performance. Some material is incorporated by reference from other 
methods in this part. Therefore, to obtain reliable results, persons 
using this method should have a thorough knowledge of at least the 
following additional test methods: Method 1, Method 6C, and Method 25A.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
              Analyte                   CAS No.          Sensitivity
------------------------------------------------------------------------
Total Organic Compounds...........             N/A   2% of span.
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of total gaseous organic concentration of vapors consisting primarily 
of alkanes. Other organic materials may be measured using the general 
procedure in this method, the appropriate calibration gas, and an 
analyzer set to the appropriate absorption band.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    A gas sample is extracted from the source through a heated sample 
line, if necessary, and glass fiber filter to a nondispersive infrared 
analyzer (NDIR). Results are reported as volume concentration 
equivalents of the calibration gas or as carbon equivalents.

3.0  Definitions

    Same as Method 25A, Section 3.0.

4.0  Interferences [Reserved]

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method. The analyzer users manual should 
be consulted for specific precautions to be taken with regard to the 
analytical procedure.
    5.2  Explosive Atmosphere. This method is often applied in highly 
explosive areas. Caution and care should be exercised in choice of 
equipment and installation.

6.0  Equipment and Supplies

    Same as Method 25A, Section 6.0, with the exception of the 
following:
    6.1  Organic Concentration Analyzer. A nondispersive infrared 
analyzer designed to measure alkane organics and capable of meeting or 
exceeding the specifications in this method.

7.0  Reagents and Standards

    Same as Method 25A, Section 7.1. No fuel gas is required for an 
NDIR.

8.0  Sample Collection, Preservation, Storage, and Transport

    Same as Method 25A, Section 8.0.

9.0  Quality Control

    Same as Method 25A, Section 9.0.

10.0  Calibration and Standardization

    Same as Method 25A, Section 10.0.

11.0  Analytical Procedure

    The sample collection and analysis are concurrent for this method 
(see Section 8.0).

12.0  Calculations and Data Analysis

    Same as Method 25A, Section 12.0.

13.0  Method Performance [Reserved]

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

    Same as Method 25A, Section 16.0.

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

Method 25C--Determination of Nonmethane Organic Compounds (NMOC) in 
Landfill Gases

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

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
                  Analyte                              CAS No.
------------------------------------------------------------------------
Nonmethane organic compounds (NMOC).......  No CAS number assigned.
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable to the sampling and 
measurement of NMOC as carbon in landfill gases (LFG).
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  A sample probe that has been perforated at one end is driven 
or augured to a depth of 0.9 m (3 ft) below the bottom of the landfill 
cover. A sample of the landfill gas is extracted with an evacuated 
cylinder. The NMOC content of the gas is determined by injecting a 
portion of the gas into a gas chromatographic column to separate the 
NMOC from carbon monoxide (CO), carbon dioxide (CO2), and 
methane (CH4); the NMOC are oxidized to CO2, 
reduced to CH4, and measured by a flame ionization detector 
(FID). In this manner, the variable response of the FID associated with 
different types of organics is eliminated.

3.0  Definitions. [Reserved]

4.0  Interferences. [Reserved]

5.0  Safety

    5.1  Since this method is complex, only experienced personnel 
should perform this test. LFG contains methane, therefore explosive 
mixtures may exist on or near the landfill. It is advisable to take 
appropriate safety precautions when testing landfills, such as 
refraining from smoking and installing explosion-proof equipment.

6.0  Equipment and Supplies

    6.1  Sample Probe. Stainless steel, with the bottom third 
perforated. The sample probe must be capped at the bottom and must have 
a threaded cap with a sampling attachment at the top.

[[Page 62067]]

The sample probe must be long enough to go through and extend no less 
than 0.9 m (3 ft) below the landfill cover. If the sample probe is to 
be driven into the landfill, the bottom cap should be designed to 
facilitate driving the probe into the landfill.
    6.2  Sampling Train.
    6.2.1  Rotameter with Flow Control Valve. Capable of measuring a 
sample flow rate of 100  10 ml/min. The control valve must 
be made of stainless steel.
    6.2.2  Sampling Valve. Stainless steel.
    6.2.3  Pressure Gauge. U-tube mercury manometer, or equivalent, 
capable of measuring pressure to within 1 mm Hg (0.5 in H2O) 
in the range of 0 to 1,100 mm Hg (0 to 590 in H2O).
    6.2.4  Sample Tank. Stainless steel or aluminum cylinder, equipped 
with a stainless steel sample tank valve.
    6.3  Vacuum Pump. Capable of evacuating to an absolute pressure of 
10 mm Hg (5.4 in H2O).
    6.4  Purging Pump. Portable, explosion proof, and suitable for 
sampling NMOC.
    6.5  Pilot Probe Procedure. The following are needed only if the 
tester chooses to use the procedure described in Section 8.2.1.
    6.5.1  Pilot Probe. Tubing of sufficient strength to withstand 
being driven into the landfill by a post driver and an outside diameter 
of at least 6 mm (0.25 in.) smaller than the sample probe. The pilot 
probe shall be capped on both ends and long enough to go through the 
landfill cover and extend no less than 0.9 m (3 ft) into the landfill.
    6.5.2  Post Driver and Compressor. Capable of driving the pilot 
probe and the sampling probe into the landfill. The Kitty Hawk portable 
post driver has been found to be acceptable.
    6.6  Auger Procedure. The following are needed only if the tester 
chooses to use the procedure described in Section 8.2.2.
    6.6.1  Auger. Capable of drilling through the landfill cover and to 
a depth of no less than 0.9 m (3 ft) into the landfill.
    6.6.2  Pea Gravel.
    6.6.3  Bentonite.
    6.7  NMOC Analyzer, Barometer, Thermometer, and Syringes. Same as 
in Sections 6.3.1, 6.3.2, 6.33, and 6.2.10, respectively, of Method 25.

7.0  Reagents and Standards

    7.1  NMOC Analysis. Same as in Method 25, Section 7.2.
    7.2 Calibration. Same as in Method 25, Section 7.4, except omit 
Section 7.4.3.
    7.3  Quality Assurance Audit Samples.
    7.3.1  It is recommended, but not required, that a performance 
audit sample be analyzed in conjunction with the field samples. The 
audit sample should be in a suitable sample matrix at a concentration 
similar to the actual field samples.
    7.3.2  When making compliance determinations, and upon 
availability, audit samples may be obtained from the appropriate EPA 
Regional Office or from the responsible enforcement authority and 
analyzed in conjunction with the field samples.


    Note: The responsible enforcement authority should be notified 
at least 30 days prior to the test date to allow sufficient time for 
sample delivery.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Sample Tank Evacuation and Leak-Check. Conduct the sample tank 
evacuation and leak-check either in the laboratory or the field. 
Connect the pressure gauge and sampling valve to the sample tank. 
Evacuate the sample tank to 10 mm Hg (5.4 in H2O) absolute 
pressure or less. Close the sampling valve, and allow the tank to sit 
for 30 minutes. The tank is acceptable if no change more than 
 2 mm is noted. Include the results of the leak-check in 
the test report.
    8.2  Sample Probe Installation. The tester may use the procedure in 
Section 8.2.1 or 8.2.2.
    8.2.1  Pilot Probe Procedure. Use the post driver to drive the 
pilot probe at least 0.9 m (3 ft) below the landfill cover. Alternative 
procedures to drive the probe into the landfill may be used subject to 
the approval of the Administrator's designated representative.
    8.2.1.1  Remove the pilot probe and drive the sample probe into the 
hole left by the pilot probe. The sample probe shall extend at least 
0.9 m (3 ft) below the landfill cover and shall protrude about 0.3 m (1 
ft) above the landfill cover. Seal around the sampling probe with 
bentonite and cap the sampling probe with the sampling probe cap.
    8.2.2  Auger Procedure. Use an auger to drill a hole to at least 
0.9 m (3 ft) below the landfill cover. Place the sample probe in the 
hole and backfill with pea gravel to a level 0.6 m (2 ft) from the 
surface. The sample probe shall protrude at least 0.3 m (1 ft) above 
the landfill cover. Seal the remaining area around the probe with 
bentonite. Allow 24 hours for the landfill gases to equilibrate inside 
the augured probe before sampling.
    8.3  Sample Train Assembly. Just before assembling the sample 
train, measure the sample tank vacuum using the pressure gauge. Record 
the vacuum, the ambient temperature, and the barometric pressure at 
this time. Assemble the sampling probe purging system as shown in 
Figure 
25C-1.
    8.4  Sampling Procedure. Open the sampling valve and use the purge 
pump and the flow control valve to evacuate at least two sample probe 
volumes from the system at a flow rate of 500 ml/min or less. Close the 
sampling valve and replace the purge pump with the sample tank 
apparatus as shown in Figure 25C-2. Open the sampling valve and the 
sample tank valve and, using the flow control valve, sample at a flow 
rate of 500 ml/min or less until either a constant flow rate can no 
longer be maintained because of reduced sample tank vacuum or the 
appropriate composite volume is attained. Disconnect the sampling tank 
apparatus and pressurize the sample cylinder to approximately 1,060 mm 
Hg (567 in. H2O) absolute pressure with helium, and record 
the final pressure. Alternatively, the sample tank may be pressurized 
in the lab.
    8.4.1  The following restrictions apply to compositing samples from 
different probe sites into a single cylinder: (1) Individual composite 
samples per cylinder must be of equal volume; this must be verified by 
recording the flow rate, sampling time, vacuum readings, or other 
appropriate volume measuring data, (2) individual composite samples 
must have a minimum volume of 1 liter unless data is provided showing 
smaller volumes can be accurately measured, and (3) composite samples 
must not be collected using the final cylinder vacuum as it diminishes 
to ambient pressure.
    8.4.2  Use Method 3C to determine the percent N2 in each 
cylinder. The presence of N2 indicates either infiltration 
of ambient air into the landfill gas sample or an inappropriate testing 
site has been chosen where anaerobic decomposition has not begun. The 
landfill gas sample is acceptable if the concentration of N2 
is less than 20 percent. Alternatively, Method 3C may be used to 
determine the oxygen content of each cylinder as an air infiltration 
test. With this option, the oxygen content of each cylinder must be 
less than 5 percent.

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

[[Page 62068]]



------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.4.1.........................  Verify that        Ensures that ambient
                                 landfill gas       air was not drawn
                                 sample contains    into the landfill
                                 less than 20       gas sample.
                                 percent N2 or 5
                                 percent O2.
10.1, 10.2....................  NMOC analyzer      Ensures precision of
                                 initial and        analytical results.
                                 daily
                                 performance
                                 checks.
11.1.4........................  Audit Sample       Evaluate analytical
                                 Analyses.          technique and
                                                    instrument
                                                    calibration.
------------------------------------------------------------------------

10.0  Calibration and Standardization

    Note: Maintain a record of performance of each item.


    10.1  Initial NMOC Analyzer Performance Test. Same as in Method 25, 
Section 10.1, except omit the linearity checks for CO2 
standards.
    10.2  NMOC Analyzer Daily Calibration.
    10.2.1  NMOC Response Factors. Same as in Method 25, Section 
10.2.2.
    10.3  Sample Tank Volume. The volume of the gas sampling tanks must 
be determined. Determine the tank volumes by weighing them empty and 
then filled with deionized water; weigh to the nearest 5 g, and record 
the results. Alternatively, measure the volume of water used to fill 
them to the nearest 5 ml.

11.0  Analytical Procedures

    11.1  The oxidation, reduction, and measurement of NMOC's is 
similar to Method 25. Before putting the NMOC analyzer into routine 
operation, conduct an initial performance test. Start the analyzer, and 
perform all the necessary functions in order to put the analyzer into 
proper working order. Conduct the performance test according to the 
procedures established in Section 10.1. Once the performance test has 
been successfully completed and the NMOC calibration response factor 
has been determined, proceed with sample analysis as follows:
    11.1.1  Daily Operations and Calibration Checks. Before and 
immediately after the analysis of each set of samples or on a daily 
basis (whichever occurs first), conduct a calibration test according to 
the procedures established in Section 10.2. If the criteria of the 
daily calibration test cannot be met, repeat the NMOC analyzer 
performance test (Section 10.1) before proceeding.
    11.1.2  Operating Conditions. Same as in Method 25, Section 11.2.1.
    11.1.3  Analysis of Sample Tank. Purge the sample loop with sample, 
and then inject the sample. Under the specified operating conditions, 
the CO2 in the sample will elute in approximately 100 
seconds. As soon as the detector response returns to baseline following 
the CO2 peak, switch the carrier gas flow to backflush, and 
raise the column oven temperature to 195 deg.C (383 deg.F) as rapidly 
as possible. A rate of 30 deg.C/min (54 deg.F/min) has been shown to be 
adequate. Record the value obtained for any measured NMOC. Return the 
column oven temperature to 85 deg.C (185 deg.F) in preparation for the 
next analysis. Analyze each sample in triplicate, and report the 
average as Ctm.
    11.2  Audit Sample Analysis. When the method is used to analyze 
samples to demonstrate compliance with a source emission regulation, an 
audit sample, if available, must be analyzed.
    11.2.1  Concurrently analyze the audit sample and the compliance 
samples in the same manner to evaluate the technique of the analyst and 
the standards preparation.
    11.2.2  The same analyst, analytical reagents, and analytical 
system must be used for the compliance samples and the audit sample. If 
this condition is met, duplicate auditing of subsequent compliance 
analyses for the same enforcement agency within a 30-day period is 
waived. An audit sample set may not be used to validate different sets 
of compliance samples under the jurisdiction of separate enforcement 
agencies, unless prior arrangements have been made with both 
enforcement agencies.
    11.3  Audit Sample Results.
    11.3.1  Calculate the audit sample concentrations and submit 
results using the instructions provided with the audit samples.
    11.3.2  Report the results of the audit samples and the compliance 
determination samples along with their identification numbers, and the 
analyst's name to the responsible enforcement authority. Include this 
information with reports of any subsequent compliance analyses for the 
same enforcement authority during the 30-day period.
    11.3.3  The concentrations of the audit samples obtained by the 
analyst must agree within 20 percent of the actual concentration. If 
the 20-percent specification is not met, reanalyze the compliance and 
audit samples, and include initial and reanalysis values in the test 
report.
    11.3.4  Failure to meet the 20-percent specification may require 
retests until the audit problems are resolved. However, if the audit 
results do not affect the compliance or noncompliance status of the 
affected facility, the Administrator may waive the reanalysis 
requirement, further audits, or retests and accept the results of the 
compliance test. While steps are being taken to resolve audit analysis 
problems, the Administrator may also choose to use the data to 
determine the compliance or noncompliance status of the affected 
facility.

12.0  Data Analysis and Calculations

    Note: All equations are written using absolute pressure; 
absolute pressures are determined by adding the measured barometric 
pressure to the measured gauge or manometer pressure.


    12.1  Nomenclature.

Bw = Moisture content in the sample, fraction.
CN2 = Measured N2 concentration, fraction.
Ct = Calculated NMOC concentration, ppmv C equivalent.
Ctm = Measured NMOC concentration, ppmv C equivalent.
Pb = Barometric pressure, mm Hg.
Pt = Gas sample tank pressure after sampling, but before 
pressurizing, mm Hg absolute.
Ptf = Final gas sample tank pressure after pressurizing, mm 
Hg absolute.
Pti = Gas sample tank pressure after evacuation, mm Hg 
absolute.
Pw = Vapor pressure of H2O (from Table 25C-1), mm 
Hg.
r = Total number of analyzer injections of sample tank during analysis 
(where j = injection number, 1 * * * r).
Tt = Sample tank temperature at completion of sampling, 
deg.K.
Tti = Sample tank temperature before sampling,  deg.K.
Ttf = Sample tank temperature after pressurizing,  deg.K.

    12.2  Water Correction. Use Table 25C-1 (Section 17.0), the LFG 
temperature, and barometric pressure at the sampling site to calculate 
Bw.
[GRAPHIC] [TIFF OMITTED] TR17OC00.383

    12.3  NMOC Concentration. Use the following equation to calculate 
the concentration of NMOC for each sample tank.

[[Page 62069]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.384

13.0  Method Performance [Reserved]

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

    1. Salo, Albert E., Samuel Witz, and Robert D. MacPhee. 
Determination of Solvent Vapor Concentrations by Total Combustion 
Analysis: A Comparison of Infrared with Flame Ionization Detectors. 
Paper No. 75-33.2. (Presented at the 68th Annual Meeting of the Air 
Pollution Control Association. Boston, Massachusetts. June 15-20, 
1975.) 
14 p.
    2. Salo, Albert E., William L. Oaks, and Robert D. MacPhee. 
Measuring the Organic Carbon Content of Source Emissions for Air 
Pollution Control. Paper No. 74-190. (Presented at the 67th Annual 
Meeting of the Air Pollution Control Association. Denver, Colorado. 
June 9-13, 1974.) 25 p.
BILLING CODE 6560-50-P

[[Page 62070]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.385

BILLING CODE 6560-50-C

[[Page 62071]]



                    Table 25C-1.--Moisture Correction
------------------------------------------------------------------------
                                        Vapor                    Vapor
                                       Pressure  Temperature,   Pressure
         Temperature,  deg.C           of H2O,       deg.C      of H2O,
                                        mm Hg                    mm Hg
------------------------------------------------------------------------
4...................................        6.1           18        15.5
6...................................        7.0           20        17.5
8...................................        8.0           22        19.8
10..................................        9.2           24        22.4
12..................................       10.5           26        25.2
14..................................       12.0           28        28.3
16..................................       13.6           30        31.8
------------------------------------------------------------------------

Method 25D--Determination of the Volatile Organic Concentration of 
Waste Samples

    Note: Performance of this method should not be attempted by 
persons unfamiliar with the operation of a flame ionization detector 
(FID) or an electrolytic conductivity detector (ELCD) because 
knowledge beyond the scope of this presentation is required.

1.0  Scope and Application

    1.1  Analyte. Volatile Organic Compounds. No CAS No. assigned.
    1.2  Applicability. This method is applicable for determining the 
volatile organic (VO) concentration of a waste sample.

2.0  Summary of Method

    2.1  Principle. A sample of waste is obtained at a point which is 
most representative of the unexposed waste (where the waste has had 
minimum opportunity to volatilize to the atmosphere). The sample is 
suspended in an organic/aqueous matrix, then heated and purged with 
nitrogen for 30 min. in order to separate certain organic compounds. 
Part of the sample is analyzed for carbon concentration, as methane, 
with an FID, and part of the sample is analyzed for chlorine 
concentration, as chloride, with an ELCD. The VO concentration is the 
sum of the carbon and chlorine content of the sample.

3.0  Definitions

    3.1  Well-mixed in the context of this method refers to turbulent 
flow which results in multiple-phase waste in effect behaving as 
single-phase waste due to good mixing.

4.0  Interferences. [Reserved]

5.0  Safety

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

6.0  Equipment and Supplies

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


    6.1  Sampling. The following equipment is required:
    6.1.1  Sampling Tube. Flexible Teflon, 0.25 in. ID (6.35 mm).
    6.1.2  Sample Container. Borosilicate glass, 40-mL, and a Teflon-
lined screw cap capable of forming an air tight seal.
    6.1.3  Cooling Coil. Fabricated from 0.25 in (6.35 mm). ID 304 
stainless steel tubing with a thermocouple at the coil outlet.
    6.2  Analysis. The following equipment is required.
    6.2.1  Purging Apparatus. For separating the VO from the waste 
sample. A schematic of the system is shown in Figure 25D-1. The purging 
apparatus consists of the following major components.
    6.2.1.1  Purging Flask. A glass container to hold the sample while 
it is heated and purged with dry nitrogen. The cap of the purging flask 
is equipped with three fittings: one for a purging lance (fitting with 
the #7 Ace-thread), one for the Teflon exit tubing (side fitting, also 
a #7 Ace-thread), and a third (a 50-mm Ace-thread) to attach the base 
of the purging flask as shown in Figure 25D-2. The base of the purging 
flask is a 50-mm ID (2 in) cylindrical glass tube. One end of the tube 
is open while the other end is sealed. Exact dimensions are shown in 
Figure 25D-2.
    6.2.1.2  Purging Lance. Glass tube, 6-mm OD (0.2 in) by 30 cm (12 
in) long. The purging end of the tube is fitted with a four-arm bubbler 
with each tip drawn to an opening 1 mm (0.04 in) in diameter. Details 
and exact dimensions are shown in Figure 25D-2.
    6.2.1.3  Coalescing Filter. Porous fritted disc incorporated into a 
container with the same dimensions as the purging flask. The details of 
the design are shown in Figure 25D-3.
    6.2.1.4  Constant Temperature Chamber. A forced draft oven capable 
of maintaining a uniform temperature around the purging flask and 
coalescing filter of 75  2 deg.C (167  
3.6 deg.F).
    6.2.1.5  Three-way Valve. Manually operated, stainless steel. To 
introduce calibration gas into system.
    6.2.1.6  Flow Controllers. Two, adjustable. One capable of 
maintaining a purge gas flow rate of 6  0.06 L/min (0.2 
 0.002 ft3/min) The other capable of maintaining 
a calibration gas flow rate of 1-100 mL/min (0.00004-0.004 
ft3/min).
    6.2.1.7  Rotameter. For monitoring the air flow through the purging 
system (0-10 L/min)(0-0.4 ft3/min).
    6.2.1.8  Sample Splitters. Two heated flow restrictors (placed 
inside oven or heated to 120  10 deg.C (248  18 
 deg.F) ). At a purge rate of 6 L/min (0.2 ft3/min), one 
will supply a constant flow to the first detector (the rest of the flow 
will be directed to the second sample splitter). The second splitter 
will split the analytical flow between the second detector and the flow 
restrictor. The approximate flow to the FID will be 40 mL/min (0.0014 
ft3/min) and to the ELCD will be 15 mL/min (0.0005 
ft3/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 (3.175 mm) stainless steel tubing.
    6.2.1.9  Flow Restrictor. Stainless steel tubing, 1/8" OD (3.175 
mm), connecting the second sample splitter to the ice bath. Length is 
determined by the resulting pressure in the purging flask (as measured 
by the pressure gauge). The resulting pressure from the use of the flow 
restrictor shall be 6-7 psig.
    6.2.1.10  Filter Flask. With one-hole stopper. Used to hold ice 
bath. Excess purge gas is vented through the flask to prevent 
condensation in the flowmeter and to trap volatile organic compounds.
    6.2.1.11  Four-way Valve. Manually operated, stainless steel. 
Placed inside oven, used to bypass purging flask.
    6.2.1.12  On/Off Valves. Two, stainless steel. One heat resistant 
up to 130  deg.C (266  deg.F) and placed between oven and ELCD. The 
other a toggle valve used to control purge gas flow.
    6.2.1.13  Pressure Gauge. Range 0-40 psi. To monitor pressure in 
purging flask and coalescing filter.
    6.2.1.14  Sample Lines. Teflon, 1/4" OD (6.35 mm), used inside the 
oven to carry purge gas to and from purging chamber and to and from 
coalescing filter to four-way valve. Also used to carry sample from 
four-way valve to first sample splitter.
    6.2.1.15  Detector Tubing. Stainless steel, 1/8" OD (3.175 mm), 
heated to 120  10 deg.C (248  18  deg.F) . Used 
to carry sample gas from each sample splitter to a detector. Each piece 
of tubing must be wrapped with heat tape and insulating tape in order 
to insure that no cold spots exist. The tubing leading to the ELCD will 
also contain a heat-resistant on-off valve (Section 6.2.1.12) which 
shall also be wrapped with heat-tape and insulation.
    6.2.2  Volatile Organic Measurement System. Consisting of an FID to 
measure

[[Page 62072]]

the carbon concentration of the sample and an ELCD to measure the 
chlorine concentration.
    6.2.2.1  FID. A heated FID meeting the following specifications is 
required.
    6.2.2.1.1  Linearity. A linear response ( 5 percent) 
over the operating range as demonstrated by the procedures established 
in Section 10.1.1.
    6.2.2.1.2  Range. A full scale range of 50 pg carbon/sec to 50 
g carbon/sec. Signal attenuators shall be available to produce 
a minimum signal response of 10 percent of full scale.
    6.2.2.1.3  Data Recording System. A digital integration system 
compatible with the FID for permanently recording the output of the 
detector. The recorder shall have the capability to start and stop 
integration at points selected by the operator or it shall be capable 
of the ``integration by slices'' technique (this technique involves 
breaking down the chromatogram into smaller increments, integrating the 
area under the curve for each portion, subtracting the background for 
each portion, and then adding all of the areas together for the final 
area count).
    6.2.2.2  ELCD. An ELCD meeting the following specifications is 
required. 1-propanol must be used as the electrolyte. The electrolyte 
flow through the conductivity cell shall be 1 to 2 mL/min (0.00004 to 
0.00007 ft\3\/min).

    Note: A \1/4\-in. ID (6.35 mm) quartz reactor tube is strongly 
recommended to reduce carbon buildup and the resulting detector 
maintenance.

    6.2.2.2.1  Linearity. A linear response ( 10 percent) 
over the response range as demonstrated by the procedures in Section 
10.1.2.
    6.2.2.2.2  Range. A full scale range of 5.0 pg/sec to 500 ng/sec 
chloride. Signal attenuators shall be available to produce a minimum 
signal response of 10 percent of full scale.
    6.2.2.2.3  Data Recording System. A digital integration system 
compatible with the output voltage range of the ELCD. The recorder must 
have the capability to start and stop integration at points selected by 
the operator or it shall be capable of performing the ``integration by 
slices'' technique.

7.0  Reagents and Standards

    7.1  Sampling.
    7.1.1  Polyethylene Glycol (PEG). Ninety-eight percent pure with an 
average molecular weight of 400. Before using the PEG, remove any 
organic compounds that might be detected as volatile organics by 
heating it to 120 deg.C (248  deg.F) and purging it with nitrogen at a 
flow rate of 1 to 2 L/min (0.04 to 0.07 ft\3\/min) for 2 hours. The 
cleaned PEG must be stored under a 1 to 2 L/min (0.04 to 0.07 ft\3\/
min) nitrogen purge until use. The purge apparatus is shown in Figure 
25D-4.
    7.2  Analysis.
    7.2.1  Sample Separation. The following are required for the sample 
purging step.
    7.2.1.1  PEG. Same as Section 7.1.1.
    7.2.1.2  Purge Gas. Zero grade nitrogen (N2), containing 
less than 1 ppm carbon.
    7.2.2  Volatile Organics Measurement. The following are required 
for measuring the VO concentration.
    7.2.2.1  Hydrogen (H2). Zero grade H2, 99.999 
percent pure.
    7.2.2.2  Combustion Gas. Zero grade air or oxygen as required by 
the FID.
    7.2.2.3  Calibration Gas. Pressurized gas cylinder containing 10 
percent propane and 1 percent 1,1-dichloroethylene by volume in 
nitrogen.
    7.2.2.4  Water. Deionized distilled water that conforms to American 
Society for Testing and Materials Specification D 1193-74, Type 3, is 
required for analysis. At the option of the analyst, the 
KMnO4 test for oxidizable organic matter may be omitted when 
high concentrations are not expected to be present.
    7.2.2.5  1-Propanol. ACS grade or better. Electrolyte Solution. For 
use in the ELCD.
    7.3  Quality Assurance Audit Samples.
    7.3.1  It is recommended, but not required, that a performance 
audit sample be analyzed in conjunction with the field samples. The 
audit sample should be in a suitable sample matrix at a concentration 
similar to the actual field samples.
    7.3.2  When making compliance determinations, and upon 
availability, audit samples may be obtained from the appropriate EPA 
regional Office or from the responsible enforcement authority and 
analyzed in conjunction with the field samples.


    Note: The responsible enforcement authority should be notified 
at least 30 days prior to the test date to allow sufficient time for 
sample delivery.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Sampling.
    8.1.1  Sampling Plan Design and Development. Use the procedures in 
chapter nine of Reference 1 in Section 16 as guidance in developing a 
sampling plan.
    8.1.2  Single Phase or Well-mixed Waste.
    8.1.2.1  Install a sampling tap to obtain the sample at a point 
which is most representative of the unexposed waste (where the waste 
has had minimum opportunity to volatilize to the atmosphere). Assemble 
the sampling apparatus as shown in Figure 25D-5.
    8.1.2.2  Prepare the sampling containers as follows: Pour 30 mL of 
clean PEG into the container. PEG will reduce but not eliminate the 
loss of organics during sample collection. Weigh the sample container 
with the screw cap, the PEG, and any labels to the nearest 0.01 g and 
record the weight (mst). Store the containers in an ice bath 
until 1 hour before sampling (PEG will solidify at ice bath 
temperatures; allow the containers to reach room temperature before 
sampling).
    8.1.2.3  Begin sampling by purging the sample lines and cooling 
coil with at least four volumes of waste. Collect the purged material 
in a separate container and dispose of it properly.
    8.1.2.4  After purging, stop the sample flow and direct the 
sampling tube to a preweighed sample container, prepared as described 
in Section 8.1.2.2. Keep the tip of the tube below the surface of the 
PEG during sampling to minimize contact with the atmosphere. Sample at 
a flow rate such that the temperature of the waste is less than 
10 deg.C (50  deg.F). Fill the sample container and immediately cap it 
(within 5 seconds) so that a minimum headspace exists in the container. 
Store immediately in a cooler and cover with ice.
    8.1.3  Multiple-phase Waste. Collect a 10 g sample of each phase of 
waste generated using the procedures described in Section 8.1.2 or 
8.1.5. Each phase of the waste shall be analyzed as a separate sample. 
Calculate the weighted average VO concentration of the waste using 
Equation 25D-13 (Section 12.14).
    8.1.4  Solid waste. Add approximately 10 g of the solid waste to a 
container prepared in the manner described in Section 8.1.2.2, 
minimizing headspace. Cap and chill immediately.
    8.1.5  Alternative to Tap Installation. If tap installation is 
impractical or impossible, fill a large, clean, empty container by 
submerging the container into the waste below the surface of the waste. 
Immediately fill a container prepared in the manner described in 
Section 8.1.2.2 with approximately 10 g of the waste collected in the 
large container. Minimize headspace, cap and chill immediately.
    8.1.6  Alternative sampling techniques may be used upon the 
approval of the Administrator.
    8.2  Sample Recovery.
    8.2.1  Assemble the purging apparatus as shown in Figures 25D-1 and 
25D-2. The oven shall be heated to

[[Page 62073]]

75  2 deg.C (167  3.6  deg.F). The sampling 
lines leading from the oven to the detectors shall be heated to 120 
 10 deg.C (248  18  deg.F) with no cold spots. 
The flame ionization detector shall be operated with a heated block. 
Adjust the purging lance so that it reaches the bottom of the chamber.
    8.2.2  Remove the sample container from the cooler, and wipe the 
exterior of the container to remove any extraneous ice, water, or other 
debris. Reweigh the sample container to the nearest 0.01 g, and record 
the weight (msf). Pour the contents of the sample container 
into the purging flask, rinse the sample container three times with a 
total of 20 mL of PEG (since the sample container originally held 30 mL 
of PEG, the total volume of PEG added to the purging flask will be 50 
mL), transferring the rinsings to the purging flask after each rinse. 
Cap purging flask between rinses. The total volume of PEG in the 
purging flask shall be 50 mL. Add 50 mL of water to the purging flask.

9.0  Quality Control

    9.1  Quality Control Samples. If audit samples are not available, 
prepare and analyze the two types of quality control samples (QCS) 
listed in Sections 9.4.1 and 9.4.2. Before placing the system in 
operation, after a shutdown of greater than six months, and after any 
major modifications, analyze each QCS in triplicate. For each detector, 
calculate the percent recovery by dividing measured concentration by 
theoretical concentration and multiplying by 100. Determine the mean 
percent recovery for each detector for each QCS triplicate analysis. 
The RSD for any triplicate analysis shall be 10 percent. For 
QCS 1 (methylene chloride), the percent recovery shall be 90 
percent for carbon as methane, and 55 percent for chlorine 
as chloride. For QCS 2 (1,3-dichloro-2-propanol), the percent recovery 
shall be 15 percent for carbon as methane, and 6 
percent for chlorine as chloride. If the analytical system does not 
meet the above-mentioned criteria for both detectors, check the system 
parameters (temperature, system pressure, purge rate, etc.), correct 
the problem, and repeat the triplicate analysis of each QCS.
    9.1.1  QCS 1, Methylene Chloride. Prepare a stock solution by 
weighing, to the nearest 0.1 mg, 55 L of HPLC grade methylene 
chloride in a tared 5 mL volumetric flask. Record the weight in 
milligrams, dilute to 5 mL with cleaned PEG, and inject 100 L 
of the stock solution into a sample prepared as a water blank (50 mL of 
cleaned PEG and 60 mL of water in the purging flask). Analyze the QCS 
according to the procedures described in Sections 10.2 and 10.3, 
excluding Section 10.2.2. To calculate the theoretical carbon 
concentration (in mg) in QCS 1, multiply mg of methylene chloride in 
the stock solution by 3.777  x  10-3. To calculate the 
theoretical chlorine concentration (in mg) in QCS 1, multiply mg of 
methylene chloride in the stock solution by 1.670  x  10-2.
    9.1.2  QCS 2, 1,3-dichloro-2-propanol. Prepare a stock solution by 
weighing, to the nearest 0.1 mg, 60 L of high purity grade 
1,3-dichloro-2-propanol in a tared 5 mL volumetric flask. Record the 
weight in milligrams, dilute to 5 mL with cleaned PEG, and inject 100 
L of the stock solution into a sample prepared as a water 
blank (50 mL of cleaned PEG and 60 mL of water in the purging flask). 
Analyze the QCS according to the procedures described in Sections 10.2 
and 10.3, excluding Section 10.2.2. To calculate the theoretical carbon 
concentration (in mg) in QCS 2, multiply mg of 1,3-dichloro-2-propanol 
in the stock solution by 7.461  x  10-3. To calculate the 
theoretical chlorine concentration (in mg) in QCS 2, multiply mg of 
1,3-dichloro-2-propanol in the stock solution by 1.099  x  
10-2.
    9.1.3  Routine QCS Analysis. For each set of compliance samples (in 
this context, set is per facility, per compliance test), analyze one 
QCS 1 and one QCS 2 sample. The percent recovery for each sample for 
each detector shall be  13 percent of the mean recovery 
established for the most recent set of QCS triplicate analysis (Section 
9.4). If the sample does not meet this criteria, check the system 
components and analyze another QCS 1 and 2 until a single set of QCS 
meet the  13 percent criteria.

10.0  Calibration and Standardization

    10.1  Initial Performance Check of Purging System. Before placing 
the system in operation, after a shutdown of greater than six months, 
after any major modifications, and at least once per month during 
continuous operation, conduct the linearity checks described in 
Sections 10.1.1 and 10.1.2. Install calibration gas at the three-way 
calibration gas valve. See Figure 25D-1.
    10.1.1  Linearity Check Procedure. Using the calibration standard 
described in Section 7.2.2.3 and by varying the injection time, it is 
possible to calibrate at multiple concentration levels. Use Equation 
25D-3 to calculate three sets of calibration gas flow rates and run 
times needed to introduce a total mass of carbon, as methane, 
(mc) of 1, 5, and 10 mg into the system (low, medium and 
high FID calibration, respectively). Use Equation 25D-4 to calculate 
three sets of calibration gas flow rates and run times needed to 
introduce a total chloride mass (mch) of 1, 5, and 10 mg 
into the system (low, medium and high ELCD calibration, respectively). 
With the system operating in standby mode, allow the FID and the ELCD 
to establish a stable baseline. Set the secondary pressure regulator of 
the calibration gas cylinder to the same pressure as the purge gas 
cylinder and set the proper flow rate with the calibration flow 
controller (see Figure 25D-1). The calibration gas flow rate can be 
measured with a flowmeter attached to the vent position of the 
calibration gas valve. Set the four-way bypass valve to standby 
position so that the calibration gas flows through the coalescing 
filter only. Inject the calibration gas by turning the calibration gas 
valve from vent position to inject position. Continue the calibration 
gas flow for the appropriate period of time before switching the 
calibration valve to vent position. Continue recording the response of 
the FID and the ELCD for 5 min after switching off calibration gas 
flow. Make triplicate injections of all six levels of calibration.
    10.1.2  Linearity Criteria. Calculate the average response factor 
(Equations 25D-5 and 25D-6) and the relative standard deviation (RSD) 
(Equation 25D-10) at each level of the calibration curve for both 
detectors. Calculate the overall mean of the three response factor 
averages for each detector. The FID linearity is acceptable if each 
response factor is within 5 percent of the overall mean and if the RSD 
for each set of triplicate injections is less than 5 percent. The ELCD 
linearity is acceptable if each response factor is within 10 percent of 
the overall mean and if the RSD for each set of triplicate injections 
is less than 10 percent. Record the overall mean value of the response 
factors for the FID and the ELCD. If the calibration for either the FID 
or the ELCD does not meet the criteria, correct the detector/system 
problem and repeat Sections 10.1.1 and 10.1.2.
    10.2  Daily Calibrations.
    10.2.1  Daily Linearity Check. Follow the procedures outlined in 
Section 10.1.1 to analyze the medium level calibration for both the FID 
and the ELCD in duplicate at the start of the day. Calculate the 
response factors and the RSDs for each detector. For the FID, the 
calibration is acceptable if the average response factor is within 5 
percent of the overall mean response factor (Section 10.1.2) and if the 
RSD for the duplicate injection is less than 5 percent. For the ELCD, 
the calibration is acceptable if the average response factor

[[Page 62074]]

is within 10 percent of the overall mean response factor (Section 
10.1.2) and if the RSD for the duplicate injection is less than 10 
percent. If the calibration for either the FID or the ELCD does not 
meet the criteria, correct the detector/system problem and repeat 
Sections 10.1.1 and 10.1.2.
    10.2.2  Calibration Range Check.
    10.2.2.1  If the waste concentration for either detector falls 
below the range of calibration for that detector, use the procedure 
outlined in Section 10.1.1 to choose two calibration points that 
bracket the new target concentration. Analyze each of these points in 
triplicate (as outlined in Section 10.1.1) and use the criteria in 
Section 10.1.2 to determine the linearity of the detector in this 
``mini-calibration'' range.
    10.2.2.2  After the initial linearity check of the mini-calibration 
curve, it is only necessary to test one of the points in duplicate for 
the daily calibration check (in addition to the points specified in 
Section 10.2.1). The average daily mini-calibration point should fit 
the linearity criteria specified in Section 10.2.1. If the calibration 
for either the FID or the ELCD does not meet the criteria, correct the 
detector/system problem and repeat the calibration procedure mentioned 
in the first paragraph of Section 10.2.2. A mini-calibration curve for 
waste concentrations above the calibration curve for either detector is 
optional.
    10.3  Analytical Balance. Calibrate against standard weights.

11.0  Analysis

    11.1  Sample Analysis.
    11.1.1  Turn on the constant temperature chamber and allow the 
temperature to equilibrate at 75  2 deg.C (167  
3.6  deg.F). Turn the four-way valve so that the purge gas bypasses the 
purging flask, the purge gas flowing through the coalescing filter and 
to the detectors (standby mode). Turn on the purge gas. Allow both the 
FID and the ELCD to warm up until a stable baseline is achieved on each 
detector. Pack the filter flask with ice. Replace ice after each run 
and dispose of the waste water properly. When the temperature of the 
oven reaches 75  2 deg.C (167  3.6  deg.F), 
start both integrators and record baseline. After 1 min, turn the four-
way valve so that the purge gas flows through the purging flask, to the 
coalescing filter and to the sample splitters (purge mode). Continue 
recording the response of the FID and the ELCD. Monitor the readings of 
the pressure gauge and the rotameter. If the readings fall below 
established setpoints, stop the purging, determine the source of the 
leak, and resolve the problem before resuming. Leaks detected during a 
sampling period invalidate that sample.
    11.1.2  As the purging continues, monitor the output of the 
detectors to make certain that the analysis is proceeding correctly and 
that the results are being properly recorded. Every 10 minutes read and 
record the purge flow rate, the pressure and the chamber temperature. 
Continue the purging for 30 minutes.
    11.1.3  For each detector output, integrate over the entire area of 
the peak starting at 1 minute and continuing until the end of the run. 
Subtract the established baseline area from the peak area. Record the 
corrected area of the peak. See Figure 25D-6 for an example 
integration.
    11.2  Water Blank. A water blank shall be analyzed for each batch 
of cleaned PEG prepared. Transfer about 60 mL of water into the purging 
flask. Add 50 mL of the cleaned PEG to the purging flask. Treat the 
blank as described in Sections 8.2 and 8.3, excluding Section 8.2.2. 
Calculate the concentration of carbon and chlorine in the blank sample 
(assume 10 g of waste as the mass). A VO concentration equivalent to 
10 percent of the applicable standard may be subtracted from 
the measured VO concentration of the waste samples. Include all blank 
results and documentation in the test report.
    11.3  Audit Sample Analysis.
    11.3.1  When the method is used to analyze samples to demonstrate 
compliance with a source emission regulation, an audit sample, if 
available, must be analyzed.
    11.3.2  Concurrently analyze the audit sample and the compliance 
samples in the same manner to evaluate the technique of the analyst and 
the standards preparation.
    11.3.3  The same analyst, analytical reagents, and analytical 
system must be used for the compliance samples and the audit sample. If 
this condition is met, duplicate auditing of subsequent compliance 
analyses for the same enforcement agency within a 30-day period is 
waived. An audit sample may not be used to validate different sets of 
compliance samples under the jurisdiction of separate enforcement 
agencies, unless prior arrangements have been made with both 
enforcement agencies.
    11.4  Audit Sample Results.
    11.4.1  Calculate the audit sample concentrations and submit 
results using the instructions provided with the audit samples.
    11.4.2  Report the results of the audit samples and the compliance 
determination samples along with their identification numbers, and the 
analyst's name to the responsible enforcement authority. Include this 
information with reports of any subsequent compliance analyses for the 
same enforcement authority during the 30-day period.

12.0  Data Analysis and Calculations

    12.1  Nomenclature.

Ab = Area under the water blank response curve, counts.
Ac = Area under the calibration response curve, counts.
As = Area under the sample response curve, counts.
C = Concentration of volatile organics in the sample, ppmw.
Cc = Concentration of carbon, as methane, in the calibration 
gas, mg/L.
Cch = Concentration of chloride in the calibration gas, mg/
L.
Cj = VO concentration of phase j, ppmw.
DRt = Average daily response factor of the FID, mg 
CH4/counts.
Drth = Average daily response factor of the ELCD, mg 
Cl-/counts.
Fj = Weight fraction of phase j present in the waste.
mc = Mass of carbon, as methane, in a calibration run, mg.
mch = Mass of chloride in a calibration run, mg.
ms = Mass of the waste sample, g.
msc = Mass of carbon, as methane, in the sample, mg.
msf = Mass of sample container and waste sample, g.
msh = Mass of chloride in the sample, mg.
mst = Mass of sample container prior to sampling, g.
mVO = Mass of volatile organics in the sample, mg.
n = Total number of phases present in the waste.
Pp = Percent propane in calibration gas (L/L).
Pvc = Percent 1,1-dichloroethylene in calibration gas (L/L).
Qc = Flow rate of calibration gas, L/min.
tc = Length of time standard gas is delivered to the 
analyzer, min.
W = Weighted average VO concentration, ppmw.

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

[[Page 62075]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.386

    12.3  Concentration of Chloride in the Calibration Gas.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.387
    
    12.4  Mass of Carbon, as Methane, in a Calibration Run.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.388
    
    12.5  Mass of Chloride in a Calibration Run.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.389
    
    12.6  FID Response Factor, mg/counts.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.390
    
    12.7  ELCD Response Factor, mg/counts.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.391
    
    12.8  Mass of Carbon in the Sample.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.392
    
    12.9  Mass of Chloride in the Sample.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.393
    
    12.10  Mass of Volatile Organics in the Sample.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.394
    
    12.11  Relative Standard Deviation.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.395
    
    12.12  Mass of Sample.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.396
    
    12.13  Concentration of Volatile Organics in Waste.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.397
    
    12.14  Weighted Average VO Concentration of Multi-phase Waste.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.398
    
13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    1. ``Test Methods for Evaluating Solid Waste, Physical/Chemistry 
Methods'', U.S. Environmental Protection Agency. Publication SW-846, 
3rd Edition, November 1986 as amended by Update I, November 1990.
BILLING CODE 6560-50-P

[[Page 62076]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
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[GRAPHIC] [TIFF OMITTED] TR17OC00.401


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[GRAPHIC] [TIFF OMITTED] TR17OC00.403


[[Page 62081]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.404


[[Page 62082]]



Method 25E--Determination of Vapor Phase Organic Concentration in 
Waste Samples

    Note:
    Performance of this method should not be attempted by persons 
unfamiliar with the operation of a flame ionization detector (FID) 
nor by those who are unfamiliar with source sampling because 
knowledge beyond the scope of this presentation is required. This 
method is not inclusive with respect to specifications (e.g., 
reagents and standards) and calibration procedures. Some material is 
incorporated by reference from other methods. Therefore, to obtain 
reliable results, persons using this method should have a thorough 
knowledge of at least the following additional test methods: Method 
106, part 61, Appendix B, and Method 18, part 60, Appendix A.

1.0  Scope and Application

    1.1  Applicability. This method is applicable for determining the 
vapor pressure of waste cited by an applicable regulation.
    1.2  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  The headspace vapor of the sample is analyzed for carbon 
content by a headspace analyzer, which uses an FID.

3.0  Definitions. [Reserved]

4.0  Interferences

    4.1  The analyst shall select the operating parameters best suited 
to the requirements for a particular analysis. The analyst shall 
produce confirming data through an adequate supplemental analytical 
technique and have the data available for review by the Administrator.

5.0  Safety. [Reserved]

6.0  Equipment and Supplies

    6.1  Sampling. The following equipment is required:
    6.1.1  Sample Containers. Vials, glass, with butyl rubber septa, 
Perkin-Elmer Corporation Numbers 0105-0129 (glass vials), B001-0728 
(gray butyl rubber septum, plug style), 0105-0131 (butyl rubber septa), 
or equivalent. The seal must be made from butyl rubber. Silicone rubber 
seals are not acceptable.
    6.1.2  Vial Sealer. Perkin-Elmer Number 105-0106, or equivalent.
    6.1.3  Gas-Tight Syringe. Perkin-Elmer Number 00230117, or 
equivalent.
    6.1.4  The following equipment is required for sampling.
    6.1.4.1  Tap.
    6.1.4.2  Tubing. Teflon, 0.25-in. ID.


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


    6.1.4.3  Cooling Coil. Stainless steel (304), 0.25 in.-ID, equipped 
with a thermocouple at the coil outlet.
    6.2  Analysis. The following equipment is required.
    6.2.1  Balanced Pressure Headspace Sampler. Perkin-Elmer HS-6, HS-
100, or equivalent, equipped with a glass bead column instead of a 
chromatographic column.
    6.2.2  FID. An FID meeting the following specifications is 
required.
    6.2.2.1  Linearity. A linear response (5 percent) over 
the operating range as demonstrated by the procedures established in 
Section 10.2.
    6.2.2.2  Range. A full scale range of 1 to 10,000 parts per million 
(ppm) propane (C3H8). Signal attenuators shall be 
available to produce a minimum signal response of 10 percent of full 
scale.
    6.2.3  Data Recording System. Analog strip chart recorder or 
digital integration system compatible with the FID for permanently 
recording the output of the detector.
    6.2.4  Temperature Sensor. Capable of reading temperatures in the 
range of 30 to 60 deg.C (86 to 140 deg.F) with an accuracy of 
0.1 deg.C (0.2 deg.F).

7.0  Reagents and Standards

    7.1  Analysis. The following items are required for analysis.
    7.1.1  Hydrogen (H2). Zero grade hydrogen, as required 
by the FID.
    7.1.2  Carrier Gas. Zero grade nitrogen, containing less than 1 ppm 
carbon (C) and less than 1 ppm carbon dioxide.
    7.1.3  Combustion Gas. Zero grade air or oxygen as required by the 
FID.
    7.2  Calibration and Linearity Check.
    7.2.1  Stock Cylinder Gas Standard. 100 percent propane. The 
manufacturer shall: (a) Certify the gas composition to be accurate to 
3 percent or better (see Section 7.2.1.1); (b) recommend a 
maximum shelf life over which the gas concentration does not change by 
greater than 5 percent from the certified value; and (c) 
affix the date of gas cylinder preparation, certified propane 
concentration, and recommended maximum shelf life to the cylinder 
before shipment to the buyer.
    7.2.1.1  Cylinder Standards Certification. The manufacturer shall 
certify the concentration of the calibration gas in the cylinder by (a) 
directly analyzing the cylinder and (b) calibrating his analytical 
procedure on the day of cylinder analysis. To calibrate his analytical 
procedure, the manufacturer shall use, as a minimum, a three-point 
calibration curve.
    7.2.1.2  Verification of Manufacturer's Calibration Standards. 
Before using, the manufacturer shall verify each calibration standard 
by (a) comparing it to gas mixtures prepared in accordance with the 
procedure described in Section 7.1 of Method 106 of Part 61, Appendix 
B, or by (b) calibrating it against Standard Reference Materials 
(SRM's) prepared by the National Bureau of Standards, if such SRM's are 
available. The agreement between the initially determined concentration 
value and the verification concentration value must be within 
5 percent. The manufacturer must reverify all calibration 
standards on a time interval consistent with the shelf life of the 
cylinder standards sold.

8.0  Sampling Collection, Preservation, Storage, and Transport

    8.1  Install a sampling tap to obtain a sample at a point which is 
most representative of the unexposed waste (where the waste has had 
minimum opportunity to volatilize to the atmosphere). Assemble the 
sampling apparatus as shown in Figure 25E-1.
    8.2  Begin sampling by purging the sample lines and cooling coil 
with at least four volumes of waste. Collect the purged material in a 
separate container and dispose of it properly.
    8.3  After purging, stop the sample flow and transfer the Teflon 
sampling tube to a sample container. Sample at a flow rate such that 
the temperature of the waste is 10 deg.C (50 deg.F). Fill the sample 
container halfway (5 percent) and cap it within 5 seconds. 
Store immediately in a cooler and cover with ice.
    8.4  Alternative sampling techniques may be used upon the approval 
of the Administrator.

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
10.2, 10.3....................  FID calibration    Ensure precision of
                                 and response       analytical results.
                                 check.
------------------------------------------------------------------------


[[Page 62083]]

10.0  Calibration and Standardization

    Note: Maintain a record of performance of each item.

    10.1  Use the procedures in Sections 10.2 to calibrate the 
headspace analyzer and FID and check for linearity before the system is 
first placed in operation, after any shutdown longer than 6 months, and 
after any modification of the system.
    10.2  Calibration and Linearity. Use the procedures in Section 10 
of Method 18 of Part 60, Appendix A, to prepare the standards and 
calibrate the flowmeters, using propane as the standard gas. Fill the 
calibration standard vials halfway (5 percent) with 
deionized water. Purge and fill the airspace with calibration standard. 
Prepare a minimum of three concentrations of calibration standards in 
triplicate at concentrations that will bracket the applicable cutoff. 
For a cutoff of 5.2 kPa (0.75 psi), prepare nominal concentrations of 
30,000, 50,000, and 70,000 ppm as propane. For a cutoff of 27.6 kPa 
(4.0 psi), prepare nominal concentrations of 200,000, 300,000, and 
400,000 ppm as propane.
    10.2.1  Use the procedures in Section 11.3 to measure the FID 
response of each standard. Use a linear regression analysis to 
calculate the values for the slope (k) and the y-intercept (b). Use the 
procedures in Sections 12.3 and 12.2 to test the calibration and the 
linearity.
    10.3  Daily FID Calibration Check. Check the calibration at the 
beginning and at the end of the daily runs by using the following 
procedures. Prepare 2 calibration standards at the nominal cutoff 
concentration using the procedures in Section 10.2. Place one at the 
beginning and one at the end of the daily run. Measure the FID response 
of the daily calibration standard and use the values for k and b from 
the most recent calibration to calculate the concentration of the daily 
standard. Use an equation similar to 25E-2 to calculate the percent 
difference between the daily standard and Cs. If the 
difference is within 5 percent, then the previous values for k and b 
can be used. Otherwise, use the procedures in Section 10.2 to 
recalibrate the FID.

11.0  Analytical Procedures

    11.1  Allow one hour for the headspace vials to equilibrate at the 
temperature specified in the regulation. Allow the FID to warm up until 
a stable baseline is achieved on the detector.
    11.2  Check the calibration of the FID daily using the procedures 
in Section 10.3.
    11.3  Follow the manufacturer's recommended procedures for the 
normal operation of the headspace sampler and FID.
    11.4  Use the procedures in Sections 12.4 and 12.5 to calculate the 
vapor phase organic vapor pressure in the samples.
    11.5  Monitor the output of the detector to make certain that the 
results are being properly recorded.

12.0  Data Analysis and Calculations

    12.1  Nomenclature.

A = Measurement of the area under the response curve, counts.
b = y-intercept of the linear regression line.
Ca = Measured vapor phase organic concentration of sample, 
ppm as propane.
Cma = Average measured vapor phase organic concentration of 
standard, ppm as propane.
Cm = Measured vapor phase organic concentration of standard, 
ppm as propane.
Cs = Calculated standard concentration, ppm as propane.
k = Slope of the linear regression line.
Pbar = Atmospheric pressure at analysis conditions, mm Hg 
(in. Hg).
P* = Organic vapor pressure in the sample, kPa (psi).
PD = Percent difference between the average measured vapor phase 
organic concentration (Cm) and the calculated standard 
concentration (Cs).
RSD = Relative standard deviation.
 =1.333  x  10-\7\ kPa/[(mm Hg)(ppm)], (4.91  x  
10-\7\ psi/[(in. Hg)(ppm)])

    12.2  Linearity. Use the following equation to calculate the 
measured standard concentration for each standard vial.
[GRAPHIC] [TIFF OMITTED] TR17OC00.405

    12.2.1  Calculate the average measured standard concentration 
(Cma) for each set of triplicate standards and use the 
following equation to calculate PD between Cma and 
Cs. The instrument linearity is acceptable if the PD is 
within five for each standard.
[GRAPHIC] [TIFF OMITTED] TR17OC00.406

    12.3.  Relative Standard Deviation (RSD). Use the following 
equation to calculate the RSD for each triplicate set of standards.
[GRAPHIC] [TIFF OMITTED] TR17OC00.407

The calibration is acceptable if the RSD is within five for each 
standard concentration.
    12.4  Concentration of organics in the headspace. Use the following 
equation to calculate the concentration of vapor phase organics in each 
sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.408

    12.5  Vapor Pressure of Organics in the Headspace Sample. Use the 
following equation to calculate the vapor pressure of organics in the 
sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.409

13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    1. Salo, Albert E., Samuel Witz, and Robert D. MacPhee. 
``Determination of Solvent Vapor Concentrations by Total Combustion 
Analysis: a Comparison of Infared with Flame Ionization Detectors. 
Paper No. 75-33.2. (Presented at the 68th Annual Meeting of the Air 
Pollution Control Association. Boston, Massachusetts.
    2. Salo, Albert E., William L. Oaks, and Robert D. MacPhee. 
``Measuring the Organic Carbon Content of Source Emissions for Air 
Pollution Control. Paper No. 74-190. (Presented at the 67th Annual 
Meeting of the Air Pollution Control Association. Denver, Colorado. 
June 9-13, 1974.) p. 25.
BILLING CODE 6560-50-P

[[Page 62084]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.412

BILLING CODE 6560-50-C

[[Page 62085]]

Method 26--Determination of Hydrogen Halide and Halogen Emissions 
From Stationary Sources Non-Isokinetic Method

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
                        Analytes                              CAS No.
------------------------------------------------------------------------
Hydrogen Chloride (HCl).................................       7647-01-0
Hydrogen Bromide (HBr)..................................      10035-10-6
Hydrogen Fluoride (HF)..................................       7664-39-3
Chlorine (Cl2)..........................................       7882-50-5
Bromine (Br2)...........................................       7726-95-6
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for determining 
emissions of hydrogen halides (HX) (HCl, HBr, and HF) and halogens 
(X2) (Cl2 and Br2) from stationary 
sources when specified by the applicable subpart. Sources, such as 
those controlled by wet scrubbers, that emit acid particulate matter 
must be sampled using Method 26A.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  An integrated sample is extracted from the source and passed 
through a prepurged heated probe and filter into dilute sulfuric acid 
and dilute sodium hydroxide solutions which collect the gaseous 
hydrogen halides and halogens, respectively. The filter collects 
particulate matter including halide salts but is not routinely 
recovered and analyzed. The hydrogen halides are solubilized in the 
acidic solution and form chloride (Cl-), bromide 
(Br-), and fluoride (F-) ions. The halogens have 
a very low solubility in the acidic solution and pass through to the 
alkaline solution where they are hydrolyzed to form a proton 
(H+), the halide ion, and the hypohalous acid (HClO or 
HBrO). Sodium thiosulfate is added in excess to the alkaline solution 
to assure reaction with the hypohalous acid to form a second halide ion 
such that 2 halide ions are formed for each molecule of halogen gas. 
The halide ions in the separate solutions are measured by ion 
chromatography (IC).

3.0  Definitions [Reserved]

4.0  Interferences

    4.1  Volatile materials, such as chlorine dioxide (ClO2) 
and ammonium chloride (NH4Cl), which produce halide ions 
upon dissolution during sampling are potential interferents. 
Interferents for the halide measurements are the halogen gases which 
disproportionate to a hydrogen halide and a hydrohalous acid upon 
dissolution in water. However, the use of acidic rather than neutral or 
basic solutions for collection of the hydrogen halides greatly reduces 
the dissolution of any halogens passing through this solution.
    4.2  The simultaneous presence of HBr and CL2 may cause 
a positive bias in the HCL result with a corresponding negative bias in 
the Cl2 result as well as affecting the HBr/Br2 
split.
    4.3  High concentrations of nitrogen oxides (NOX) may 
produce sufficient nitrate (NO3- to interfere 
with measurements of very low Br- levels.
    4.4  A glass wool plug should not be used to remove particulate 
matter since a negative bias in the data could result.
    4.5  There is anecdotal evidence that HF may be outgassed from new 
teflon components. If HF is a target analyte, then preconditioning of 
new teflon components, by heating should be considered.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user to establish appropriate safety and health practices and 
determine the applicability of regulatory limitations before performing 
this test method.
    5.2  Corrosive Reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water for at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burns as thermal 
burns.
    5.2.1  Sodium Hydroxide (NaOH). Causes severe damage to eyes and 
skin. Inhalation causes irritation to nose, throat, and lungs. Reacts 
exothermically with limited amounts of water.
    5.2.2  Sulfuric Acid (H2SO4). Rapidly 
destructive to body tissue. Will cause third degree burns. Eye damage 
may result in blindness. Inhalation may be fatal from spasm of the 
larynx, usually within 30 minutes. May cause lung tissue damage with 
edema. 1 mg/m3 for 8 hours will cause lung damage or, in 
higher concentrations, death. Provide ventilation to limit inhalation. 
Reacts violently with metals and organics.

6.0  Equipment and Supplies

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


    6.1  Sampling. The sampling train is shown in Figure 26-1, and 
component parts are discussed below.
    6.1.1  Probe. Borosilicate glass, approximately \3/8\-in. (9-mm) 
I.D. with a heating system to prevent moisture condensation. A Teflon-
glass filter in a mat configuration should be installed to remove 
particulate matter from the gas stream (see Section 6.1.6).
    6.1.2  Three-way Stopcock. A borosilicate-glass three-way stopcock 
with a heating system to prevent moisture condensation. The heated 
stopcock should connect to the outlet of the heated filter and the 
inlet of the first impinger. The heating system should be capable of 
preventing condensation up to the inlet of the first impinger. Silicone 
grease may be used, if necessary, to prevent leakage.
    6.1.3  Impingers. Four 30-ml midget impingers with leak-free glass 
connectors. Silicone grease may be used, if necessary, to prevent 
leakage. For sampling at high moisture sources or for sampling times 
greater than one hour, a midget impinger with a shortened stem (such 
that the gas sample does not bubble through the collected condensate) 
should be used in front of the first impinger.
    6.1.4  Drying Tube or Impinger. Tube or impinger, of Mae West 
design, filled with 6- to 16-mesh indicating type silica gel, or 
equivalent, to dry the gas sample and to protect the dry gas meter and 
pump. If the silica gel has been used previously, dry at 175  deg.C 
(350  deg.F) for 2 hours. New silica gel may be used as received. 
Alternatively, other types of desiccants (equivalent or better) may be 
used.
    6.1.5  Heating System. Any heating system capable of maintaining a 
temperature around the probe and filter holder greater than 120  deg.C 
(248  deg.F) during sampling, or such other temperature as specified by 
an applicable subpart of the standards or approved by the Administrator 
for a particular application.
    6.1.6  Filter Holder and Support. The filter holder shall be made 
of Teflon or quartz. The filter support shall be made of Teflon. All 
Teflon filter holders and supports are available from Savillex Corp., 
5325 Hwy 101, Minnetonka, MN 55345.
    6.1.7  Sample Line. Leak-free, with compatible fittings to connect 
the last impinger to the needle valve.
    6.1.8  Rate Meter. Rotameter, or equivalent, capable of measuring 
flow rate to within 2 percent of the selected flow rate of 2 liters/min 
(0.07 ft3/min).
    6.1.9  Purge Pump, Purge Line, Drying Tube, Needle Valve, and Rate 
Meter. Pump capable of purging the

[[Page 62086]]

sampling probe at 2 liters/min, with drying tube, filled with silica 
gel or equivalent, to protect pump, and a rate meter capable of 
measuring 0 to 5 liters/min (0.2 ft3/min).
    6.1.10  Stopcock Grease, Valve, Pump, Volume Meter, Barometer, and 
Vacuum Gauge. Same as in Method 6, Sections 6.1.1.4, 6.1.1.7, 6.1.1.8, 
6.1.1.10, 6.1.2, and 6.1.3.
    6.1.11  Temperature Measuring Devices. Temperature sensors to 
monitor the temperature of the probe and to monitor the temperature of 
the sampling system from the outlet of the probe to the inlet of the 
first impinger.
    6.1.12  Ice Water Bath. To minimize loss of absorbing solution.
    6.2  Sample Recovery.
    6.2.1  Wash Bottles. Polyethylene or glass, 500-ml or larger, two.
    6.2.2  Storage Bottles. 100- or 250-ml, high-density polyethylene 
bottles with Teflon screw cap liners to store impinger samples.
    6.3  Sample Preparation and Analysis. The materials required for 
volumetric dilution and chromatographic analysis of samples are 
described below.
    6.3.1  Volumetric Flasks. Class A, 100-ml size.
    6.3.2  Volumetric Pipets. Class A, assortment. To dilute samples to 
the calibration range of the ion chromatograph.
    6.3.3  Ion Chromatograph (IC). Suppressed or non-suppressed, with a 
conductivity detector and electronic integrator operating in the peak 
area mode. Other detectors, strip chart recorders, and peak height 
measurements may be used.

7.0  Reagents and Standards

    Note: Unless otherwise indicated, all reagents must conform to 
the specifications established by the Committee on Analytical 
Reagents of the American Chemical Society (ACS reagent grade). When 
such specifications are not available, the best available grade 
shall be used.


    7.1  Sampling.
    7.1.1  Filter. A 25-mm (1 in) (or other size) Teflon glass mat, 
Pallflex TX40HI75 (Pallflex Inc., 125 Kennedy Drive, Putnam, CT 06260). 
This filter is in a mat configuration to prevent fine particulate 
matter from entering the sampling train. Its composition is 75% Teflon/
25% borosilicate glass. Other filters may be used, but they must be in 
a mat (as opposed to a laminate) configuration and contain at least 75% 
Teflon. For practical rather than scientific reasons, when the stack 
gas temperature exceeds 210  deg.C (410  deg.F) and the HCl 
concentration is greater than 20 ppm, a quartz-fiber filter may be used 
since Teflon becomes unstable above this temperature.
    7.1.2  Water. Deionized, distilled water that conforms to American 
Society of Testing and Materials (ASTM) Specification D 1193-77 or 91, 
Type 3 (incorporated by reference--see Sec. 60.17).
    7.1.3  Acidic Absorbing Solution, 0.1 N Sulfuric Acid 
(H2SO4). To prepare 100 ml of the absorbing 
solution for the front impinger pair, slowly add 0.28 ml of 
concentrated H2SO4 to about 90 ml of water while 
stirring, and adjust the final volume to 100 ml using additional water. 
Shake well to mix the solution.
    7.1.4  Silica Gel. Indicating type, 6 to 16 mesh. If previously 
used, dry at 180  deg.C (350  deg.F) for 2 hours. New silica gel may be 
used as received. Alternatively, other types of desiccants may be used, 
subject to the approval of the Administrator.
    7.1.5  Alkaline Adsorbing Solution, 0.1 N Sodium Hydroxide (NaOH). 
To prepare 100 ml of the scrubber solution for the third and fourth 
impinger, dissolve 0.40 g of solid NaOH in about 90 ml of water, and 
adjust the final solution volume to 100 ml using additional water. 
Shake well to mix the solution.
    7.1.6  Sodium Thiosulfate (Na2S2O3 
5 H2O)
    7.2  Sample Preparation and Analysis.
    7.2.1  Water. Same as in Section 7.1.2.
    7.2.2  Absorbing Solution Blanks. A separate blank solution of each 
absorbing reagent should be prepared for analysis with the field 
samples. Dilute 30 ml of each absorbing solution to approximately the 
same final volume as the field samples using the blank sample of rinse 
water.
    7.2.3  Halide Salt Stock Standard Solutions. Prepare concentrated 
stock solutions from reagent grade sodium chloride (NaCl), sodium 
bromide (NaBr), and sodium fluoride (NaF). Each must be dried at 
110 deg.C (230 deg.F) for two or more hours and then cooled to room 
temperature in a desiccator immediately before weighing. Accurately 
weigh 1.6 to 1.7 g of the dried NaCl to within 0.1 mg, dissolve in 
water, and dilute to 1 liter. Calculate the exact Cl- 
concentration using Equation 26-1 in Section 12.2. In a similar manner, 
accurately weigh and solubilize 1.2 to 1.3 g of dried NaBr and 2.2 to 
2.3 g of NaF to make 1-liter solutions. Use Equations 26-2 and 26-3 in 
Section 12.2, to calculate the Br- and F- 
concentrations. Alternately, solutions containing a nominal certified 
concentration of 1000 mg/l NaCl are commercially available as 
convenient stock solutions from which standards can be made by 
appropriate volumetric dilution. Refrigerate the stock standard 
solutions and store no longer than one month.
    7.2.4  Chromatographic Eluent. Effective eluents for nonsuppressed 
IC using a resin-or silica-based weak ion exchange column are a 4 mM 
potassium hydrogen phthalate solution, adjusted to pH 4.0 using a 
saturated sodium borate solution, and a 4 mM 4-hydroxy benzoate 
solution, adjusted to pH 8.6 using 1 N NaOH. An effective eluent for 
suppressed ion chromatography is a solution containing 3 mM sodium 
bicarbonate and 2.4 mM sodium carbonate. Other dilute solutions 
buffered to a similar pH and containing no interfering ions may be 
used. When using suppressed ion chromatography, if the ``water dip'' 
resulting from sample injection interferes with the chloride peak, use 
a 2 mM NaOH/2.4 mM sodium bicarbonate eluent.
    7.3  Quality Assurance Audit Samples. When making compliance 
determinations, and upon availability, audit samples may be obtained 
from the appropriate EPA regional Office or from the responsible 
enforcement authority.

    Note: The responsible enforcement authority should be notified 
at least 30 days prior to the test date to allow sufficient time for 
sample delivery.

8.0  Sample Collection, Preservation, Storage, and Transport

    Note: Because of the complexity of this method, testers and 
analyst should be trained and experienced with the procedure to 
ensure reliable results.


    8.1  Sampling.
    8.1.1  Preparation of Collection Train. Prepare the sampling train 
as follows: Pour 15 ml of the acidic absorbing solution into each one 
of the first pair of impingers, and 15 ml of the alkaline absorbing 
solution into each one of the second pair of impingers. Connect the 
impingers in series with the knockout impinger first, if used, followed 
by the two impingers containing the acidic absorbing solution and the 
two impingers containing the alkaline absorbing solution. Place a fresh 
charge of silica gel, or equivalent, in the drying tube or impinger at 
the end of the impinger train.
    8.1.2  Adjust the probe temperature and the temperature of the 
filter and the stopcock, i.e., the heated area in Figure 26-1 to a 
temperature sufficient to prevent water condensation. This temperature 
should be at least 20  deg.C (68  deg.F) above the source temperature, 
and greater than 120  deg.C (248  deg.F). The temperature should be 
monitored

[[Page 62087]]

throughout a sampling run to ensure that the desired temperature is 
maintained. It is important to maintain a temperature around the probe 
and filter of greater than 120  deg.C (248  deg.F) since it is 
extremely difficult to purge acid gases off these components. (These 
components are not quantitatively recovered and hence any collection of 
acid gases on these components would result in potential undereporting 
of these emission. The applicable subparts may specify alternative 
higher temperatures.)
    8.1.3  Leak-Check Procedure.
    8.1.3.1  Sampling Train. A leak-check prior to the sampling run is 
optional; however, a leak-check after the sampling run is mandatory. 
The leak-check procedure is as follows: Temporarily attach a suitable 
[e.g., 0-40 cc/min (0-2.4 in\3\/min)] rotameter to the outlet of the 
dry gas meter and place a vacuum gauge at or near the probe inlet. Plug 
the probe inlet, pull a vacuum of at least 250 mm Hg (10 in. Hg), and 
note the flow rate as indicated by the rotameter. A leakage rate not in 
excess of 2 percent of the average sampling rate is acceptable.


    Note: Carefully release the probe inlet plug before turning off 
the pump.


    8.1.3.2  Pump. It is suggested (not mandatory) that the pump be 
leak-checked separately, either prior to or after the sampling run. If 
done prior to the sampling run, the pump leak-check shall precede the 
leak-check of the sampling train described immediately above; if done 
after the sampling run, the pump leak-check shall follow the train 
leak-check. To leak-check the pump, proceed as follows: Disconnect the 
drying tube from the probe-impinger assembly. Place a vacuum gauge at 
the inlet to either the drying tube or pump, pull a vacuum of 250 mm 
(10 in) Hg, plug or pinch off the outlet of the flow meter, and then 
turn off the pump. The vacuum should remain stable for at least 30 sec. 
Other leak-check procedures may be used, subject to the approval of the 
Administrator, U.S. Environmental Protection Agency.
    8.1.4  Purge Procedure. Immediately before sampling, connect the 
purge line to the stopcock, and turn the stopcock to permit the purge 
pump to purge the probe (see Figure 1A of Figure 26-1). Turn on the 
purge pump, and adjust the purge rate to 2 liters/min (0.07 ft\3\/min). 
Purge for at least 5 minutes before sampling.
    8.1.5  Sample Collection. Turn on the sampling pump, pull a slight 
vacuum of approximately 25 mm Hg (1 in Hg) on the impinger train, and 
turn the stopcock to permit stack gas to be pulled through the impinger 
train (see Figure 1C of Figure 26-1). Adjust the sampling rate to 2 
liters/min, as indicated by the rate meter, and maintain this rate to 
within 10 percent during the entire sampling run. Take readings of the 
dry gas meter volume and temperature, rate meter, and vacuum gauge at 
least once every five minutes during the run. A sampling time of one 
hour is recommended. Shorter sampling times may introduce a significant 
negative bias in the HCl concentration. At the conclusion of the 
sampling run, remove the train from the stack, cool, and perform a 
leak-check as described in Section 8.1.3.1.
    8.2  Sample Recovery.
    8.2.1  Disconnect the impingers after sampling. Quantitatively 
transfer the contents of the acid impingers and the knockout impinger, 
if used, to a leak-free storage bottle. Add the water rinses of each of 
these impingers and connecting glassware to the storage bottle.
    8.2.2  Repeat this procedure for the alkaline impingers and 
connecting glassware using a separate storage bottle. Add 25 mg of 
sodium thiosulfate per the product of ppm of halogen anticipated to be 
in the stack gas times the volume (dscm) of stack gas sampled (0.7 mg 
per ppm-dscf).


    Note: This amount of sodium thiosulfate includes a safety factor 
of approximately 5 to assure complete reaction with the hypohalous 
acid to form a second Cl- ion in the alkaline solution.


    8.2.3  Save portions of the absorbing reagents (0.1 N 
H2SO4 and 0.1 N NaOH) equivalent to the amount 
used in the sampling train (these are the absorbing solution blanks 
described in Section 7.2.2); dilute to the approximate volume of the 
corresponding samples using rinse water directly from the wash bottle 
being used. Add the same amount of sodium thiosulfate solution to the 
0.1 N NaOH absorbing solution blank. Also, save a portion of the rinse 
water used to rinse the sampling train. Place each in a separate, 
prelabeled storage bottle. The sample storage bottles should be sealed, 
shaken to mix, and labeled. Mark the fluid level.
    8.3  Sample Preparation for Analysis. Note the liquid levels in the 
storage bottles and confirm on the analysis sheet whether or not 
leakage occurred during transport. If a noticeable leakage has 
occurred, either void the sample or use methods, subject to the 
approval of the Administrator, to correct the final results. 
Quantitatively transfer the sample solutions to 100-ml volumetric 
flasks, and dilute to 100 ml with water.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
11.2..........................  Audit sample       Evaluate analytical
                                 analysis.          technique,
                                                    preparation of
                                                    standards.
------------------------------------------------------------------------

10.0  Calibration and Standardization

    Note: Maintain a laboratory log of all calibrations.

    10.1  Volume Metering System, Temperature Sensors, Rate Meter, and 
Barometer. Same as in Method 6, Sections 10.1, 10.2, 10.3, and 10.4.
    10.2  Ion Chromatograph.
    10.2.1  To prepare the calibration standards, dilute given amounts 
(1.0 ml or greater) of the stock standard solutions to convenient 
volumes, using 0.1 N H2SO4 or 0.1 N NaOH, as 
appropriate. Prepare at least four calibration standards for each 
absorbing reagent containing the appropriate stock solutions such that 
they are within the linear range of the field samples.
    10.2.2  Using one of the standards in each series, ensure adequate 
baseline separation for the peaks of interest.
    10.2.3  Inject the appropriate series of calibration standards, 
starting with the lowest concentration standard first both before and 
after injection of the quality control check sample, reagent blanks, 
and field samples. This allows compensation for any instrument drift 
occurring during sample analysis. The values from duplicate injections 
of these calibration samples should agree within 5 percent of their 
mean for the analysis to be valid.
    10.2.4  Determine the peak areas, or heights, for the standards and 
plot individual values versus halide ion concentrations in g/
ml.
    10.2.5  Draw a smooth curve through the points. Use linear 
regression to calculate a formula describing the resulting linear 
curve.

11.0  Analytical Procedures

    11.1  Sample Analysis.
    11.1.1  The IC conditions will depend upon analytical column type 
and whether suppressed or non-

[[Page 62088]]

suppressed IC is used. An example chromatogram from a non-suppressed 
system using a 150-mm Hamilton PRP-X100 anion column, a 2 ml/min flow 
rate of a 4 mM 4-hydroxy benzoate solution adjusted to a pH of 8.6 
using 1 N NaOH, a 50 l sample loop, and a conductivity 
detector set on 1.0 S full scale is shown in Figure 26-2.
    11.1.2  Before sample analysis, establish a stable baseline. Next, 
inject a sample of water, and determine if any Cl-, 
Br-, or F- appears in the chromatogram. If any of 
these ions are present, repeat the load/injection procedure until they 
are no longer present. Analysis of the acid and alkaline absorbing 
solution samples requires separate standard calibration curves; prepare 
each according to Section 10.2. Ensure adequate baseline separation of 
the analyses.
    11.1.3  Between injections of the appropriate series of calibration 
standards, inject in duplicate the reagent blanks, quality control 
sample, and the field samples. Measure the areas or heights of the 
Cl-, Br-, and F- peaks. Use the mean 
response of the duplicate injections to determine the concentrations of 
the field samples and reagent blanks using the linear calibration 
curve. The values from duplicate injections should agree within 5 
percent of their mean for the analysis to be valid. If the values of 
duplicate injections are not within 5 percent of the mean, the 
duplicate injections shall be repeated and all four values used to 
determine the average response. Dilute any sample and the blank with 
equal volumes of water if the concentration exceeds that of the highest 
standard.
    11.2  Audit Sample Analysis.
    11.2.1  When the method is used to analyze samples to demonstrate 
compliance with a source emission regulation, a set of two EPA audit 
samples must be analyzed, subject to availability.
    11.2.2  Concurrently analyze the audit samples and the compliance 
samples in the same manner to evaluate the technique of the analyst and 
the standards preparation.
    11.2.3  The same analyst, analytical reagents, and analytical 
system shall be used for the compliance samples and the EPA audit 
samples. If this condition is met, duplicate auditing of subsequent 
compliance analyses for the same enforcement agency within a 30-day 
period is waived. An audit sample set may not be used to validate 
different sets of compliance samples under the jurisdiction of separate 
enforcement agencies, unless prior arrangements have been made with 
both enforcement agencies.
    11.3  Audit Sample Results.
    11.3.1  Calculate the concentrations in mg/L of audit sample and 
submit results following the instructions provided with the audit 
samples.
    11.3.2  Report the results of the audit samples and the compliance 
determination samples along with their identification numbers, and the 
analyst's name to the responsible enforcement authority. Include this 
information with reports of any subsequent compliance analyses for the 
same enforcement authority during the 30-day period.
    11.3.3  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 and 
audit samples, and include initial and reanalysis values in the test 
report.
    11.3.4  Failure to meet the 10 percent specification may require 
retests until the audit problems are resolved. However, if the audit 
results do not affect the compliance or noncompliance status of the 
affected facility, the Administrator may waive the reanalysis 
requirement, further audits, or retests and accept the results of the 
compliance test. While steps are being taken to resolve audit analysis 
problems, the Administrator may also choose to use the data to 
determine the compliance or noncompliance status of the affected 
facility.

12.0  Data Analysis and Calculations

    Note: Retain at least one extra decimal figure beyond those 
contained in the available data in intermediate calculations, and 
round off only the final answer appropriately.


    12.1  Nomenclature.

BX-=Mass concentration of applicable absorbing 
solution blank, g halide ion (Cl-, Br-, 
F-) /ml, not to exceed 1 g/ml which is 10 times the 
published analytical detection limit of 0.1 g/ml.
C=Concentration of hydrogen halide (HX) or halogen (X2), dry 
basis, mg/dscm.
K = 10-3 mg/g.
KHCl = 1.028 (g HCl/g-mole)/(g 
Cl-/g-mole).
KHBr = 1.013 (g HBr/g-mole)/(g 
Br-/g-mole).
KHF = 1.053 (g HF/g-mole)/(g 
F-/g-mole).
mHX = Mass of HCl, HBr, or HF in sample, g.
mX2 = Mass of Cl2 or Br2 in sample, 
g.
SX- = Analysis of sample, g halide ion 
(Cl-, Br-, F-)/ml.
Vm(std)= Dry gas volume measured by the dry gas meter, 
corrected to standard conditions, dscm.
Vs = Volume of filtered and diluted sample, ml.

    12.2  Calculate the exact Cl-, Br-, and 
F- concentration in the halide salt stock standard solutions 
using the following equations.
[GRAPHIC] [TIFF OMITTED] TR17OC00.413

    12.3  Sample Volume, Dry Basis, Corrected to Standard Conditions. 
Calculate the sample volume using Eq. 6-1 of Method 6.
    12.4  Total g HCl, HBr, or HF Per Sample.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.414
    
    12.5  Total g Cl2 or Br2 Per Sample.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.415
    

[[Page 62089]]


    12.6  Concentration of Hydrogen Halide or Halogen in Flue Gas.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.416
    
13.0  Method Performance

    13.1 Precision and Bias. The within-laboratory relative standard 
deviations are 6.2 and 3.2 percent at HCl concentrations of 3.9 and 
15.3 ppm, respectively. The method does not exhibit a bias to 
Cl2 when sampling at concentrations less than 50 ppm.
    13.2  Sample Stability. The collected Cl-samples can be 
stored for up to 4 weeks.
    13.3  Detection Limit. A typical IC instrumental detection limit 
for Cl- is 0.2 g/ml. Detection limits for the other 
analyses should be similar. Assuming 50 ml liquid recovered from both 
the acidified impingers, and the basic impingers, and 0.06 dscm of 
stack gas sampled, then the analytical detection limit in the stack gas 
would be about 0.1 ppm for HCl and Cl2, respectively.

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

    1. Steinsberger, S. C. and J. H. Margeson, ``Laboratory and 
Field Evaluation of a Methodology for Determination of Hydrogen 
Chloride Emissions from Municipal and Hazardous Waste 
Incinerators,'' U.S. Environmental Protection Agency, Office of 
Research and Development, Report No. 600/3-89/064, April 1989. 
Available from the National Technical Information Service, 
Springfield, VA 22161 as PB89220586/AS.
    2. State of California, Air Resources Board, Method 421, 
``Determination of Hydrochloric Acid Emissions from Stationary 
Sources,'' March 18, 1987.
    3. Cheney, J.L. and C.R. Fortune. Improvements in the 
Methodology for Measuring Hydrochloric Acid in Combustion Source 
Emissions. J. Environ. Sci. Health. A19(3): 337-350. 1984.
    4. Stern, D. A., B. M. Myatt, J. F. Lachowski, and K. T. 
McGregor. Speciation of Halogen and Hydrogen Halide Compounds in 
Gaseous Emissions. In: Incineration and Treatment of Hazardous 
Waste: Proceedings of the 9th Annual Research Symposium, Cincinnati, 
Ohio, May 2-4, 1983. Publication No. 600/9-84-015. July 1984. 
Available from National Technical Information Service, Springfield, 
VA 22161 as PB84-234525.
    5. Holm, R. D. and S. A. Barksdale. Analysis of Anions in 
Combustion Products. In: Ion Chromatographic Analysis of 
Environmental Pollutants. E. Sawicki, J. D. Mulik, and E. 
Wittgenstein (eds.). Ann Arbor, Michigan, Ann Arbor Science 
Publishers. 1978. pp. 99-110.

BILLING CODE 6560-50-P

[[Page 62090]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.417


[[Page 62091]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.418

BILLING CODE 6560-50-C

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

    Note: This method does not include all of the specifications 
(e.g. equipment and supplies) and procedures (e.g. sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in this part. 
Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of at least the following 
additional test methods: Method 2, Method 5, and Method 26.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
                        Analytes                              CAS No.
------------------------------------------------------------------------
Hydrogen Chloride (HCl).................................       7647-01-0
Hydrogen Bromide (HBr)..................................      10035-10-6
Hydrogen Fluoride (HF)..................................       7664-39-3
Chlorine (Cl2)..........................................       7882-50-5
Bromine (Br2)...........................................       7726-95-6
------------------------------------------------------------------------

    1.2  This method is applicable for determining emissions of 
hydrogen halides (HX) [HCl, HBr, and HF] and halogens (X2) 
[Cl2 and Br2] from stationary sources when 
specified by the applicable subpart. This method collects the emission 
sample isokinetically and is therefore particularly suited for sampling 
at sources, such as those controlled by wet scrubbers, emitting acid 
particulate matter (e.g., hydrogen halides dissolved in water 
droplets).
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  Principle. Gaseous and particulate pollutants are withdrawn 
isokinetically from the source and collected in an optional cyclone, on 
a filter, and in absorbing solutions. The cyclone collects any liquid 
droplets and is not necessary if the source emissions do not contain 
them; however, it is preferable to include the cyclone in the sampling 
train to protect the filter from any liquid present. The filter 
collects particulate matter including halide salts but is not routinely 
recovered or analyzed. Acidic and alkaline absorbing solutions collect 
the gaseous hydrogen halides and halogens, respectively. Following 
sampling of emissions containing liquid droplets, any halides/halogens 
dissolved in the liquid in the cyclone and on the filter are vaporized 
to gas and collected in the impingers by pulling conditioned ambient 
air through the sampling train. The hydrogen halides are solubilized in 
the acidic solution and form chloride (Cl-), bromide 
(Br-), 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

[[Page 62092]]

from the filter and the probe is analyzed following the procedures in 
Method 5.


    Note: If the tester intends to use this sampling arrangement to 
sample concurrently for particulate matter, the alternative Teflon 
probe liner, cyclone, and filter holder should not be used. The 
Teflon filter support must be used. The tester must also meet the 
probe and filter temperature requirements of both sampling trains.

3.0  Definitions. [Reserved]

4.0  Interferences

    4.1  Volatile materials, such as chlorine dioxide (ClO2) 
and ammonium chloride (NH4Cl), which produce halide ions 
upon dissolution during sampling are potential interferents. 
Interferents for the halide measurements are the halogen gases which 
disproportionate to a hydrogen halide and 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.
    4.2  The simultaneous presence of both HBr and Cl2 may 
cause a positive bias in the HCl result with a corresponding negative 
bias in the Cl2 result as well as affecting the HBr/
Br2 split.
    4.3  High concentrations of nitrogen oxides (NOX) may 
produce sufficient nitrate (NO3-) to interfere 
with measurements of very low Br-levels.
    4.4  There is anecdotal evidence that HF may be outgassed from new 
Teflon components. If HF is a target analyte then preconditioning of 
new Teflon components, by heating, should be considered.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user to establish appropriate safety and health practices and 
determine the applicability of regulatory limitations before performing 
this test method.
    5.2  Corrosive Reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water for at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burns as thermal 
burns.
    5.2.1  Sodium Hydroxide (NaOH). Causes severe damage to eyes and 
skin. Inhalation causes irritation to nose, throat, and lungs. Reacts 
exothermically with limited amounts of water.
    5.2.2  Sulfuric Acid (H2SO4). Rapidly 
destructive to body tissue. Will cause third degree burns. Eye damage 
may result in blindness. Inhalation may be fatal from spasm of the 
larynx, usually within 30 minutes. May cause lung tissue damage with 
edema. 1 mg/m3 for 8 hours will cause lung damage or, in 
higher concentrations, death. Provide ventilation to limit inhalation. 
Reacts violently with metals and organics.

6.0.  Equipment and Supplies

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


    6.1  Sampling. The sampling train is shown in Figure 26A-1; the 
apparatus is similar to the Method 5 train where noted as follows:
    6.1.1  Probe Nozzle. Borosilicate or quartz glass; constructed and 
calibrated according to Method 5, Sections 6.1.1.1 and 10.1, and 
coupled to the probe liner using a Teflon union; a stainless steel nut 
is recommended for this union. When the stack temperature exceeds 210 
deg.C (410  deg.F), a one-piece glass nozzle/liner assembly must be 
used.
    6.1.2  Probe Liner. Same as Method 5, Section 6.1.1.2, except metal 
liners shall not be used. Water-cooling of the stainless steel sheath 
is recommended at temperatures exceeding 500  deg.C (932  deg.F). 
Teflon may be used in limited applications where the minimum stack 
temperature exceeds 120  deg.C (250  deg.F) but never exceeds the 
temperature where Teflon is estimated to become unstable [approximately 
210  deg.C (410  deg.F)].
    6.1.3  Pitot Tube, Differential Pressure Gauge, Filter Heating 
System, Metering System, Barometer, Gas Density Determination 
Equipment. Same as Method 5, Sections 6.1.1.3, 6.1.1.4, 6.1.1.6, 
6.1.1.9, 6.1.2, and 6.1.3.
    6.1.4  Cyclone (Optional). Glass or Teflon. Use of the cyclone is 
required only when the sample gas stream is saturated with moisture; 
however, the cyclone is recommended to protect the filter from any 
liquid droplets present.
    6.1.5  Filter Holder. Borosilicate or quartz glass, or Teflon 
filter holder, with a Teflon filter support and a sealing gasket. The 
sealing gasket shall be constructed of Teflon or equivalent materials. 
The holder design shall provide a positive seal against leakage at any 
point along the filter circumference. The holder shall be attached 
immediately to the outlet of the cyclone.
    6.1.6  Impinger Train. The following system shall be used to 
determine the stack gas moisture content and to collect the hydrogen 
halides and halogens: five or six impingers connected in series with 
leak-free ground glass fittings or any similar leak-free 
noncontaminating fittings. The first impinger shown in Figure 26A-1 
(knockout or condensate impinger) is optional and is recommended as a 
water knockout trap for use under high moisture conditions. If used, 
this impinger should be constructed as described below for the alkaline 
impingers, but with a shortened stem, and should contain 50 ml of 0.1 N 
H2SO4. The following two impingers (acid 
impingers which each contain 100 ml of 0.1 N 
H2SO4) shall be of the Greenburg-Smith design 
with the standard tip (Method 5, Section 6.1.1.8). The next two 
impingers (alkaline impingers which each contain 100 ml of 0.1 N NaOH) 
and the last impinger (containing silica gel) shall be of the modified 
Greenburg-Smith design (Method 5, Section 6.1.1.8). The condensate, 
acid, and alkaline impingers shall contain known quantities of the 
appropriate absorbing reagents. The last impinger shall contain a known 
weight of silica gel or equivalent desiccant. Teflon impingers are an 
acceptable alternative.
    6.1.7  Heating System. Any heating system capable of maintaining a 
temperature around the probe and filter holder greater than 120  deg.C 
(248  deg.F) during sampling, or such other temperature as specified by 
an applicable subpart of the standards or approved by the Administrator 
for a particular application.
    6.1.8  Ambient Air Conditioning Tube (Optional). Tube tightly 
packed with approximately 150 g of fresh 8 to 20 mesh sodium hydroxide-
coated silica, or equivalent, (Ascarite II has been found suitable) to 
dry and remove acid gases from the ambient air used to remove moisture 
from the filter and cyclone, when the cyclone is used. The inlet and 
outlet ends of the tube should be packed with at least 1-cm thickness 
of glass wool or filter material suitable to prevent escape of fines. 
Fit one end with flexible tubing, etc. to allow connection to probe 
nozzle following the test run.
    6.2  Sample Recovery.
    6.2.1  Probe-Liner and Probe-Nozzle Brushes, Wash Bottles, Glass 
Sample Storage Containers, Petri Dishes, Graduated Cylinder and/or 
Balance, and Rubber Policeman. Same as Method 5, Sections 6.2.1, 6.2.2, 
6.2.3, 6.2.4, 6.2.5, and 6.2.7.
    6.2.2  Plastic Storage Containers. Screw-cap polypropylene or 
polyethylene containers to store silica gel. High-density polyethylene 
bottles with Teflon screw cap liners to store impinger reagents, 1-
liter.

[[Page 62093]]

    6.2.3  Funnels. Glass or high-density polyethylene, to aid in 
sample recovery.
    6.3  Sample Preparation and Analysis.
    6.3.1  Volumetric Flasks. Class A, various sizes.
    6.3.2  Volumetric Pipettes. Class A, assortment. To dilute samples 
to calibration range of the ion chromatograph (IC).
    6.3.3  Ion Chromatograph (IC). Suppressed or nonsuppressed, with a 
conductivity detector and electronic integrator operating in the peak 
area mode. Other detectors, a strip chart recorder, and peak heights 
may be used.

7.0  Reagents and Standards

    Note: Unless otherwise indicated, all reagents must conform to 
the specifications established by the Committee on Analytical 
Reagents of the American Chemical Society (ACS reagent grade). When 
such specifications are not available, the best available grade 
shall be used.

    7.1  Sampling.
    7.1.1  Filter. Teflon mat (e.g., Pallflex TX40HI45) filter. When 
the stack gas temperature exceeds 210 deg.C (410 deg.F) a quartz fiber 
filter may be used.
    7.1.2  Water. Deionized, distilled water that conforms to American 
Society of Testing and Materials (ASTM) Specification D 1193-77 or 91, 
Type 3 (incorporated by reference--see Sec. 60.17).
    7.1.3  Acidic Absorbing Solution, 0.1 N Sulfuric Acid 
(H2SO4). To prepare 1 L, slowly add 2.80 ml of 
concentrated 17.9 M H2SO4 to about 900 ml of water while stirring, and 
adjust the final volume to 1 L using additional water. Shake well to 
mix the solution.
    7.1.4  Silica Gel, Crushed Ice, and Stopcock Grease. Same as Method 
5, Sections 7.1.2, 7.1.4, and 7.1.5, respectively.
    7.1.5  Alkaline Absorbing Solution, 0.1 N Sodium Hydroxide (NaOH). 
To prepare 1 L, dissolve 4.00 g of solid NaOH in about 900 ml of water 
and adjust the final volume to 1 L using additional water. Shake well 
to mix the solution.
    7.1.6  Sodium Thiosulfate, 
(Na2S2O33.5 
H2O).
    7.2  Sample Preparation and Analysis.
    7.2.1  Water. Same as in Section 7.1.2.
    7.2.2  Absorbing Solution Blanks. A separate blank solution of each 
absorbing reagent should be prepared for analysis with the field 
samples. Dilute 200 ml of each absorbing solution (250 ml of the acidic 
absorbing solution, if a condensate impinger is used) to the same final 
volume as the field samples using the blank sample of rinse water. If a 
particulate determination is conducted, collect a blank sample of 
acetone.
    7.2.3  Halide Salt Stock Standard Solutions. Prepare concentrated 
stock solutions from reagent grade sodium chloride (NaCl), sodium 
bromide (NaBr), and sodium fluoride (NaF). Each must be dried at 
110 deg.C (230 deg.F) for two or more hours and then cooled to room 
temperature in a desiccator immediately before weighing. Accurately 
weigh 1.6 to 1.7 g of the dried NaCl to within 0.1 mg, dissolve in 
water, and dilute to 1 liter. Calculate the exact 
Cl-concentration using Equation 26A-1 in Section 12.2. In a 
similar manner, accurately weigh and solubilize 1.2 to 1.3 g of dried 
NaBr and 2.2 to 2.3 g of NaF to make 1-liter solutions. Use Equations 
26A-2 and 26A-3 in Section 12.2, to calculate the Br-and 
F-concentrations. Alternately, solutions containing a 
nominal certified concentration of 1000 mg/L NaCl are commercially 
available as convenient stock solutions from which standards can be 
made by appropriate volumetric dilution. Refrigerate the stock standard 
solutions and store no longer than one month.
    7.2.4  Chromatographic Eluent. Same as Method 26, Section 7.2.4.
    7.2.5  Water. Same as Section 7.1.1.
    7.2.6  Acetone. Same as Method 5, Section 7.2.
    7.3  Quality Assurance Audit Samples. When making compliance 
determinations, and upon availability, audit samples may be obtained 
from the appropriate EPA regional Office or from the responsible 
enforcement authority.


    Note: The responsible enforcement authority should be notified 
at least 30 days prior to the test date to allow sufficient time for 
sample delivery.

8.0  Sample Collection, Preservation, Storage, and Transport

    Note: Because of the complexity of this method, testers and 
analysts should be trained and experienced with the procedures to 
ensure reliable results.


    8.1  Sampling.
    8.1.1  Pretest Preparation. Follow the general procedure given in 
Method 5, Section 8.1, except the filter need only be desiccated and 
weighed if a particulate determination will be conducted.
    8.1.2  Preliminary Determinations. Same as Method 5, Section 8.2.
    8.1.3  Preparation of Sampling Train. Follow the general procedure 
given in Method 5, Section 8.1.3, except for the following variations: 
Add 50 ml of 0.1 N H2SO4 to the condensate 
impinger, if used. Place 100 ml of 0.1 N H2SO4 in 
each of the next two impingers. Place 100 ml of 0.1 N NaOH in each of 
the following two impingers. Finally, transfer approximately 200-300 g 
of preweighed silica gel from its container to the last impinger. Set 
up the train as in Figure 26A-1. When used, the optional cyclone is 
inserted between the probe liner and filter holder and located in the 
heated filter box.
    8.1.4  Leak-Check Procedures. Follow the leak-check procedures 
given in Method 5, Sections 8.4.2 (Pretest Leak-Check), 8.4.3 (Leak-
Checks During the Sample Run), and 8.4.4 (Post-Test Leak-Check).
    8.1.5  Sampling Train Operation. Follow the general procedure given 
in Method 5, Section 8.5. It is important to maintain a temperature 
around the probe, filter (and cyclone, if used) of greater than 
120 deg.C (248  deg.F) since it is extremely difficult to purge acid 
gases off these components. (These components are not quantitatively 
recovered and hence any collection of acid gases on these components 
would result in potential undereporting these emissions. The applicable 
subparts may specify alternative higher temperatures.) For each run, 
record the data required on a data sheet such as the one shown in 
Method 5, Figure 5-3. If the condensate impinger becomes too full, it 
may be emptied, recharged with 50 ml of 0.1 N 
H2SO4, and replaced during the sample run. The 
condensate emptied must be saved and included in the measurement of the 
volume of moisture collected and included in the sample for analysis. 
The additional 50 ml of absorbing reagent must also be considered in 
calculating the moisture. Before the sampling train integrity is 
compromised by removing the impinger, conduct a leak-check as described 
in Method 5, Section 8.4.2.
    8.1.6  Post-Test Moisture Removal (Optional). When the optional 
cyclone is included in the sampling train or when liquid is visible on 
the filter at the end of a sample run even in the absence of a cyclone, 
perform the following procedure. Upon completion of the test run, 
connect the ambient air conditioning tube at the probe inlet and 
operate the train with the filter heating system 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 liquid. If 
liquid is visible, repeat this step for 15 minutes and observe again. 
Keep repeating until the cyclone is dry.


[[Page 62094]]


    Note: It is critical that this is repeated until the cyclone is 
completely dry.

    8.2  Sample Recovery. Allow the probe to cool. When the probe can 
be handled safely, wipe off all the external surfaces of the tip of the 
probe nozzle and place a cap loosely over the tip to prevent gaining or 
losing particulate matter. Do not cap the probe tip tightly while the 
sampling train is cooling down because this will create a vacuum in the 
filter holder, drawing water from the impingers into the holder. Before 
moving the sampling train to the cleanup site, remove the probe from 
the sample train, wipe off any silicone grease, and cap the open outlet 
of the impinger train, being careful not to lose any condensate that 
might be present. Wipe off any silicone grease and cap the filter or 
cyclone inlet. Remove the umbilical cord from the last impinger and cap 
the impinger. If a flexible line is used between the first impinger and 
the filter holder, disconnect it at the filter holder and let any 
condensed water drain into the first impinger. Wipe off any silicone 
grease and cap the filter holder outlet and the impinger inlet. Ground 
glass stoppers, plastic caps, serum caps, Teflon tape, Parafilm, or 
aluminum foil may be used to close these openings. Transfer the probe 
and filter/impinger assembly to the cleanup area. This area should be 
clean and protected from the weather to minimize sample contamination 
or loss. Inspect the train prior to and during disassembly and note any 
abnormal conditions. Treat samples as follows:
    8.2.1  Container No. 1 (Optional; Filter Catch for Particulate 
Determination). Same as Method 5, Section 8.7.6.1, Container No. 1.
    8.2.2  Container No. 2 (Optional; Front-Half Rinse for Particulate 
Determination). Same as Method 5, Section 8.7.6.2, Container No. 2.
    8.2.3  Container No. 3 (Knockout and Acid Impinger Catch for 
Moisture and Hydrogen Halide Determination). Disconnect the impingers. 
Measure the liquid in the acid and knockout impingers to 1 
ml by using a graduated cylinder or by weighing it to 0.5 g 
by using a balance. Record the volume or weight of liquid present. This 
information is required to calculate the moisture content of the 
effluent gas. Quantitatively transfer this liquid to a leak-free sample 
storage container. Rinse these impingers and connecting glassware 
including the back portion of the filter holder (and flexible tubing, 
if used) with water and add these rinses to the storage container. Seal 
the container, shake to mix, and label. The fluid level should be 
marked so that if any sample is lost during transport, a correction 
proportional to the lost volume can be applied. Retain rinse water and 
acidic absorbing solution blanks to be analyzed with the samples.
    8.2.4  Container No. 4 (Alkaline Impinger Catch for Halogen and 
Moisture Determination). Measure and record the liquid in the alkaline 
impingers as described in Section 8.2.3. Quantitatively transfer this 
liquid to a leak-free sample storage container. Rinse these two 
impingers and connecting glassware with water and add these rinses to 
the container. Add 25 mg of sodium thiosulfate per ppm halogen 
anticipated to be in the stack gas multiplied by the volume (dscm) of 
stack gas sampled (0.7 mg/ppm-dscf). Seal the container, shake to mix, 
and label; mark the fluid level. Retain alkaline absorbing solution 
blank to be analyzed with the samples.

    Note: 25 mg per sodium thiosulfate per ppm halogen anticipated 
to be in the stack includes a safety factor of approximately 5 to 
assure complete reaction with the hypohalous acid to form a second 
Cl- ion in the alkaline solution.

    8.2.5  Container No. 5 (Silica Gel for Moisture Determination). 
Same as Method 5, Section 8.7.6.3, Container No. 3.
    8.2.6  Container Nos. 6 through 9 (Reagent Blanks). Save portions 
of the absorbing reagents (0.1 N H2SO4 and 0.1 N 
NaOH) equivalent to the amount used in the sampling train; dilute to 
the approximate volume of the corresponding samples using rinse water 
directly from the wash bottle being used. Add the same ratio of sodium 
thiosulfate solution used in container No. 4 to the 0.1 N NaOH 
absorbing reagent blank. Also, save a portion of the rinse water alone 
and a portion of the acetone equivalent to the amount used to rinse the 
front half of the sampling train. Place each in a separate, prelabeled 
sample container.
    8.2.7  Prior to shipment, recheck all sample containers to ensure 
that the caps are well-secured. Seal the lids of all containers around 
the circumference with Teflon tape. Ship all liquid samples upright and 
all particulate filters with the particulate catch facing upward.

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.1.4, 10.1...................  Sampling           Ensure accurate
                                 equipment leak-    measurement of stack
                                 check and          gas flow rate,
                                 calibration.       sample volume.
11.5..........................  Audit sample       Evaluate analyst's
                                 analysis.          technique and
                                                    standards
                                                    preparation.
------------------------------------------------------------------------

    9.1  Volume Metering System Checks. Same as Method 5, Section 9.2.

10.0  Calibration and Standardization

    Note: Maintain a laboratory log of all calibrations.

    10.1  Probe Nozzle, Pitot Tube Assembly, Dry Gas Metering System, 
Probe Heater, Temperature Sensors, Leak-Check of Metering System, and 
Barometer. Same as Method 5, Sections 10.1, 10.2, 10.3, 10.4, 10.5, 
8.4.1, and 10.6, respectively.

    10.2  Ion Chromatograph.
    10.2.1  To prepare the calibration standards, dilute given amounts 
(1.0 ml or greater) of the stock standard solutions to convenient 
volumes, using 0.1 N H2SO4 or 0.1 N NaOH, as 
appropriate. Prepare at least four calibration standards for each 
absorbing reagent containing the three stock solutions such that they 
are within the linear range of the field samples.
    10.2.2  Using one of the standards in each series, ensure adequate 
baseline separation for the peaks of interest.
    10.2.3  Inject the appropriate series of calibration standards, 
starting with the lowest concentration standard first both before and 
after injection of the quality control check sample, reagent blanks, 
and field samples. This allows compensation for any instrument drift 
occurring during sample analysis. The values from duplicate injections 
of these calibration samples should agree within 5 percent of their 
mean for the analysis to be valid.
    10.2.4  Determine the peak areas, or height, of the standards and 
plot individual values versus halide ion concentrations in g/
ml.
    10.2.5  Draw a smooth curve through the points. Use linear 
regression to calculate a formula describing the resulting linear 
curve.

11.0  Analytical Procedures

    Note: the liquid levels in the sample containers and confirm on 
the analysis sheet

[[Page 62095]]

whether or not leakage occurred during transport. If a noticeable 
leakage has occurred, either void the sample or use methods, subject 
to the approval of the Administrator, to correct the final results.


    11.1  Sample Analysis.
    11.1.1  The IC conditions will depend upon analytical column type 
and whether suppressed or non-suppressed IC is used. An example 
chromatogram from a non-suppressed system using a 150-mm Hamilton PRP-
X100 anion column, a 2 ml/min flow rate of a 4 mM 4-hydroxy benzoate 
solution adjusted to a pH of 8.6 using 1 N NaOH, a 50 l sample 
loop, and a conductivity detector set on 1.0 S full scale is 
shown in Figure 26-2.
    11.1.2  Before sample analysis, establish a stable baseline. Next, 
inject a sample of water, and determine if any Cl-, 
Br-, or F- appears in the chromatogram. If any of 
these ions are present, repeat the load/injection procedure until they 
are no longer present. Analysis of the acid and alkaline absorbing 
solution samples requires separate standard calibration curves; prepare 
each according to Section 10.2. Ensure adequate baseline separation of 
the analyses.
    11.1.3  Between injections of the appropriate series of calibration 
standards, inject in duplicate the reagent blanks, quality control 
sample, and the field samples. Measure the areas or heights of the 
Cl-, Br-, and F- peaks. Use the mean 
response of the duplicate injections to determine the concentrations of 
the field samples and reagent blanks using the linear calibration 
curve. The values from duplicate injections should agree within 5 
percent of their mean for the analysis to be valid. If the values of 
duplicate injections are not within 5 percent of the mean, the 
duplicator injections shall be repeated and all four values used to 
determine the average response. Dilute any sample and the blank with 
equal volumes of water if the concentration exceeds that of the highest 
standard.
    11.2  Container Nos. 1 and 2 and Acetone Blank (Optional; 
Particulate Determination). Same as Method 5, Sections 11.2.1 and 
11.2.2, respectively.
    11.3  Container No. 5. Same as Method 5, Section 11.2.3 for silica 
gel.
    11.4  Audit Sample Analysis.
    11.4.1  When the method is used to analyze samples to demonstrate 
compliance with a source emission regulation, a set of two EPA audit 
samples must be analyzed, subject to availability.
    11.4.2  Concurrently analyze the audit samples and the compliance 
samples in the same manner to evaluate the technique of the analyst and 
the standards preparation.
    11.4.3  The same analyst, analytical reagents, and analytical 
system shall be used for the compliance samples and the EPA audit 
samples. If this condition is met, duplicate auditing of subsequent 
compliance analyses for the same enforcement agency within a 30-day 
period is waived. An audit sample set may not be used to validate 
different sets of compliance samples under the jurisdiction of separate 
enforcement agencies, unless prior arrangements have been made with 
both enforcement agencies.
    11.5  Audit Sample Results.
    11.5.1  Calculate the concentrations in mg/L of audit sample and 
submit results following the instructions provided with the audit 
samples.
    11.5.2  Report the results of the audit samples and the compliance 
determination samples along with their identification numbers, and the 
analyst's name to the responsible enforcement authority. Include this 
information with reports of any subsequent compliance analyses for the 
same enforcement authority during the 30-day period.
    11.5.3  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 and 
audit samples, and include initial and reanalysis values in the test 
report.
    11.5.4  Failure to meet the 10 percent specification may require 
retests until the audit problems are resolved. However, if the audit 
results do not affect the compliance or noncompliance status of the 
affected facility, the Administrator may waive the reanalysis 
requirement, further audits, or retests and accept the results of the 
compliance test. While steps are being taken to resolve audit analysis 
problems, the Administrator may also choose to use the data to 
determine the compliance or noncompliance status of the affected 
facility.

12.0  Data Analysis and Calculations

    Note: Retain at least one extra decimal figure beyond those 
contained in the available data in intermediate calculations, and 
round off only the final answer appropriately.


    12.1  Nomenclature. Same as Method 5, Section 12.1. In addition:

BX- = Mass concentration of applicable absorbing solution 
blank, g halide ion (Cl-, Br-, 
F-)/ml, not to exceed 1 g/ml which is 10 times the 
published analytical detection limit of 0.1 g/ml. (It is also 
approximately 5 percent of the mass concentration anticipated to result 
from a one hour sample at 10 ppmv HCl.)
C = Concentration of hydrogen halide (HX) or halogen (X2), 
dry basis, mg/dscm.
K = 10-3 mg/g.
KHCl = 1.028 (g HCl/g-mole)/(g 
Cl-/g-mole).
KHBr = 1.013 (g HBr/g-mole)/(g 
Br-/g-mole).
KHF = 1.053 (g HF/g-mole)/(g 
F-/g-mole).
mHX = Mass of HCl, HBr, or HF in sample, ug.
mX2 = Mass of Cl2 or Br2 in sample, 
ug.
SX- = Analysis of sample, ug halide ion (Cl-, 
Br-, F-)/ml.
Vs = Volume of filtered and diluted sample, ml.

    12.2  Calculate the exact Cl-, Br-, and 
F- concentration in the halide salt stock standard solutions 
using the following equations.
[GRAPHIC] [TIFF OMITTED] TR17OC00.419

[GRAPHIC] [TIFF OMITTED] TR17OC00.420

    12.3  Average Dry Gas Meter Temperature and Average Orifice 
Pressure Drop. See data sheet (Figure 5-3 of Method 5).
    12.4  Dry Gas Volume. Calculate Vm(std) and adjust for 
leakage, if necessary, using the equation in Section 12.3 of Method 5.

[[Page 62096]]

    12.5  Volume of Water Vapor and Moisture Content. Calculate the 
volume of water vapor Vw(std) and moisture content 
Bws from the data obtained in this method (Figure 5-3 of 
Method 5); use Equations 5-2 and 5-3 of Method 5.
    12.6  Isokinetic Variation and Acceptable Results. Use Method 5, 
Section 12.11.
    12.7  Acetone Blank Concentration, Acetone Wash Blank Residue 
Weight, Particulate Weight, and Particulate Concentration. For 
particulate determination.
    12.8  Total g HCl, HBr, or HF Per Sample.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.421
    
    12.9  Total g Cl2 or Br2 Per Sample.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.422
    
    12.10  Concentration of Hydrogen Halide or Halogen in Flue Gas.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.423
    
    12.11 Stack Gas Velocity and Volumetric Flow Rate. Calculate the 
average stack gas velocity and volumetric flow rate, if needed, using 
data obtained in this method and the equations in Sections 12.3 and 
12.4 of Method 2.

3.0  Method Performance

    13.1  Precision and Bias. The method has a possible measurable 
negative bias below 20 ppm HCl perhaps due to reaction with small 
amounts of moisture in the probe and filter. Similar bias for the other 
hydrogen halides is possible.
    13.2  Sample Stability. The collected Cl-samples can be stored for 
up to 4 weeks for analysis for HCl and Cl2.
    13.3  Detection Limit. A typical analytical detection limit for HCl 
is 0.2 g/ml. Detection limits for the other analyses should be 
similar. Assuming 300 ml of liquid recovered for the acidified 
impingers and a similar amounts recovered from the basic impingers, and 
1 dscm of stack gas sampled, the analytical detection limits in the 
stack gas would be about 0.04 ppm for HCl and Cl2, respectively.

14.0  Pollution Prevention, [Reserved]

15.0  Waste Management, [Reserved]

16.0  References

    1. Steinsberger, S. C. and J. H. Margeson. Laboratory and Field 
Evaluation of a Methodology for Determination of Hydrogen Chloride 
Emissions from Municipal and Hazardous Waste Incinerators. U.S. 
Environmental Protection Agency, Office of Research and Development. 
Publication No. 600/3-89/064. April 1989. Available from National 
Technical Information Service, Springfield, VA 22161 as PB89220586/
AS.
    2. State of California Air Resources Board. Method 421--
Determination of Hydrochloric Acid Emissions from Stationary 
Sources. March 18, 1987.
    3. Cheney, J.L. and C.R. Fortune. Improvements in the 
Methodology for Measuring Hydrochloric Acid in Combustion Source 
Emissions. J. Environ. Sci. Health. A19(3): 337-350. 1984.
    4. Stern, D.A., B.M. Myatt, J.F. Lachowski, and K.T. McGregor. 
Speciation of Halogen and Hydrogen Halide Compounds in Gaseous 
Emissions. In: Incineration and Treatment of Hazardous Waste: 
Proceedings of the 9th Annual Research Symposium, Cincinnati, Ohio, 
May 2-4, 1983. Publication No. 600/9-84-015. July 1984. Available 
from National Technical Information Service, Springfield, VA 22161 
as PB84-234525.
    5. Holm, R.D. and S.A. Barksdale. Analysis of Anions in 
Combustion Products. In: Ion Chromatographic Analysis of 
Environmental Pollutants, E. Sawicki, J.D. Mulik, and E. 
Wittgenstein (eds.). Ann Arbor, Michigan, Ann Arbor Science 
Publishers. 1978. pp. 99-110.
BILLING CODE 6560-50-P

[[Page 62097]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.424

BILLING CODE 6560-50-C

[[Page 62098]]

Method 27--Determination of Vapor Tightness of Gasoline Delivery 
Tank Using Pressure Vaccuum Test

1.0  Scope and Application

    1.1  Applicability. This method is applicable for the determination 
of vapor tightness of a gasoline delivery collection equipment.

2.0  Summary of Method

    2.1  Pressure and vacuum are applied alternately to the 
compartments of a gasoline delivery tank and the change in pressure or 
vacuum is recorded after a specified period of time.

3.0  Definitions

    3.1  Allowable pressure change (p) means the allowable 
amount of decrease in pressure during the static pressure test, within 
the time period t, as specified in the appropriate regulation, in mm 
H2O.
    3.2  Allowable vacuum change (v) means the allowable 
amount of decrease in vacuum during the static vacuum test, within the 
time period t, as specified in the appropriate regulation, in mm 
H2O.
    3.3  Compartment means a liquid-tight division of a delivery tank.
    3.4  Delivery tank means a container, including associated pipes 
and fittings, that is attached to or forms a part of any truck, 
trailer, or railcar used for the transport of gasoline.
    3.5  Delivery tank vapor collection equipment means any piping, 
hoses, and devices on the delivery tank used to collect and route 
gasoline vapors either from the tank to a bulk terminal vapor control 
system or from a bulk plant or service station into the tank.
    3.6  Gasoline means a petroleum distillate or petroleum distillate/
alcohol blend having a Reid vapor pressure of 27.6 kilopascals or 
greater which is used as a fuel for internal combustion engines.
    3.7  Initial pressure (Pi) means the pressure applied to 
the delivery tank at the beginning of the static pressure test, as 
specified in the appropriate regulation, in mm H2O.
    3.8  Initial vacuum (Vi) means the vacuum applied to the 
delivery tank at the beginning of the static vacuum test, as specified 
in the appropriate regulation, in mm H3.
    3.9  Time period of the pressure or vacuum test (t) means the time 
period of the test, as specified in the appropriate regulation, during 
which the change in pressure or vacuum is monitored, in minutes.

4.0  Interferences [Reserved]

5.0  Safety

    5.1  Gasoline contains several volatile organic compounds (e.g. 
benzene and hexane) which presents a potential for fire and/or 
explosions. It is advisable to take appropriate precautions when 
testing a gasoline vessel's vapor tightness, such as refraining from 
smoking and using explosion-proof equipment.
    5.2  This method may involve hazardous materials, operations, and 
equipment. This test method may not address all of the safety problems 
associated with its use. It is the responsibility of the user of this 
test method to establish appropriate safety and health practices and 
determine the applicability of regulatory limitations prior to 
performing this test method

6.0 Equipment and Supplies

    The following equipment and supplies are required for testing:
    6.1  Pressure Source. Pump or compressed gas cylinder of air or 
inert gas sufficient to pressurize the delivery tank to 500 mm (20 in.) 
H2O above atmospheric pressure.
    6.2  Regulator. Low pressure regulator for controlling 
pressurization of the delivery tank.
    6.3  Vacuum Source. Vacuum pump capable of evacuating the delivery 
tank to 250 mm (10 in.) H2O below atmospheric pressure.
    6.4  Pressure-Vacuum Supply Hose.
    6.5  Manometer. Liquid manometer, or equivalent instrument, capable 
of measuring up to 500 mm (20 in.) H2O gauge pressure with 
 2.5 mm (0.1 in.) H2O precision.
    6.6  Pressure-Vacuum Relief Valves. The test apparatus shall be 
equipped with an inline pressure-vacuum relief valve set to activate at 
675 mm (26.6 in.) H2O above atmospheric pressure or 250 mm 
(10 in.) H2O below atmospheric pressure, with a capacity equal to the 
pressurizing or evacuating pumps.
    6.7  Test Cap for Vapor Recovery Hose. This cap shall have a tap 
for manometer connection and a fitting with shut-off valve for 
connection to the pressure-vacuum supply hose.
    6.8  Caps for Liquid Delivery Hoses.

7.0  Reagents and Standards [Reserved]

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Pretest Preparations.
    8.1.1  Summary. Testing problems may occur due to the presence of 
volatile vapors and/or temperature fluctuations inside the delivery 
tank. Under these conditions, it is often difficult to obtain a stable 
initial pressure at the beginning of a test, and erroneous test results 
may occur. To help prevent this, it is recommended that prior to 
testing, volatile vapors be removed from the tank and the temperature 
inside the tank be allowed to stabilize. Because it is not always 
possible to completely attain these pretest conditions, a provision to 
ensure reproducible results is included. The difference in results for 
two consecutive runs must meet the criteria in Sections 8.2.2.5 and 
8.2.3.5.
    8.1.2  Emptying of Tank. The delivery tank shall be emptied of all 
liquid.
    8.1.3  Purging of Vapor. As much as possible the delivery tank 
shall be purged of all volatile vapors by any safe, acceptable method. 
One method is to carry a load of non-volatile liquid fuel, such as 
diesel or heating oil, immediately prior to the test, thus flushing out 
all the volatile gasoline vapors. A second method is to remove the 
volatile vapors by blowing ambient air into each tank compartment for 
at least 20 minutes. This second method is usually not as effective and 
often causes stabilization problems, requiring a much longer time for 
stabilization during the testing.
    8.1.4  Temperature Stabilization. As much as possible, the test 
shall be conducted under isothermal conditions. The temperature of the 
delivery tank should be allowed to equilibrate in the test environment. 
During the test, the tank should be protected from extreme 
environmental and temperature variability, such as direct sunlight.
    8.2  Test Procedure.
    8.2.1  Preparations.
    8.2.1.1  Open and close each dome cover.
    8.2.1.2  Connect static electrical ground connections to the tank. 
Attach the liquid delivery and vapor return hoses, remove the liquid 
delivery elbows, and plug the liquid delivery fittings.


    Note: The purpose of testing the liquid delivery hoses is to 
detect tears or holes that would allow liquid leakage during a 
delivery. Liquid delivery hoses are not considered to be possible 
sources of vapor leakage, and thus, do not have to be attached for a 
vapor leakage test. Instead, a liquid delivery hose could be either 
visually inspected, or filled with water to detect any liquid 
leakage.


    8.2.1.3  Attach the test cap to the end of the vapor recovery hose.
    8.2.1.4  Connect the pressure-vacuum supply hose and the pressure-
vacuum relief valve to the shut-off valve. Attach a manometer to the 
pressure tap.
    8.2.1.5  Connect compartments of the tank internally to each other 
if possible.

[[Page 62099]]

If not possible, each compartment must be tested separately, as if it 
were an individual delivery tank.
    8.2.2  Pressure Test.
    8.2.2.1  Connect the pressure source to the pressure-vacuum supply 
hose.
    8.2.2.2  Open the shut-off valve in the vapor recovery hose cap. 
Apply air pressure slowly, pressurize the tank to Pi, the 
initial pressure specified in the regulation.
    8.2.2.3  Close the shut-off and allow the pressure in the tank to 
stabilize, adjusting the pressure if necessary to maintain pressure of 
Pi. When the pressure stabilizes, record the time and 
initial pressure.
    8.2.2.4  At the end of the time period (t) specified in the 
regulation, record the time and final pressure.
    8.2.2.5  Repeat steps 8.2.2.2 through 8.2.2.4 until the change in 
pressure for two consecutive runs agrees within 12.5 mm (0.5 in.) 
H2O. Calculate the arithmetic average of the two results.
    8.2.2.6  Compare the average measured change in pressure to the 
allowable pressure change, p, specified in the regulation. If 
the delivery tank does not satisfy the vapor tightness criterion 
specified in the regulation, repair the sources of leakage, and repeat 
the pressure test until the criterion is met.
    8.2.2.7  Disconnect the pressure source from the pressure-vacuum 
supply hose, and slowly open the shut-off valve to bring the tank to 
atmospheric pressure.
    8.2.3  Vacuum Test.
    8.2.3.1  Connect the vacuum source to the pressure-vacuum supply 
hose.
    8.2.3.2  Open the shut-off valve in the vapor recovery hose cap. 
Slowly evacuate the tank to Vi, the initial vacuum specified 
in the regulation.
    8.2.3.3  Close the shut-off valve and allow the pressure in the 
tank to stabilize, adjusting the pressure if necessary to maintain a 
vacuum of Vi. When the pressure stabilizes, record the time 
and initial vacuum.
    8.2.3.4  At the end of the time period specified in the regulation 
(t), record the time and final vacuum.
    8.2.3.5  Repeat steps 8.2.3.2 through 8.2.3.4 until the change in 
vacuum for two consecutive runs agrees within 12.5 mm (0.5 in.) 
H2O. Calculate the arithmetic average of the two results.
    8.2.3.6  Compare the average measured change in vacuum to the 
allowable vacuum change, v, as specified in the regulation. If 
the delivery tank does not satisfy the vapor tightness criterion 
specified in the regulation, repair the sources of leakage, and repeat 
the vacuum test until the criterion is met.
    8.2.3.7  Disconnect the vacuum source from the pressure-vacuum 
supply hose, and slowly open the shut-off valve to bring the tank to 
atmospheric pressure.
    8.2.4  Post-Test Clean-up. Disconnect all test equipment and return 
the delivery tank to its pretest condition.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
          Section(s)                 measure               Effect
------------------------------------------------------------------------
8.2.2.5, 8.3.3.5..............  Repeat test        Ensures data
                                 procedures until   precision.
                                 change in
                                 pressure or
                                 vacuum for two
                                 consecutive runs
                                 agrees within
                                 
                                 12.5 mm (0.5
                                 in.) H2O.
------------------------------------------------------------------------

10.0  Calibration and Standardization [Reserved]

11.0  Analytical Procedures [Reserved]

12.0  Data Analysis and Calculations [Reserved]

13.0  Method Performance

    13.1  Precision. The vapor tightness of a gasoline delivery tank 
under positive or negative pressure, as measured by this method, is 
precise within 12.5 mm (0.5 in.) H2O
    13.2  Bias. No bias has been identified.

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  Alternative Procedures

    16.1  The pumping of water into the bottom of a delivery tank is an 
acceptable alternative to the pressure source described above. 
Likewise, the draining of water out of the bottom of a delivery tank 
may be substituted for the vacuum source. Note that some of the 
specific step-by-step procedures in the method must be altered slightly 
to accommodate these different pressure and vacuum sources.
    16.2  Techniques other than specified above may be used for purging 
and pressurizing a delivery tank, if prior approval is obtained from 
the Administrator. Such approval will be based upon demonstrated 
equivalency with the above method.

17.0  References [Reserved]

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

Method 28--Certification and Auditing of Wood Heaters

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in this part. 
Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of at least the following 
additional test methods: Method 1, Method 2, Method 3, Method 4, 
Method 5, Method 5G, Method 5H, Method 6, Method 6C, and Method 16A.

1.0  Scope and Application

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

2.0  Summary of Method

    2.1  Particulate matter emissions are measured from a wood heater 
burning a prepared test fuel crib in a test facility maintained at a 
set of prescribed conditions. Procedures for determining burn rates and 
particulate emission rates and for reducing data are provided.

3.0  Definitions

    3.1  2  x  4 or 4  x  4 means two inches by four inches or four 
inches by four inches (50 mm by 100 mm or 100 mm by 100 mm), as nominal 
dimensions for lumber.
    3.2  Burn rate means the rate at which test fuel is consumed in a 
wood heater. Measured in kilograms or lbs of wood (dry basis) per hour 
(kg/hr or lb/hr).
    3.3  Certification or audit test means a series of at least four 
test runs conducted for certification or audit purposes that meets the 
burn rate specifications in Section 8.4.
    3.4  Firebox means the chamber in the wood heater in which the test 
fuel charge is placed and combusted.
    3.5  Height means the vertical distance extending above the loading 
door, if fuel could reasonably occupy that space, but not more than 2 
inches above the top (peak height) of the loading door, to the floor of 
the firebox

[[Page 62100]]

(i.e., below a permanent grate) if the grate allows a 1-inch diameter 
piece of wood to pass through the grate, or, if not, to the top of the 
grate. Firebox height is not necessarily uniform but must account for 
variations caused by internal baffles, air channels, or other permanent 
obstructions.
    3.6  Length means the longest horizontal fire chamber dimension 
that is parallel to a wall of the chamber.
    3.7  Pellet burning wood heater means a wood heater which meets the 
following criteria: (1) The manufacturer makes no reference to burning 
cord wood in advertising or other literature, (2) the unit is safety 
listed for pellet fuel only, (3) the unit operating and instruction 
manual must state that the use of cordwood is prohibited by law, and 
(4) the unit must be manufactured and sold including the hopper and 
auger combination as integral parts.
    3.8  Secondary air supply means an air supply that introduces air 
to the wood heater such that the burn rate is not altered by more than 
25 percent when the secondary air supply is adjusted during the test 
run. The wood heater manufacturer can document this through design 
drawings that show the secondary air is introduced only into a mixing 
chamber or secondary chamber outside the firebox.
    3.9  Test facility means the area in which the wood heater is 
installed, operated, and sampled for emissions.
    3.10  Test fuel charge means the collection of test fuel pieces 
placed in the wood heater at the start of the emission test run.
    3.11  Test fuel crib means the arrangement of the test fuel charge 
with the proper spacing requirements between adjacent fuel pieces.
    3.12  Test fuel loading density means the weight of the as-fired 
test fuel charge per unit volume of usable firebox.
    3.13  Test fuel piece means the 2  x  4 or 4  x  4 wood piece cut 
to the length required for the test fuel charge and used to construct 
the test fuel crib.
    3.14  Test run means an individual emission test which encompasses 
the time required to consume the mass of the test fuel charge.
    3.15  Usable firebox volume means the volume of the firebox 
determined using its height, length, and width as defined in this 
section.
    3.16  Width means the shortest horizontal fire chamber dimension 
that is parallel to a wall of the chamber.
    3.17  Wood heater means an enclosed, woodburning appliance capable 
of and intended for space heating or domestic water heating, as defined 
in the applicable regulation.

4.0  Interferences [Reserved]

5.0  Safety

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

6.0  Equipment and Supplies

    Same as Section 6.0 of either Method 5G or Method 5H, with the 
addition of the following:
    6.1  Insulated Solid Pack Chimney. For installation of wood 
heaters. Solid pack insulated chimneys shall have a minimum of 2.5 cm 
(1 in.) solid pack insulating material surrounding the entire flue and 
possess a label demonstrating conformance to U.L. 103 (incorporated by 
reference--see Sec. 60.17).
    6.2  Platform Scale and Monitor. For monitoring of fuel load weight 
change. The scale shall be capable of measuring weight to within 0.05 
kg (0.1 lb) or 1 percent of the initial test fuel charge weight, 
whichever is greater.
    6.3  Wood Heater Temperature Monitors. Seven, each capable of 
measuring temperature to within 1.5 percent of expected absolute 
temperatures.
    6.4  Test Facility Temperature Monitor. A thermocouple located 
centrally in a vertically oriented 150 mm (6 in.) long, 50 mm (2 in.) 
diameter pipe shield that is open at both ends, capable of measuring 
temperature to within 1.5 percent of expected temperatures.
    6.5  Balance (optional). Balance capable of weighing the test fuel 
charge to within 0.05 kg (0.1 lb).
    6.6  Moisture Meter. Calibrated electrical resistance meter for 
measuring test fuel moisture to within 1 percent moisture content.
    6.7  Anemometer. Device capable of detecting air velocities less 
than 0.10 m/sec (20 ft/min), for measuring air velocities near the test 
appliance.
    6.8  Barometer. Mercury, aneroid or other barometer capable of 
measuring atmospheric pressure to within 2.5 mm Hg (0.1 in. Hg).
    6.9  Draft Gauge. Electromanometer or other device for the 
determination of flue draft or static pressure readable to within 0.50 
Pa (0.002 in. H2O).
    6.10  Humidity Gauge. Psychrometer or hygrometer for measuring room 
humidity.
    6.11  Wood Heater Flue.
    6.11.1  Steel flue pipe extending to 2.6  0.15 m (8.5 
 0.5 ft) above the top of the platform scale, and above 
this level, insulated solid pack type chimney extending to 4.6 
 0.3 m (15  1 ft) above the platform scale, and 
of the size specified by the wood heater manufacturer. This applies to 
both freestanding and insert type wood heaters.
    6.11.2  Other chimney types (e.g., solid pack insulated pipe) may 
be used in place of the steel flue pipe if the wood heater 
manufacturer's written appliance specifications require such chimney 
for home installation (e.g., zero clearance wood heater inserts). Such 
alternative chimney or flue pipe must remain and be sealed with the 
wood heater following the certification test.
    6.12  Test Facility. The test facility shall meet the following 
requirements during testing:
    6.12.1  The test facility temperature shall be maintained between 
18 and 32  deg.C (65 and 90  deg.F) during each test run.
    6.12.2  Air velocities within 0.6 m (2 ft) of the test appliance 
and exhaust system shall be less than 0.25 m/sec (50 ft/min) without 
fire in the unit.
    6.12.3  The flue shall discharge into the same space or into a 
space freely communicating with the test facility. Any hood or similar 
device used to vent combustion products shall not induce a draft 
greater than 1.25 Pa (0.005 in. H2O) on the wood heater 
measured when the wood heater is not operating.
    6.12.4  For test facilities with artificially induced barometric 
pressures (e.g., pressurized chambers), the barometric pressure in the 
test facility shall not exceed 775 mm Hg (30.5 in. Hg) during any test 
run.

7.0  Reagents and Standards

    Same as Section 6.0 of either Method 5G or Method 5H, with the 
addition of the following:
    7.1  Test Fuel. The test fuel shall conform to the following 
requirements:
    7.1.1  Fuel Species. Untreated, air-dried, Douglas fir lumber. 
Kiln-dried lumber is not permitted. The lumber shall be certified C 
grade (standard) or better Douglas fir by a lumber grader at the mill 
of origin as specified in the West Coast Lumber Inspection Bureau 
Standard No. 16 (incorporated by reference--see Sec. 60.17).
    7.1.2  Fuel Moisture. The test fuel shall have a moisture content 
range between 16 to 20 percent on a wet basis (19 to 25 percent dry 
basis). Addition of moisture to previously dried wood is not allowed. 
It is recommended that the test fuel be stored in a temperature and 
humidity-controlled room.

[[Page 62101]]

    7.1.3  Fuel Temperature. The test fuel shall be at the test 
facility temperature of 18 to 32  deg.C (65 to 90  deg.F).
    7.1.4  Fuel Dimensions. The dimensions of each test fuel piece 
shall conform to the nominal measurements of 2 x 4 and 4 x 4 lumber. 
Each piece of test fuel (not including spacers) shall be of equal 
length, except as necessary to meet requirements in Section 8.8, and 
shall closely approximate \5/6\ the dimensions of the length of the 
usable firebox. The fuel piece dimensions shall be determined in 
relation to the appliance's firebox volume according to guidelines 
listed below:
    7.1.4.1  If the usable firebox volume is less than or equal to 
0.043 m3 (1.5 ft3), use 2 x 4 lumber.
    7.1.4.2  If the usable firebox volume is greater than 0.043 
m3 (1.5 ft3) and less than or equal to 0.085 
m3 (3.0 ft3), use 2 x 4 and 4 x 4 lumber. About 
half the weight of the test fuel charge shall be 2 x 4 lumber, and the 
remainder shall be 4 x 4 lumber.
    7.1.4.3  If the usable firebox volume is greater than 0.085 
m3 (3.0 ft3), use 4 x 4 lumber.
    7.2  Test Fuel Spacers. Air-dried, Douglas fir lumber meeting the 
requirements outlined in Sections 7.1.1 through 7.1.3. The spacers 
shall be 130 x 40 x 20 mm (5 x 1.5 x 0.75 in.).

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Test Run Requirements.
    8.1.1  Burn Rate Categories. One emission test run is required in 
each of the following burn rate categories:

                                              Burn Rate Categories
                                       [Average kg/hr (lb/hr), dry basis]
----------------------------------------------------------------------------------------------------------------
              Category 1                      Category 2               Category 3               Category 4
----------------------------------------------------------------------------------------------------------------
0.80.................................  0.80 to 1.25...........  1.25 to 1.90...........  Maximum.
(1.76)...............................  (1.76 to 2.76).........  (2.76 to 4.19).........  burn rate.
----------------------------------------------------------------------------------------------------------------

    8.1.1.1  Maximum Burn Rate. For Category 4, the wood heater shall 
be operated with the primary air supply inlet controls fully open (or, 
if thermostatically controlled, the thermostat shall be set at maximum 
heat output) during the entire test run, or the maximum burn rate 
setting specified by the manufacturer's written instructions.
    8.1.1.2  Other Burn Rate Categories. For burn rates in Categories 1 
through 3, the wood heater shall be operated with the primary air 
supply inlet control, or other mechanical control device, set at a 
predetermined position necessary to obtain the average burn rate 
required for the category.
    8.1.1.3  Alternative Burn Rates for Burn Rate Categories 1 and 2.
    8.1.1.3.1  If a wood heater cannot be operated at a burn rate below 
0.80 kg/hr (1.76 lb/hr), two test runs shall be conducted with burn 
rates within Category 2. If a wood heater cannot be operated at a burn 
rate below 1.25 kg/hr (2.76 lb/hr), the flue shall be dampered or the 
air supply otherwise controlled in order to achieve two test runs 
within Category 2.
    8.1.1.3.2  Evidence that a wood heater cannot be operated at a burn 
rate less than 0.80 kg/hr shall include documentation of two or more 
attempts to operate the wood heater in burn rate Category 1 and fuel 
combustion has stopped, or results of two or more test runs 
demonstrating that the burn rates were greater than 0.80 kg/hr when the 
air supply controls were adjusted to the lowest possible position or 
settings. Stopped fuel combustion is evidenced when an elapsed time of 
30 minutes or more has occurred without a measurable ( 0.05 kg (0.1 lb) 
or 1.0 percent, whichever is greater) weight change in the test fuel 
charge. See also Section 8.8.3. Report the evidence and the reasoning 
used to determine that a test in burn rate Category 1 cannot be 
achieved; for example, two unsuccessful attempts to operate at a burn 
rate of 0.4 kg/hr are not sufficient evidence that burn rate Category 1 
cannot be achieved.

    Note: After July 1, 1990, if a wood heater cannot be operated at 
a burn rate less than 0.80 kg/hr, at least one test run with an 
average burn rate of 1.00 kg/hr or less shall be conducted. 
Additionally, if flue dampering must be used to achieve burn rates 
below 1.25 kg/hr (or 1.0 kg/hr), results from a test run conducted 
at burn rates below 0.90 kg/hr need not be reported or included in 
the test run average provided that such results are replaced with 
results from a test run meeting the criteria above.


    8.2  Catalytic Combustor and Wood Heater Aging. The catalyst-
equipped wood heater or a wood heater of any type shall be aged before 
the certification test begins. The aging procedure shall be conducted 
and documented by a testing laboratory accredited according to 
procedures in Sec. 60.535 of 40 CFR part 60.
    8.2.1  Catalyst-equipped Wood Heater. Operate the catalyst-equipped 
wood heater using fuel meeting the specifications outlined in Sections 
7.1.1 through 7.1.3, or cordwood with a moisture content between 15 and 
25 percent on a wet basis. Operate the wood heater at a medium burn 
rate (Category 2 or 3) with a new catalytic combustor in place and in 
operation for at least 50 hours. Record and report hourly catalyst exit 
temperature data (Section 8.6.2) and the hours of operation.
    8.2.2  Non-Catalyst Wood Heater. Operate the wood heater using the 
fuel described in Section 8.4.1 at a medium burn rate for at least 10 
hours. Record and report the hours of operation.
    8.3  Pretest Recordkeeping. Record the test fuel charge dimensions 
and weights, and wood heater and catalyst descriptions as shown in the 
example in Figure 28-1.
    8.4  Wood Heater Installation. Assemble the wood heater appliance 
and parts in conformance with the manufacturer's written installation 
instructions. Place the wood heater centrally on the platform scale and 
connect the wood heater to the flue described in Section 6.11. Clean 
the flue with an appropriately sized, wire chimney brush before each 
certification test.
    8.5  Wood Heater Temperature Monitors.
    8.5.1  For catalyst-equipped wood heaters, locate a temperature 
monitor (optional) about 25 mm (1 in.) upstream of the catalyst at the 
centroid of the catalyst face area, and locate a temperature monitor 
(mandatory) that will indicate the catalyst exhaust temperature. This 
temperature monitor is centrally located within 25 mm (1 in.) 
downstream at the centroid of catalyst face area. Record these 
locations.
    8.5.2  Locate wood heater surface temperature monitors at five 
locations on the wood heater firebox exterior surface. Position the 
temperature monitors centrally on the top surface, on two sidewall 
surfaces, and on the bottom and back surfaces. Position the monitor 
sensing tip on the firebox exterior surface inside of any heat shield, 
air circulation walls, or other

[[Page 62102]]

wall or shield separated from the firebox exterior surface. Surface 
temperature locations for unusual design shapes (e.g., spherical, etc.) 
shall be positioned so that there are four surface temperature monitors 
in both the vertical and horizontal planes passing at right angles 
through the centroid of the firebox, not including the fuel loading 
door (total of five temperature monitors).
    8.6  Test Facility Conditions.
    8.6.1  Locate the test facility temperature monitor on the 
horizontal plane that includes the primary air intake opening for the 
wood heater. Locate the temperature monitor 1 to 2 m (3 to 6 ft) from 
the front of the wood heater in the 90 deg. sector in front of the wood 
heater.
    8.6.2  Use an anemometer to measure the air velocity. Measure and 
record the room air velocity before the pretest ignition period 
(Section 8.7) and once immediately following the test run completion.
    8.6.3  Measure and record the test facility's ambient relative 
humidity, barometric pressure, and temperature before and after each 
test run.
    8.6.4  Measure and record the flue draft or static pressure in the 
flue at a location no greater than 0.3 m (1 ft) above the flue 
connector at the wood heater exhaust during the test run at the 
recording intervals (Section 8.8.2).
    8.7  Wood Heater Firebox Volume.
    8.7.1  Determine the firebox volume using the definitions for 
height, width, and length in Section 3. Volume adjustments due to 
presence of firebrick and other permanent fixtures may be necessary. 
Adjust width and length dimensions to extend to the metal wall of the 
wood heater above the firebrick or permanent obstruction if the 
firebrick or obstruction extending the length of the side(s) or back 
wall extends less than one-third of the usable firebox height. Use the 
width or length dimensions inside the firebrick if the firebrick 
extends more than one-third of the usable firebox height. If a log 
retainer or grate is a permanent fixture and the manufacturer 
recommends that no fuel be placed outside the retainer, the area 
outside of the retainer is excluded from the firebox volume 
calculations.
    8.7.2  In general, exclude the area above the ash lip if that area 
is less than 10 percent of the usable firebox volume. Otherwise, take 
into account consumer loading practices. For instance, if fuel is to be 
loaded front-to-back, an ash lip may be considered usable firebox 
volume.
    8.7.3  Include areas adjacent to and above a baffle (up to two 
inches above the fuel loading opening) if four inches or more 
horizontal space exist between the edge of the baffle and a vertical 
obstruction (e.g., sidewalls or air channels).
    8.8  Test Fuel Charge.
    8.8.1  Prepare the test fuel pieces in accordance with the 
specifications outlined in Sections 7.1 and 7.2. Determine the test 
fuel moisture content with a calibrated electrical resistance meter or 
other equivalent performance meter. If necessary, convert fuel moisture 
content values from dry basis (%Md) to wet basis 
(%Mw) in Section 12.2 using Equation 28-1. Determine fuel 
moisture for each fuel piece (not including spacers) by averaging at 
least three moisture meter readings, one from each of three sides, 
measured parallel to the wood grain. Average all the readings for all 
the fuel pieces in the test fuel charge. If an electrical resistance 
type meter is used, penetration of insulated electrodes shall be one-
fourth the thickness of the test fuel piece or 19 mm (0.75 in.), 
whichever is greater. Measure the moisture content within a 4-hour 
period prior to the test run. Determine the fuel temperature by 
measuring the temperature of the room where the wood has been stored 
for at least 24 hours prior to the moisture determination.
    8.8.2  Attach the spacers to the test fuel pieces with uncoated, 
ungalvanized nails or staples as illustrated in Figure 28-2. Attachment 
of spacers to the top of the test fuel piece(s) on top of the test fuel 
charge is optional.
    8.8.3  To avoid stacking difficulties, or when a whole number of 
test fuel pieces does not result, all piece lengths shall be adjusted 
uniformly to remain within the specified loading density. The shape of 
the test fuel crib shall be geometrically similar to the shape of the 
firebox volume without resorting to special angular or round cuts on 
the individual fuel pieces.
    8.8.4  The test fuel loading density shall be 112  11.2 
kg/m3 (7  0.7 
lb/ft3) of usable firebox volume on a wet basis.
    8.9  Sampling Equipment. Prepare the sampling equipment as defined 
by the selected method (i.e., either Method 5G or Method 5H). Collect 
one particulate emission sample for each test run.
    8.10  Secondary Air Adjustment Validation.
    8.10.1  If design drawings do not show the introduction of 
secondary air into a chamber outside the firebox (see ``secondary air 
supply'' under Section 3.0, Definitions), conduct a separate test of 
the wood heater's secondary air supply. Operate the wood heater at a 
burn rate in Category 1 (Section 8.1.1) with the secondary air supply 
operated following the manufacturer's written instructions. Start the 
secondary air validation test run as described in Section 8.8.1, except 
no emission sampling is necessary and burn rate data shall be recorded 
at 5-minute intervals.
    8.10.2  After the start of the test run, operate the wood heater 
with the secondary air supply set as per the manufacturer's 
instructions, but with no adjustments to this setting. After 25 percent 
of the test fuel has been consumed, adjust the secondary air supply 
controls to another setting, as per the manufacturer's instructions. 
Record the burn rate data (5-minute intervals) for 20 minutes following 
the air supply adjustment.
    8.10.3  Adjust the air supply control(s) to the original 
position(s), operate at this condition for at least 20 minutes, and 
repeat the air supply adjustment procedure above. Repeat the procedure 
three times at equal intervals over the entire burn period as defined 
in Section 8.8. If the secondary air adjustment results in a burn rate 
change of more than an average of 25 percent between the 20-minute 
periods before and after the secondary adjustments, the secondary air 
supply shall be considered a primary air supply, and no adjustment to 
this air supply is allowed during the test run.
    8.10.4  The example sequence below describes a typical secondary 
air adjustment validation check. The first cycle begins after at least 
25 percent of the test fuel charge has been consumed.

Cycle 1
    Part 1, sec air adjusted to final position--20 min
    Part 2, sec air adjusted to final position--20 min
    Part 3, sec air adjusted to final position--20 min
Cycle 2
    Part 1, sec air adjusted to final position--20 min
    Part 2, sec air adjusted to final position--20 min
    Part 3, sec air adjusted to final position--20 min
Cycle 3
    Part 1, sec air adjusted to final position--20 min
    Part 2, sec air adjusted to final position--20 min
    Part 3, sec air adjusted to final position--20 min

Note that the cycles may overlap; that is, Part 3 of Cycle 1 may 
coincide in part or in total with Part 1 of Cycle 2. The calculation of 
the secondary air percent effect for this example is as follows:

[[Page 62103]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.425

    8.11  Pretest Ignition. Build a fire in the wood heater in 
accordance with the manufacturer's written instructions.
    8.11.1  Pretest Fuel Charge. Crumpled newspaper loaded with 
kindling may be used to help ignite the pretest fuel. The pretest fuel, 
used to sustain the fire, shall meet the same fuel requirements 
prescribed in Section 7.1. The pretest fuel charge shall consist of 
whole 2 x 4's that are no less than \1/3\ the length of the test fuel 
pieces. Pieces of 4 x 4 lumber in approximately the same weight ratio 
as for the test fuel charge may be added to the pretest fuel charge.
    8.11.2  Wood Heater Operation and Adjustments. Set the air inlet 
supply controls at any position that will maintain combustion of the 
pretest fuel load. At least one hour before the start of the test run, 
set the air supply controls at the approximate positions necessary to 
achieve the burn rate desired for the test run. Adjustment of the air 
supply controls, fuel addition or subtractions, and coalbed raking 
shall be kept to a minimum but are allowed up to 15 minutes prior to 
the start of the test run. For the purposes of this method, coalbed 
raking is the use of a metal tool (poker) to stir coals, break burning 
fuel into smaller pieces, dislodge fuel pieces from positions of poor 
combustion, and check for the condition of uniform charcoalization. 
Record all adjustments made to the air supply controls, adjustments to 
and additions or subtractions of fuel, and any other changes to wood 
heater operations that occur during pretest ignition period. Record 
fuel weight data and wood heater temperature measurements at 10-minute 
intervals during the hour of the pretest ignition period preceding the 
start of the test run. During the 15-minute period prior to the start 
of the test run, the wood heater loading door shall not be open more 
than a total of 1 minute. Coalbed raking is the only adjustment allowed 
during this period.


    Note: One purpose of the pretest ignition period is to achieve 
uniform charcoalization of the test fuel bed prior to loading the 
test fuel charge. Uniform charcoalization is a general condition of 
the test fuel bed evidenced by an absence of large pieces of burning 
wood in the coal bed and the remaining fuel pieces being brittle 
enough to be broken into smaller charcoal pieces with a metal poker. 
Manipulations to the fuel bed prior to the start of the test run 
should be done to achieve uniform charcoalization while maintaining 
the desired burn rate. In addition, some wood heaters (e.g., high 
mass units) may require extended pretest burn time and fuel 
additions to reach an initial average surface temperature sufficient 
to meet the thermal equilibrium criteria in Section 8.3.


    8.11.3  The weight of pretest fuel remaining at the start of the 
test run is determined as the difference between the weight of the wood 
heater with the remaining pretest fuel and the tare weight of the 
cleaned, dry wood heater with or without dry ash or sand added 
consistent with the manufacturer's instructions and the owner's manual. 
The tare weight of the wood heater must be determined with the wood 
heater (and ash, if added) in a dry condition.
    8.12  Test Run. Complete a test run in each burn rate category, as 
follows:
    8.12.1  Test Run Start.
    8.12.1.1  When the kindling and pretest fuel have been consumed to 
leave a fuel weight between 20 and 25 percent of the weight of the test 
fuel charge, record the weight of the fuel remaining and start the test 
run. Record and report any other criteria, in addition to those 
specified in this section, used to determine the moment of the test run 
start (e.g., firebox or catalyst temperature), whether such criteria 
are specified by the wood heater manufacturer or the testing 
laboratory. Record all wood heater individual surface temperatures, 
catalyst temperatures, any initial sampling method measurement values, 
and begin the particulate emission sampling. Within 1 minute following 
the start of the test run, open the wood heater door, load the test 
fuel charge, and record the test fuel charge weight. Recording of 
average, rather than individual, surface temperatures is acceptable for 
tests conducted in accordance with Sec. 60.533(o)(3)(i) of 40 CFR part 
60.
    8.12.1.2  Position the fuel charge so that the spacers are parallel 
to the floor of the firebox, with the spacer edges abutting each other. 
If loading difficulties result, some fuel pieces may be placed on edge. 
If the usable firebox volume is between 0.043 and 0.085 m3 
(1.5 and 3.0 ft3), alternate the piece sizes in vertical 
stacking layers to the extent possible. For example, place 2  x  4's on 
the bottom layer in direct contact with the coal bed and 4  x  4's on 
the next layer, etc. (See Figure 28-3). Position the fuel pieces 
parallel to each other and parallel to the longest wall of the firebox 
to the extent possible within the specifications in Section 8.8.
    8.12.1.3  Load the test fuel in appliances having unusual or 
unconventional firebox design maintaining air space intervals between 
the test fuel pieces and in conformance with the manufacturer's written 
instructions. For any appliance that will not accommodate the loading 
arrangement specified in the paragraph above, the test facility 
personnel shall contact the Administrator for an alternative loading 
arrangement.
    8.12.1.4  The wood heater door may remain open and the air supply 
controls adjusted up to five minutes after the start of the test run in 
order to make adjustments to the test fuel charge and to ensure 
ignition of the test fuel charge has occurred. Within the five minutes 
after the start of the test run, close the wood heater door and adjust 
the air supply controls to the position determined to produce the 
desired burn rate. No other adjustments to the air supply controls or 
the test fuel charge are allowed (except as specified in Sections 
8.12.3 and 8.12.4) after the first five minutes of the test run. Record 
the length of time the wood heater door remains open, the adjustments 
to the air supply controls, and any other operational adjustments.
    8.12.2  Data Recording. Record on a data sheet similar to that 
shown in Figure 28-4, at intervals no greater than 10 minutes, fuel 
weight data, wood heater individual surface and catalyst temperature 
measurements, other wood heater operational data (e.g., draft), test 
facility temperature and sampling method data.
    8.12.3  Test Fuel Charge Adjustment. The test fuel charge may be 
adjusted (i.e., repositioned) once during a test run if more than 60 
percent of the initial test fuel charge weight has been consumed and 
more than 10 minutes have elapsed without a measurable (0.05 kg (0.1 
lb) or 1.0 percent, whichever is greater) weight change. The time used 
to make this adjustment shall be less than 15 seconds.
    8.12.4  Air Supply Adjustment. Secondary air supply controls may be 
adjusted once during the test run following the manufacturer's written 
instructions (see Section 8.10). No other air supply adjustments are 
allowed during the test run. Recording of wood heater flue draft during 
the test run is optional for tests conducted in

[[Page 62104]]

accordance with Sec. 60.533(o)(3)(i) of 40 CFR part 60.
    8.12.5  Auxiliary Wood Heater Equipment Operation. Heat exchange 
blowers sold with the wood heater shall be operated during the test run 
following the manufacturer's written instructions. If no manufacturer's 
written instructions are available, operate the heat exchange blower in 
the ``high'' position. (Automatically operated blowers shall be 
operated as designed.) Shaker grates, by-pass controls, or other 
auxiliary equipment may be adjusted only one time during the test run 
following the manufacturer's written instructions.
    Record all adjustments on a wood heater operational written record.


    Note: If the wood heater is sold with a heat exchange blower as 
an option, test the wood heater with the heat exchange blower 
operating as described in Sections 8.1 through 8.12 and report the 
results. As an alternative to repeating all test runs without the 
heat exchange blower operating, one additional test run may be 
without the blower operating as described in Section 8.12.5 at a 
burn rate in Category 2 (Section 8.1.1). If the emission rate 
resulting from this test run without the blower operating is equal 
to or less than the emission rate plus 1.0 g/hr (0.0022 lb/hr) for 
the test run in burn rate Category 2 with the blower operating, the 
wood heater may be considered to have the same average emission rate 
with or without the blower operating. Additional test runs without 
the blower operating are unnecessary.


    8.13  Test Run Completion. Continue emission sampling and wood 
heater operation for 2 hours. The test run is completed when the 
remaining weight of the test fuel charge is 0.00 kg (0.0 lb). End the 
test run when the scale has indicated a test fuel charge weight of 0.00 
kg (0.0 lb) or less for 30 seconds. At the end of the test run, stop 
the particulate sampling, and record the final fuel weight, the run 
time, and all final measurement values.
    8.14  Wood Heater Thermal Equilibrium. The average of the wood 
heater surface temperatures at the end of the test run shall agree with 
the average surface temperature at the start of the test run to within 
70  deg.C (126  deg.F).
    8.15  Consecutive Test Runs. Test runs on a wood heater may be 
conducted consecutively provided that a minimum one-hour interval 
occurs between test runs.
    8.16  Additional Test Runs. The testing laboratory may conduct more 
than one test run in each of the burn rate categories specified in 
Section 8.1.1. If more than one test run is conducted at a specified 
burn rate, the results from at least two-thirds of the test runs in 
that burn rate category shall be used in calculating the weighted 
average emission rate (see Section 12.2). The measurement data and 
results of all test runs shall be reported regardless of which values 
are used in calculating the weighted average emission rate (see Note in 
Section 8.1).

9.0  Quality Control

    Same as Section 9.0 of either Method 5G or Method 5H.

10.0  Calibration and Standardizations

    Same as Section 10.0 of either Method 5G or Method 5H, with the 
addition of the following:
    10.1  Platform Scale. Perform a multi-point calibration (at least 
five points spanning the operational range) of the platform scale 
before its initial use. The scale manufacturer's calibration results 
are sufficient for this purpose. Before each certification test, audit 
the scale with the wood heater in place by weighing at least one 
calibration weight (Class F) that corresponds to between 20 percent and 
80 percent of the expected test fuel charge weight. If the scale cannot 
reproduce the value of the calibration weight within 0.05 kg (0.1 lb) 
or 1 percent of the expected test fuel charge weight, whichever is 
greater, recalibrate the scale before use with at least five 
calibration weights spanning the operational range of the scale.
    10.2  Balance (optional). Calibrate as described in Section 10.1.
    10.3  Temperature Monitor. Calibrate as in Method 2, Section 4.3, 
before the first certification test and semiannually thereafter.
    10.4  Moisture Meter. Calibrate as per the manufacturer's 
instructions before each certification test.
    10.5  Anemometer. Calibrate the anemometer as specified by the 
manufacturer's instructions before the first certification test and 
semiannually thereafter.
    10.6  Barometer. Calibrate against a mercury barometer before the 
first certification test and semiannually thereafter.
    10.7  Draft Gauge. Calibrate as per the manufacturer's 
instructions; a liquid manometer does not require calibration.
    10.8  Humidity Gauge. Calibrate as per the manufacturer's 
instructions before the first certification test and semiannually 
thereafter.

11.0  Analytical Procedures

    Same as Section 11.0 of either Method 5G or Method 5H.

12.0  Data Analysis and Calculations

    Same as Section 12.0 of either Method 5G or Method 5H, with the 
addition of the following:
    12.1  Nomenclature.

BR = Dry wood burn rate, kg/hr (lb/hr)
Ei = Emission rate for test run, i, from Method 5G or 5H, g/
hr (lb/hr)
Ew = Weighted average emission rate, g/hr (lb/hr)
ki = Test run weighting factor = Pi+1 - 
Pi-1
%Md = Fuel moisture content, dry basis, percent.
%Mw = Average moisture in test fuel charge, wet basis, 
percent.
n = Total number of test runs.
Pi = Probability for burn rate during test run, i, obtained 
from Table 28-1. Use linear interpolation to determine probability 
values for burn rates between those listed on the table.
Wwd = Total mass of wood burned during the test run, kg 
(lb).

    12.2  Wet Basis Fuel Moisture Content.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.426
    
    12.3  Weighted Average Emission Rate. Calculate the weighted 
average emission rate (Ew) using Equation 28-1:
[GRAPHIC] [TIFF OMITTED] TR17OC00.427


    Note: Po always equals 0, P(n+1) always 
equals 1, P1 corresponds to the probability of the lowest 
recorded burn rate, P2 corresponds to the probability of 
the next lowest burn rate, etc. An example calculation is in Section 
12.3.1.


    12.3.1  Example Calculation of Weighted Average Emission Rate.

------------------------------------------------------------------------
                                                 Burn rate    Emissions
        Burn rate category          Test  No.   (Dry-kg/hr)     (g/hr)
------------------------------------------------------------------------
1................................            1         0.65          5.0
2\1\.............................            2         0.85          6.7
2................................            3         0.90          4.7

[[Page 62105]]

 
2................................            4         1.00          5.3
3................................            5         1.45          3.8
4................................            6         2.00         5.1
------------------------------------------------------------------------
\1\ As permitted in Section 6.6, this test run may be omitted from the
  calculation of the weighted average emission rate because three runs
  were conducted for this burn rate category.


----------------------------------------------------------------------------------------------------------------
                          Test No.                             Burn rate        Pi           Ei           Ki
----------------------------------------------------------------------------------------------------------------
0...........................................................  ...........        0.000  ...........  ...........
1...........................................................         0.65        0.121          5.0        0.300
2...........................................................         0.90        0.300          4.7        0.259
3...........................................................         1.00        0.380          5.3        0.422
4...........................................................         1.45        0.722          3.8        0.532
5...........................................................         2.00        0.912          5.1        0.278
6...........................................................  ...........        1.000  ...........  ...........
----------------------------------------------------------------------------------------------------------------
K1 = P2 - P0 = 0.300 - 0 = 0.300
K2 = P3 - P1 = 0.381 - 0.121 = 0.259
K3 = P4 - P2 = 0.722 - 0.300 = 0.422
K4 = P5 - P3 = 0.912 - 0.380 = 0.532
K5 = P6 - P4 = 1.000 - 0.722 = 0.278

Weighted Average Emission Rate, Ew, Calculation
[GRAPHIC] [TIFF OMITTED] TR17OC00.428

    12.4  Average Wood Heater Surface Temperatures. Calculate the 
average of the wood heater surface temperatures for the start of the 
test run (Section 8.12.1) and for the test run completion (Section 
8.13). If the two average temperatures do not agree within 70  deg.C 
(125  deg.F), report the test run results, but do not include the test 
run results in the test average. Replace such test run results with 
results from another test run in the same burn rate category.
    12.5  Burn Rate. Calculate the burn rate (BR) using Equation 28-3:
    [GRAPHIC] [TIFF OMITTED] TR17OC00.429
    
    12.6  Reporting Criteria. Submit both raw and reduced test data for 
wood heater tests.
    12.6.1  Suggested Test Report Format.
    12.6.1.1  Introduction.
    12.6.1.1.1  Purpose of test-certification, audit, efficiency, 
research and development.
    12.6.1.1.2  Wood heater identification-manufacturer, model number, 
catalytic/noncatalytic, options.
    12.6.1.1.3  Laboratory-name, location (altitude), participants.
    12.6.1.1.4  Test information-date wood heater received, date of 
tests, sampling methods used, number of test runs.
    12.6.1.2  Summary and Discussion of Results
    12.6.1.2.1  Table of results (in order of increasing burn rate)-
test run number, burn rate, particulate emission rate, efficiency (if 
determined), averages (indicate which test runs are used).
    12.6.1.2.2  Summary of other data-test facility conditions, surface 
temperature averages, catalyst temperature averages, pretest fuel 
weights, test fuel charge weights, run times.
    12.6.1.2.3  Discussion-Burn rate categories achieved, test run 
result selection, specific test run problems and solutions.
    12.6.1.3  Process Description.
    12.6.1.3.1  Wood heater dimensions-volume, height, width, lengths 
(or other linear dimensions), weight, volume adjustments.
    12.6.1.3.2  Firebox configuration-air supply locations and 
operation, air supply introduction location, refractory location and 
dimensions, catalyst location, baffle and by-pass location and 
operation (include line drawings or photographs).
    12.6.1.3.3  Process operation during test-air supply settings and 
adjustments, fuel bed adjustments, draft.
    12.6.1.3.4  Test fuel-test fuel properties (moisture and 
temperature), test fuel crib description (include line drawing or 
photograph), test fuel loading density.
    12.6.1.4  Sampling Locations.
    12.6.1.4.1  Describe sampling location relative to wood heater. 
Include drawing or photograph.
    12.6.1.5  Sampling and Analytical Procedures
    12.6.1.5.1  Sampling methods-brief reference to operational and 
sampling procedures and optional and alternative procedures used.
    12.6.1.5.2  Analytical methods-brief description of sample recovery 
and analysis procedures.
    12.6.1.6  Quality Control and Assurance Procedures and Results
    12.6.1.6.1  Calibration procedures and results-certification 
procedures, sampling and analysis procedures.
    12.6.1.6.2  Test method quality control procedures-leak-checks, 
volume

[[Page 62106]]

meter checks, stratification (velocity) checks, proportionality 
results.
    12.6.1.7  Appendices
    12.6.1.7.1  Results and Example Calculations. Complete summary 
tables and accompanying examples of all calculations.
    12.6.1.7.2  Raw Data. Copies of all uncorrected data sheets for 
sampling measurements, temperature records and sample recovery data. 
Copies of all pretest burn rate and wood heater temperature data.
    12.6.1.7.3  Sampling and Analytical Procedures. Detailed 
description of procedures followed by laboratory personnel in 
conducting the certification test, emphasizing particular parts of the 
procedures differing from the methods (e.g., approved alternatives).
    12.6.1.7.4  Calibration Results. Summary of all calibrations, 
checks, and audits pertinent to certification test results with dates.
    12.6.1.7.5  Participants. Test personnel, manufacturer 
representatives, and regulatory observers.
    12.6.1.7.6  Sampling and Operation Records. Copies of uncorrected 
records of activities not included on raw data sheets (e.g., wood 
heater door open times and durations).
    12.6.1.7.7  Additional Information. Wood heater manufacturer's 
written instructions for operation during the certification test.
    12.6.2.1  Wood Heater Identification. Report wood heater 
identification information. An example data form is shown in Figure 28-
4.
    12.6.2.2  Test Facility Information. Report test facility 
temperature, air velocity, and humidity information. An example data 
form is shown on Figure 28-4.
    12.6.2.3  Test Equipment Calibration and Audit Information. Report 
calibration and audit results for the platform scale, test fuel 
balance, test fuel moisture meter, and sampling equipment including 
volume metering systems and gaseous analyzers.
    12.6.2.4  Pretest Procedure Description. Report all pretest 
procedures including pretest fuel weight, burn rates, wood heater 
temperatures, and air supply settings. An example data form is shown on 
Figure 28-4.
    12.6.2.5  Particulate Emission Data. Report a summary of test 
results for all test runs and the weighted average emission rate. 
Submit copies of all data sheets and other records collected during the 
testing. Submit examples of all calculations.

13.0  Method Performance, [Reserved]

14.0  Pollution Prevention, [Reserved]

15.0  Waste Management, [Reserved]

16.0  Alternative Procedures

    16.1  Pellet Burning Heaters. Certification testing requirements 
and procedures for pellet burning wood heaters are identical to those 
for other wood heaters, with the following exceptions:
    16.1.1  Test Fuel Properties. The test fuel shall be all wood 
pellets with a moisture content no greater than 20 percent on a wet 
basis (25 percent on a dry basis). Determine the wood moisture content 
with either ASTM D 2016-74 or 83, (Method A), ASTM D 4444-92, or ASTM D 
4442-84 or 92 (all noted ASTM standards are incorporated by reference--
see Sec. 60.17).
    16.1.2  Test Fuel Charge Specifications. The test fuel charge size 
shall be as per the manufacturer's written instructions for maintaining 
the desired burn rate.
    16.1.3  Wood Heater Firebox Volume. The firebox volume need not be 
measured or determined for establishing the test fuel charge size. The 
firebox dimensions and other heater specifications needed to identify 
the heater for certification purposes shall be reported.
    16.1.4  Heater Installation. Arrange the heater with the fuel 
supply hopper on the platform scale as described in Section 8.6.1.
    16.1.5  Pretest Ignition. Start a fire in the heater as directed by 
the manufacturer's written instructions, and adjust the heater controls 
to achieve the desired burn rate. Operate the heater at the desired 
burn rate for at least 1 hour before the start of the test run.
    16.1.6  Test Run. Complete a test run in each burn rate category as 
follows:
    16.1.6.1  Test Run Start. When the wood heater has operated for at 
least 1 hour at the desired burn rate, add fuel to the supply hopper as 
necessary to complete the test run, record the weight of the fuel in 
the supply hopper (the wood heater weight), and start the test run. Add 
no additional fuel to the hopper during the test run.
    Record all the wood heater surface temperatures, the initial 
sampling method measurement values, the time at the start of the test, 
and begin the emission sampling. Make no adjustments to the wood heater 
air supply or wood supply rate during the test run.
    16.1.6.2  Data Recording. Record the fuel (wood heater) weight 
data, wood heater temperature and operational data, and emission 
sampling data as described in Section 8.12.2.
    16.1.6.3  Test Run Completion. Continue emission sampling and wood 
heater operation for 2 hours. At the end of the test run, stop the 
particulate sampling, and record the final fuel weight, the run time, 
and all final measurement values, including all wood heater individual 
surface temperatures.
    16.1.7  Calculations. Determine the burn rate using the difference 
between the initial and final fuel (wood heater) weights and the 
procedures described in Section 12.4. Complete the other calculations 
as described in Section 12.0.

17.0  References

    Same as Method 5G, with the addition of the following:

    1. Radian Corporation. OMNI Environmental Services, Inc., 
Cumulative Probability for a Given Burn Rate Based on Data Generated 
in the CONEG and BPA Studies. Package of materials submitted to the 
Fifth Session of the Regulatory Negotiation Committee, July 16-17, 
1986.

18.0  Tables, Diagrams, Flowcharts, and Validation Data

          Table 28-1.--Burn Rate Weighted Probabilities for Calculating Weighted Average Emission Rates
----------------------------------------------------------------------------------------------------------------
                                    Cumulative                      Cumulative                      Cumulative
     Burn rate  (kg/hr-dry)         probability   Burn rate  (kg/   probability   Burn rate  (kg/   probability
                                        (P)           hr-dry)           (P)           hr-dry)           (P)
----------------------------------------------------------------------------------------------------------------
0.00............................           0.000            1.70           0.840            3.40           0.989
0.05............................           0.002            1.75           0.857            3.45           0.989
0.10............................           0.007            1.80           0.875            3.50           0.990
0.15............................           0.012            1.85           0.882            3.55           0.991
0.20............................           0.016            1.90           0.895            3.60           0.991
0.25............................           0.021            1.95           0.906            3.65           0.992
0.30............................           0.028            2.00           0.912            3.70           0.992
0.35............................           0.033            2.05           0.920            3.75           0.992

[[Page 62107]]

 
0.40............................           0.041            2.10           0.925            3.80           0.993
0.45............................           0.054            2.15           0.932            3.85           0.994
0.50............................           0.065            2.20           0.936            3.90           0.994
0.55............................           0.086            2.25           0.940            3.95           0.994
0.60............................           0.100            2.30           0.945            4.00           0.994
0.65............................           0.121            2.35           0.951            4.05           0.995
0.70............................           0.150            2.40           0.956            4.10           0.995
0.75............................           0.185            2.45           0.959            4.15           0.995
0.80............................           0.220            2.50           0.964            4.20           0.995
0.85............................           0.254            2.55           0.968            4.25           0.995
0.90............................           0.300            2.60           0.972            4.30           0.996
0.95............................           0.328            2.65           0.975            4.35           0.996
1.00............................           0.380            2.70           0.977            4.40           0.996
1.05............................           0.407            2.75           0.979            4.45           0.996
1.10............................           0.460            2.80           0.980            4.50           0.996
1.15............................           0.490            2.85           0.981            4.55           0.996
1.20............................           0.550            2.90           0.982            4.60           0.996
1.25............................           0.572            2.95           0.984            4.65           0.996
1.30............................           0.620            3.00           0.984            4.70           0.996
1.35............................           0.654            3.05           0.985            4.75           0.997
1.40............................           0.695            3.10           0.986            4.80           0.997
1.45............................           0.722            3.15           0.987            4.85           0.997
1.50............................           0.750            3.20           0.987            4.90           0.997
1.55............................           0.779            3.25           0.988            4.95           0.997
1.60............................           0.800            3.30           0.988  5.0           1.000
                                                                                               0
1.65............................           0.825            3.35           0.989  ..............  ..............
----------------------------------------------------------------------------------------------------------------

BILLING CODE 6560-50-P

[[Page 62108]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.430


[[Page 62109]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.431


[[Page 62110]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.432

BILLING CODE 6560-50-C

[[Page 62111]]

Method 28A--Measurement of Air- to-Fuel Ratio and Mimimum 
Achievable Burn Rates for Wood-Fired Appliances

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

1.0  Scope and Application

    1.1  Analyte. Particulate matter (PM). No CAS number assigned.
    1.2  Applicability. This method is applicable for the measurement 
of air-to-fuel ratios and minimum achievable burn rates, for 
determining whether a wood-fired appliance is an affected facility, as 
specified in 40 CFR 60.530.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  A gas sample is extracted from a location in the stack of a 
wood-fired appliance while the appliance is operating at a prescribed 
set of conditions. The gas sample is analyzed for carbon dioxide 
(CO2), oxygen (O2), and carbon monoxide (CO). 
These stack gas components are measured for determining the dry 
molecular weight of the exhaust gas. Total moles of exhaust gas are 
determined stoichiometrically. Air-to-fuel ratio is determined by 
relating the mass of dry combustion air to the mass of dry fuel 
consumed.

3.0  Definitions

    Same as Method 28, Section 3.0, with the addition of the following:
    3.1 Air-to-fuel ratio means the ratio of the mass of dry combustion 
air introduced into the firebox to the mass of dry fuel consumed (grams 
of dry air per gram of dry wood burned).

4.0  Interferences [Reserved]

5.0  Safety

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

6.0  Equipment and Supplies

    6.1  Test Facility. Insulated Solid Pack Chimney, Platform Scale 
and Monitor, Test Facility Temperature Monitor, Balance, Moisture 
Meter, Anemometer, Barometer, Draft Gauge, Humidity Gauge, Wood Heater 
Flue, and Test Facility. Same as Method 28, Sections 6.1, 6.2, and 6.4 
to 6.12, respectively.
    6.2  Sampling System. Probe, Condenser, Valve, Pump, Rate Meter, 
Flexible Bag, Pressure Gauge, and Vacuum Gauge. Same as Method 3, 
Sections 6.2.1 to 6.2.8, respectively. Alternatively, the sampling 
system described in Method 5H, Section 6.1 may be used.
    6.3  Exhaust Gas Analysis. Use one or both of the following:
    6.3.1  Orsat Analyzer. Same as Method 3, Section 6.1.3
    6.3.2  Instrumental Analyzers. Same as Method 5H, Sections 6.1.3.4 
and 6.1.3.5, for CO2 and CO analyzers, except use a CO 
analyzer with a range of 0 to 5 percent and use a CO2 
analyzer with a range of 0 to 5 percent. Use an O2 analyzer 
capable of providing a measure of O2 in the range of 0 to 25 
percent by volume at least once every 10 minutes.

7.0  Reagents and Standards

    7.1  Test Fuel and Test Fuel Spacers. Same as Method 28, Sections 
7.1 and 7.2, respectively.
    7.2  Cylinder Gases. For each of the three analyzers, use the same 
concentration as specified in Sections 7.2.1, 7.2.2, and 7.2.3 of 
Method 6C.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Wood Heater Air Supply Adjustments.
    8.1.1  This section describes how dampers are to be set or adjusted 
and air inlet ports closed or sealed during Method 28A tests. The 
specifications in this section are intended to ensure that affected 
facility determinations are made on the facility configurations that 
could reasonably be expected to be employed by the user. They are also 
intended to prevent circumvention of the standard through the addition 
of an air port that would often be blocked off in actual use. These 
specifications are based on the assumption that consumers will remove 
such items as dampers or other closure mechanism stops if this can be 
done readily with household tools; that consumers will block air inlet 
passages not visible during normal operation of the appliance using 
aluminum tape or parts generally available at retail stores; and that 
consumers will cap off any threaded or flanged air inlets. They also 
assume that air leakage around glass doors, sheet metal joints or 
through inlet grilles visible during normal operation of the appliance 
would not be further blocked or taped off by a consumer.
    8.1.2  It is not the intention of this section to cause an 
appliance that is clearly designed, intended, and, in most normal 
installations, used as a fireplace to be converted into a wood heater 
for purposes of applicability testing. Such a fireplace would be 
identifiable by such features as large or multiple glass doors or 
panels that are not gasketed, relatively unrestricted air inlets 
intended, in large part, to limit smoking and fogging of glass 
surfaces, and other aesthetic features not normally included in wood 
heaters.
    8.1.3  Adjustable Air Supply Mechanisms. Any commercially available 
flue damper, other adjustment mechanism or other air inlet port that is 
designed, intended or otherwise reasonably expected to be adjusted or 
closed by consumers, installers, or dealers and which could restrict 
air into the firebox shall be set so as to achieve minimum air into the 
firebox (i.e., closed off or set in the most closed position).
    8.1.3.1  Flue dampers, mechanisms and air inlet ports which could 
reasonably be expected to be adjusted or closed would include:
    8.1.3.1.1  All internal or externally adjustable mechanisms 
(including adjustments that affect the tightness of door fittings) that 
are accessible either before and/or after installation.
    8.1.3.1.2  All mechanisms, other inlet ports, or inlet port stops 
that are identified in the owner's manual or in any dealer literature 
as being adjustable or alterable. For example, an inlet port that could 
be used to provide access to an outside air duct but which is 
identified as being closable through use of additional materials 
whether or not they are supplied with the facility.
    8.1.3.1.3  Any combustion air inlet port or commercially available 
flue damper or mechanism stop, which would readily lend itself to 
closure by consumers who are handy with household tools by the removal 
of parts or the addition of parts generally available at retail stores 
(e.g., addition of a pipe cap or plug, addition of a small metal plate 
to an inlet hole on a nondecorative sheet metal surface, or removal of 
riveted or screwed damper stops).
    8.1.3.1.4  Any flue damper, other adjustment mechanisms or other 
air inlet ports that are found and documented in several (e.g., a 
number

[[Page 62112]]

sufficient to reasonably conclude that the practice is not unique or 
uncommon) actual installations as having been adjusted to a more closed 
position, or closed by consumers, installers, or dealers.
    8.1.4  Air Supply Adjustments During Test. The test shall be 
performed with all air inlets identified under this section in the 
closed or most closed position or in the configuration which otherwise 
achieves the lowest air inlet (i.e., greatest blockage).


    Note: For the purposes of this section, air flow shall not be 
minimized beyond the point necessary to maintain combustion or 
beyond the point that forces smoke into the room.


    8.1.5  Notwithstanding Section 8.1.1, any flue damper, adjustment 
mechanism, or air inlet port (whether or not equipped with flue dampers 
or adjusting mechanisms) that is visible during normal operation of the 
appliance and which could not reasonably be closed further or blocked 
except through means that would significantly degrade the aesthetics of 
the facility (e.g., through use of duct tape) will not be closed 
further or blocked.
    8.2  Sampling System.
    8.2.1  Sampling Location. Same as Method 5H, Section 8.1.2.
    8.2.2  Sampling System Set Up. Set up the sampling equipment as 
described in Method 3, Section 8.1.
    8.3  Wood Heater Installation, Test Facility Conditions, Wood 
Heater Firebox Volume, and Test Fuel Charge. Same as Method 28, 
Sections 8.4 and 8.6 to 8.8, respectively.
    8.4  Pretest Ignition. Same as Method 28, Section 8.11. Set the 
wood heater air supply settings to achieve a burn rate in Category 1 or 
the lowest achievable burn rate (see Section 8.1).
    8.5  Test Run. Same as Method 28, Section 8.12. Begin sample 
collection at the start of the test run as defined in Method 28, 
Section 8.12.1.
    8.5.1  Gas Analysis.
    8.5.1.1  If Method 3 is used, collect a minimum of two bag samples 
simultaneously at a constant sampling rate for the duration of the test 
run. A minimum sample volume of 30 liters (1.1 ft3) per bag 
is recommended.
    8.5.1.2  If instrumental gas concentration measurement procedures 
are used, conduct the gas measurement system performance tests, 
analyzer calibration, and analyzer calibration error check outlined in 
Method 6C, Sections 8.2.3, 8.2.4, 8.5, and 10.0, respectively. Sample 
at a constant rate for the duration of the test run.
    8.5.2  Data Recording. Record wood heater operational data, test 
facility temperature, sample train flow rate, and fuel weight data at 
intervals of no greater than 10 minutes.
    8.5.3  Test Run Completion. Same as Method 28, Section 8.13.

9.0  Quality Control

    9.1  Data Validation. The following quality control procedure is 
suggested to provide a check on the quality of the data.
    9.1.1  Calculate a fuel factor, Fo, using Equation 28A-1 
in Section 12.2.
    9.1.2  If CO is present in quantities measurable by this method, 
adjust the O2 and CO2 values before performing 
the calculation for Fo as shown in Section 12.3 and 12.4.
    9.1.3  Compare the calculated Fo factor with the 
expected Fo range for wood (1.000--1.120). Calculated 
Fo values beyond this acceptable range should be 
investigated before accepting the test results. For example, the 
strength of the solutions in the gas analyzer and the analyzing 
technique should be checked by sampling and analyzing a known 
concentration, such as air. If no detectable or correctable measurement 
error can be identified, the test should be repeated. Alternatively, 
determine a range of air-to-fuel ratio results that could include the 
correct value by using an Fo value of 1.05 and calculating a 
potential range of CO2 and O2 values. Acceptance 
of such results will be based on whether the calculated range includes 
the exemption limit and the judgment of the Administrator.
    9.2  Method 3 Analyses. Compare the results of the analyses of the 
two bag samples. If all the gas components (O2, CO, and 
CO2) values for the two analyses agree within 0.5 percent 
(e.g., 6.0 percent O2 for bag 1 and 6.5 percent 
O2 for bag 2, agree within 0.5 percent), the results of the 
bag analyses may be averaged for the calculations in Section 12. If the 
analysis results do not agree within 0.5 percent for each component, 
calculate the air-to-fuel ratio using both sets of analyses and report 
the results.

10.0  Calibration and Standardization, [Reserved]

11.0  Analytical Procedures

    11.1  Method 3 Integrated Bag Samples. Within 4 hours after the 
sample collection, analyze each bag sample for percent CO2, 
O2, and CO using an Orsat analyzer as described in Method 3, 
Section 11.0.
    11.2  Instrumental Analyzers. Average the percent CO2, 
CO, and O2 values for the test run.

12.0  Data Analyses and Calculations

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

Md = Dry molecular weight, g/g-mole (lb/lb-mole).
NT = Total gram-moles of dry exhaust gas per kg of wood 
burned (lb-moles/lb).
%CO2 = Percent CO2 by volume (dry basis).
%CO = Percent CO by volume (dry basis).
%N2 = Percent N2 by volume (dry basis).
%O2 = Percent O2 by volume (dry basis).
YHC = Assumed mole fraction of HC (dry as CH4) = 
0.0088 for catalytic wood heaters; = 0.0132 for noncatalytic wood 
heaters. = 0.0080 for pellet-fired wood heaters.
YCO = Measured mole fraction of CO (e.g., 1 percent CO = .01 
mole fraction), g/g-mole (lb/lb-mole).
YCO2 = Measured mole fraction of COCO2 (e.g., 10 
percent CO2 = .10 mole fraction), g/g-mole (lb/lb-mole).
0.280 = Molecular weight of N2 or CO, divided by 100.
0.320 = Molecular weight of O2 divided by 100.
0.440 = Molecular weight of CO2 divided by 100.
20.9 = Percent O2 by volume in ambient air.
42.5 = Gram-moles of carbon in 1 kg of dry wood assuming 51 percent 
carbon by weight dry basis (.0425 lb/lb-mole).
510 = Grams of carbon in exhaust gas per kg of wood burned.
1,000 = Grams in 1 kg.

    12.2  Fuel Factor. Use Equation 28A-1 to calculate the fuel factor.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.433
    
    12. 3  Adjusted %CO2. Use Equation 28A-2 to adjust 
CO2 values if measurable CO is present.
[GRAPHIC] [TIFF OMITTED] TR17OC00.434


[[Page 62113]]


    12.4  Adjusted %O2. Use Equation 28A-3 to adjust 
O2 value if measurable CO is present.
[GRAPHIC] [TIFF OMITTED] TR17OC00.435

    12.5  Dry Molecular Weight. Use Equation 28A-4 to calculate the dry 
molecular weight of the stack gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.436


    Note: The above equation does not consider argon in air (about 
0.9 percent, molecular weight of 39.9). A negative error of about 
0.4 percent is introduced. Argon may be included in the analysis 
using procedures subject to approval of the Administrator.


    12.6  Dry Moles of Exhaust Gas. Use Equation 28A-5 to calculate the 
total moles of dry exhaust gas produced per kilogram of dry wood 
burned.
[GRAPHIC] [TIFF OMITTED] TR17OC00.437

    12.7  Air-to-Fuel Ratio. Use Equation 28A-6 to calculate the air-
to-fuel ratio on a dry mass basis.
[GRAPHIC] [TIFF OMITTED] TR17OC00.438

    12.8  Burn Rate. Calculate the fuel burn rate as in Method 28, 
Section 12.4.

13.0  Method Performance, [Reserved]

14.0  Pollution Prevention, [Reserved]

15.0  Waste Management, [Reserved]

16.0  References

    Same as Section 16.0 of Method 3 and Section 17 of Method 5G.

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

Method 29--Determination of Metals Emissions From Stationary 
Sources

    Note: This method does not include all of the specifications 
(e.g. equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in this part. 
Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of at least the following 
additional test methods: Method 5 and Method 12.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
                         Analyte                              CAS No.
------------------------------------------------------------------------
Antimony (Sb)...........................................       7440-36-0
Arsenic (As)............................................       7440-38-2
Barium (Ba).............................................       7440-39-3
Beryllium (Be)..........................................       7440-41-7
Cadmium (Cd)............................................       7440-43-9
Chromium (Cr)...........................................       7440-47-3
Cobalt (Co).............................................       7440-48-4
Copper (Cu).............................................       7440-50-8
Lead (Pb)...............................................       7439-92-1
Manganese (Mn)..........................................       7439-96-5
Mercury (Hg)............................................       7439-97-6
Nickel (Ni).............................................       7440-02-0
Phosphorus (P)..........................................       7723-14-0
Selenium (Se)...........................................       7782-49-2
Silver (Ag).............................................       7440-22-4
Thallium (Tl)...........................................       7440-28-0
Zinc (Zn)...............................................       7440-66-6
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable to the determination 
of metals emissions from stationary sources. This method may be used to 
determine particulate emissions in addition to the metals emissions if 
the prescribed procedures and precautions are followed.
    1.2.1  Hg emissions can be measured, alternatively, using EPA 
Method 101A of Appendix B, 40 CFR Part 61. Method 101-A measures only 
Hg but it can be of special interest to sources which need to measure 
both Hg and Mn emissions.

2.0  Summary of Method

    2.1  Principle. A stack sample is withdrawn isokinetically from the 
source, particulate emissions are collected in the probe and on a 
heated filter, and gaseous emissions are then collected in an aqueous 
acidic solution of hydrogen peroxide (analyzed for all metals including 
Hg) and an aqueous acidic solution of potassium permanganate (analyzed 
only for Hg). The recovered samples are digested, and appropriate 
fractions are analyzed for Hg by cold vapor atomic absorption 
spectroscopy (CVAAS) and for Sb, As, Ba, Be, Cd, Cr, Co, Cu, Pb, Mn, 
Ni, P, Se, Ag, Tl, and Zn by inductively coupled argon plasma emission 
spectroscopy (ICAP) or atomic absorption spectroscopy (AAS). Graphite 
furnace atomic absorption spectroscopy (GFAAS) is used for analysis of 
Sb, As, Cd, Co, Pb, Se, and Tl if these elements require greater 
analytical sensitivity than can be obtained by ICAP. If one so chooses, 
AAS may be used for analysis of all listed metals if the resulting in-
stack method detection limits meet the goal of the testing program. 
Similarly, inductively coupled plasma-mass spectroscopy (ICP-MS) may be 
used for analysis of Sb, As, Ba, Be, Cd, Cr, Co, Cu, Pb, Mn, Ni, Ag, Tl 
and Zn.

3.0  Definitions. [Reserved]

4.0  Interferences

    4.1  Iron (Fe) can be a spectral interference during the analysis 
of As, Cr, and Cd by ICAP. Aluminum (Al) can be a spectral interference 
during the analysis of As and Pb by ICAP. Generally, these 
interferences can be reduced by diluting the analytical sample, but 
such dilution raises the in-stack detection limits. Background and 
overlap corrections may be used to adjust for spectral interferences. 
Refer to Method 6010 of Reference 2 in Section 16.0 or the other 
analytical methods used for details on potential interferences to this 
method. For all GFAAS analyses, use matrix modifiers to limit 
interferences, and matrix match all standards.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and to determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Corrosive Reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing

[[Page 62114]]

chemical splashes. If contact occurs, immediately flush with copious 
amounts of water at least 15 minutes. Remove clothing under shower and 
decontaminate. Treat residual chemical burn as thermal burn.
    5.2.1  Nitric Acid (HNO3). Highly corrosive to eyes, 
skin, nose, and lungs. Vapors cause bronchitis, pneumonia, or edema of 
lungs. Reaction to inhalation may be delayed as long as 30 hours and 
still be fatal. Provide ventilation to limit exposure. Strong oxidizer. 
Hazardous reaction may occur with organic materials such as solvents.
    5.2.2  Sulfuric Acid (H2SO4). Rapidly 
destructive to body tissue. Will cause third degree burns. Eye damage 
may result in blindness. Inhalation may be fatal from spasm of the 
larynx, usually within 30 minutes. May cause lung tissue damage with 
edema. 1 mg/m\3\ for 8 hours will cause lung damage or, in higher 
concentrations, death. Provide ventilation to limit inhalation. Reacts 
violently with metals and organics.
    5.2.3  Hydrochloric Acid (HC1). Highly corrosive liquid with toxic 
vapors. Vapors are highly irritating to eyes, skin, nose, and lungs, 
causing severe damage. May cause bronchitis, pneumonia, or edema of 
lungs. Exposure to concentrations of 0.13 to 0.2 percent can be lethal 
to humans in a few minutes. Provide ventilation to limit exposure. 
Reacts with metals, producing hydrogen gas.
    5.2.4  Hydrofluoric Acid (HF). Highly corrosive to eyes, skin, 
nose, throat, and lungs. Reaction to exposure may be delayed by 24 
hours or more. Provide ventilation to limit exposure.
    5.2.5  Hydrogen Peroxide (H2O2). Irritating 
to eyes, skin, nose, and lungs. 30% H2O2 is a 
strong oxidizing agent. Avoid contact with skin, eyes, and combustible 
material. Wear gloves when handling.
    5.2.6  Potassium Permanganate (KMnO4). Caustic, strong 
oxidizer. Avoid bodily contact with.
    5.2.7  Potassium Persulfate. Strong oxidizer. Avoid bodily contact 
with. Keep containers well closed and in a cool place.
    5.3  Reaction Pressure. Due to the potential reaction of the 
potassium permanganate with the acid, there could be pressure buildup 
in the acidic KMnO4 absorbing solution storage bottle. 
Therefore these bottles shall not be fully filled and shall be vented 
to relieve excess pressure and prevent explosion potentials. Venting is 
required, but not in a manner that will allow contamination of the 
solution. A No. 70-72 hole drilled in the container cap and Teflon 
liner has been used.

6.0  Equipment and Supplies

    6.1  Sampling. A schematic of the sampling train is shown in Figure 
29-1. It has general similarities to the Method 5 train.
    6.1.1  Probe Nozzle (Probe Tip) and Borosilicate or Quartz Glass 
Probe Liner. Same as Method 5, Sections 6.1.1.1 and 6.1.1.2, except 
that glass nozzles are required unless alternate tips are constructed 
of materials that are free from contamination and will not interfere 
with the sample. If a probe tip other than glass is used, no correction 
to the sample test results to compensate for the nozzle's effect on the 
sample is allowed. Probe fittings of plastic such as Teflon, 
polypropylene, etc. are recommended instead of metal fittings to 
prevent contamination. If one chooses to do so, a single glass piece 
consisting of a combined probe tip and probe liner may be used.
    6.1.2  Pitot Tube and Differential Pressure Gauge. Same as Method 
2, Sections 6.1 and 6.2, respectively.
    6.1.3  Filter Holder. Glass, same as Method 5, Section 6.1.1.5, 
except use a Teflon filter support or other non-metallic, non-
contaminating support in place of the glass frit.
    6.1.4  Filter Heating System. Same as Method 5, Section 6.1.1.6.
    6.1.5  Condenser. Use the following system for condensing and 
collecting gaseous metals and determining the moisture content of the 
stack gas. The condensing system shall consist of four to seven 
impingers connected in series with leak-free ground glass fittings or 
other leak-free, non-contaminating fittings. Use the first impinger as 
a moisture trap. The second impinger (which is the first 
HNO3/H2O2 impinger) shall be identical 
to the first impinger in Method 5. The third impinger (which is the 
second HNO3/H2O2 impinger) shall be a 
Greenburg Smith impinger with the standard tip as described for the 
second impinger in Method 5, Section 6.1.1.8. The fourth (empty) 
impinger and the fifth and sixth (both acidified KMnO4) 
impingers are the same as the first impinger in Method 5. Place a 
temperature sensor capable of measuring to within 1  deg.C (2  deg.F) 
at the outlet of the last impinger. If no Hg analysis is planned, then 
the fourth, fifth, and sixth impingers are not used.
    6.1.6  Metering System, Barometer, and Gas Density Determination 
Equipment. Same as Method 5, Sections 6.1.1.9, 6.1.2, and 6.1.3, 
respectively.
    6.1.7  Teflon Tape. For capping openings and sealing connections, 
if necessary, on the sampling train.
    6.2  Sample Recovery. Same as Method 5, Sections 6.2.1 through 
6.2.8 (Probe-Liner and Probe-Nozzle Brushes or Swabs, Wash Bottles, 
Sample Storage Containers, Petri Dishes, Glass Graduated Cylinder, 
Plastic Storage Containers, Funnel and Rubber Policeman, and Glass 
Funnel), respectively, with the following exceptions and additions:
    6.2.1  Non-metallic Probe-Liner and Probe-Nozzle Brushes or Swabs. 
Use non-metallic probe-liner and probe-nozzle brushes or swabs for 
quantitative recovery of materials collected in the front-half of the 
sampling train.
    6.2.2  Sample Storage Containers. Use glass bottles (see Section 
8.1 of this Method) with Teflon-lined caps that are non-reactive to the 
oxidizing solutions, with capacities of 1000- and 500-ml, for storage 
of acidified KMnO4--containing samples and blanks. Glass or 
polyethylene bottles may be used for other sample types.
    6.2.3  Graduated Cylinder. Glass or equivalent.
    6.2.4  Funnel. Glass or equivalent.
    6.2.5  Labels. For identifying samples.
    6.2.6  Polypropylene Tweezers and/or Plastic Gloves. For recovery 
of the filter from the sampling train filter holder.
    6.3  Sample Preparation and Analysis.
    6.3.1  Volumetric Flasks, 100-ml, 250-ml, and 1000-ml. For 
preparation of standards and sample dilutions.
    6.3.2  Graduated Cylinders. For preparation of reagents.
    6.3.3  Parr Bombs or Microwave Pressure Relief Vessels with Capping 
Station (CEM Corporation model or equivalent). For sample digestion.
    6.3.4  Beakers and Watch Glasses. 250-ml beakers, with watch glass 
covers, for sample digestion.
    6.3.5  Ring Stands and Clamps. For securing equipment such as 
filtration apparatus.
    6.3.6  Filter Funnels. For holding filter paper.
    6.3.7  Disposable Pasteur Pipets and Bulbs.
    6.3.8  Volumetric Pipets.
    6.3.9  Analytical Balance. Accurate to within 0.1 mg.
    6.3.10  Microwave or Conventional Oven. For heating samples at 
fixed power levels or temperatures, respectively.
    6.3.11  Hot Plates.
    6.3.12  Atomic Absorption Spectrometer (AAS). Equipped with a 
background corrector.
    6.3.12.1  Graphite Furnace Attachment. With Sb, As, Cd, Co, Pb, Se, 
and Tl hollow cathode lamps (HCLs) or electrodeless discharge lamps 
(EDLs). Same as Reference 2 in Section 16.0.

[[Page 62115]]

Methods 7041 (Sb), 7060 (As), 7131 (Cd), 7201 (Co), 7421 (Pb), 7740 
(Se), and 7841 (Tl).
    6.3.12.2  Cold Vapor Mercury Attachment. With a mercury HCL or EDL, 
an air recirculation pump, a quartz cell, an aerator apparatus, and a 
heat lamp or desiccator tube. The heat lamp shall be capable of raising 
the temperature at the quartz cell by 10 deg.C above ambient, so that 
no condensation forms on the wall of the quartz cell. Same as Method 
7470 in Reference 2 in Section 16.0. See Note 2: Section 11.1.3 for 
other acceptable approaches for analysis of Hg in which analytical 
detection limits of 0.002 ng/ml were obtained.
    6.3.13  Inductively Coupled Argon Plasma Spectrometer. With either 
a direct or sequential reader and an alumina torch. Same as EPA Method 
6010 in Reference 2 in Section 16.0.
    6.3.14  Inductively Coupled Plasma-Mass Spectrometer.
    Same as EPA Method 6020 in Reference 2 in Section 16.0.

7.0  Reagents and Standards

    7.1  Unless otherwise indicated, it is intended that all reagents 
conform to the specifications established by the Committee on 
Analytical Reagents of the American Chemical Society, where such 
specifications are available. Otherwise, use the best available grade.
    7.2  Sampling Reagents.
    7.2.1  Sample Filters. Without organic binders. The filters shall 
contain less than 1.3 g/in.\2\ of each of the metals to be 
measured. Analytical results provided by filter manufacturers stating 
metals content of the filters are acceptable. However, if no such 
results are available, analyze filter blanks for each target metal 
prior to emission testing. Quartz fiber filters meeting these 
requirements are recommended. However, if glass fiber filters become 
available which meet these requirements, they may be used. Filter 
efficiencies and unreactiveness to sulfur dioxide (SO2) or 
sulfur trioxide (SO3) shall be as described in Section 7.1.1 
of Method 5.
    7.2.2  Water. To conform to ASTM Specification D1193-77 or 91, Type 
II (incorporated by reference--see Sec. 60.17). If necessary, analyze 
the water for all target metals prior to field use. All target metals 
should be less than 1 ng/ml.
    7.2.3  HNO3, Concentrated. Baker Instra-analyzed or 
equivalent.
    7.2.4  HCl, Concentrated. Baker Instra-analyzed or equivalent.
    7.2.5  H2O2, 30 Percent (V/V).
    7.2.6  KMnO4.
    7.2.7  H2SO4, Concentrated.
    7.2.8  Silica Gel and Crushed Ice. Same as Method 5, Sections 7.1.2 
and 7.1.4, respectively.
    7.3  Pretest Preparation of Sampling Reagents.
    7.3.1  HNO3/H2O2 Absorbing 
Solution, 5 Percent HNO3/10 Percent 
H2O2. Add carefully with stirring 50 ml of 
concentrated HNO3 to a 1000-ml volumetric flask containing 
approximately 500 ml of water, and then add carefully with stirring 333 
ml of 30 percent H2O2. Dilute to volume with 
water. Mix well. This reagent shall contain less than 2 ng/ml of each 
target metal.
    7.3.2  Acidic KMnO4 Absorbing Solution, 4 Percent 
KMnO4 (W/V), 10 Percent H2SO4 (V/V). 
Prepare fresh daily. Mix carefully, with stirring, 100 ml of 
concentrated H2SO4 into approximately 800 ml of 
water, and add water with stirring to make a volume of 1 liter: this 
solution is 10 percent H2SO4 (V/V). Dissolve, 
with stirring, 40 g of KMnO4 into 10 percent 
H2SO4 (V/V) and add 10 percent 
H2SO4 (V/V) with stirring to make a volume of 1 
liter. Prepare and store in glass bottles to prevent degradation. This 
reagent shall contain less than 2 ng/ml of Hg.
    Precaution: To prevent autocatalytic decomposition of the 
permanganate solution, filter the solution through Whatman 541 filter 
paper.
    7.3.3  HNO3, 0.1 N. Add with stirring 6.3 ml of 
concentrated HNO3 (70 percent) to a flask containing 
approximately 900 ml of water. Dilute to 1000 ml with water. Mix well. 
This reagent shall contain less than 2 ng/ml of each target metal.
    7.3.4  HCl, 8 N. Carefully add with stirring 690 ml of concentrated 
HCl to a flask containing 250 ml of water. Dilute to 1000 ml with 
water. Mix well. This reagent shall contain less than 2 ng/ml of Hg.
    7.4  Glassware Cleaning Reagents.
    7.4.1  HNO3, Concentrated. Fisher ACS grade or 
equivalent.
    7.4.2  Water. To conform to ASTM Specifications D1193, Type II.
    7.4.3  HNO3, 10 Percent (V/V). Add with stirring 500 ml 
of concentrated HNO3 to a flask containing approximately 
4000 ml of water. Dilute to 5000 ml with water. Mix well. This reagent 
shall contain less than 2 ng/ml of each target metal.
    7.5  Sample Digestion and Analysis Reagents. The metals standards, 
except Hg, may also be made from solid chemicals as described in 
Reference 3 in Section 16.0. Refer to References 1, 2, or 5 in Section 
16.0 for additional information on Hg standards. The 1000 g/ml 
Hg stock solution standard may be made according to Section 7.2.7 of 
Method 101A.
    7.5.1  HCl, Concentrated.
    7.5.2  HF, Concentrated.
    7.5.3  HNO3, Concentrated. Baker Instra-analyzed or 
equivalent.
    7.5.4  HNO3, 50 Percent (V/V). Add with stirring 125 ml 
of concentrated HNO3 to 100 ml of water. Dilute to 250 ml 
with water. Mix well. This reagent shall contain less than 2 ng/ml of 
each target metal.
    7.5.5  HNO3, 5 Percent (V/V). Add with stirring 50 ml of 
concentrated HNO3 to 800 ml of water. Dilute to 1000 ml with 
water. Mix well. This reagent shall contain less than 2 ng/ml of each 
target metal.
    7.5.6  Water. To conform to ASTM Specifications D1193, Type II.
    7.5.7  Hydroxylamine Hydrochloride and Sodium Chloride Solution. 
See Reference 2 In Section 16.0 for preparation.
    7.5.8  Stannous Chloride. See Reference 2 in Section 16.0 for 
preparation.
    7.5.9  KMnO4, 5 Percent (W/V). See Reference 2 in 
Section 16.0 for preparation.
    7.5.10  H2SO4, Concentrated.
    7.5.11  Potassium Persulfate, 5 Percent (W/V). See Reference 2 in 
Section 16.0 for preparation.
    7.5.12  Nickel Nitrate, Ni(N03) 2 
6H20.
    7.5.13  Lanthanum Oxide, La203.
    7.5.14  Hg Standard (AAS Grade), 1000 g/ml.
    7.5.15  Pb Standard (AAS Grade), 1000 g/ml.
    7.5.16  As Standard (AAS Grade), 1000 g/ml.
    7.5.17  Cd Standard (AAS Grade), 1000 g/ml.
    7.5.18  Cr Standard (AAS Grade), 1000 g/ml.
    7.5.19  Sb Standard (AAS Grade), 1000 g/ml.
    7.5.20  Ba Standard (AAS Grade), 1000 g/ml.
    7.5.21  Be Standard (AAS Grade), 1000 g/ml.
    7.5.22  Co Standard (AAS Grade), 1000 g/ml.
    7.5.23  Cu Standard (AAS Grade), 1000 g/ml.
    7.5.24  Mn Standard (AAS Grade), 1000 g/ml.
    7.5.25  Ni Standard (AAS Grade), 1000 g/ml.
    7.5.26  P Standard (AAS Grade), 1000 g/ml.
    7.5.27  Se Standard (AAS Grade), 1000 g/ml.
    7.5.28  Ag Standard (AAS Grade), 1000 g/ml.
    7.5.29  Tl Standard (AAS Grade), 1000 g/ml.

[[Page 62116]]

    7.5.30  Zn Standard (AAS Grade), 1000 g/ml.
    7.5.31  Al Standard (AAS Grade), 1000 g/ml.
    7.5.32  Fe Standard (AAS Grade), 1000 g/ml.
    7.5.33  Hg Standards and Quality Control Samples. Prepare fresh 
weekly a 10 g/ml intermediate Hg standard by adding 5 ml of 
1000 g/ml Hg stock solution prepared according to Method 101A 
to a 500-ml volumetric flask; dilute with stirring to 500 ml by first 
carefully adding 20 ml of 15 percent HNO3 and then adding 
water to the 500-ml volume. Mix well. Prepare a 200 ng/ml working Hg 
standard solution fresh daily: add 5 ml of the 10 g/ml 
intermediate standard to a 250-ml volumetric flask, and dilute to 250 
ml with 5 ml of 4 percent KMnO4, 5 ml of 15 percent 
HNO3, and then water. Mix well. Use at least five separate 
aliquots of the working Hg standard solution and a blank to prepare the 
standard curve. These aliquots and blank shall contain 0.0, 1.0, 2.0, 
3.0, 4.0, and 5.0 ml of the working standard solution containing 0, 
200, 400, 600, 800, and 1000 ng Hg, respectively. Prepare quality 
control samples by making a separate 10 g/ml standard and 
diluting until in the calibration range.
    7.5.34  ICAP Standards and Quality Control Samples. Calibration 
standards for ICAP analysis can be combined into four different mixed 
standard solutions as follows:

               Mixed Standard Solutions for ICAP Analysis
------------------------------------------------------------------------
             Solution                             Elements
------------------------------------------------------------------------
I.................................  As, Be, Cd, Mn, Pb, Se, Zn.
II................................  Ba, Co, Cu, Fe.
III...............................  Al, Cr, Ni.
IV................................  Ag, P, Sb, Tl.
------------------------------------------------------------------------

    Prepare these standards by combining and diluting the appropriate 
volumes of the 1000 g/ml solutions with 5 percent 
HNO3. A minimum of one standard and a blank can be used to 
form each calibration curve. However, prepare a separate quality 
control sample spiked with known amounts of the target metals in 
quantities in the mid-range of the calibration curve. Suggested 
standard levels are 25 g/ml for Al, Cr and Pb, 15 g/
ml for Fe, and 10 g/ml for the remaining elements. Prepare any 
standards containing less than 1 g/ml of metal on a daily 
basis. Standards containing greater than 1 g/ml of metal 
should be stable for a minimum of 1 to 2 weeks. For ICP-MS, follow 
Method 6020 in EPA Publication SW-846 Third Edition (November 1986) 
including updates I, II, IIA, IIB and III, as incorporated by reference 
in Sec. 60.17(i).
    7.5.35  GFAAS Standards. Sb, As, Cd, Co, Pb, Se, and Tl. Prepare a 
10 g/ml standard by adding 1 ml of 1000 g/ml standard 
to a 100-ml volumetric flask. Dilute with stirring to 100 ml with 10 
percent HNO3. For GFAAS, matrix match the standards. Prepare 
a 100 ng/ml standard by adding 1 ml of the 10 g/ml standard to 
a 100-ml volumetric flask, and dilute to 100 ml with the appropriate 
matrix solution. Prepare other standards by diluting the 100 ng/ml 
standards. Use at least five standards to make up the standard curve. 
Suggested levels are 0, 10, 50, 75, and 100 ng/ml. Prepare quality 
control samples by making a separate 10 g/ml standard and 
diluting until it is in the range of the samples. Prepare any standards 
containing less than 1 g/ml of metal on a daily basis. 
Standards containing greater than 1 g/ml of metal should be 
stable for a minimum of 1 to 2 weeks.
    7.5.36  Matrix Modifiers.
    7.5.36.1  Nickel Nitrate, 1 Percent (V/V). Dissolve 4.956 g of 
Ni(N03)26H20 or other nickel 
compound suitable for preparation of this matrix modifier in 
approximately 50 ml of water in a 100-ml volumetric flask. Dilute to 
100 ml with water.
    7.5.36.2  Nickel Nitrate, 0.1 Percent (V/V). Dilute 10 ml of 1 
percent nickel nitrate solution to 100 ml with water. Inject an equal 
amount of sample and this modifier into the graphite furnace during 
GFAAS analysis for As.
    7.5.36.3  Lanthanum. Carefully dissolve 0.5864 g of 
La203 in 10 ml of concentrated HN03, 
and dilute the solution by adding it with stirring to approximately 50 
ml of water. Dilute to 100 ml with water, and mix well. Inject an equal 
amount of sample and this modifier into the graphite furnace during 
GFAAS analysis for Pb.
    7.5.37  Whatman 40 and 541 Filter Papers (or equivalent). For 
filtration of digested samples.

8.0  Sample Collection, Preservation, Transport, and Storage

    8.1  Sampling. The complexity of this method is such that, to 
obtain reliable results, both testers and analysts must be trained and 
experienced with the test procedures, including source sampling; 
reagent preparation and handling; sample handling; safety equipment and 
procedures; analytical calculations; reporting; and the specific 
procedural descriptions throughout this method.
    8.1.1  Pretest Preparation. Follow the same general procedure given 
in Method 5, Section 8.1, except that, unless particulate emissions are 
to be determined, the filter need not be desiccated or weighed. First, 
rinse all sampling train glassware with hot tap water and then wash in 
hot soapy water. Next, rinse glassware three times with tap water, 
followed by three additional rinses with water. Then soak all glassware 
in a 10 percent (V/V) nitric acid solution for a minimum of 4 hours, 
rinse three times with water, rinse a final time with acetone, and 
allow to air dry. Cover all glassware openings where contamination can 
occur until the sampling train is assembled for sampling.
    8.1.2  Preliminary Determinations. Same as Method 5, Section 8.1.2.
    8.1.3  Preparation of Sampling Train.
    8.1.3.1  Set up the sampling train as shown in Figure 29-1. Follow 
the same general procedures given in Method 5, Section 8.3, except 
place 100 ml of the HNO3/H2O2 solution 
(Section 7.3.1 of this method) in each of the second and third 
impingers as shown in Figure 29-1. Place 100 ml of the acidic 
KMnO4 absorbing solution (Section 7.3.2 of this method) in 
each of the fifth and sixth impingers as shown in Figure 29-1, and 
transfer approximately 200 to 300 g of pre-weighed silica gel from its 
container to the last impinger. Alternatively, the silica gel may be 
weighed directly in the impinger just prior to final train assembly.
    8.1.3.2  Based on the specific source sampling conditions, the use 
of an empty first impinger can be eliminated if the moisture to be 
collected in the impingers will be less than approximately 100 ml.
    8.1.3.3  If Hg analysis will not be performed, the fourth, fifth, 
and sixth impingers as shown in Figure 29-1 are not required.
    8.1.3.4  To insure leak-free sampling train connections and to 
prevent possible sample contamination problems, use Teflon tape or 
other non-contaminating material instead of silicone grease.
    Precaution: Exercise extreme care to prevent contamination within 
the train. Prevent the acidic KMnO4 from contacting any 
glassware that contains sample material to be analyzed for Mn. Prevent 
acidic H2O2 from mixing with the acidic 
KMnO4.
    8.1.4  Leak-Check Procedures. Follow the leak-check procedures 
given in Method 5, Section 8.4.2 (Pretest Leak-Check), Section 8.4.3 
(Leak-Checks During the Sample Run), and Section 8.4.4 (Post-Test Leak-
Checks).
    8.1.5  Sampling Train Operation. Follow the procedures given in 
Method 5, Section 8.5. When sampling for Hg, use a procedure analogous 
to that

[[Page 62117]]

described in Section 8.1 of Method 101A, 40 CFR Part 61, Appendix B, if 
necessary to maintain the desired color in the last acidified 
permanganate impinger. For each run, record the data required on a data 
sheet such as the one shown in Figure 5-3 of Method 5.
    8.1.6  Calculation of Percent Isokinetic. Same as Method 5, Section 
12.11.
    8.2  Sample Recovery.
    8.2.1  Begin cleanup procedures as soon as the probe is removed 
from the stack at the end of a sampling period. The probe should be 
allowed to cool prior to sample recovery. When it can be safely 
handled, wipe off all external particulate matter near the tip of the 
probe nozzle and place a rinsed, non-contaminating cap over the probe 
nozzle to prevent losing or gaining particulate matter. Do not cap the 
probe tip tightly while the sampling train is cooling; a vacuum can 
form in the filter holder with the undesired result of drawing liquid 
from the impingers onto the filter.
    8.2.2  Before moving the sampling train to the cleanup site, remove 
the probe from the sampling train and cap the open outlet. Be careful 
not to lose any condensate that might be present. Cap the filter inlet 
where the probe was fastened. Remove the umbilical cord from the last 
impinger and cap the impinger. Cap the filter holder outlet and 
impinger inlet. Use non-contaminating caps, whether ground-glass 
stoppers, plastic caps, serum caps, or Teflon tape to close 
these openings.
    8.2.3  Alternatively, the following procedure may be used to 
disassemble the train before the probe and filter holder/oven are 
completely cooled: Initially disconnect the filter holder outlet/
impinger inlet and loosely cap the open ends. Then disconnect the probe 
from the filter holder or cyclone inlet and loosely cap the open ends. 
Cap the probe tip and remove the umbilical cord as previously 
described.
    8.2.4  Transfer the probe and filter-impinger assembly to a cleanup 
area that is clean and protected from the wind and other potential 
causes of contamination or loss of sample. Inspect the train before and 
during disassembly and note any abnormal conditions. Take special 
precautions to assure that all the items necessary for recovery do not 
contaminate the samples. The sample is recovered and treated as follows 
(see schematic in Figures 29-2a and 29-2b):
    8.2.5  Container No. 1 (Sample Filter). Carefully remove the filter 
from the filter holder and place it in its labeled petri dish 
container. To handle the filter, use either acid-washed polypropylene 
or Teflon coated tweezers or clean, disposable surgical gloves rinsed 
with water and dried. If it is necessary to fold the filter, make 
certain the particulate cake is inside the fold. Carefully transfer the 
filter and any particulate matter or filter fibers that adhere to the 
filter holder gasket to the petri dish by using a dry (acid-cleaned) 
nylon bristle brush. Do not use any metal-containing materials when 
recovering this train. Seal the labeled petri dish.
    8.2.6  Container No. 2 (Acetone Rinse). Perform this procedure only 
if a determination of particulate emissions is to be made. 
Quantitatively recover particulate matter and any condensate from the 
probe nozzle, probe fitting, probe liner, and front half of the filter 
holder by washing these components with a total of 100 ml of acetone, 
while simultaneously taking great care to see that no dust on the 
outside of the probe or other surfaces gets in the sample. The use of 
exactly 100 ml is necessary for the subsequent blank correction 
procedures. Distilled water may be used instead of acetone when 
approved by the Administrator and shall be used when specified by the 
Administrator; in these cases, save a water blank and follow the 
Administrator's directions on analysis.
    8.2.6.1  Carefully remove the probe nozzle, and clean the inside 
surface by rinsing with acetone from a wash bottle while brushing with 
a non-metallic brush. Brush until the acetone rinse shows no visible 
particles, then make a final rinse of the inside surface with acetone.
    8.2.6.2  Brush and rinse the sample exposed inside parts of the 
probe fitting with acetone in a similar way until no visible particles 
remain. Rinse the probe liner with acetone by tilting and rotating the 
probe while squirting acetone into its upper end so that all inside 
surfaces will be wetted with acetone. Allow the acetone to drain from 
the lower end into the sample container. A funnel may be used to aid in 
transferring liquid washings to the container. Follow the acetone rinse 
with a non-metallic probe brush. Hold the probe in an inclined 
position, squirt acetone into the upper end as the probe brush is being 
pushed with a twisting action three times through the probe. Hold a 
sample container underneath the lower end of the probe, and catch any 
acetone and particulate matter which is brushed through the probe until 
no visible particulate matter is carried out with the acetone or until 
none remains in the probe liner on visual inspection. Rinse the brush 
with acetone, and quantitatively collect these washings in the sample 
container. After the brushing, make a final acetone rinse of the probe 
as described above.
    8.2.6.3  It is recommended that two people clean the probe to 
minimize sample losses. Between sampling runs, keep brushes clean and 
protected from contamination. Clean the inside of the front-half of the 
filter holder by rubbing the surfaces with a non-metallic brush and 
rinsing with acetone. Rinse each surface three times or more if needed 
to remove visible particulate. Make a final rinse of the brush and 
filter holder. After all acetone washings and particulate matter have 
been collected in the sample container, tighten the lid so that acetone 
will not leak out when shipped to the laboratory. Mark the height of 
the fluid level to determine whether or not leakage occurred during 
transport. Clearly label the container to identify its contents.
    8.2.7  Container No. 3 (Probe Rinse). Keep the probe assembly clean 
and free from contamination during the probe rinse. Rinse the probe 
nozzle and fitting, probe liner, and front-half of the filter holder 
thoroughly with a total of 100 ml of 0.1 N HNO3, and place 
the wash into a sample storage container. Perform the rinses as 
applicable and generally as described in Method 12, Section 8.7.1. 
Record the volume of the rinses. Mark the height of the fluid level on 
the outside of the storage container and use this mark to determine if 
leakage occurs during transport. Seal the container, and clearly label 
the contents. Finally, rinse the nozzle, probe liner, and front-half of 
the filter holder with water followed by acetone, and discard these 
rinses.


    Note: The use of a total of exactly 100 ml is necessary for the 
subsequent blank correction procedures.

    8.2.8  Container No. 4 (Impingers 1 through 3, Moisture Knockout 
Impinger, when used, HNO3/H2O2 
Impingers Contents and Rinses). Due to the potentially large quantity 
of liquid involved, the tester may place the impinger solutions from 
impingers 1 through 3 in more than one container, if necessary. Measure 
the liquid in the first three impingers to within 0.5 ml using a 
graduated cylinder. Record the volume. This information is required to 
calculate the moisture content of the sampled flue gas. Clean each of 
the first three impingers, the filter support, the back half of the 
filter housing, and connecting glassware by thoroughly rinsing with 100 
ml of 0.1 N HNO3 using the procedure as applicable in Method 
12, Section 8.7.3.


    Note: The use of exactly 100 ml of 0.1 N HNO3 rinse 
is necessary for the subsequent blank correction procedures. Combine 
the rinses and impinger solutions, measure and

[[Page 62118]]

record the final total volume. Mark the height of the fluid level, 
seal the container, and clearly label the contents.


    8.2.9  Container Nos. 5A (0.1 N HNO3), 5B 
(KMnO4/H2SO4 absorbing solution), and 
5C (8 N HCl rinse and dilution).
    8.2.9.1  When sampling for Hg, pour all the liquid from the 
impinger (normally impinger No. 4) that immediately preceded the two 
permanganate impingers into a graduated cylinder and measure the volume 
to within 0.5 ml. This information is required to calculate the 
moisture content of the sampled flue gas. Place the liquid in Container 
No. 5A. Rinse the impinger with exactly 100 ml of 0.1 N HNO3 
and place this rinse in Container No. 5A.
    8.2.9.2  Pour all the liquid from the two permanganate impingers 
into a graduated cylinder and measure the volume to within 0.5 ml. This 
information is required to calculate the moisture content of the 
sampled flue gas. Place this acidic KMnO4 solution into 
Container No. 5B. Using a total of exactly 100 ml of fresh acidified 
KMnO4 solution for all rinses (approximately 33 ml per 
rinse), rinse the two permanganate impingers and connecting glassware a 
minimum of three times. Pour the rinses into Container No. 5B, 
carefully assuring transfer of all loose precipitated materials from 
the two impingers. Similarly, using 100 ml total of water, rinse the 
permanganate impingers and connecting glass a minimum of three times, 
and pour the rinses into Container 5B, carefully assuring transfer of 
any loose precipitated material. Mark the height of the fluid level, 
and clearly label the contents. Read the Precaution: in Section 7.3.2.


    Note: Due to the potential reaction of KMnO4 with 
acid, pressure buildup can occur in the sample storage bottles. Do 
not fill these bottles completely and take precautions to relieve 
excess pressure. A No. 70-72 hole drilled in the container cap and 
Teflon liner has been used successfully.


    8.2.9.3  If no visible deposits remain after the water rinse, no 
further rinse is necessary. However, if deposits remain on the impinger 
surfaces, wash them with 25 ml of 8 N HCl, and place the wash in a 
separate sample container labeled No. 5C containing 200 ml of water. 
First, place 200 ml of water in the container. Then wash the impinger 
walls and stem with the HCl by turning the impinger on its side and 
rotating it so that the HCl contacts all inside surfaces. Use a total 
of only 25 ml of 8 N HCl for rinsing both permanganate impingers 
combined. Rinse the first impinger, then pour the actual rinse used for 
the first impinger into the second impinger for its rinse. Finally, 
pour the 25 ml of 8 N HCl rinse carefully into the container. Mark the 
height of the fluid level on the outside of the container to determine 
if leakage occurs during transport.
    8.2.10  Container No. 6 (Silica Gel). Note the color of the 
indicating silica gel to determine whether it has been completely spent 
and make a notation of its condition. Transfer the silica gel from its 
impinger to its original container and seal it. The tester may use a 
funnel to pour the silica gel and a rubber policeman to remove the 
silica gel from the impinger. The small amount of particles that might 
adhere to the impinger wall need not be removed. Do not use water or 
other liquids to transfer the silica gel since weight gained in the 
silica gel impinger is used for moisture calculations. Alternatively, 
if a balance is available in the field, record the weight of the spent 
silica gel (or silica gel plus impinger) to the nearest 0.5 g.
    8.2.11  Container No. 7 (Acetone Blank). If particulate emissions 
are to be determined, at least once during each field test, place a 
100-ml portion of the acetone used in the sample recovery process into 
a container labeled No. 7. Seal the container.
    8.2.12  Container No. 8A (0.1 N HNO3 Blank). At least 
once during each field test, place 300 ml of the 0.1 N HNO3 
solution used in the sample recovery process into a container labeled 
No. 8A. Seal the container.
    8.2.13  Container No. 8B (Water Blank). At least once during each 
field test, place 100 ml of the water used in the sample recovery 
process into a container labeled No. 8B. Seal the container.
    8.2.14  Container No. 9 (5 Percent HNO3/10 Percent 
H2O2 Blank). At least once during each field 
test, place 200 ml of the 5 Percent HNO3/10 Percent 
H2O2 solution used as the nitric acid impinger 
reagent into a container labeled No. 9. Seal the container.
    8.2.15  Container No. 10 (Acidified KMnO4 Blank). At 
least once during each field test, place 100 ml of the acidified 
KMnO4 solution used as the impinger solution and in the 
sample recovery process into a container labeled No. 10. Prepare the 
container as described in Section 8.2.9.2. Read the Precaution: in 
Section 7.3.2 and read the NOTE in Section 8.2.9.2.
    8.2.16  Container No. 11 (8 N HCl Blank). At least once during each 
field test, place 200 ml of water into a sample container labeled No. 
11. Then carefully add with stirring 25 ml of 8 N HCl. Mix well and 
seal the container.
    8.2.17  Container No. 12 (Sample Filter Blank). Once during each 
field test, place into a petri dish labeled No. 12 three unused blank 
filters from the same lot as the sampling filters. Seal the petri dish.
    8.3  Sample Preparation. Note the level of the liquid in each of 
the containers and determine if any sample was lost during shipment. If 
a noticeable amount of leakage has occurred, either void the sample or 
use methods, subject to the approval of the Administrator, to correct 
the final results. A diagram illustrating sample preparation and 
analysis procedures for each of the sample train components is shown in 
Figure 29-3.
    8.3.1  Container No. 1 (Sample Filter).
    8.3.1.1  If particulate emissions are being determined, first 
desiccate the filter and filter catch without added heat (do not heat 
the filters to speed the drying) and weigh to a constant weight as 
described in Section 11.2.1 of Method 5.
    8.3.1.2  Following this procedure, or initially, if particulate 
emissions are not being determined in addition to metals analysis, 
divide the filter with its filter catch into portions containing 
approximately 0.5 g each. Place the pieces in the analyst's choice of 
either individual microwave pressure relief vessels or Parr Bombs. Add 
6 ml of concentrated HNO3 and 4 ml of concentrated HF to 
each vessel. For microwave heating, microwave the samples for 
approximately 12 to 15 minutes total heating time as follows: heat for 
2 to 3 minutes, then turn off the microwave for 2 to 3 minutes, then 
heat for 2 to 3 minutes, etc., continue this alternation until the 12 
to 15 minutes total heating time are completed (this procedure should 
comprise approximately 24 to 30 minutes at 600 watts). Microwave 
heating times are approximate and are dependent upon the number of 
samples being digested simultaneously. Sufficient heating is evidenced 
by sorbent reflux within the vessel. For conventional heating, heat the 
Parr Bombs at 140  deg.C (285  deg.F) for 6 hours. Then cool the 
samples to room temperature, and combine with the acid digested probe 
rinse as required in Section 8.3.3.
    8.3.1.3  If the sampling train includes an optional glass cyclone 
in front of the filter, prepare and digest the cyclone catch by the 
procedures described in Section 8.3.1.2 and then combine the digestate 
with the digested filter sample.
    8.3.2  Container No. 2 (Acetone Rinse). Note the level of liquid in 
the

[[Page 62119]]

container and confirm on the analysis sheet whether or not leakage 
occurred during transport. If a noticeable amount of leakage has 
occurred, either void the sample or use methods, subject to the 
approval of the Administrator, to correct the final results. Measure 
the liquid in this container either volumetrically within 1 ml or 
gravimetrically within 0.5 g. Transfer the contents to an acid-cleaned, 
tared 250-ml beaker and evaporate to dryness at ambient temperature and 
pressure. If particulate emissions are being determined, desiccate for 
24 hours without added heat, weigh to a constant weight according to 
the procedures described in Section 11.2.1 of Method 5, and report the 
results to the nearest 0.1 mg. Redissolve the residue with 10 ml of 
concentrated HNO3. Quantitatively combine the resultant 
sample, including all liquid and any particulate matter, with Container 
No. 3 before beginning Section 8.3.3.
    8.3.3  Container No. 3 (Probe Rinse). Verify that the pH of this 
sample is 2 or lower. If it is not, acidify the sample by careful 
addition with stirring of concentrated HNO3 to pH 2. Use 
water to rinse the sample into a beaker, and cover the beaker with a 
ribbed watch glass. Reduce the sample volume to approximately 20 ml by 
heating on a hot plate at a temperature just below boiling. Digest the 
sample in microwave vessels or Parr Bombs by quantitatively 
transferring the sample to the vessel or bomb, carefully adding the 6 
ml of concentrated HNO3, 4 ml of concentrated HF, and then 
continuing to follow the procedures described in Section 8.3.1.2. Then 
combine the resultant sample directly with the acid digested portions 
of the filter prepared previously in Section 8.3.1.2. The resultant 
combined sample is referred to as ``Sample Fraction 1''. Filter the 
combined sample using Whatman 541 filter paper. Dilute to 300 ml (or 
the appropriate volume for the expected metals concentration) with 
water. This diluted sample is ``Analytical Fraction 1''. Measure and 
record the volume of Analytical Fraction 1 to within 0.1 ml. 
Quantitatively remove a 50-ml aliquot and label as ``Analytical 
Fraction 1B''. Label the remaining 250-ml portion as ``Analytical 
Fraction 1A''. Analytical Fraction 1A is used for ICAP or AAS analysis 
for all desired metals except Hg. Analytical Fraction 1B is used for 
the determination of front-half Hg.
    8.3.4  Container No. 4 (Impingers 1-3). Measure and record the 
total volume of this sample to within 0.5 ml and label it ``Sample 
Fraction 2''. Remove a 75- to 100-ml aliquot for Hg analysis and label 
the aliquot ``Analytical Fraction 2B''. Label the remaining portion of 
Container No. 4 as ``Sample Fraction 2A''. Sample Fraction 2A defines 
the volume of Analytical Fraction 2A prior to digestion. All of Sample 
Fraction 2A is digested to produce ``Analytical Fraction 2A''. 
Analytical Fraction 2A defines the volume of Sample Fraction 2A after 
its digestion and the volume of Analytical Fraction 2A is normally 150 
ml. Analytical Fraction 2A is analyzed for all metals except Hg. Verify 
that the pH of Sample Fraction 2A is 2 or lower. If necessary, use 
concentrated HNO3 by careful addition and stirring to lower 
Sample Fraction 2A to pH 2. Use water to rinse Sample Fraction 2A into 
a beaker and then cover the beaker with a ribbed watchglass. Reduce 
Sample Fraction 2A to approximately 20 ml by heating on a hot plate at 
a temperature just below boiling. Then follow either of the digestion 
procedures described in Sections 8.3.4.1 or 8.3.4.2.
    8.3.4.1  Conventional Digestion Procedure. Add 30 ml of 50 percent 
HNO3, and heat for 30 minutes on a hot plate to just below 
boiling. Add 10 ml of 3 percent H2O2 and heat for 
10 more minutes. Add 50 ml of hot water, and heat the sample for an 
additional 20 minutes. Cool, filter the sample, and dilute to 150 ml 
(or the appropriate volume for the expected metals concentrations) with 
water. This dilution produces Analytical Fraction 2A. Measure and 
record the volume to within 0.1 ml.
    8.3.4.2  Microwave Digestion Procedure. Add 10 ml of 50 percent 
HNO3 and heat for 6 minutes total heating time in 
alternations of 1 to 2 minutes at 600 Watts followed by 1 to 2 minutes 
with no power, etc., similar to the procedure described in Section 
8.3.1. Allow the sample to cool. Add 10 ml of 3 percent 
H2O2 and heat for 2 more minutes. Add 50 ml of 
hot water, and heat for an additional 5 minutes. Cool, filter the 
sample, and dilute to 150 ml (or the appropriate volume for the 
expected metals concentrations) with water. This dilution produces 
Analytical Fraction 2A. Measure and record the volume to within 0.1 ml.


    Note: All microwave heating times given are approximate and are 
dependent upon the number of samples being digested at a time. 
Heating times as given above have been found acceptable for 
simultaneous digestion of up to 12 individual samples. Sufficient 
heating is evidenced by solvent reflux within the vessel.


    8.3.5  Container No. 5A (Impinger 4), Container Nos. 5B and 5C 
(Impingers 5 and 6). Keep the samples in Containers Nos. 5A, 5B, and 5C 
separate from each other. Measure and record the volume of 5A to within 
0.5 ml. Label the contents of Container No. 5A to be Analytical 
Fraction 3A. To remove any brown MnO2 precipitate from the 
contents of Container No. 5B, filter its contents through Whatman 40 
filter paper into a 500 ml volumetric flask and dilute to volume with 
water. Save the filter for digestion of the brown MnO2 
precipitate. Label the 500 ml filtrate from Container No. 5B to be 
Analytical Fraction 3B. Analyze Analytical Fraction 3B for Hg within 48 
hours of the filtration step. Place the saved filter, which was used to 
remove the brown MnO2 precipitate, into an appropriately 
sized vented container, which will allow release of any gases including 
chlorine formed when the filter is digested. In a laboratory hood which 
will remove any gas produced by the digestion of the MnO2, 
add 25 ml of 8 N HCl to the filter and allow to digest for a minimum of 
24 hours at room temperature. Filter the contents of Container No. 5C 
through a Whatman 40 filter into a 500-ml volumetric flask. Then filter 
the result of the digestion of the brown MnO2 from Container 
No. 5B through a Whatman 40 filter into the same 500-ml volumetric 
flask, and dilute and mix well to volume with water. Discard the 
Whatman 40 filter. Mark this combined 500-ml dilute HCl solution as 
Analytical Fraction 3C.
    8.3.6  Container No. 6 (Silica Gel). Weigh the spent silica gel (or 
silica gel plus impinger) to the nearest 0.5 g using a balance.

9.0  Quality Control

    9.1  Field Reagent Blanks, if analyzed. Perform the digestion and 
analysis of the blanks in Container Nos. 7 through 12 that were 
produced in Sections 8.2.11 through 8.2.17, respectively. For Hg field 
reagent blanks, use a 10 ml aliquot for digestion and analysis.
    9.1.1  Digest and analyze one of the filters from Container No. 12 
per Section 8.3.1, 100 ml from Container No. 7 per Section 8.3.2, and 
100 ml from Container No. 8A per Section 8.3.3. This step produces 
blanks for Analytical Fractions 1A and 1B.
    9.1.2  Combine 100 ml of Container No. 8A with 200 ml from 
Container No. 9, and digest and analyze the resultant volume per 
Section 8.3.4. This step produces blanks for Analytical Fractions 2A 
and 2B.
    9.1.3  Digest and analyze a 100-ml portion of Container No. 8A to 
produce a blank for Analytical Fraction 3A.
    9.1.4  Combine 100 ml from Container No. 10 with 33 ml from 
Container No. 8B to produce a blank for Analytical Fraction 3B. Filter 
the resultant 133 ml as described for

[[Page 62120]]

Container No. 5B in Section 8.3.5, except do not dilute the 133 ml. 
Analyze this blank for Hg within 48 hr of the filtration step, and use 
400 ml as the blank volume when calculating the blank mass value. Use 
the actual volumes of the other analytical blanks when calculating 
their mass values.
    9.1.5  Digest the filter that was used to remove any brown 
MnO2 precipitate from the blank for Analytical Fraction 3B 
by the same procedure as described in Section 8.3.5 for the similar 
sample filter. Filter the digestate and the contents of Container No. 
11 through Whatman 40 paper into a 500-ml volumetric flask, and dilute 
to volume with water. These steps produce a blank for Analytical 
Fraction 3C.
    9.1.6  Analyze the blanks for Analytical Fraction Blanks 1A and 2A 
per Section 11.1.1 and/or Section 11.1.2. Analyze the blanks for 
Analytical Fractions 1B, 2B, 3A, 3B, and 3C per Section 11.1.3. 
Analysis of the blank for Analytical Fraction 1A produces the front-
half reagent blank correction values for the desired metals except for 
Hg; Analysis of the blank for Analytical Fraction 1B produces the 
front-half reagent blank correction value for Hg. Analysis of the blank 
for Analytical Fraction 2A produces the back-half reagent blank 
correction values for all of the desired metals except for Hg, while 
separate analyses of the blanks for Analytical Fractions 2B, 3A, 3B, 
and 3C produce the back-half reagent blank correction value for Hg.
    9.2  Quality Control Samples. Analyze the following quality control 
samples.
    9.2.1  ICAP and ICP-MS Analysis. Follow the respective quality 
control descriptions in Section 8 of Methods 6010 and 6020 in EPA 
Publication SW-846 Third Edition (November 1986) including updates I, 
II, IIA, IIB and III, as incorporated by reference in Sec. 60.17(i). 
For the purposes of a source test that consists of three sample runs, 
modify those requirements to include the following: two instrument 
check standard runs, two calibration blank runs, one interference check 
sample at the beginning of the analysis (analyze by Method of Standard 
Additions unless within 25 percent), one quality control sample to 
check the accuracy of the calibration standards (required to be within 
25 percent of calibration), and one duplicate analysis (required to be 
within 20 percent of average or repeat all analyses).
    9.2.2  Direct Aspiration AAS and/or GFAAS Analysis for Sb, As, Ba, 
Be, Cd, Cu, Cr, Co, Pb, Ni, Mn, Hg, P, Se, Ag, Tl, and Zn. Analyze all 
samples in duplicate. Perform a matrix spike on at least one front-half 
sample and one back-half sample, or one combined sample. If recoveries 
of less than 75 percent or greater than 125 percent are obtained for 
the matrix spike, analyze each sample by the Method of Standard 
Additions. Analyze a quality control sample to check the accuracy of 
the calibration standards. If the results are not within 20 percent, 
repeat the calibration.
    9.2.3  CVAAS Analysis for Hg. Analyze all samples in duplicate. 
Analyze a quality control sample to check the accuracy of the 
calibration standards (if not within 15 percent, repeat calibration). 
Perform a matrix spike on one sample (if not within 25 percent, analyze 
all samples by the Method of Standard Additions). Additional 
information on quality control can be obtained from Method 7470 in EPA 
Publication SW-846 Third Edition (November 1986) including updates I, 
II, IIA, IIB and III, as incorporated by reference in Sec. 60.17(i), or 
in Standard Methods for Water and Wastewater Method 303F.

10.0  Calibration and Standardization

    Note: Maintain a laboratory log of all calibrations.


    10.1  Sampling Train Calibration. Calibrate the sampling train 
components according to the indicated sections of Method 5: Probe 
Nozzle (Section 10.1); Pitot Tube (Section 10.2); Metering System 
(Section 10.3); Probe Heater (Section 10.4); Temperature Sensors 
(Section 10.5); Leak-Check of the Metering System (Section 8.4.1); and 
Barometer (Section 10.6).
    10.2  Inductively Coupled Argon Plasma Spectrometer Calibration. 
Prepare standards as outlined in Section 7.5. Profile and calibrate the 
instrument according to the manufacturer's recommended procedures using 
those standards. Check the calibration once per hour. If the instrument 
does not reproduce the standard concentrations within 10 percent, 
perform the complete calibration procedures. Perform ICP-MS analysis by 
following Method 6020 in EPA Publication SW-846 Third Edition (November 
1986) including updates I, II, IIA, IIB and III, as incorporated by 
reference in Sec. 60.17(i).
    10.3  Atomic Absorption Spectrometer--Direct Aspiration AAS, GFAAS, 
and CVAAS analyses. Prepare the standards as outlined in Section 7.5 
and use them to calibrate the spectrometer. Calibration procedures are 
also outlined in the EPA methods referred to in Table 29-2 and in 
Method 7470 in EPA Publication SW-846 Third Edition (November 1986) 
including updates I, II, IIA, IIB and III, as incorporated by reference 
in Sec. 60.17(i), or in Standard Methods for Water and Wastewater 
Method 303F (for Hg). Run each standard curve in duplicate and use the 
mean values to calculate the calibration line. Recalibrate the 
instrument approximately once every 10 to 12 samples.

11.0  Analytical Procedure

    11.1  Sample Analysis. For each sampling train sample run, seven 
individual analytical samples are generated; two for all desired metals 
except Hg, and five for Hg. A schematic identifying each sample 
container and the prescribed analytical preparation and analysis scheme 
is shown in Figure 29-3. The first two analytical samples, labeled 
Analytical Fractions 1A and 1B, consist of the digested samples from 
the front-half of the train. Analytical Fraction 1A is for ICAP, ICP-MS 
or AAS analysis as described in Sections 11.1.1 and 11.1.2, 
respectively. Analytical Fraction 1B is for front-half Hg analysis as 
described in Section 11.1.3. The contents of the back-half of the train 
are used to prepare the third through seventh analytical samples. The 
third and fourth analytical samples, labeled Analytical Fractions 2A 
and 2B, contain the samples from the moisture removal impinger No. 1, 
if used, and HNO3/H2O2 impingers Nos. 
2 and 3. Analytical Fraction 2A is for ICAP, ICP-MS or AAS analysis for 
target metals, except Hg. Analytical Fraction 2B is for analysis for 
Hg. The fifth through seventh analytical samples, labeled Analytical 
Fractions 3A, 3B, and 3C, consist of the impinger contents and rinses 
from the empty impinger No. 4 and the H2SO4/
KMnO4 Impingers Nos. 5 and 6. These analytical samples are 
for analysis for Hg as described in Section 11.1.3. The total back-half 
Hg catch is determined from the sum of Analytical Fractions 2B, 3A, 3B, 
and 3C. Analytical Fractions 1A and 2A can be combined proportionally 
prior to analysis.
    11.1.1  ICAP and ICP-MS Analysis. Analyze Analytical Fractions 1A 
and 2A by ICAP using Method 6010 or Method 200.7 (40 CFR 136, Appendix 
C). Calibrate the ICAP, and set up an analysis program as described in 
Method 6010 or Method 200.7. Follow the quality control procedures 
described in Section 9.2.1. Recommended wavelengths for analysis are as 
shown in Table 29-2. These wavelengths represent the best combination 
of specificity and potential detection limit. Other wavelengths may be 
substituted if they can provide the needed specificity and detection 
limit, and are treated with the same corrective techniques for

[[Page 62121]]

spectral interference. Initially, analyze all samples for the target 
metals (except Hg) plus Fe and Al. If Fe and Al are present, the sample 
might have to be diluted so that each of these elements is at a 
concentration of less than 50 ppm so as to reduce their spectral 
interferences on As, Cd, Cr, and Pb. Perform ICP-MS analysis by 
following Method 6020 in EPA Publication SW-846 Third Edition (November 
1986) including updates I, II, IIA, IIB and III, as incorporated by 
reference in Sec. 60.17(i).


    Note: When analyzing samples in a HF matrix, an alumina torch 
should be used; since all front-half samples will contain HF, use an 
alumina torch.

    11.1.2  AAS by Direct Aspiration and/or GFAAS. If analysis of 
metals in Analytical Fractions 1A and 2A by using GFAAS or direct 
aspiration AAS is needed, use Table 29-3 to determine which techniques 
and procedures to apply for each target metal. Use Table 29-3, if 
necessary, to determine techniques for minimization of interferences. 
Calibrate the instrument according to Section 10.3 and follow the 
quality control procedures specified in Section 9.2.2.
    11.1.3  CVAAS Hg analysis. Analyze Analytical Fractions 1B, 2B, 3A, 
3B, and 3C separately for Hg using CVAAS following the method outlined 
in Method 7470 in EPA Publication SW-846 Third Edition (November 1986) 
including updates I, II, IIA, IIB and III, as incorporated by reference 
in Sec. 60.17(i), or in Standard Methods for Water and Wastewater 
Analysis, 15th Edition, Method 303F, or, optionally using Note No. 2 at 
the end of this section. Set up the calibration curve (zero to 1000 ng) 
as described in Method 7470 or similar to Method 303F using 300-ml BOD 
bottles instead of Erlenmeyers. Perform the following for each Hg 
analysis. From each original sample, select and record an aliquot in 
the size range from 1 ml to 10 ml. If no prior knowledge of the 
expected amount of Hg in the sample exists, a 5 ml aliquot is suggested 
for the first dilution to 100 ml (see Note No. 1 at end of this 
section). The total amount of Hg in the aliquot shall be less than 1 
g and within the range (zero to 1000 ng) of the calibration 
curve. Place the sample aliquot into a separate 300-ml BOD bottle, and 
add enough water to make a total volume of 100 ml. Next add to it 
sequentially the sample digestion solutions and perform the sample 
preparation described in the procedures of Method 7470 or Method 303F. 
(See Note No. 2 at the end of this section). If the maximum readings 
are off-scale (because Hg in the aliquot exceeded the calibration 
range; including the situation where only a 1-ml aliquot of the 
original sample was digested), then dilute the original sample (or a 
portion of it) with 0.15 percent HNO3 (1.5 ml concentrated 
HNO3 per liter aqueous solution) so that when a 1- to 10-ml 
aliquot of the ``0.15 HNO3 percent dilution of the original 
sample'' is digested and analyzed by the procedures described above, it 
will yield an analysis within the range of the calibration curve.


    Note No. 1: When Hg levels in the sample fractions are below the 
in-stack detection limit given in Table 29-1, select a 10 ml aliquot 
for digestion and analysis as described.


    Note No. 2: Optionally, Hg can be analyzed by using the CVAAS 
analytical procedures given by some instrument manufacturer's 
directions. These include calibration and quality control procedures 
for the Leeman Model PS200, the Perkin Elmer FIAS systems, and 
similar models, if available, of other instrument manufacturers. For 
digestion and analyses by these instruments, perform the following 
two steps: (1), Digest the sample aliquot through the addition of 
the aqueous hydroxylamine hydrochloride/sodium chloride solution the 
same as described in this section: (The Leeman, Perkin Elmer, and 
similar instruments described in this note add automatically the 
necessary stannous chloride solution during the automated analysis 
of Hg.); (2), Upon completion of the digestion described in (1), 
analyze the sample according to the instrument manufacturer's 
directions. This approach allows multiple (including duplicate) 
automated analyses of a digested sample aliquot.

12.0  Data Analysis and Calculations

    12.1  Nomenclature.

A = Analytical detection limit, g/ml.
B = Liquid volume of digested sample prior to aliquotting for analysis, 
ml.
C = Stack sample gas volume, dsm\3\.
Ca1 = Concentration of metal in Analytical Fraction 1A as 
read from the standard curve, g/ml.
Ca2 = Concentration of metal in Analytical Fraction 2A as 
read from the standard curve, (g/ml).
Cs = Concentration of a metal in the stack gas, mg/dscm.
D = In-stack detection limit, g/m\3\.
Fa = Aliquot factor, volume of Sample Fraction 2 divided by 
volume of Sample Fraction 2A (see Section 8.3.4.)
Fd = Dilution factor (Fd = the inverse of the 
fractional portion of the concentrated sample in the solution actually 
used in the instrument to produce the reading Ca1. For 
example, if a 2 ml aliquot of Analytical Fraction 1A is diluted to 10 
ml to place it in the calibration range, Fd = 5).
Hgbh = Total mass of Hg collected in the back-half of the 
sampling train, g.
Hgbh2 = Total mass of Hg collected in Sample Fraction 2, 
g.
Hgbh3(A,B,C) = Total mass of Hg collected separately in 
Fraction 3A, 3B, or 3C, g.
Hgbhb = Blank correction value for mass of Hg detected in 
back-half field reagent blanks, g.
Hgfh = Total mass of Hg collected in the front-half of the 
sampling train (Sample Fraction 1), g.
Hgfhb = Blank correction value for mass of Hg detected in 
front-half field reagent blank, g.
Hgt = Total mass of Hg collected in the sampling train, 
g.
Mbh = Total mass of each metal (except Hg) collected in the 
back-half of the sampling train (Sample Fraction 2), g.
Mbhb = Blank correction value for mass of metal detected in 
back-half field reagent blank, g.
Mfh = Total mass of each metal (except Hg) collected in the 
front half of the sampling train (Sample Fraction 1), g.
Mfhb = Blank correction value for mass of metal detected in 
front-half field reagent blank, g.
Mt = Total mass of each metal (separately stated for each 
metal) collected in the sampling train, g.
Mt = Total mass of that metal collected in the sampling 
train, g; (substitute Hgt for Mt for the 
Hg calculation).
Qbh2 = Quantity of Hg, g, TOTAL in the ALIQUOT of 
Analytical Fraction 2B selected for digestion and analysis . NOTE: For 
example, if a 10 ml aliquot of Analytical Fraction 2B is taken and 
digested and analyzed (according to Section 11.1.3 and its NOTES Nos. 1 
and 2), then calculate and use the total amount of Hg in the 10 ml 
aliquot for Qbh2.
Qbh3(A,B,C) = Quantity of Hg, g, TOTAL, separately, 
in the ALIQUOT of Analytical Fraction 3A, 3B, or 3C selected for 
digestion and analysis (see NOTES in Sections 12.7.1 and 12.7.2 
describing the quantity ``Q'' and calculate similarly).
Qfh = Quantity of Hg, g, TOTAL in the ALIQUOT of 
Analytical Fraction 1B selected for digestion and analysis. NOTE: For 
example, if a 10 ml aliquot of Analytical Fraction 1B is taken and 
digested and analyzed (according to Section 11.1.3 and its NOTES Nos. 1 
and 2), then calculate and use the total amount of Hg in the 10 ml 
aliquot for Qfh.
Va = Total volume of digested sample solution (Analytical 
Fraction 2A),

[[Page 62122]]

ml (see Section 8.3.4.1 or 8.3.4.2, as applicable).
Vf1B = Volume of aliquot of Analytical Fraction 1B analyzed, 
ml. NOTE: For example, if a 1 ml aliquot of Analytical Fraction 1B was 
diluted to 50 ml with 0.15 percent HNO3 as described in 
Section 11.1.3 to bring it into the proper analytical range, and then 1 
ml of that 50-ml was digested according to Section 11.1.3 and analyzed, 
Vf1B would be 0.02 ml.
Vf2B = Volume of Analytical Fraction 2B analyzed, ml. NOTE: 
For example, if 1 ml of Analytical Fraction 2B was diluted to 10 ml 
with 0.15 percent HNO3 as described in Section 11.1.3 to 
bring it into the proper analytical range, and then 5 ml of that 10 ml 
was analyzed, Vf2B would be 0.5 ml.
Vf3(A,B,C) = Volume, separately, of Analytical Fraction 3A, 
3B, or 3C analyzed, ml (see previous notes in Sections 12.7.1 and 
12.7.2, describing the quantity ``V'' and calculate similarly).
Vm(std) = Volume of gas sample as measured by the dry gas 
meter, corrected to dry standard conditions, dscm.
Vsoln,1 = Total volume of digested sample solution 
(Analytical Fraction 1), ml.
Vsoln,1 = Total volume of Analytical Fraction 1, ml.
Vsoln,2 = Total volume of Sample Fraction 2, ml.
    Vsoln,3(A,B,C) = Total volume, separately, of Analytical 
Fraction 3A, 3B, or 3C, ml.
K4 = 10-\3\ mg/g.

    12.2  Dry Gas Volume. Using the data from this test, calculate 
Vm(std), the dry gas sample volume at standard conditions as 
outlined in Section 12.3 of Method 5.
    12.3  Volume of Water Vapor and Moisture Content. Using the total 
volume of condensate collected during the source sampling, calculate 
the volume of water vapor Vw(std) and the moisture content 
Bws of the stack gas. Use Equations 5-2 and 5-3 of Method 5.
    12.4  Stack Gas Velocity. Using the data from this test and 
Equation 2-9 of Method 2, calculate the average stack gas velocity.
    12.5  In-Stack Detection Limits. Calculate the in-stack method 
detection limits shown in Table 29-4 using the conditions described in 
Section 13.3.1 as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.439

    12.6  Metals (Except Hg) in Source Sample.
    12.6.1  Analytical Fraction 1A, Front-Half, Metals (except Hg). 
Calculate separately the amount of each metal collected in Sample 
Fraction 1 of the sampling train using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.440


    Note: If Analytical Fractions 1A and 2A are combined, use 
proportional aliquots. Then make appropriate changes in Equations 
29-2 through 29-4 to reflect this approach.


    12.6.2  Analytical Fraction 2A, Back-Half, Metals (except Hg). 
Calculate separately the amount of each metal collected in Fraction 2 
of the sampling train using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.441

    12.6.3  Total Train, Metals (except Hg). Calculate the total amount 
of each of the quantified metals collected in the sampling train as 
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.442


    Note: If the measured blank value for the front half 
(Mfhb) is in the range 0.0 to ``A'' g (where 
``A'' g equals the value determined by multiplying 1.4 
g/in.2 times the actual area in in.2 
of the sample filter), use Mfhb to correct the emission 
sample value (Mfh); if Mfhb exceeds ``A'' 
g, use the greater of I or II:
    I. ``A'' g.
    II. The lesser of (a) Mfhb, or (b) 5 percent of 
Mfh. If the measured blank value for the back-half 
(Mbhb) is in the range 0.0 to 1 g, use 
Mbhb to correct the emission sample value 
(Mbh); if Mbhb exceeds 1 g, use the 
greater of I or II:
    I. 1 g.
    II. The lesser of (a) Mbhb, or (b) 5 percent of 
Mbh.


    12.7  Hg in Source Sample.
    12.7.1  Analytical Fraction 1B; Front-Half Hg. Calculate the amount 
ofHg collected in the front-half, Sample Fraction 1, of the sampling 
train by using Equation 29-5:
[GRAPHIC] [TIFF OMITTED] TR17OC00.443

    12.7.2  Analytical Fractions 2B, 3A, 3B, and 3C; Back Half Hg.
    12.7.2.1  Calculate the amount of Hg collected in Sample Fraction 2 
by using Equation 29-6:
[GRAPHIC] [TIFF OMITTED] TR17OC00.444

    12.7.2.2  Calculate each of the back-half Hg values for Analytical 
Fractions 3A, 3B, and 3C by using Equation 29-7:
[GRAPHIC] [TIFF OMITTED] TR17OC00.445

    12.7.2.3  Calculate the total amount of Hg collected in the back-
half of the sampling train by using Equation 29-8:
[GRAPHIC] [TIFF OMITTED] TR17OC00.446

    12.7.3  Total Train Hg Catch. Calculate the total amount of Hg 
collected in the sampling train by using Equation 29-9:

[[Page 62123]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.447


    Note: If the total of the measured blank values 
(Hgfhb + Hgbhb) is in the range of 0.0 to 0.6 
g, then use the total to correct the sample value 
(Hgfh + Hgbh); if it exceeds 0.6 g, 
use the greater of I. or II:
    I. 0.6 g.
    II. The lesser of (a) (Hgfhb + Hgbhb), or 
(b) 5 percent of the sample value (Hgfh + 
Hgbh).


    12.8  Individual Metal Concentrations in Stack Gas. Calculate the 
concentration of each metal in the stack gas (dry basis, adjusted to 
standard conditions) by using Equation 29-10:
[GRAPHIC] [TIFF OMITTED] TR17OC00.448

    12.9  Isokinetic Variation and Acceptable Results. Same as Method 
5, Sections 12.11 and 12.12, respectively.

13.0  Method Performance

    13.1  Range. For the analysis described and for similar analyses, 
the ICAP response is linear over several orders of magnitude. Samples 
containing metal concentrations in the nanograms per ml (ng/ml) to 
micrograms per ml (g/ml) range in the final analytical 
solution can be analyzed using this method. Samples containing greater 
than approximately 50 g/ml As, Cr, or Pb should be diluted to 
that level or lower for final analysis. Samples containing greater than 
approximately 20 g/ml of Cd should be diluted to that level 
before analysis.
    13.2  Analytical Detection Limits.


    Note: See Section 13.3 for the description of in-stack detection 
limits.


    13.2.1  ICAP analytical detection limits for the sample solutions 
(based on SW-846, Method 6010) are approximately as follows: Sb (32 ng/
ml), As (53 ng/ml), Ba (2 ng/ml), Be (0.3 ng/ml), Cd (4 ng/ml), Cr (7 
ng/ml), Co (7 ng/ml), Cu (6 ng/ml), Pb (42 ng/ml), Mn (2 ng/ml), Ni (15 
ng/ml), P (75 ng/ml), Se (75 ng/ml), Ag (7 ng/ml), Tl (40 ng/ml), and 
Zn (2 ng/ml). ICP-MS analytical detection limits (based on SW-846, 
Method 6020) are lower generally by a factor of ten or more. Be is 
lower by a factor of three. The actual sample analytical detection 
limits are sample dependent and may vary due to the sample matrix.
    13.2.2  The analytical detection limits for analysis by direct 
aspiration AAS (based on SW-846, Method 7000 series) are approximately 
as follows: Sb (200 ng/ml), As (2 ng/ml), Ba (100 ng/ml), Be (5 ng/ml), 
Cd (5 ng/ml), Cr (50 ng/ml), Co (50 ng/ml), Cu (20 ng/ml), Pb (100 ng/
ml), Mn (10 ng/ml), Ni (40 ng/ml), Se (2 ng/ml), Ag (10 ng/ml), Tl (100 
ng/ml), and Zn (5 ng/ml).
    13.2.3  The detection limit for Hg by CVAAS (on the resultant 
volume of the digestion of the aliquots taken for Hg analyses) can be 
approximately 0.02 to 0.2 ng/ml, depending upon the type of CVAAS 
analytical instrument used. 13.2.4  The use of GFAAS can enhance the 
detection limits compared to direct aspiration AAS as follows: Sb (3 
ng/ml), As (1 ng/ml), Be (0.2 ng/ml), Cd (0.1 ng/ml), Cr (1 ng/ml), Co 
(1 ng/ml), Pb (1 ng/ml), Se (2 ng/ml), and Tl (1 ng/ml).
    13.3  In-stack Detection Limits.
    13.3.1  For test planning purposes in-stack detection limits can be 
developed by using the following information: (1) The procedures 
described in this method, (2) the analytical detection limits described 
in Section 13.2 and in SW-846,(3) the normal volumes of 300 ml 
(Analytical Fraction 1) for the front-half and 150 ml (Analytical 
Fraction 2A) for the back-half samples, and (4) a stack gas sample 
volume of 1.25 m3. The resultant in-stack method detection 
limits for the above set of conditions are presented in Table 29-1 and 
were calculated by using Eq. 29-1 shown in Section 12.5.
    13.3.2  To ensure optimum precision/resolution in the analyses, the 
target concentrations of metals in the analytical solutions should be 
at least ten times their respective analytical detection limits. Under 
certain conditions, and with greater care in the analytical procedure, 
these concentrations can be as low as approximately three times the 
respective analytical detection limits without seriously impairing the 
precision of the analyses. On at least one sample run in the source 
test, and for each metal analyzed, perform either repetitive analyses, 
Method of Standard Additions, serial dilution, or matrix spike 
addition, etc., to document the quality of the data.
    13.3.3  Actual in-stack method detection limits are based on actual 
source sampling parameters and analytical results as described above. 
If required, the method in-stack detection limits can be improved over 
those shown in Table 29-1 for a specific test by either increasing the 
sampled stack gas volume, reducing the total volume of the digested 
samples, improving the analytical detection limits, or any combination 
of the three. For extremely low levels of Hg only, the aliquot size 
selected for digestion and analysis can be increased to as much as 10 
ml, thus improving the in-stack detection limit by a factor of ten 
compared to a 1 ml aliquot size.
    13.3.3.1  A nominal one hour sampling run will collect a stack gas 
sampling volume of about 1.25 m3. If the sampling time is 
increased to four hours and 5 m3 are collected, the in-stack 
method detection limits would be improved by a factor of four compared 
to the values shown in Table 29-1.
    13.3.3.2  The in-stack detection limits assume that all of the 
sample is digested and the final liquid volumes for analysis are the 
normal values of 300 ml for Analytical Fraction 1, and 150 ml for 
Analytical Fraction 2A. If the volume of Analytical Fraction 1 is 
reduced from 300 to 30 ml, the in-stack detection limits for that 
fraction of the sample would be improved by a factor of ten. If the 
volume of Analytical Fraction 2A is reduced from 150 to 25 ml, the in-
stack detection limits for that fraction of the sample would be 
improved by a factor of six. Matrix effect checks are necessary on 
sample analyses and typically are of much greater significance for 
samples that have been concentrated to less than the normal original 
sample volume. Reduction of Analytical Fractions 1 and 2A to volumes of 
less than 30 and 25 ml, respectively, could interfere with the 
redissolving of the residue and could increase interference by other 
compounds to an intolerable level.
    13.3.3.3  When both of the modifications described in Sections 
13.3.3.1 and 13.3.3.2 are used simultaneously on one sample, the 
resultant improvements are multiplicative. For example, an increase in 
stack gas volume by a factor of four and a reduction in the total 
liquid sample digested volume of both Analytical Fractions 1 and 2A by 
a factor of six would result in an improvement by a factor of twenty-
four of the in-stack method detection limit.
    13.4  Precision. The precision (relative standard deviation) for 
each metal detected in a method development test performed at a sewage 
sludge incinerator were found to be as follows:

Sb (12.7 percent), As (13.5 percent), Ba (20.6 percent), Cd (11.5 
percent), Cr (11.2 percent), Cu (11.5 percent), Pb (11.6 percent), P 
(14.6 percent), Se (15.3 percent), Tl (12.3 percent), and Zn (11.8 
percent). The precision for Ni was 7.7 percent for another test 
conducted at a source simulator. Be, Mn, and Ag were not detected in 
the tests. However,

[[Page 62124]]

based on the analytical detection limits of the ICAP for these metals, 
their precisions could be similar to those for the other metals when 
detected at similar levels.

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

    1. Method 303F in Standard Methods for the Examination of Water 
Wastewater, 15th Edition, 1980. Available from the American Public 
Health Association, 1015 18th Street N.W., Washington, D.C. 20036.
    2. EPA Methods 6010, 6020, 7000, 7041, 7060, 7131, 7421, 7470, 
7740, and 7841, Test Methods for Evaluating Solid Waste: Physical/
Chemical Methods. SW-846, Third Edition, November 1986, with updates 
I, II, IIA, IIB and III. Office of Solid Waste and Emergency 
Response, U. S. Environmental Protection Agency, Washington, D.C. 
20460.
    3. EPA Method 200.7, Code of Federal Regulations, Title 40, Part 
136, Appendix C. July 1, 1987.
    4. EPA Methods 1 through 5, Code of Federal Regulations, Title 
40, Part 60, Appendix A, July 1, 1991.
    5. EPA Method 101A, Code of Federal Regulations, Title 40, Part 
61, Appendix B, July 1, 1991.

17.0  Tables, Diagrams, Flowcharts, and Validation Data

 Table 29-1.--In Stack Method Detection Limits (ug/m3) for the Front-Half, the Back Half, and the Total Sampling
                                       Train Using ICAP, GFAAS, and CVAAS
----------------------------------------------------------------------------------------------------------------
                                                    Front-half:                     Back-half:
                      Metal                          probe and      Back-half:    impringers  4-    Total train
                                                      filter       impinters 1-3        6 a
----------------------------------------------------------------------------------------------------------------
Antimony........................................     1 7.7 (0.7)     1 3.8 (0.4)  ..............    1 11.5 (1.1)
Arsenic.........................................    1 12.7 (0.3)     1 6.4 (0.1)  ..............    1 19.1 (0.4)
Barium..........................................             0.5             0.3  ..............             0.8
Beryllium.......................................   1 0.07 (0.05)   1 0.04 (0.03)  ..............   1 0.11 (0.08)
Cadmium.........................................    1 1.0 (0.02)    1 0.5 (0.01)  ..............    1 1.5 (0.03)
Chromium........................................     1 1.7 (0.2)     1 0.8 (0.1)  ..............     1 2.5 (0.3)
Cobalt..........................................     1 1.7 (0.2)     1 0.8 (0.1)  ..............     1 2.5 (0.3)
Copper..........................................             1.4             0.7  ..............             2.1
Lead............................................    1 10.1 (0.2)     1 5.0 (0.1)  ..............    1 15.1 (0.3)
Manganese.......................................     1 0.5 (0.2)     1 0.2 (0.1)  ..............     1 0.7 (0.3)
Mercury.........................................          2 0.06           2 0.3           2 0.2          2 0.56
Nickel..........................................             3.6             1.8  ..............             5.4
Phosphorus......................................              18               9  ..............              27
Selenium........................................      1 18 (0.5)       1 9 (0.3)  ..............      1 27 (0.8)
Silver..........................................             1.7       0.9 (0.7)  ..............             2.6
Thallium........................................     1 9.6 (0.2)     1 4.8 (0.1)  ..............    1 14.4 (0.3)
Zinc............................................             0.5             0.3  ..............            0.8
----------------------------------------------------------------------------------------------------------------
\a\ Mercury analysis only.
\1\ Detection limit when analyzed by ICAP or GFAAS as shown in parentheses (see Section 11.1.2).
\2\ Detection limit when anaylzed by CVAAS, estimated for Back-half and Total Train. See Sections 13.2 and
  11.1.3. Note: Actual method in-stack detection limits may vary from these values, as described in Section
  13.3.3.


         Table 29-2.--Recommended Wavelengths for ICAP Analysis
------------------------------------------------------------------------
                                                            Wavelength
                         Analyte                               (nm)
------------------------------------------------------------------------
Aluminum (Al)...........................................         308.215
Antimony (Sb)...........................................         206.833
Arsenic (As)............................................         193.696
Barium (Ba).............................................         455.403
Beryllium (Be)..........................................         313.042
Cadmium (Cd)............................................         226.502
Chromium (Cr)...........................................         267.716
Cobalt (Co).............................................         228.616
Copper (Cu).............................................         328.754
Iron (Fe)...............................................         259.940
Lead (Pb)...............................................         220.353
Manganese (Mn)..........................................         257.610
Nickel (Ni).............................................         231.604
Phosphorus (P)..........................................         214.914
Selenium (Se)...........................................         196.026
Silver (Ag).............................................         328.068
Thallium (T1)...........................................         190,864
Zinc (Zn)...............................................         213,856
------------------------------------------------------------------------


         Table 29-3.--Applicable Techniques, Methods and Minimization of Interferences for AAS Analysis
----------------------------------------------------------------------------------------------------------------
                                                                                   Interferences
      Metal              Technique        SW-846 \1\   Wavelength ----------------------------------------------
                                         Methods No.      (nm)            Cause               Minimization
----------------------------------------------------------------------------------------------------------------
Fe...............  Aspiration..........         7380        248.3  Contamination......  Great care taken to
                                                                                         avoid contamination.
Pb...............  Aspiration..........         7420        283.3  217.0 nm alternate.  Background correction
                                                                                         required.
Pb...............  Furnace.............         7421        283.3  Poor recoveries....  Matrix modifier, add 10
                                                                                         l of
                                                                                         phosphorus acid to 1 ml
                                                                                         of prepared sample in
                                                                                         sampler cup.
Mn...............  Aspiration..........         7460        279.5  403.1 nm alternate.  Background correction
                                                                                         required.
Ni...............  Aspiration..........         7520        232.0  352.4 nm alternate   Background correction
                                                                    Fe, Co, and Cr.      required. Matrix
                                                                   Nonlinear response.   matching or nitrous-
                                                                                         oxide/acetylene flame
                                                                                        Sample dilution or use
                                                                                         352.3 nm line

[[Page 62125]]

 
Se...............  Furnace.............         7740        196.0  Volatility.........  Spike samples and
                                                                                         reference materials and
                                                                                         add nickel nitrate to
                                                                                         minimize
                                                                                         volatilization.
                                                                   Adsorption &         Background correction is
                                                                    scatter.             required and Zeeman
                                                                                         background correction
                                                                                         can be useful.
Ag...............  Aspiration..........         7760        328.1  Adsorption &         Background correction is
                                                                    scatter AgCl         required. Avoid
                                                                    insoluble.           hydrochloric acid
                                                                                         unless silver is in
                                                                                         solution as a chloride
                                                                                         complex. Sample and
                                                                                         standards monitored for
                                                                                         aspiration rate.
Tl...............  Aspiration..........         7840        276.8                       Background correction is
                                                                                         required. Hydrochloric
                                                                                         acid should not be
                                                                                         used.
Tl...............  Furnace.............         7841        276.8  Hydrochloric acid    Background correction is
                                                                    or chloride.         required. Verify that
                                                                                         losses are not
                                                                                         occurring for
                                                                                         volatilization by
                                                                                         spiked samples or
                                                                                         standard addition;
                                                                                         Palladium is a suitable
                                                                                         matrix modifier. 4
Zn...............  Aspiration..........         7950        213.9  High Si, Cu, & P     Strontium removes Cu and
                                                                    Contamination.       phosphate.
                                                                                        Great care taken to
                                                                                         avoid contamination.
Sb...............  Aspiration..........         7040        217.6  1000 mg/ml Pb, Ni,   Use secondary wavelength
                                                                    Cu, or acid.         of 231.1 nm; match
                                                                                         sample & standards acid
                                                                                         concentration or use
                                                                                         nitrous oxide/acetylene
                                                                                         flame.
Sb...............  Furnace.............         7041        217.6  High Pb............  Secondary wavelength or
                                                                                         Zeeman correction.
As...............  Furnace.............         7060        193.7  Arsenic              Spike samples and add
                                                                    Volatilization       nickel nitrate solution
                                                                    Aluminum.            to digestates prior to
                                                                                         analysis. Use Zeeman
                                                                                         background correction.
Ba...............  Aspiration..........         7080        553.6
                                                                   Calcium............
                                                                   Barium Ionization..  High hollow cathode
                                                                                         current and narrow band
                                                                                         set.
                                                                                        2 ml of KCl per 100 m1
                                                                                         of sample.
Be...............  Aspiration..........         7090        234.9  500 ppm Al. High Mg  Add 0.1% fluoride.
                                                                    and Si.
Be...............  Furnace.............         7091        234.9  Be in optical path.  Optimize parameters to
                                                                                         minimize effects.
Cd...............  Aspiration..........         7130        228.8  Absorption and       Background correction is
                                                                    light scattering.    required.
Cd...............  Furnace.............         7131        228.8  As above...........  As above.
                                                                   Excess Chloride....  Ammonium phosphate used
                                                                     .................   as a matrix modifier.
                                                                   Pipet Tips.........  Use cadmium-free tips.
Cr...............  Aspiration..........         7190        357.9  Alkali metal.......  KCl ionization
                                                                                         suppressant in samples
                                                                                         and standards--Consult
                                                                                         mfgs' literature.
Co...............  Furnace.............         7201        240.7  Excess chloride....  Use Method of Standard
                                                                                         Additions.
Cr...............  Furnace.............         7191        357.9  200 mg/L Ca and P..  All calcium nitrate for
                                                                                         a know constant effect
                                                                                         and to eliminate effect
                                                                                         of phosphate.
Cu...............  Aspiration..........         7210        324.7  Absorption and       Consult manufacturer's
                                                                    Scatter.             manual.
----------------------------------------------------------------------------------------------------------------
\1\ Refer to EPA publication SW-846 (Reference 2 in Section 16.0).


[[Page 62126]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.449


[[Page 62127]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.450


[[Page 62128]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.451


[[Page 62129]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.452

BILLING CODE 6560-50-C

    217. In Part 60, Appendix B is amended by revising Performance 
Specifications 2, 3, 4, 4A, 5, 6, 7, 8, and 9 to read as follows:

[[Page 62130]]

Performance Specification 2--Specifications and Test Procedures for 
SO2 and NOX Continuous Emission Monitoring 
Systems in Stationary Sources

1.0  Scope and Application

    1.1  Analytes

------------------------------------------------------------------------
                         Analyte                             CAS Nos.
------------------------------------------------------------------------
Sulfur Dioxide (SO2)....................................       7449-09-5
Nitrogen Oxides (NOx)...................................      10102-44-0
                                                           (NO2), 10024-
                                                               97-2 (NO)
------------------------------------------------------------------------

    1.2  Applicability.
    1.2.1  This specification is for evaluating the acceptability of 
SO2 and NOX continuous emission monitoring 
systems (CEMS) at the time of installation or soon after and whenever 
specified in the regulations. The CEMS may include, for certain 
stationary sources, a diluent (O2 or CO2) 
monitor.
    1.2.2  This specification is not designed to evaluate the installed 
CEMS performance over an extended period of time nor does it identify 
specific calibration techniques and other auxiliary procedures to 
assess the CEMS performance. The source owner or operator is 
responsible to calibrate, maintain, and operate the CEMS properly. The 
Administrator may require, under Section 114 of the Act, the operator 
to conduct CEMS performance evaluations at other times besides the 
initial test to evaluate the CEMS performance. See 40 CFR Part 60, 
Sec. 60.13(c).

2.0  Summary of Performance Specification

    Procedures for measuring CEMS relative accuracy and calibration 
drift are outlined. CEMS installation and measurement location 
specifications, equipment specifications, performance specifications, 
and data reduction procedures are included. Conformance of the CEMS 
with the Performance Specification is determined.

3.0  Definitions

    3.1  Calibration Drift (CD) means the difference in the CEMS output 
readings from the established reference value after a stated period of 
operation during which no unscheduled maintenance, repair, or 
adjustment took place.
    3.2  Centroidal Area means a concentric area that is geometrically 
similar to the stack or duct cross section and is no greater than l 
percent of the stack or duct cross-sectional area.
    3.3  Continuous Emission Monitoring System means the total 
equipment required for the determination of a gas concentration or 
emission rate. The sample interface, pollutant analyzer, diluent 
analyzer, and data recorder are the major subsystems of the CEMS.
    3.4  Data Recorder means that portion of the CEMS that provides a 
permanent record of the analyzer output. The data recorder may include 
automatic data reduction capabilities.
    3.5  Diluent Analyzer means that portion of the CEMS that senses 
the diluent gas (i.e., CO2 or O2) and generates 
an output proportional to the gas concentration.
    3.6  Path CEMS means a CEMS that measures the gas concentration 
along a path greater than 10 percent of the equivalent diameter of the 
stack or duct cross section.
    3.7  Point CEMS means a CEMS that measures the gas concentration 
either at a single point or along a path equal to or less than 10 
percent of the equivalent diameter of the stack or duct cross section.
    3.8  Pollutant Analyzer means that portion of the CEMS that senses 
the pollutant gas and generates an output proportional to the gas 
concentration.
    3.9  Relative Accuracy (RA) means the absolute mean difference 
between the gas concentration or emission rate determined by the CEMS 
and the value determined by the reference method (RM), plus the 2.5 
percent error confidence coefficient of a series of tests, divided by 
the mean of the RM tests or the applicable emission limit.
    3.10  Sample Interface means that portion of the CEMS used for one 
or more of the following: sample acquisition, sample delivery, sample 
conditioning, or protection of the monitor from the effects of the 
stack effluent.
    3.11  Span Value means the concentration specified for the affected 
source category in an applicable subpart of the regulations that is 
used to set the calibration gas concentration and in determining 
calibration drift.

4.0  Interferences. [Reserved]

5.0  Safety

    The procedures required under this performance specification may 
involve hazardous materials, operations, and equipment. This 
performance specification may not address all of the safety problems 
associated with these procedures. It is the responsibility of the user 
to establish appropriate safety and health practices and determine the 
applicable regulatory limitations prior to performing these procedures. 
The CEMS user's manual and materials recommended by the reference 
method should be consulted for specific precautions to be taken.

6.0  Equipment and Supplies

    6.1  CEMS Equipment Specifications.
    6.1.1  Data Recorder Scale. The CEMS data recorder output range 
must include zero and a high-level value. The high-level value is 
chosen by the source owner or operator and is defined as follows:
    6.1.1.1  For a CEMS intended to measure an uncontrolled emission 
(e.g., SO2 measurements at the inlet of a flue gas 
desulfurization unit), the high-level value should be between 1.25 and 
2 times the maximum potential emission level over the appropriate 
averaging time, unless otherwise specified in an applicable subpart of 
the regulations.
    6.1.1.2  For a CEMS installed to measure controlled emissions or 
emissions that are in compliance with an applicable regulation, the 
high-level value between 1.5 times the pollutant concentration 
corresponding to the emission standard level and the span value given 
in the applicable regulations is adequate.
    6.1.1.3  Alternative high-level values may be used, provided the 
source can measure emissions which exceed the full-scale limit in 
accordance with the requirements of applicable regulations.
    6.1.1.4  If an analog data recorder is used, the data recorder 
output must be established so that the high-level value would read 
between 90 and 100 percent of the data recorder full scale. (This scale 
requirement may not be applicable to digital data recorders.) The zero 
and high level calibration gas, optical filter, or cell values should 
be used to establish the data recorder scale.
    6.1.2  The CEMS design should also allow the determination of 
calibration drift at the zero and high-level values. If this is not 
possible or practical, the design must allow these determinations to be 
conducted at a low-level value (zero to 20 percent of the high-level 
value) and at a value between 50 and 100 percent of the high-level 
value. In special cases, the Administrator may approve a single-point 
calibration-drift determination.
    6.2  Other equipment and supplies, as needed by the applicable 
reference method(s) (see Section 8.4.2 of this Performance 
Specification), may be required.

7.0  Reagents and Standards

    7.1  Reference Gases, Gas Cells, or Optical Filters. As specified 
by the CEMS manufacturer for calibration of the CEMS (these need not be 
certified).
    7.2  Reagents and Standards. May be required as needed by the 
applicable reference method(s) (see Section 8.4.2 of this Performance 
Specification).

[[Page 62131]]

    8.0  Performance Specification Test Procedure
    8.1  Installation and Measurement Location Specifications.
    8.1.1  CEMS Installation. Install the CEMS at an accessible 
location where the pollutant concentration or emission rate 
measurements are directly representative or can be corrected so as to 
be representative of the total emissions from the affected facility or 
at the measurement location cross section. Then select representative 
measurement points or paths for monitoring in locations that the CEMS 
will pass the RA test (see Section 8.4). If the cause of failure to 
meet the RA test is determined to be the measurement location and a 
satisfactory correction technique cannot be established, the 
Administrator may require the CEMS to be relocated. Suggested 
measurement locations and points or paths that are most likely to 
provide data that will meet the RA requirements are listed below.
    8.1.2  CEMS Measurement Location. It is suggested that the 
measurement location be (1) at least two equivalent diameters 
downstream from the nearest control device, the point of pollutant 
generation, or other point at which a change in the pollutant 
concentration or emission rate may occur and (2) at least a half 
equivalent diameter upstream from the effluent exhaust or control 
device.
    8.1.2.1  Point CEMS. It is suggested that the measurement point be 
(1) no less than 1.0 meter (3.3 ft) from the stack or duct wall or (2) 
within or centrally located over the centroidal area of the stack or 
duct cross section.
    8.1.2.2  Path CEMS. It is suggested that the effective measurement 
path (1) be totally within the inner area bounded by a line 1.0 meter 
(3.3 ft) from the stack or duct wall, or (2) have at least 70 percent 
of the path within the inner 50 percent of the stack or duct cross-
sectional area, or (3) be centrally located over any part of the 
centroidal area.
    8.1.3  Reference Method Measurement Location and Traverse Points.
    8.1.3.1  Select, as appropriate, an accessible RM measurement point 
at least two equivalent diameters downstream from the nearest control 
device, the point of pollutant generation, or other point at which a 
change in the pollutant concentration or emission rate may occur, and 
at least a half equivalent diameter upstream from the effluent exhaust 
or control device. When pollutant concentration changes are due solely 
to diluent leakage (e.g., air heater leakages) and pollutants and 
diluents are simultaneously measured at the same location, a half 
diameter may be used in lieu of two equivalent diameters. The CEMS and 
RM locations need not be the same.
    8.1.3.2  Select traverse points that assure acquisition of 
representative samples over the stack or duct cross section. The 
minimum requirements are as follows: Establish a ``measurement line'' 
that passes through the centroidal area and in the direction of any 
expected stratification. If this line interferes with the CEMS 
measurements, displace the line up to 30 cm (12 in.) (or 5 percent of 
the equivalent diameter of the cross section, whichever is less) from 
the centroidal area. Locate three traverse points at 16.7, 50.0, and 
83.3 percent of the measurement line. If the measurement line is longer 
than 2.4 meters (7.8 ft) and pollutant stratification is not expected, 
the three traverse points may be located on the line at 0.4, 1.2, and 
2.0 meters from the stack or duct wall. This option must not be used 
after wet scrubbers or at points where two streams with different 
pollutant concentrations are combined. If stratification is suspected, 
the following procedure is suggested. For rectangular ducts, locate at 
least nine sample points in the cross section such that sample points 
are the centroids of similarly-shaped, equal area divisions of the 
cross section. Measure the pollutant concentration, and, if applicable, 
the diluent concentration at each point using appropriate reference 
methods or other appropriate instrument methods that give responses 
relative to pollutant concentrations. Then calculate the mean value for 
all sample points. For circular ducts, conduct a 12-point traverse 
(i.e., six points on each of the two perpendicular diameters) locating 
the sample points as described in 40 CFR 60, Appendix A, Method 1. 
Perform the measurements and calculations as described above. Determine 
if the mean pollutant concentration is more than 10% different from any 
single point. If so, the cross section is considered to be stratified, 
and the tester may not use the alternative traverse point locations 
(...0.4, 1.2, and 2.0 meters from the stack or duct wall.) but must use 
the three traverse points at 16.7, 50.0, and 83.3 percent of the entire 
measurement line. Other traverse points may be selected, provided that 
they can be shown to the satisfaction of the Administrator to provide a 
representative sample over the stack or duct cross section. Conduct all 
necessary RM tests within 3 cm (1.2 in.) of the traverse points, but no 
closer than 3 cm (1.2 in.) to the stack or duct wall.
    8.2  Pretest Preparation. Install the CEMS, prepare the RM test 
site according to the specifications in Section 8.1, and prepare the 
CEMS for operation according to the manufacturer's written 
instructions.
    8.3  Calibration Drift Test Procedure.
    8.3.1  CD Test Period. While the affected facility is operating at 
more than 50 percent of normal load, or as specified in an applicable 
subpart, determine the magnitude of the CD once each day (at 24-hour 
intervals) for 7 consecutive days according to the procedure given in 
Sections 8.3.2 through 8.3.4.
    8.3.2  The purpose of the CD measurement is to verify the ability 
of the CEMS to conform to the established CEMS calibration used for 
determining the emission concentration or emission rate. Therefore, if 
periodic automatic or manual adjustments are made to the CEMS zero and 
calibration settings, conduct the CD test immediately before these 
adjustments, or conduct it in such a way that the CD can be determined.
    8.3.3  Conduct the CD test at the two points specified in Section 
6.1.2. Introduce to the CEMS the reference gases, gas cells, or optical 
filters (these need not be certified). Record the CEMS response and 
subtract this value from the reference value (see example data sheet in 
Figure 2-1).
    8.4  Relative Accuracy Test Procedure.
    8.4.1  RA Test Period. Conduct the RA test according to the 
procedure given in Sections 8.4.2 through 8.4.6 while the affected 
facility is operating at more than 50 percent of normal load, or as 
specified in an applicable subpart. The RA test may be conducted during 
the CD test period.
    8.4.2  Reference Methods. Unless otherwise specified in an 
applicable subpart of the regulations, Methods 3B, 4, 6, and 7, or 
their approved alternatives, are the reference methods for diluent 
(O2 and CO2), moisture, SO2, and 
NOx, respectively.
    8.4.3  Sampling Strategy for RM Tests. Conduct the RM tests in such 
a way that they will yield results representative of the emissions from 
the source and can be correlated to the CEMS data. It is preferable to 
conduct the diluent (if applicable), moisture (if needed), and 
pollutant measurements simultaneously. However, diluent and moisture 
measurements that are taken within an hour of the pollutant 
measurements may be used to calculate dry pollutant concentration and 
emission rates. In order to correlate the CEMS and RM data properly, 
note the beginning and end of each RM test period of each run 
(including the exact time of day) on the CEMS chart recordings or other 
permanent record of

[[Page 62132]]

output. Use the following strategies for the RM tests:
    8.4.3.1  For integrated samples (e.g., Methods 6 and Method 4), 
make a sample traverse of at least 21 minutes, sampling for an equal 
time at each traverse point (see Section 8.1.3.2 for discussion of 
traverse points.
    8.4.3.2  For grab samples (e.g., Method 7), take one sample at each 
traverse point, scheduling the grab samples so that they are taken 
simultaneously (within a 3-minute period) or at an equal interval of 
time apart over the span of time the CEM pollutant is measured. A test 
run for grab samples must be made up of at least three separate 
measurements.


    Note: At times, CEMS RA tests are conducted during new source 
performance standards performance tests. In these cases, RM results 
obtained during CEMS RA tests may be used to determine compliance as 
long as the source and test conditions are consistent with the 
applicable regulations.

    8.4.4  Number of RM Tests. Conduct a minimum of nine sets of all 
necessary RM test runs.


    Note: More than nine sets of RM tests may be performed. If this 
option is chosen, a maximum of three sets of the test results may be 
rejected so long as the total number of test results used to 
determine the RA is greater than or equal to nine. However, all data 
must be reported, including the rejected data.


    8.4.5  Correlation of RM and CEMS Data. Correlate the CEMS and the 
RM test data as to the time and duration by first determining from the 
CEMS final output (the one used for reporting) the integrated average 
pollutant concentration or emission rate for each pollutant RM test 
period. Consider system response time, if important, and confirm that 
the pair of results are on a consistent moisture, temperature, and 
diluent concentration basis. Then, compare each integrated CEMS value 
against the corresponding average RM value. Use the following 
guidelines to make these comparisons.
    8.4.5.1  If the RM has an integrated sampling technique, make a 
direct comparison of the RM results and CEMS integrated average value.
    8.4.5.2  If the RM has a grab sampling technique, first average the 
results from all grab samples taken during the test run, and then 
compare this average value against the integrated value obtained from 
the CEMS chart recording or output during the run. If the pollutant 
concentration is varying with time over the run, the arithmetic average 
of the CEMS value recorded at the time of each grab sample may be used.
    8.4.6  Calculate the mean difference between the RM and CEMS values 
in the units of the emission standard, the standard deviation, the 
confidence coefficient, and the relative accuracy according to the 
procedures in Section 12.0.
    8.5  Reporting. At a minimum (check with the appropriate regional 
office, State, or Local agency for additional requirements, if any), 
summarize in tabular form the results of the CD tests and the RA tests 
or alternative RA procedure, as appropriate. Include all data sheets, 
calculations, charts (records of CEMS responses), cylinder gas 
concentration certifications, and calibration cell response 
certifications (if applicable) necessary to confirm that the 
performance of the CEMS met the performance specifications.

9.0  Quality Control [Reserved]

10.0  Calibration and Standardization [Reserved]

11.0  Analytical Procedure

    Sample collection and analysis are concurrent for this Performance 
Specification (see Section 8.0). Refer to the RM for specific 
analytical procedures.

12.0  Calculations and Data Analysis

    Summarize the results on a data sheet similar to that shown in 
Figure 2-2 (in Section 18.0).
    12.1  All data from the RM and CEMS must be on a consistent dry 
basis and, as applicable, on a consistent diluent basis and in the 
units of the emission standard. Correct the RM and CEMS data for 
moisture and diluent as follows:
    12.1.1  Moisture Correction (as applicable). Correct each wet RM 
run for moisture with the corresponding Method 4 data; correct each wet 
CEMS run using the corresponding CEMS moisture monitor date using 
Equation 2-1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.453

    12.1.2  Correction to Units of Standard (as applicable). Correct 
each dry RM run to the units of the emission standard with the 
corresponding Method 3B data; correct each dry CEMS run using the 
corresponding CEMS diluent monitor data as follows:
    12.1.2.1  Correct to Diluent Basis. The following is an example of 
concentration (ppm) correction to 7% oxygen.
[GRAPHIC] [TIFF OMITTED] TR17OC00.454

    The following is an example of mass/gross calorific value (lbs/
million Btu) correction.

lbs/MMBtu = Conc(dry) (F-factor) (20.9/20.9-%02)

    12.2  Arithmetic Mean. Calculate the arithmetic mean of the 
difference, d, of a data set as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.455

Where:

n = Number of data points.
[GRAPHIC] [TIFF OMITTED] TR17OC00.456


[[Page 62133]]


    12.3  Standard Deviation. Calculate the standard deviation, 
Sd, as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.457

    12.4  Confidence Coefficient. Calculate the 2.5 percent error 
confidence coefficient (one-tailed), CC, as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.458

Where:

t0.975 = t-value (see Table 2-1).

    12.5  Relative Accuracy. Calculate the RA of a set of data as 
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.459

Where:

|d| = Absolute value of the mean differences (from Equation 2-3).
|CC| = Absolute value of the confidence coefficient (from Equation 2-
3).
RM = Average RM value. In cases where the average emissions for the 
test are less than 50 percent of the applicable standard, substitute 
the emission standard value in the denominator of Eq. 2-6 in place of 
RM. In all other cases, use RM.

13.0  Method Performance

    13.1  Calibration Drift Performance Specification. The CEMS 
calibration must not drift or deviate from the reference value of the 
gas cylinder, gas cell, or optical filter by more than 2.5 percent of 
the span value. If the CEMS includes pollutant and diluent monitors, 
the CD must be determined separately for each in terms of 
concentrations (See Performance Specification 3 for the diluent 
specifications), and none of the CDs may exceed the specification.
    13.2  Relative Accuracy Performance Specification. The RA of the 
CEMS must be no greater than 20 percent when RM is used in the 
denominator of Eq. 2-6 (average emissions during test are greater than 
50 percent of the emission standard) or 10 percent when the applicable 
emission standard is used in the denominator of Eq. 2-6 (average 
emissions during test are less than 50 percent of the emission 
standard).
    13.3  For instruments that use common components to measure more 
than one effluent gas constituent, all channels must simultaneously 
pass the RA requirement, unless it can be demonstrated that any 
adjustments made to one channel did not affect the others.

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  Alternative Procedures

    Paragraphs 60.13(j)(1) and (2) of 40 CFR part 60 contain criteria 
for which the reference method procedure for determining relative 
accuracy (see Section 8.4 of this Performance Specification) may be 
waived and the following procedure substituted.
    16.1  Conduct a complete CEMS status check following the 
manufacturer's written instructions. The check should include operation 
of the light source, signal receiver, timing mechanism functions, data 
acquisition and data reduction functions, data recorders, mechanically 
operated functions (mirror movements, zero pipe operation, calibration 
gas valve operations, etc.), sample filters, sample line heaters, 
moisture traps, and other related functions of the CEMS, as applicable. 
All parts of the CEMS shall be functioning properly before proceeding 
to the alternative RA procedure.
    16.2  Alternative RA Procedure.
    16.2.1  Challenge each monitor (both pollutant and diluent, if 
applicable) with cylinder gases of known concentrations or calibration 
cells that produce known responses at two measurement points within the 
ranges shown in Table 2-2 (Section 18).
    16.2.2  Use a separate cylinder gas (for point CEMS only) or 
calibration cell (for path CEMS or where compressed gas cylinders can 
not be used) for measurement points 1 and 2. Challenge the CEMS and 
record the responses three times at each measurement point. The 
Administrator may allow dilution of cylinder gas using the performance 
criteria in Test Method 205, 40 CFR Part 51, Appendix M. Use the 
average of the three responses in determining relative accuracy.
    16.2.3  Operate each monitor in its normal sampling mode as nearly 
as possible. When using cylinder gases, pass the cylinder gas through 
all filters, scrubbers, conditioners, and other monitor components used 
during normal sampling and as much of the sampling probe as practical. 
When using calibration cells, the CEMS components used in the normal 
sampling mode should not be by-passed during the RA determination. 
These include light sources, lenses, detectors, and reference cells. 
The CEMS should be challenged at each measurement point for a 
sufficient period of time to assure adsorption-desorption reactions on 
the CEMS surfaces have stabilized.
    16.2.4  Use cylinder gases that have been certified by comparison 
to National Institute of Standards and Technology (NIST) gaseous 
standard reference material (SRM) or NIST/EPA approved gas 
manufacturer's certified reference material (CRM) (See Reference 2 in 
Section 17.0) following EPA Traceability Protocol Number 1 (See 
Reference 3 in Section 17.0). As an alternative to Protocol Number 1 
gases, CRM's may be used directly as alternative RA cylinder gases. A 
list of gas manufacturers that have prepared approved CRM's is 
available from EPA at the address shown in Reference 2. Procedures for 
preparation of CRM's are described in Reference 2.
    16.2.5  Use calibration cells certified by the manufacturer to 
produce a known response in the CEMS. The cell certification procedure 
shall include determination of CEMS response produced by the 
calibration cell in direct comparison with measurement of gases of 
known concentration. This can be accomplished using SRM or CRM gases in 
a laboratory source simulator or through extended tests using reference 
methods at the CEMS location in the exhaust stack. These procedures are 
discussed in Reference 4 in Section 17.0. The calibration cell 
certification procedure is subject to approval of the Administrator.
    16.3  The differences between the known concentrations of the 
cylinder gases and the concentrations indicated by the CEMS are used to 
assess the accuracy of the CEMS. The calculations and limits of 
acceptable relative accuracy are as follows:
    16.3.1  For pollutant CEMS:
    [GRAPHIC] [TIFF OMITTED] TR17OC00.460
    

[[Page 62134]]


Where:

d = Average difference between responses and the concentration/
responses (see Section 16.2.2).
AC = The known concentration/response of the cylinder gas or 
calibration cell.

16.3.2 For diluent CEMS:

RA = |d|  O.7 percent O2 or CO2, as 
applicable.


    Note: Waiver of the relative accuracy test in favor of the 
alternative RA procedure does not preclude the requirements to 
complete the CD tests nor any other requirements specified in an 
applicable subpart for reporting CEMS data and performing CEMS drift 
checks or audits.

17.0  References

    1. Department of Commerce. Experimental Statistics. Handbook 91. 
Washington, D.C. p. 3-31, paragraphs 3-3.1.4.
    2. ``A Procedure for Establishing Traceability of Gas Mixtures 
to Certain National Bureau of Standards Standard Reference 
Materials.'' Joint publication by NBS and EPA. EPA 600/7-81-010. 
Available from U.S. Environmental Protection Agency, Quality 
Assurance Division (MD-77), Research Triangle Park, North Carolina 
27711.
    3. ``Traceability Protocol for Establishing True Concentrations 
of Gases Used for Calibration and Audits of Continuous Source 
Emission Monitors. (Protocol Number 1).'' June 1978. Protocol Number 
1 is included in the Quality Assurance Handbook for Air Pollution 
Measurement Systems, Volume III, Stationary Source Specific Methods. 
EPA-600/4-77-027b. August 1977.
    4. ``Gaseous Continuous Emission Monitoring Systems--Performance 
Specification Guidelines for SO2, NOX, 
CO2, O2, and TRS.'' EPA-450/3-82-026. 
Available from the U.S. EPA, Emission Measurement Center, Emission 
Monitoring and Data Analysis Division (MD-19), Research Triangle 
Park, North Carolina 27711.

18.0  Tables, Diagrams, Flowcharts, and Validation Data

                                              Table 2-1.--t-Values
----------------------------------------------------------------------------------------------------------------
                       na                           t0.975         na         t0.975         na         t0.975
----------------------------------------------------------------------------------------------------------------
2..............................................       12.706            7        2.447           12        2.201
3..............................................        4.303            8        2.365           13        2.179
4..............................................        3.182            9        2.306           14        2.160
5..............................................        2.776           10        2.262           15        2.145
6..............................................        2.571           11        2.228           16       2.131
----------------------------------------------------------------------------------------------------------------
a The values in this table are already corrected for n-1 degrees of freedom. Use n equal to the number of
  individual values.


                                                              Table 2-2.--Measurement Range
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                                                                                            Diluent monitor for
         Measurement point                        Pollutant monitor              -----------------------------------------------------------------------
                                                                                                  CO2                                 O2
--------------------------------------------------------------------------------------------------------------------------------------------------------
1..................................  20-30% of span value.......................  5-8% by volume....................  4-6% by volume.
2..................................  50-60% of span value.......................  10-14% by volume..................  8-12% by volume.


------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                                                                                                                                                                   Percent of span value (C-M)/
                                       Day             Date and time              Calibration value (C)             Monitor value (M)         Difference (C-M)          span value  x  100
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Low-level........................  ...........  ..........................  .................................  ..........................  .....................  ..............................
                                   ...........  ..........................  .................................  ..........................  .....................  ..............................
                                   ...........  ..........................  .................................  ..........................  .....................  ..............................
                                   ...........  ..........................  .................................  ..........................  .....................  ..............................
                                   ...........  ..........................  .................................  ..........................  .....................  ..............................
                                   ...........  ..........................  .................................  ..........................  .....................  ..............................
                                   ...........  ..........................  .................................  ..........................  .....................  ..............................
                                   ...........  ..........................  .................................  ..........................  .....................  ..............................
High-level.......................  ...........  ..........................  .................................  ..........................  .....................  ..............................
                                   ...........  ..........................  .................................  ..........................  .....................  ..............................
                                   ...........  ..........................  .................................  ..........................  .....................  ..............................
                                   ...........  ..........................  .................................  ..........................  .....................  ..............................
                                   ...........  ..........................  .................................  ..........................  .....................  ..............................
                                   ...........  ..........................  .................................  ..........................  .....................  ..............................
                                   ...........  ..........................  .................................  ..........................  .....................  ..............................
                                   ...........  ..........................  .................................  ..........................  .....................  ..............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

Figure 2-1. Calibration Drift Determination

[[Page 62135]]



                                                                          Figure 2-2. Relative Accuracy Determination.
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                                                            SO2                            NOXb                   CO2 or O2a                   SO2a                            NOXa
           Run No.             Date and time ---------------------------------------------------------------------------------------------------------------------------------------------------
                                                RM       CEMS        Diff       RM       CEMS        Diff       RM       CEMS       RM       CEMS        Diff       RM       CEMS        Diff
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
                                                           ppmc
                                              ppmc                %c          %c                 mass/GCV
                                            mass/GCV
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
1............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
2............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
3............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
4............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
5............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
6............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
7............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
8............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
9............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
10...........................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
11...........................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
12...........................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Average
Confidence Interval
Accuracy
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
a For steam generators.
b Average of three samples.
c Make sure that RM and CEMS data are on a consistent basis, either wet or dry.


[[Page 62136]]

Performance Specification 3--Specifications and Test Procedures for 
O2 and CO2 Continuous Emission Monitoring 
Systems in Stationary Sources

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
                        Analytes                              CAS No.
------------------------------------------------------------------------
Carbon Dioxide (CO2)....................................        124-38-9
Oxygen (O2).............................................       7782-44-7
------------------------------------------------------------------------

    1.2  Applicability.
    1.2.1  This specification is for evaluating acceptability of 
O2 and CO2 continuous emission monitoring systems 
(CEMS) at the time of installation or soon after and whenever specified 
in an applicable subpart of the regulations. This specification applies 
to O2 or CO2 monitors that are not included under 
Performance Specification 2 (PS 2).
    1.2.2  This specification is not designed to evaluate the installed 
CEMS performance over an extended period of time, nor does it identify 
specific calibration techniques and other auxiliary procedures to 
assess the CEMS performance. The source owner or operator, is 
responsible to calibrate, maintain, and operate the CEMS properly. The 
Administrator may require, under Section 114 of the Act, the operator 
to conduct CEMS performance evaluations at other times besides the 
initial test to evaluate the CEMS performance. See 40 CFR part 60, 
Section 60.13(c).
    1.2.3  The definitions, installation and measurement location 
specifications, calculations and data analysis, and references are the 
same as in PS 2, Sections 3, 8.1, 12, and 17, respectively, and also 
apply to O2 and CO2 CEMS under this 
specification. The performance and equipment specifications and the 
relative accuracy (RA) test procedures for O2 and 
CO2 CEMS do not differ from those for SO2 and 
NOx CEMS (see PS 2), except as noted below.

2.0  Summary of Performance Specification

    The RA and calibration drift (CD) tests are conducted to determine 
conformance of the CEMS to the specification.

3.0  Definitions

    Same as in Section 3.0 of PS 2.

4.0  Interferences [Reserved]

5.0  Safety

    This performance specification may involve hazardous materials, 
operations, and equipment. This performance specification may not 
address all of the safety problems associated with its use. It is the 
responsibility of the user to establish appropriate safety and health 
practices and determine the applicable regulatory limitations prior to 
performing this performance specification. The CEMS users manual should 
be consulted for specific precautions to be taken with regard to the 
analytical procedures.

6.0  Equipment and Supplies

    Same as Section 6.0 of PS2.

7.0  Reagents and Standards

    Same as Section 7.0 of PS2.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Relative Accuracy Test Procedure. Sampling Strategy for 
reference method (RM) Tests, Correlation of RM and CEMS Data, and 
Number of RM Tests. Same as PS 2, Sections 8.4.3, 8.4.5, and 8.4.4, 
respectively.
    8.2  Reference Method. Unless otherwise specified in an applicable 
subpart of the regulations, Method 3B or other approved alternative is 
the RM for O2 or CO2.

9.0  Quality Control [Reserved]

10.0  Calibration and Standardization [Reserved]

11.0  Analytical Procedure

    Sample collection and analyses are concurrent for this performance 
specification (see Section 8). Refer to the RM for specific analytical 
procedures.

12.0  Calculations and Data Analysis

    Summarize the results on a data sheet similar to that shown in 
Figure 2.2 of PS2. Calculate the arithmetic difference between the RM 
and the CEMS output for each run. The average difference of the nine 
(or more) data sets constitute the RA.

13.0  Method Performance

    13.1  Calibration Drift Performance Specification. The CEMS 
calibration must not drift by more than 0.5 percent O2 or 
CO2 from the reference value of the gas, gas cell, or 
optical filter.
    13.2  CEMS Relative Accuracy Performance Specification. The RA of 
the CEMS must be no greater than 1.0 percent O2 or 
CO2.

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

    Same as in Section 17.0 of PS 2.

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

Performance Specification 4--Specifications and Test Procedures for 
Carbon Monoxide Continuous Emission Monitoring Systems in 
Stationary Sources

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
                        Analyte                              CAS No.
------------------------------------------------------------------------
Carbon Monoxide (CO)...................................        630-08-0
------------------------------------------------------------------------

    1.2  Applicability.
    1.2.1  This specification is for evaluating the acceptability of 
carbon monoxide (CO) continuous emission monitoring systems (CEMS) at 
the time of installation or soon after and whenever specified in an 
applicable subpart of the regulations. This specification was developed 
primarily for CEMS having span values of 1,000 ppmv CO.
    1.2.2  This specification is not designed to evaluate the installed 
CEMS performance over an extended period of time nor does it identify 
specific calibration techniques and other auxiliary procedures to 
assess CEMS performance. The source owner or operator, is responsible 
to calibrate, maintain, and operate the CEMS. The Administrator may 
require, under Section 114 of the Act, the source owner or operator to 
conduct CEMS performance evaluations at other times besides the initial 
test to evaluate the CEMS performance. See 40 CFR part 60, Section 
60.13(c).
    1.2.3  The definitions, performance specification test procedures, 
calculations, and data analysis procedures for determining calibration 
drift (CD) and relative accuracy (RA) of Performance Specification 2 
(PS 2), Sections 3, 8.0, and 12, respectively, apply to this 
specification.

2.0  Summary of Performance Specification

    The CD and RA tests are conducted to determine conformance of the 
CEMS to the specification.

[[Page 62137]]

3.0  Definitions

    Same as in Section 3.0 of PS 2.

4.0  Interferences [Reserved]

5.0  Safety

    This performance specification may involve hazardous materials, 
operations, and equipment. This performance specification may not 
address all of the safety problems associated with its use. It is the 
responsibility of the user to establish appropriate safety and health 
practices and determine the applicable regulatory limitations prior to 
performing this performance specification. The CEMS users manual should 
be consulted for specific precautions to be taken with regard to the 
analytical procedures.

6.0  Equipment and Supplies

    Same as Section 6.0 of PS 2.

7.0  Reagents and Standards

    Same as Section 7.0 of PS 2.

8.0   Sample Collection, Preservation, Storage, and Transport

    8.1  Relative Accuracy Test Procedure. Sampling Strategy for 
reference method (RM) Tests, Number of RM Tests, and Correlation of RM 
and CEMS Data are the same as PS 2, Sections 8.4.3, 8.4.4, and 8.4.5, 
respectively.
    8.2  Reference Methods. Unless otherwise specified in an applicable 
subpart of the regulation, Method 10, 10A, 10B or other approved 
alternative are the RM for this PS. When evaluating nondispersive 
infrared CEMS using Method 10 as the RM, the alternative interference 
trap specified in Section 16.0 of Method 10 shall be used.

9.0  Quality Control [Reserved]

10.0  Calibration and Standardization [Reserved]

11.0  Analytical Procedure

    Sample collection and analysis are concurrent for this performance 
specification (see Section 8.0). Refer to the RM for specific 
analytical procedures.

12.0  Calculations and Data Analysis

    Same as Section 12.0 of PS 2.

13.0 Method Performance

    13.1 Calibration Drift. The CEMS calibration must not drift or 
deviate from the reference value of the calibration gas, gas cell, or 
optical filter by more than 5 percent of the established span value for 
6 out of 7 test days (e.g., the established span value is 1000 ppm for 
Subpart J affected facilities).
    13.2  Relative Accuracy. The RA of the CEMS must be no greater than 
10 percent when the average RM value is used to calculate RA or 5 
percent when the applicable emission standard is used to calculate RA.

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  Alternative Procedures [Reserved]

17.0  References

    1. Ferguson, B.B., R.E. Lester, and W.J. Mitchell. Field 
Evaluation of Carbon Monoxide and Hydrogen Sulfide Continuous 
Emission Monitors at an Oil Refinery. U.S. Environmental Protection 
Agency. Research Triangle Park, N.C. Publication No. EPA-600/4-82-
054. August 1982. 100 p.
    2. ``Gaseous Continuous Emission Monitoring Systems--Performance 
Specification Guidelines for SO2, NOx, 
CO2, O2, and TRS.'' EPA-450/3-82-026. U.S. 
Environmental Protection Agency, Technical Support Division (MD-19), 
Research Triangle Park, NC 27711.
    3. Repp, M. Evaluation of Continuous Monitors for Carbon 
Monoxide in Stationary Sources. U.S. Environmental Protection 
Agency. Research Triangle Park, N.C. Publication No. EPA-600/2-77-
063. March 1977. 155 p.
    4. Smith, F., D.E. Wagoner, and R.P. Donovan. Guidelines for 
Development of a Quality Assurance Program: Volume VIII--
Determination of CO Emissions from Stationary Sources by NDIR 
Spectrometry. U.S. Environmental Protection Agency. Research 
Triangle Park, N.C. Publication No. EPA-650/4-74-005-h. February 
1975. 96 p.

18.0  Tables, Diagrams, Flowcharts, and Validation Data

    Same as Section 18.0 of PS 2.

Performance Specification 4A--Specifications and Test Procedures 
for Carbon Monoxide Continuous Emission Monitoring Systems in 
Stationary Sources

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
                        Analyte                              CAS No.
------------------------------------------------------------------------
Carbon Monoxide (CO)...................................        630-80-0
------------------------------------------------------------------------

    1.2  Applicability.
    1.2.1  This specification is for evaluating the acceptability of 
carbon monoxide (CO) continuous emission monitoring systems (CEMS) at 
the time of installation or soon after and whenever specified in an 
applicable subpart of the regulations. This specification was developed 
primarily for CEMS that comply with low emission standards (less than 
200 ppmv).
    1.2.2  This specification is not designed to evaluate the installed 
CEMS performance over an extended period of time nor does it identify 
specific calibration techniques and other auxiliary procedures to 
assess CEMS performance. The source owner or operator is responsible to 
calibrate, maintain, and operate the CEMS. The Administrator may 
require, under Section 114 of the Act, the source owner or operator to 
conduct CEMS performance evaluations at other times besides the initial 
test to evaluate CEMS performance. See 40 CFR Part 60, Section 
60.13(c).
    1.2.3  The definitions, performance specification, test procedures, 
calculations and data analysis procedures for determining calibration 
drifts (CD) and relative accuracy (RA), of Performance Specification 2 
(PS 2), Sections 3, 8.0, and 12, respectively, apply to this 
specification.

2.0  Summary of Performance Specification

    The CD and RA tests are conducted to determine conformance of the 
CEMS to the specification.

3.0  Definitions

    Same as in Section 3.0 of PS 2.

4.0  Interferences. [Reserved]

5.0  Safety

    This performance specification may involve hazardous materials, 
operations, and equipment. This performance specification may not 
address all of the safety problems associated with its use. It is the 
responsibility of the user to establish appropriate safety and health 
practices and determine the applicable regulatory limitations prior to 
performing this performance specification. The CEMS users manual should 
be consulted for specific precautions to be taken with regard to the 
analytical procedures.

6.0  Equipment and Supplies

    Same as Section 6.0 of PS 2 with the following additions.
    6.1  Data Recorder Scale.
    6.1.1 This specification is the same as Section 6.1 of PS 2. The 
CEMS shall be capable of measuring emission levels under normal 
conditions and under periods of short-duration peaks of high 
concentrations. This dual-range capability may be met using two 
separate analyzers (one for each range) or by using dual-range units 
which have the capability of measuring both levels with a single unit. 
In the latter case, when the reading goes above the full-scale 
measurement value of the lower range, the higher-range operation shall 
be started automatically. The CEMS recorder range must include zero and 
a

[[Page 62138]]

high-level value. Under applications of consistent low emissions, a 
single-range analyzer is allowed provided normal and spike emissions 
can be quantified. In this case, set an appropriate high-level value to 
include all emissions.
    6.1.2  For the low-range scale of dual-range units, the high-level 
value shall be between 1.5 times the pollutant concentration 
corresponding to the emission standard level and the span value. For 
the high-range scale, the high-level value shall be set at 2000 ppm, as 
a minimum, and the range shall include the level of the span value. 
There shall be no concentration gap between the low-and high-range 
scales.

7.0  Reagents and Standards

    Same as Section 7.0 of PS 2.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Relative Accuracy Test Procedure. Sampling Strategy for 
reference method (RM) Tests, Number of RM Tests, and Correlation of RM 
and CEMS Data are the same as PS 2, Sections 8.4.3, 8.4.4, and 8.4.5, 
respectively.
    8.2  Reference Methods. Unless otherwise specified in an applicable 
subpart of the regulation, Methods 10, 10A, 10B, or other approved 
alternative is the RM for this PS. When evaluating nondispersive 
infrared CEMS using Method 10 as the RM, the alternative interference 
trap specified in Section 16.0 of Method 10 shall be used.
    8.3  Response Time Test Procedure. The response time test applies 
to all types of CEMS, but will generally have significance only for 
extractive systems.
    8.3.1  Introduce zero gas into the analyzer. When the system output 
has stabilized (no change greater than 1 percent of full scale for 30 
sec), introduce an upscale calibration gas and wait for a stable value. 
Record the time (upscale response time) required to reach 95 percent of 
the final stable value. Next, reintroduce the zero gas and wait for a 
stable reading before recording the response time (downscale response 
time). Repeat the entire procedure three times and determine the mean 
upscale and downscale response times. The slower or longer of the two 
means is the system response time.
    8.4  Interference Check. The CEMS must be shown to be free from the 
effects of any interferences.

9.0  Quality Control. [Reserved]

10.0  Calibration and Standardization. [Reserved]

11.0  Analytical Procedure

    Sample collection and analysis are concurrent for this performance 
specification (see Section 8.0). Refer to the RM for specific 
analytical procedures.

12.0  Calculations and Data Analysis. Same as Section 12.0 of PS 2

13.0  Method Performance

    13.1  Calibration Drift. The CEMS calibration must not drift or 
deviate from the reference value of the calibration gas, gas cell, or 
optical filter by more than 5 percent of the established span value for 
6 out of 7 test days.
    13.2  Relative Accuracy. The RA of the CEMS must be no greater than 
10 percent when the average RM value is used to calculate RA, 5 percent 
when the applicable emission standard is used to calculate RA, or 
within 5 ppmv when the RA is calculated as the absolute average 
difference between the RM and CEMS plus the 2.5 percent confidence 
coefficient.
    13.3  Response Time. The CEMS response time shall not exceed 1.5 
min to achieve 95 percent of the final stable value.

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  Alternative Procedures

    16.1  Under conditions where the average CO emissions are less than 
10 percent of the standard and this is verified by Method 10, a 
cylinder gas audit may be performed in place of the RA test to 
determine compliance with these limits. In this case, the cylinder gas 
shall contain CO in 12 percent carbon dioxide as an interference check. 
If this option is exercised, Method 10 must be used to verify that 
emission levels are less than 10 percent of the standard.

17.0  References

    Same as Section 17 of PS 4.

18.0  Tables, Diagrams, Flowcharts, and Validation Data

    Same as Section 18.0 of PS 2.

Performance Specification 5--Specifications and Test Procedures for 
TRS Continuous Emission Monitoring Systems in Stationary Sources

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
                        Analyte                              CAS No.
------------------------------------------------------------------------
Total Reduced Sulfur (TRS).............................              NA
------------------------------------------------------------------------

    1.2  Applicability. This specification is for evaluating the 
applicability of TRS continuous emission monitoring systems (CEMS) at 
the time of installation or soon after and whenever specified in an 
applicable subpart of the regulations. The CEMS may include oxygen 
monitors which are subject to Performance Specification 3 (PS 3).
    1.3  The definitions, performance specification, test procedures, 
calculations and data analysis procedures for determining calibration 
drifts (CD) and relative accuracy (RA) of PS 2, Sections 3.0, 8.0, and 
12.0, respectively, apply to this specification.

2.0  Summary of Performance Specification

    The CD and RA tests are conducted to determine conformance of the 
CEMS to the specification.

3.0  Definitions

    Same as in Section 3.0 of PS 2.

4.0  Interferences [Reserved]

5.0   Safety

    This performance specification may involve hazardous materials, 
operations, and equipment. This performance specification may not 
address all of the safety problems associated with its use. It is the 
responsibility of the user to establish appropriate safety and health 
practices and determine the applicable regulatory limitations prior to 
performing this performance specification. The CEMS users manual should 
be consulted for specific precautions to be taken with regard to the 
analytical procedures.

6.0  Equipment and Supplies

    Same as Section 6.0 of PS 2.

7.0  Reagents and Standards

    Same as Section 7.0 of PS 2.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Relative Accuracy Test Procedure. Sampling Strategy for 
reference method (RM) Tests, Number of RM Tests, and Correlation of RM 
and CEMS Data are the same as PS 2, Sections 8.4.3, 8.4.4, and 8.4.5, 
respectively.


    Note: For Method 16, a sample is made up of at least three 
separate injects equally space over time. For Method 16A, a sample 
is collected for at least 1 hour.

    8.2  Reference Methods. Unless otherwise specified in the 
applicable subpart of the regulations, Method 16,

[[Page 62139]]

Method 16A, 16B or other approved alternative is the RM for TRS.

9.0  Quality Control [Reserved]

10.0  Calibration and Standardization [Reserved]

11.0  Analytical Procedure

    Sample collection and analysis are concurrent for this performance 
specification (see Section 8.0). Refer to the reference method for 
specific analytical procedures.

12.0  Calculations and Data Analysis

    Same as Section 12.0 of PS 2.

13.0  Method Performance

    13.1 Calibration Drift. The CEMS detector calibration must not 
drift or deviate from the reference value of the calibration gas by 
more than 5 percent of the established span value for 6 out of 7 test 
days. This corresponds to 1.5 ppm drift for Subpart BB sources where 
the span value is 30 ppm. If the CEMS includes pollutant and diluent 
monitors, the CD must be determined separately for each in terms of 
concentrations (see PS 3 for the diluent specifications).
    13.2  Relative Accuracy. The RA of the CEMS must be no greater than 
20 percent when the average RM value is used to calculate RA or 10 
percent when the applicable emission standard is used to calculate RA.

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  Alternative Procedures [Reserved]

17.0  References

    1. Department of Commerce. Experimental Statistics, National 
Bureau of Standards, Handbook 91. 1963. Paragraphs 3-3.1.4, p. 3-31.
    2. A Guide to the Design, Maintenance and Operation of TRS 
Monitoring Systems. National Council for Air and Stream Improvement 
Technical Bulletin No. 89. September 1977.
    3. Observation of Field Performance of TRS Monitors on a Kraft 
Recovery Furnace. National Council for Air and Stream Improvement 
Technical Bulletin No. 91. January 1978.

18.0  Tables, Diagrams, Flowcharts, and Validation Data

    Same as Section 18.0 of PS 2.

Performance Specification 6--Specifications and Test Procedures for 
Continuous Emission Rate Monitoring Systems in Stationary Sources

1.0  Scope and Application

    1.1  Applicability. This specification is used for evaluating the 
acceptability of continuous emission rate monitoring systems (CERMSs).
    1.2  The installation and measurement location specifications, 
performance specification test procedure, calculations, and data 
analysis procedures, of Performance Specifications (PS 2), Sections 8.0 
and 12, respectively, apply to this specification.

2.0  Summary of Performance Specification

    The calibration drift (CD) and relative accuracy (RA) tests are 
conducted to determine conformance of the CERMS to the specification.

3.0  Definitions

    The definitions are the same as in Section 3 of PS 2, except this 
specification refers to the continuous emission rate monitoring system 
rather than the continuous emission monitoring system. The following 
definitions are added:
    3.1  Continuous Emission Rate Monitoring System (CERMS). The total 
equipment required for the determining and recording the pollutant mass 
emission rate (in terms of mass per unit of time).
    3.2  Flow Rate Sensor. That portion of the CERMS that senses the 
volumetric flow rate and generates an output proportional to that flow 
rate. The flow rate sensor shall have provisions to check the CD for 
each flow rate parameter that it measures individually (e.g., velocity, 
pressure).

4.0  Interferences [Reserved]

5.0  Safety

    This performance specification may involve hazardous materials, 
operations, and equipment. This performance specification may not 
address all of the safety problems associated with its use. It is the 
responsibility of the user to establish appropriate safety and health 
practices and determine the applicable regulatory limitations prior to 
performing this performance specification. The CERMS users manual 
should be consulted for specific precautions to be taken with regard to 
the analytical procedures.

6.0  Equipment and Supplies

    Same as Section 6.0 of PS 2.

7.0  Reagents and Standards

    Same as Section 7.0 of PS 2.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Calibration Drift Test Procedure.
    8.1.1  The CD measurements are to verify the ability of the CERMS 
to conform to the established CERMS calibrations used for determining 
the emission rate. Therefore, if periodic automatic or manual 
adjustments are made to the CERMS zero and calibration settings, 
conduct the CD tests immediately before these adjustments, or conduct 
them in such a way that CD can be determined.
    8.1.2  Conduct the CD tests for pollutant concentration at the two 
values specified in Section 6.1.2 of PS 2. For other parameters that 
are selectively measured by the CERMS (e.g., velocity, pressure, flow 
rate), use two analogous values (e.g., Low: 0-20% of full scale, High: 
50-100% of full scale). Introduce to the CERMS the reference signals 
(these need not be certified). Record the CERMS response to each and 
subtract this value from the respective reference value (see example 
data sheet in Figure 6-1).
    8.2  Relative Accuracy Test Procedure.
    8.2.1  Sampling Strategy for reference method (RM) Tests, 
Correlation of RM and CERMS Data, and Number of RM Tests are the same 
as PS 2, Sections 8.4.3, 8.4.5, and 8.4.4, respectively. Summarize the 
results on a data sheet. An example is shown in Figure 6-1. The RA test 
may be conducted during the CD test period.
    8.2.2  Reference Methods. Unless otherwise specified in the 
applicable subpart of the regulations, the RM for the pollutant gas is 
the Appendix A method that is cited for compliance test purposes, or 
its approved alternatives. Methods 2, 2A, 2B, 2C, or 2D, as applicable, 
are the RMs for the determination of volumetric flow rate.

9.0  Quality Control [Reserved]

10.0  Calibration and Standardization [Reserved]

11.0  Analytical Procedure

    Same as Section 11.0 of PS 2.

12.0  Calculations and Data Analysis

    Same as Section 12.0 of PS 2.

13.0  Method Performance

    13.1  Calibration Drift. Since the CERMS includes analyzers for 
several measurements, the CD shall be determined separately for each 
analyzer in terms of its specific measurement. The calibration for each 
analyzer associated with the measurement of flow rate shall not drift 
or deviate from each reference value of flow rate by more than 3 
percent of the respective high-level value. The CD specification for 
each analyzer for which other PSs have been established (e.g., PS 2 for 
SO2

[[Page 62140]]

and NOX), shall be the same as in the applicable PS.
    13.2  CERMS Relative Accuracy. The RA of the CERMS shall be no 
greater than 20 percent of the mean value of the RM's test data in 
terms of the units of the emission standard, or 10 percent of the 
applicable standard, whichever is greater.

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  Alternative Procedures

    Same as in Section 16.0 of PS 2.

17.0  References

    1. Brooks, E.F., E.C. Beder, C.A. Flegal, D.J. Luciani, and R. 
Williams. Continuous Measurement of Total Gas Flow Rate from 
Stationary Sources. U.S. Environmental Protection Agency. Research 
Triangle Park, North Carolina. Publication No. EPA-650/2-75-020. 
February 1975. 248 p.

18.0  Tables, Diagrams, Flowcharts, and Validation Data

----------------------------------------------------------------------------------------------------------------
                                                                    Emission rate (kg/hr)a
                                            --------------------------------------------------------------------
      Run No.             Date and time                                                      Difference  (RMs-
                                                     CERMS                   RMs                   CERMS)
----------------------------------------------------------------------------------------------------------------
1                                                                                          .....................
----------------------------------------------------------------------------------------------------------------
2                                                                                          .....................
----------------------------------------------------------------------------------------------------------------
3                                                                                          .....................
----------------------------------------------------------------------------------------------------------------
4                                                                                          .....................
----------------------------------------------------------------------------------------------------------------
5                                                                                          .....................
----------------------------------------------------------------------------------------------------------------
6                                                                                          .....................
----------------------------------------------------------------------------------------------------------------
7                                                                                          .....................
----------------------------------------------------------------------------------------------------------------
8                                                                                          .....................
----------------------------------------------------------------------------------------------------------------
9                                                                                          .....................
----------------------------------------------------------------------------------------------------------------
\a\ The RMs and CERMS data as corrected to a consistent basis (i.e., moisture, temperature, and pressure
  conditions).

Figure 6-1.--Emission Rate Determinations

Performance Specification 7--Specifications and Test Procedures for 
Hydrogen Sulfide Continuous Emission Monitoring Systems in 
Stationary Sources

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
                         Analyte                              CAS No.
------------------------------------------------------------------------
Hydrogen Sulfide........................................       7783-06-4
------------------------------------------------------------------------

    1.2  Applicability.
    1.2.1  This specification is to be used for evaluating the 
acceptability of hydrogen sulfide (H2S) continuous emission 
monitoring systems (CEMS) at the time of or soon after installation and 
whenever specified in an applicable subpart of the regulations.
    1.2.2  This specification is not designed to evaluate the installed 
CEMS performance over an extended period of time nor does it identify 
specific calibration techniques and other auxiliary procedures to 
assess CEMS performance. The source owner or operator, however, is 
responsible to calibrate, maintain, and operate the CEMS. To evaluate 
CEMS performance, the Administrator may require, under Section 114 of 
the Act, the source owner or operator to conduct CEMS performance 
evaluations at other times besides the initial test. See Section 
60.13(c).

2.0  Summary

    Calibration drift (CD) and relative accuracy (RA) tests are 
conducted to determine that the CEMS conforms to the specification.

3.0  Definitions

    Same as Section 3.0 of PS 2.

4.0  Interferences. [Reserved]

5.0  Safety

    The procedures required under this performance specification may 
involve hazardous materials, operations, and equipment. This 
performance specification may not address all of the safety problems 
associated with these procedures. It is the responsibility of the user 
to establish appropriate safety problems associated with these 
procedures. It is the responsibility of the user to establish 
appropriate safety and health practices and determine the application 
regulatory limitations prior to performing these procedures. The CEMS 
user's manual and materials recommended by the reference method should 
be consulted for specific precautions to be taken.

6.0  Equipment and Supplies

    6.1  Instrument Zero and Span. This specification is the same as 
Section 6.1 of PS 2.
    6.2  Calibration Drift. The CEMS calibration must not drift or 
deviate from the reference value of the calibration gas or reference 
source by more than 5 percent of the established span value for 6 out 
of 7 test days (e.g., the established span value is 300 ppm for Subpart 
J fuel gas combustion devices).
    6.3  Relative Accuracy. The RA of the CEMS must be no greater than 
20 percent when the average reference method (RM) value is used to 
calculate RA or 10 percent when the applicable emission standard is 
used to calculate RA.

7.0  Reagents and Standards

    Same as Section 7.0 of PS 2.

8.0  Sample Collection, Preservation, Storage, and Transport.

    8.1  Installation and Measurement Location Specification. Same as 
Section 8.1 of PS 2.
    8.2  Pretest Preparation. Same as Section 8.2 of PS 2.
    8.3  Calibration Drift Test Procedure. Same as Section 8.3 of PS 2.
    8.4  Relative Accuracy Test Procedure.

[[Page 62141]]

    8.4.1  Sampling Strategy for RM Tests, Correlation of RM and CEMS 
Data, and Number of RM Tests. These are the same as that in PS 2, 
Sections 8.4.3, 8.4.5, and 8.4.4, respectively.
    8.4.2  Reference Methods. Unless otherwise specified in an 
applicable subpart of the regulation, Method 11 is the RM for this PS.
    8.5  Reporting. Same as Section 8.5 of PS 2.

9.0  Quality Control. [Reserved]

10.0  Calibration and Standardizations. [Reserved]

11.0  Analytical Procedures

    Sample Collection and analysis are concurrent for this PS (see 
Section 8.0). Refer to the RM for specific analytical procedures.

12.0  Data Analysis and Calculations

    Same as Section 12.0 of PS 2.

13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    1. U.S. Environmental Protection Agency. Standards of 
Performance for New Stationary Sources; Appendix B; Performance 
Specifications 2 and 3 for SO2, NOX, 
CO2, and O2 Continuous Emission Monitoring 
Systems; Final Rule. 48 CFR 23608. Washington, D.C. U.S. Government 
Printing Office. May 25, 1983.
    2. U.S. Government Printing Office. Gaseous Continuous Emission 
Monitoring Systems--Performance Specification Guidelines for 
SO2, NOX, CO2, O2, and 
TRS. U.S. Environmental Protection Agency. Washington, D.C. EPA-450/
3-82-026. October 1982. 26 p.
    3. Maines, G.D., W.C. Kelly (Scott Environmental Technology, 
Inc.), and J.B. Homolya. Evaluation of Monitors for Measuring 
H2S in Refinery Gas. Prepared for the U.S. Environmental 
Protection Agency. Research Triangle Park, N.C. Contract No. 68-02-
2707. 1978. 60 p.
    4. Ferguson, B.B., R.E. Lester (Harmon Engineering and Testing), 
and W.J. Mitchell. Field Evaluation of Carbon Monoxide and Hydrogen 
Sulfide Continuous Emission Monitors at an Oil Refinery. Prepared 
for the U.S. Environmental Protection Agency. Research Triangle 
Park, N.C. Publication No. EPA-600/4-82-054. August 1982. 100 p.

17.0  Tables, Diagrams, Flowcharts, and Validation Data

    Same as Section 18.0 of PS 2.

Performance Specification 8 Performance Specifications for Volatile 
Organic Compound Continuous Emission Monitoring Systems in 
Stationary Sources

1.0  Scope and Application

    1.1  Analytes. Volatile Organic Compounds (VOCs).
    1.2  Applicability.
    1.2.1  This specification is to be used for evaluating a continuous 
emission monitoring system (CEMS) that measures a mixture of VOC's and 
generates a single combined response value. The VOC detection principle 
may be flame ionization (FI), photoionization (PI), non-dispersive 
infrared absorption (NDIR), or any other detection principle that is 
appropriate for the VOC species present in the emission gases and that 
meets this performance specification. The performance specification 
includes procedures to evaluate the acceptability of the CEMS at the 
time of or soon after its installation and whenever specified in 
emission regulations or permits. This specification is not designed to 
evaluate the installed CEMS performance over an extended period of 
time, nor does it identify specific calibration techniques and other 
auxiliary procedures to assess the CEMS performance. The source owner 
or operator, however, is responsible to calibrate, maintain, and 
operate the CEMS properly. To evaluate the CEMS performance, the 
Administrator may require, under Section 114 of the Act, the operator 
to conduct CEMS performance evaluations in addition to the initial 
test. See Section 60.13(c).
    1.2.2  In most emission circumstances, most VOC monitors can 
provide only a relative measure of the total mass or volume 
concentration of a mixture of organic gases, rather than an accurate 
quantification. This problem is removed when an emission standard is 
based on a total VOC measurement as obtained with a particular 
detection principle. In those situations where a true mass or volume 
VOC concentration is needed, the problem can be mitigated by using the 
VOC CEMS as a relative indicator of total VOC concentration if 
statistical analysis indicates that a sufficient margin of compliance 
exists for this approach to be acceptable. Otherwise, consideration can 
be given to calibrating the CEMS with a mixture of the same VOC's in 
the same proportions as they actually occur in the measured source. In 
those circumstances where only one organic species is present in the 
source, or where equal incremental amounts of each of the organic 
species present generate equal CEMS responses, the latter choice can be 
more easily achieved.

2.0  Summary of Performance Specification

    2.1  Calibration drift and relative accuracy tests are conducted to 
determine adherence of the CEMS with specifications given for those 
items. The performance specifications include criteria for installation 
and measurement location, equipment and performance, and procedures for 
testing and data reduction.

3.0  Definitions.

    Same as Section 3.0 of PS 2.

4.0  Interferences. [Reserved]

5.0  Safety

    The procedures required under this performance specification may 
involve hazardous materials, operations, and equipment. This 
performance specification may not address all of the safety problems 
associated with these procedures. It is the responsibility of the user 
to establish appropriate safety problems associated with these 
procedures. It is the responsibility of the user to establish 
appropriate safety and health practices and determine the application 
regulatory limitations prior to performing these procedures. The CEMS 
user's manual and materials recommended by the reference method should 
be consulted for specific precautions to be taken.

6.0  Equipment and Supplies

    6.1  VOC CEMS Selection. When possible, select a VOC CEMS with the 
detection principle of the reference method specified in the regulation 
or permit (usually either FI, NDIR, or PI). Otherwise, use knowledge of 
the source process chemistry, previous emission studies, or gas 
chromatographic analysis of the source gas to select an appropriate VOC 
CEMS. Exercise extreme caution in choosing and installing any CEMS in 
an area with explosive hazard potential.
    6.2  Data Recorder Scale. Same as Section 6.1 of PS 2.

7.0  Reagents and Standards. [Reserved]

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Installation and Measurement Location Specifications. Same as 
Section 8.1 of PS 2.
    8.2  Pretest Preparation. Same as Section 8.2 of PS 2.
    8.3  Reference Method (RM). Use the method specified in the 
applicable regulation or permit, or any approved alternative, as the 
RM.
    8.4  Sampling Strategy for RM Tests, Correlation of RM and CEMS 
Data, and Number of RM Tests. Follow PS 2, Sections 8.4.3, 8.4.5, and 
8.4.4, respectively.
    8.5  Reporting. Same as Section 8.5 of PS 2.

[[Page 62142]]

9.0  Quality Control. [Reserved]

10.0  Calibration and Standardization. [Reserved]

11.0  Analytical Procedure

    Sample collection and analysis are concurrent for this PS (see 
Section 8.0). Refer to the RM for specific analytical procedures.

12.0  Calculations and Data Analysis

    Same as Section 12.0 of PS 2.

13.0  Method Performance

    13.1  Calibration Drift. The CEMS calibration must not drift by 
more than 2.5 percent of the span value.
    13.2  CEMS Relative Accuracy. Unless stated otherwise in the 
regulation or permit, the RA of the CEMS must not be greater than 20 
percent of the mean value of the RM test data in terms of the units of 
the emission standard, or 10 percent of the applicable standard, 
whichever is greater.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    Same as Section 17.0 of PS 2.

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

Performance Specification 9--Specifications and Test Procedures for 
Gas Chromatographic Continuous Emission Monitoring Systems in 
Stationary Sources

1.0  Scope and Application

    1.1  Applicability. These requirements apply to continuous emission 
monitoring systems (CEMSs) that use gas chromatography (GC) to measure 
gaseous organic compound emissions. The requirements include procedures 
intended to evaluate the acceptability of the CEMS at the time of its 
installation and whenever specified in regulations or permits. Quality 
assurance procedures for calibrating, maintaining, and operating the 
CEMS properly at all times are also given in this procedure.

2.0  Summary of Performance Specification

    2.1  Calibration precision, calibration error, and performance 
audit tests are conducted to determine conformance of the CEMS with 
these specifications. Daily calibration and maintenance requirements 
are also specified.

3.0  Definitions

    3.1  Gas Chromatograph (GC). That portion of the system that 
separates and detects organic analytes and generates an output 
proportional to the gas concentration. The GC must be temperature 
controlled.


    Note: The term temperature controlled refers to the ability to 
maintain a certain temperature around the column. Temperature-
programmable GC is not required for this performance specification, 
as long as all other requirements for precision, linearity and 
accuracy listed in this performance specification are met. It should 
be noted that temperature programming a GC will speed up peak 
elution, thus allowing increased sampling frequency.


    3.1.1  Column. Analytical column capable of separating the analytes 
of interest.
    3.1.2  Detector. A detection system capable of detecting and 
quantifying all analytes of interest.
    3.1.3  Integrator. That portion of the system that quantifies the 
area under a particular sample peak generated by the GC.
    3.1.4  Data Recorder. A strip chart recorder, computer, or digital 
recorder capable of recording all readings within the instrument's 
calibration range.
    3.2  Calibration Precision. The error between triplicate injections 
of each calibration standard.

4.0  Interferences [Reserved]

5.0  Safety

    The procedures required under this performance specification may 
involve hazardous materials, operations, and equipment. This 
performance specification does not purport to address all of the safety 
problems associated with these procedures. It is the responsibility of 
the user to establish appropriate safety problems associated with these 
procedures. It is the responsibility of the user to establish 
appropriate safety and health practices and determine the application 
regulatory limitations prior to performing these procedures. The CEMS 
user's manual and materials recommended by the reference method should 
be consulted for specific precautions to be taken.

6.0  Equipment and Supplies

    6.1  Presurvey Sample Analysis and GC Selection. Determine the 
pollutants to be monitored from the applicable regulation or permit and 
determine the approximate concentration of each pollutant (this 
information can be based on past compliance test results). Select an 
appropriate GC configuration to measure the organic compounds. The GC 
components should include a heated sample injection loop (or other 
sample introduction systems), separatory column, temperature-controlled 
oven, and detector. If the source chooses dual column and/or dual 
detector configurations, each column/detector is considered a separate 
instrument for the purpose of this performance specification and thus 
the procedures in this performance specification shall be carried out 
on each system. If this method is applied in highly explosive areas, 
caution should be exercised in selecting the equipment and method of 
installation.
    6.2  Sampling System. The sampling system shall be heat traced and 
maintained at a minimum of 120  deg.C with no cold spots. All system 
components shall be heated, including the probe, calibration valve, 
sample lines, sampling loop (or sample introduction system), GC oven, 
and the detector block (when appropriate for the type of detector being 
utilized, e.g., flame ionization detector).

7.0  Reagents and Standards

    7.1  Calibration Gases. Obtain three concentrations of calibration 
gases certified by the manufacturer to be accurate to within 2 percent 
of the value on the label. A gas dilution system may be used to prepare 
the calibration gases from a high concentration certified standard if 
the gas dilution system meets the requirements specified in Test Method 
205, 40 CFR Part 51, Appendix M. The performance test specified in Test 
Method 205 shall be repeated quarterly, and the results of the Method 
205 test shall be included in the report. The calibration gas 
concentration of each target analyte shall be as follows (measured 
concentration is based on the presurvey concentration determined in 
Section 6.1).


    Note: If the low level calibration gas concentration falls at or 
below the limit of detection for the instrument for any target 
pollutant, a calibration gas with a concentration at 4 to 5 times 
the limit of detection for the instrument may be substituted for the 
low-level calibration gas listed in Section 7.1.1.

    7.1.1  Low-level. 40-60 percent of measured concentration.
    7.1.2  Mid-level. 90-110 percent of measured concentration.
    7.1.3  High-level. 140-160 percent of measured concentration, or 
select highest expected concentration.
    7.2  Performance Audit Gas. A certified EPA audit gas shall be 
used, when possible. A gas mixture containing all the target compounds 
within the calibration range and certified by EPA's Traceability 
Protocol for Assay and Certification of Gaseous Calibration Standards 
may be used when EPA performance audit materials

[[Page 62143]]

are not available. The instrument relative error shall be  
10 percent of the certified value of the audit gas.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Installation and Measurement Location Specifications. Install 
the CEMs in a location where the measurements are representative of the 
source emissions. Consider other factors, such as ease of access for 
calibration and maintenance purposes. The location should not be close 
to air in-leakages. The sampling location should be at least two 
equivalent duct diameters downstream from the nearest control device, 
point of pollutant generation, or other point at which a change in the 
pollutant concentration or emission rate occurs. The location should be 
at least 0.5 diameter upstream from the exhaust or control device. To 
calculate equivalent duct diameter, see Section 12.2 of Method 1 (40 
CFR Part 60, Appendix A). Sampling locations not conforming to the 
requirements in this section may be used if necessary upon approval of 
the Administrator.
    8.2  Pretest Preparation Period. Using the procedures described in 
Method 18
(40 CFR Part 60, Appendix A), perform initial tests to determine GC 
conditions that provide good resolution and minimum analysis time for 
compounds of interest. Resolution interferences that may occur can be 
eliminated by appropriate GC column and detector choice or by shifting 
the retention times through changes in the column flow rate and the use 
of temperature programming.
    8.3  7-Day Calibration Error (CE) Test Period. At the beginning of 
each 24-hour period, set the initial instrument setpoints by conducting 
a multi-point calibration for each compound. The multi-point 
calibration shall meet the requirements in Section 13.3. Throughout the 
24-hour period, sample and analyze the stack gas at the sampling 
intervals prescribed in the regulation or permit. At the end of the 24 
hour period, inject the three calibration gases for each compound in 
triplicate and determine the average instrument response. Determine the 
CE for each pollutant at each level using the equation in Section 9-2.
    Each CE shall be  10 percent. Repeat this procedure six 
more times for a total of 7 consecutive days.
    8.4  Performance Audit Test Periods. Conduct the performance audit 
once during the initial 7-day CE test and quarterly thereafter. Sample 
and analyze the EPA audit gas(es) (or the gas mixture prepared by EPA's 
traceability protocol if an EPA audit gas is not available) three 
times. Calculate the average instrument response. Report the audit 
results as part of the reporting requirements in the appropriate 
regulation or permit (if using a gas mixture, report the certified 
cylinder concentration of each pollutant).
    8.5  Reporting. Follow the reporting requirements of the applicable 
regulation or permit. If the reporting requirements include the results 
of this performance specification, summarize in tabular form the 
results of the CE tests. Include all data sheets, calculations, CEMS 
data records, performance audit results, and calibration gas 
concentrations and certifications.

9.0  Quality Control [Reserved]

10.0  Calibration and Standardization

    10.1  Initial Multi-Point Calibration. After initial startup of the 
GC, after routine maintenance or repair, or at least once per month, 
conduct a multi-point calibration of the GC for each target analyte. 
The multi-point calibration for each analyte shall meet the 
requirements in Section 13.3.
    10.2  Daily Calibration. Once every 24 hours, analyze the mid-level 
calibration standard for each analyte in triplicate. Calculate the 
average instrument response for each analyte. The average instrument 
response shall not vary more than 10 percent from the certified 
concentration value of the cylinder for each analyte. If the difference 
between the analyzer response and the cylinder concentration for any 
target compound is greater than 10 percent, immediately inspect the 
instrument making any necessary adjustments, and conduct an initial 
multi-point calibration as described in Section 10.1.

11.0  Analytical Procedure. Sample Collection and Analysis Are 
Concurrent for This Performance Specification (See Section 8.0)

12.0  Calculations and Data Analysis

12.1  Nomenclature.

Cm = average instrument response, ppm.
Ca = cylinder gas value, ppm.
F = Flow rate of stack gas through sampling system, in Liters/min.
n = Number of measurement points.
r2 = Coefficient of determination.
V = Sample system volume, in Liters, which is the volume inside the 
sample probe and tubing leading from the stack to the sampling loop.
x = CEMS response.
y = Actual value of calibration standard.
    12.2  Coefficient of Determination. Calculate r2 using 
linear regression analysis and the average concentrations obtained at 
three calibration points as shown in Equation 9-1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.461

    12.3  Calibration Error Determination. Determine the percent 
calibration error (CE) at each concentration for each pollutant using 
the following equation.
[GRAPHIC] [TIFF OMITTED] TR17OC00.462

    12.4  Sampling System Time Constant (T).
    [GRAPHIC] [TIFF OMITTED] TR17OC00.463
    
13.0  Method Performance

    13.1  Calibration Error (CE). The CEMS must allow the determination 
of CE at all three calibration levels. The average CEMS calibration 
response must not differ by more than 10 percent of calibration gas 
value at each level after each 24-hour period of the initial test.
    13.2  Calibration Precision and Linearity. For each triplicate 
injection at each concentration level for each target analyte, any one 
injection shall not deviate more than 5 percent from the average 
concentration measured at that level. The linear regression curve for 
each organic compound at all three levels shall have an r2 
0.995 (using Equation 9-1).
    13.3  Measurement Frequency. The sample to be analyzed shall flow 
continuously through the sampling system. The sampling system time

[[Page 62144]]

constant shall be 5 minutes or the sampling frequency 
specified in the applicable regulation, whichever is less. Use Equation 
9-3 to determine T. The analytical system shall be capable of measuring 
the effluent stream at the frequency specified in the appropriate 
regulation or permit.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References. [Reserved]

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

    218. In Part 60, Appendix B is amended by adding Performance 
Specification 15 as follows:

Appendix B--Performance Specifications

* * * * *

Performance Specification 15--Performance Specification for 
Extractive FTIR Continuous Emissions Monitor Systems in Stationary 
Sources

1.0  Scope and Application

    1.1  Analytes. This performance specification is applicable for 
measuring all hazardous air pollutants (HAPs) which absorb in the 
infrared region and can be quantified using Fourier Transform Infrared 
Spectroscopy (FTIR), as long as the performance criteria of this 
performance specification are met. This specification is to be used for 
evaluating FTIR continuous emission monitoring systems for measuring 
HAPs regulated under Title III of the 1990 Clean Air Act Amendments. 
This specification also applies to the use of FTIR CEMs for measuring 
other volatile organic or inorganic species.
    1.2  Applicability. A source which can demonstrate that the 
extractive FTIR system meets the criteria of this performance 
specification for each regulated pollutant may use the FTIR system to 
continuously monitor for the regulated pollutants.

2.0  Summary of Performance Specification

    For compound-specific sampling requirements refer to FTIR sampling 
methods (e.g., reference 1). For data reduction procedures and 
requirements refer to the EPA FTIR Protocol (reference 2), hereafter 
referred to as the ``FTIR Protocol.'' This specification describes 
sampling and analytical procedures for quality assurance. The infrared 
spectrum of any absorbing compound provides a distinct signature. The 
infrared spectrum of a mixture contains the superimposed spectra of 
each mixture component. Thus, an FTIR CEM provides the capability to 
continuously measure multiple components in a sample using a single 
analyzer. The number of compounds that can be speciated in a single 
spectrum depends, in practice, on the specific compounds present and 
the test conditions.

3.0  Definitions

    For a list of definitions related to FTIR spectroscopy refer to 
Appendix A of the FTIR Protocol. Unless otherwise specified, 
spectroscopic terms, symbols and equations in this performance 
specification are taken from the FTIR Protocol or from documents cited 
in the Protocol. Additional definitions are given below.
    3.1  FTIR Continuous Emission Monitoring System (FTIR CEM).
    3.1.1  FTIR System. Instrument to measure spectra in the mid-
infrared spectral region (500 to 4000 cm-1). It contains an 
infrared source, interferometer, sample gas containment cell, infrared 
detector, and computer. The interferometer consists of a beam splitter 
that divides the beam into two paths, one path a fixed distance and the 
other a variable distance. The computer is equipped with software to 
run the interferometer and store the raw digitized signal from the 
detector (interferogram). The software performs the mathematical 
conversion (the Fourier transform) of the interferogram into a spectrum 
showing the frequency dependent sample absorbance. All spectral data 
can be stored on computer media.
    3.1.2  Gas Cell. A gas containment cell that can be evacuated. It 
contains the sample as the infrared beam passes from the 
interferometer, through the sample, and to the detector. The gas cell 
may have multi-pass mirrors depending on the required detection 
limit(s) for the application.
    3.1.3  Sampling System. Equipment used to extract sample from the 
test location and transport the gas to the FTIR analyzer. Sampling 
system components include probe, heated line, heated non-reactive pump, 
gas distribution manifold and valves, flow measurement devices and any 
sample conditioning systems.
    3.2  Reference CEM. An FTIR CEM, with sampling system, that can be 
used for comparison measurements.
    3.3  Infrared Band (also Absorbance Band or Band). Collection of 
lines arising from rotational transitions superimposed on a vibrational 
transition. An infrared absorbance band is analyzed to determine the 
analyte concentration.
    3.4  Sample Analysis. Interpreting infrared band shapes, 
frequencies, and intensities to obtain sample component concentrations. 
This is usually performed by a software routine using a classical least 
squares (cls), partial least squares (pls), or K- or P- matrix method.
    3.5  (Target) Analyte. A compound whose measurement is required, 
usually to some established limit of detection and analytical 
uncertainty.
    3.6  Interferant. A compound in the sample matrix whose infrared 
spectrum overlaps at least part of an analyte spectrum complicating the 
analyte measurement. The interferant may not prevent the analyte 
measurement, but could increase the analytical uncertainty in the 
measured concentration. Reference spectra of interferants are used to 
distinguish the interferant bands from the analyte bands. An 
interferant for one analyte may not be an interferant for other 
analytes.
    3.7  Reference Spectrum. Infrared spectra of an analyte, or 
interferant, prepared under controlled, documented, and reproducible 
laboratory conditions (see Section 4.6 of the FTIR Protocol). A 
suitable library of reference spectra can be used to measure target 
analytes in gas samples.
    3.8  Calibration Spectrum. Infrared spectrum of a compound suitable 
for characterizing the FTIR instrument configuration (Section 4.5 in 
the FTIR Protocol).
    3.9  One hundred percent line. A double beam transmittance spectrum 
obtained by combining two successive background single beam spectra. 
Ideally, this line is equal to 100 percent transmittance (or zero 
absorbance) at every point in the spectrum. The zero absorbance line is 
used to measure the RMS noise of the system.
    3.10  Background Deviation. Any deviation (from 100 percent) in the 
one hundred percent line (or from zero absorbance). Deviations greater 
than  5 percent in any analytical region are unacceptable. 
Such deviations indicate a change in the instrument throughput relative 
to the single-beam background.
    3.11  Batch Sampling. A gas cell is alternately filled and 
evacuated. A Spectrum of each filled cell (one discreet sample) is 
collected and saved.
    3.12  Continuous Sampling. Sample is continuously flowing through a 
gas cell. Spectra of the flowing sample are collected at regular 
intervals.
    3.13  Continuous Operation. In continuous operation an FTIR CEM 
system, without user intervention, samples flue gas, records spectra of 
samples, saves the spectra to a disk, analyzes the spectra for the 
target

[[Page 62145]]

analytes, and prints concentrations of target analytes to a computer 
file. User intervention is permitted for initial set-up of sampling 
system, initial calibrations, and periodic maintenance.
    3.14  Sampling Time. In batch sampling--the time required to fill 
the cell with flue gas. In continuous sampling--the time required to 
collect the infrared spectrum of the sample gas.
    3.15  PPM-Meters. Sample concentration expressed as the 
concentration-path length product, ppm (molar) concentration multiplied 
by the path length of the FTIR gas cell. Expressing concentration in 
these units provides a way to directly compare measurements made using 
systems with different optical configurations. Another useful 
expression is (ppm-meters)/K, where K is the absolute temperature of 
the sample in the gas cell.
    3.16  CEM Measurement Time Constant. The Time Constant (TC, minutes 
for one cell volume to flow through the cell) determines the minimum 
interval for complete removal of an analyte from the FTIR cell. It 
depends on the sampling rate (Rs in Lpm), the FTIR cell 
volume (Vcell in L) and the chemical and physical properties 
of an analyte.
[GRAPHIC] [TIFF OMITTED] TR17OC00.464

For example, if the sample flow rate (through the FTIR cell) is 5 Lpm 
and the cell volume is 7 liters, then TC is equal to 1.4 minutes (0.71 
cell volumes per minute). This performance specification defines 5 * TC 
as the minimum interval between independent samples.
    3.17  Independent Measurement. Two independent measurements are 
spectra of two independent samples. Two independent samples are 
separated by, at least 5 cell volumes. The interval between independent 
measurements depends on the cell volume and the sample flow rate 
(through the cell). There is no mixing of gas between two independent 
samples. Alternatively, estimate the analyte residence time 
empirically: (1) Fill cell to ambient pressure with a (known analyte 
concentration) gas standard, (2) measure the spectrum of the gas 
standard, (3) purge the cell with zero gas at the sampling rate and 
collect a spectrum every minute until the analyte standard is no longer 
detected spectroscopically. If the measured time corresponds to less 
than 5 cell volumes, use 5 * TC as the minimum interval between 
independent measurements. If the measured time is greater than 5 * TC, 
then use this time as the minimum interval between independent 
measurements.
    3.18  Test Condition. A period of sampling where all process, and 
sampling conditions, and emissions remain constant and during which a 
single sampling technique and a single analytical program are used. One 
Run may include results for more than one test condition. Constant 
emissions means that the composition of the emissions remains 
approximately stable so that a single analytical program is suitable 
for analyzing all of the sample spectra. A greater than two-fold change 
in analyte or interferant concentrations or the appearance of 
additional compounds in the emissions, may constitute a new test 
condition and may require modification of the analytical program.
    3.19  Run. A single Run consists of spectra (one spectrum each) of 
at least 10 independent samples over a minimum of one hour. The 
concentration results from the spectra can be averaged together to give 
a run average for each analyte measured in the test run.

4.0  Interferences

    Several compounds, including water, carbon monoxide, and carbon 
dioxide, are known interferences in the infrared region in which the 
FTIR instrument operates. Follow the procedures in the FTIR protocol 
for subtracting or otherwise dealing with these and other 
interferences.

5.0  Safety

    The procedures required under this performance specification may 
involve hazardous materials, operations, and equipment. This 
performance specification may not address all of the safety problems 
associated with these procedures. It is the responsibility of the user 
to establish appropriate safety and health practices and determine the 
applicable regulatory limitations prior to performing these procedures. 
The CEMS users manual and materials recommended by this performance 
specification should be consulted for specific precautions to be taken.

6.0  Equipment and Supplies

    6.1  Installation of sampling equipment should follow requirements 
of FTIR test Methods such as references 1 and 3 and the EPA FTIR 
Protocol (reference 2). Select test points where the gas stream 
composition is representative of the process emissions. If comparing to 
a reference method, the probe tips for the FTIR CEM and the RM should 
be positioned close together using the same sample port if possible.
    6.2  FTIR Specifications. The FTIR CEM must be equipped with 
reference spectra bracketing the range of path length-concentrations 
(absorbance intensities) to be measured for each analyte. The effective 
concentration range of the analyzer can be adjusted by changing the 
path length of the gas cell or by diluting the sample. The optical 
configuration of the FTIR system must be such that maximum absorbance 
of any target analyte is no greater than 1.0 and the minimum absorbance 
of any target analyte is at least 10 times the RMSD noise in the 
analytical region. For example, if the measured RMSD in an analytical 
region is equal to 10-3, then the peak analyte absorbance is 
required to be at least 0.01. Adequate measurement of all of the target 
analytes may require changing path lengths during a run, conducting 
separate runs for different analytes, diluting the sample, or using 
more than one gas cell.
    6.3  Data Storage Requirements. The system must have sufficient 
capacity to store all data collected in one week of routine sampling. 
Data must be stored to a write-protected medium, such as write-once-
read-many (WORM) optical storage medium or to a password protected 
remote storage location. A back-up copy of all data can be temporarily 
saved to the computer hard drive. The following items must be stored 
during testing.
     At least one sample interferogram per sampling Run or one 
interferogram per hour, whichever is greater. This assumes that no 
sampling or analytical conditions have changed during the run.
     All sample absorbance spectra (about 12 per hr, 288 per 
day).
     All background spectra and interferograms (variable, but 
about 5 per day).
     All CTS spectra and interferograms (at least 2 each 24 
hour period).
     Documentation showing a record of resolution, path length, 
apodization, sampling time, sampling conditions, and test conditions 
for all sample, CTS, calibration, and background spectra.
    Using a resolution of 0.5 cm-1, with analytical range of 
3500 cm-1, assuming about 65 Kbytes per spectrum and 130 Kb 
per interferogram, the storage requirement is about 164 Mb for one week 
of continuous sampling. Lower spectral resolution requires less storage 
capacity. All of the above data must be stored for at least two weeks. 
After two weeks, storage requirements include: (1) all analytical 
results (calculated concentrations), (2) at least 1 sample spectrum 
with corresponding background and sample interferograms for each test 
condition, (3) CTS and calibration spectra with at least one 
interferogram for CTS and all interferograms for calibrations, (4) a

[[Page 62146]]

record of analytical input used to produce results, and (5) all other 
documentation. These data must be stored according to the requirements 
of the applicable regulation.

7.0  Reagents and Standards [Reserved]

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

9.0  Quality Control

    These procedures shall be used for periodic quarterly or semiannual 
QA/QC checks on the operation of the FTIR CEM. Some procedures test 
only the analytical program and are not intended as a test of the 
sampling system.
    9.1  Audit Sample. This can serve as a check on both the sampling 
system and the analytical program.
    9.1.1  Sample Requirements. The audit sample can be a mixture or a 
single component. It must contain target analyte(s) at approximately 
the expected flue gas concentration(s). If possible, each mixture 
component concentration should be NIST traceable ( 2 
percent accuracy). If a cylinder mixture standard(s) cannot be 
obtained, then, alternatively, a gas phase standard can be generated 
from a condensed phase analyte sample. Audit sample contents and 
concentrations are not revealed to the FTIR CEM operator until after 
successful completion of procedures in 5.3.2.
    9.1.2  Test Procedure. An audit sample is obtained from the 
Administrator. Spike the audit sample using the analyte spike procedure 
in Section 11. The audit sample is measured directly by the FTIR system 
(undiluted) and then spiked into the effluent at a known dilution 
ratio. Measure a series of spiked and unspiked samples using the same 
procedures as those used to analyze the stack gas. Analyze the results 
using Sections 12.1 and 12.2. The measured concentration of each 
analyte must be within  5 percent of the expected 
concentration (plus the uncertainty), i.e., the calculated correction 
factor must be within 0.93 and 1.07 for an audit with an analyte 
uncertainty of  2 percent.
    9.2  Audit Spectra. Audit spectra can be used to test the 
analytical program of the FTIR CEM, but provide no test of the sampling 
system.
    9.2.1  Definition and Requirements. Audit spectra are absorbance 
spectra that; (1) have been well characterized, and (2) contain 
absorbance bands of target analyte(s) and potential interferants at 
intensities equivalent to what is expected in the source effluent. 
Audit spectra are provided by the administrator without identifying 
information. Methods of preparing Audit spectra include; (1) 
mathematically adding sample spectra or adding reference and 
interferant spectra, (2) obtaining sample spectra of mixtures prepared 
in the laboratory, or (3) they may be sample spectra collected 
previously at a similar source. In the last case it must be 
demonstrated that the analytical results are correct and reproducible. 
A record associated with each Audit spectrum documents its method of 
preparation. The documentation must be sufficient to enable an 
independent analyst to reproduce the Audit spectra.
    9.2.2  Test Procedure. Audit spectra concentrations are measured 
using the FTIR CEM analytical program. Analytical results must be 
within  5 percent of the certified audit concentration for 
each analyte (plus the uncertainty in the audit concentration). If the 
condition is not met, demonstrate how the audit spectra are 
unrepresentative of the sample spectra. If the audit spectra are 
representative, modify the FTIR CEM analytical program until the test 
requirement is met. Use the new analytical program in subsequent FTIR 
CEM analyses of effluent samples.
    9.3  Submit Spectra For Independent Analysis. This procedure tests 
only the analytical program and not the FTIR CEM sampling system. The 
analyst can submit FTIR CEM spectra for independent analysis by EPA. 
Requirements for submission include; (1) three representative 
absorbance spectra (and stored interferograms) for each test period to 
be reviewed, (2) corresponding CTS spectra, (3) corresponding 
background spectra and interferograms, (4) spectra of associated spiked 
samples if applicable, and (5) analytical results for these sample 
spectra. The analyst will also submit documentation of process times 
and conditions, sampling conditions associated with each spectrum, file 
names and sampling times, method of analysis and reference spectra 
used, optical configuration of FTIR CEM including cell path length and 
temperature, spectral resolution and apodization used for every 
spectrum. Independent analysis can also be performed on site in 
conjunction with the FTIR CEM sampling and analysis. Sample spectra are 
stored on the independent analytical system as they are collected by 
the FTIR CEM system. The FTIR CEM and the independent analyses are then 
performed separately. The two analyses will agree to within 
120 percent for each analyte using the procedure in Section 
12.3. This assumes both analytical routines have properly accounted for 
differences in optical path length, resolution, and temperature between 
the sample spectra and the reference spectra.

10.0  Calibration and Standardization

    10.1  Calibration Transfer Standards. For CTS requirements see 
Section 4.5 of the FTIR Protocol. A well characterized absorbance band 
in the CTS gas is used to measure the path length and line resolution 
of the instrument. The CTS measurements made at the beginning of every 
24 hour period must agree to within  5 percent after 
correction for differences in pressure.
    Verify that the frequency response of the instrument and CTS 
absorbance intensity are correct by comparing to other CTS spectra or 
by referring to the literature.
    10.2  Analyte Calibration. If EPA library reference spectra are not 
available, use calibration standards to prepare reference spectra 
according to Section 6 of the FTIR Protocol. A suitable set of analyte 
reference data includes spectra of at least 2 independent samples at 
each of at least 2 different concentrations. The concentrations bracket 
a range that includes the expected analyte absorbance intensities. The 
linear fit of the reference analyte band areas must have a fractional 
calibration uncertainty (FCU in Appendix F of the FTIR Protocol) of no 
greater than 10 percent. For requirements of analyte standards refer to 
Section 4.6 of the FTIR Protocol.
    10.3  System Calibration. The calibration standard is introduced at 
a point on the sampling probe. The sampling system is purged with the 
calibration standard to verify that the absorbance measured in this way 
is equal to the absorbance in the analyte calibration. Note that the 
system calibration gives no indication of the ability of the sampling 
system to transport the target analyte(s) under the test conditions.
    10.4  Analyte Spike. The target analyte(s) is spiked at the outlet 
of the sampling probe, upstream of the particulate filter, and combined 
with effluent at a ratio of about 1 part spike to 9 parts effluent. The 
measured absorbance of the spike is compared to the expected absorbance 
of the spike plus the analyte concentration already in the effluent. 
This measures sampling system bias, if any, as distinguished from 
analyzer bias. It is important that spiked sample pass through all of 
the sampling system components before analysis.
    10.5  Signal-to-Noise Ratio (S/N). The measure of S/N in this 
performance specification is the root-mean-square (RMS) noise level as 
given in Appendix

[[Page 62147]]

C of the FTIR Protocol. The RMS noise level of a contiguous segment of 
a spectrum is defined as the RMS difference (RMSD) between the n 
contiguous absorbance values (Ai) which form the segment and 
the mean value (AM) of that segment.
[GRAPHIC] [TIFF OMITTED] TR17OC00.465

A decrease in the S/N may indicate a loss in optical throughput, or 
detector or interferometer malfunction.
    10.6  Background Deviation. The 100 percent baseline must be 
between 95 and 105 percent transmittance (absorbance of 0.02 to -0.02) 
in every analytical region. When background deviation exceeds this 
range, a new background spectrum must be collected using nitrogen or 
other zero gas.
    10.7  Detector Linearity. Measure the background and CTS at three 
instrument aperture settings; one at the aperture setting to be used in 
the testing, and one each at settings one half and twice the test 
aperture setting. Compare the three CTS spectra. CTS band areas should 
agree to within the uncertainty of the cylinder standard. If test 
aperture is the maximum aperture, collect CTS spectrum at maximum 
aperture, then close the aperture to reduce the IR through-put by half. 
Collect a second background and CTS at the smaller aperture setting and 
compare the spectra as above. Instead of changing the aperture neutral 
density filters can be used to attenuate the infrared beam. Set up the 
FTIR system as it will be used in the test measurements. Collect a CTS 
spectrum. Use a neutral density filter to attenuate the infrared beam 
(either immediately after the source or the interferometer) to 
approximately \1/2\ its original intensity. Collect a second CTS 
spectrum. Use another filter to attenuate the infrared beam to 
approximately \1/4\ its original intensity. Collect a third background 
and CTS spectrum. Compare the CTS spectra as above. Another check on 
linearity is to observe the single beam background in frequency regions 
where the optical configuration is known to have a zero response. 
Verify that the detector response is ``flat'' and equal to zero in 
these regions. If detector response is not linear, decrease aperture, 
or attenuate the infrared beam. Repeat the linearity check until system 
passes the requirement.

11.0  Analytical Procedure

    11.1  Initial Certification. First, perform the evaluation 
procedures in Section 6.0 of the FTIR Protocol. The performance of an 
FTIR CEM can be certified upon installation using EPA Method 301 type 
validation (40 CFR, Part 63, Appendix A), or by comparison to a 
reference Method if one exists for the target analyte(s). Details of 
each procedure are given below. Validation testing is used for initial 
certification upon installation of a new system. Subsequent performance 
checks can be performed with more limited analyte spiking. Performance 
of the analytical program is checked initially, and periodically as 
required by EPA, by analyzing audit spectra or audit gases.
    11.1.1  Validation. Use EPA Method 301 type sampling (reference 4, 
Section 5.3 of Method 301) to validate the FTIR CEM for measuring the 
target analytes. The analyte spike procedure is as follows: (1) a known 
concentration of analyte is mixed with a known concentration of a non-
reactive tracer gas, (2) the undiluted spike gas is sent directly to 
the FTIR cell and a spectrum of this sample is collected, (3) pre-heat 
the spiked gas to at least the sample line temperature, (4) introduce 
spike gas at the back of the sample probe upstream of the particulate 
filter, (5) spiked effluent is carried through all sampling components 
downstream of the probe, (6) spike at a ratio of roughly 1 part spike 
to 9 parts flue gas (or more dilute), (7) the spike-to-flue gas ratio 
is estimated by comparing the spike flow to the total sample flow, and 
(8) the spike ratio is verified by comparing the tracer concentration 
in spiked flue gas to the tracer concentration in undiluted spike gas. 
The analyte flue gas concentration is unimportant as long as the spiked 
component can be measured and the sample matrix (including 
interferences) is similar to its composition under test conditions. 
Validation can be performed using a single FTIR CEM analyzing sample 
spectra collected sequentially. Since flue gas analyte (unspiked) 
concentrations can vary, it is recommended that two separate sampling 
lines (and pumps) are used; one line to carry unspiked flue gas and the 
other line to carry spiked flue gas. Even with two sampling lines the 
variation in unspiked concentration may be fast compared to the 
interval between consecutive measurements. Alternatively, two FTIR CEMs 
can be operated side-by-side, one measuring spiked sample, the other 
unspiked sample. In this arrangement spiked and unspiked measurements 
can be synchronized to minimize the affect of temporal variation in the 
unspiked analyte concentration. In either sampling arrangement, the 
interval between measured concentrations used in the statistical 
analysis should be, at least, 5 cell volumes (5 * TC in equation 1). A 
validation run consists of, at least, 24 independent analytical 
results, 12 spiked and 12 unspiked samples. See Section 3.17 for 
definition of an ``independent'' analytical result. The results are 
analyzed using Sections 12.1 and 12.2 to determine if the measurements 
passed the validation requirements. Several analytes can be spiked and 
measured in the same sampling run, but a separate statistical analysis 
is performed for each analyte. In lieu of 24 independent measurements, 
averaged results can be used in the statistical analysis. In this 
procedure, a series of consecutive spiked measurements are combined 
over a sampling period to give a single average result. The related 
unspiked measurements are averaged in the same way. The minimum 12 
spiked and 12 unspiked result averages are obtained by averaging 
measurements over subsequent sampling periods of equal duration. The 
averaged results are grouped together and statistically analyzed using 
Section 12.2.
    11.1.1.1  Validation with a Single Analyzer and Sampling Line. If 
one sampling line is used, connect the sampling system components and 
purge the entire sampling system and cell with at least 10 cell volumes 
of sample gas. Begin sampling by collecting spectra of 2 independent 
unspiked samples. Introduce the spike gas into the back of the probe, 
upstream of the particulate filter. Allow 10 cell volumes of spiked 
flue gas to purge the cell and sampling system. Collect spectra of 2 
independent spiked samples. Turn off the spike flow and allow 10 cell 
volumes of unspiked flue gas to purge the FTIR cell and sampling 
system. Repeat this procedure 6 times until the 24 samples are 
collected. Spiked and unspiked samples can also be measured in groups 
of 4 instead of in pairs. Analyze the results using Sections 12.1 and 
12.2. If the statistical analysis passes the validation criteria, then 
the validation is completed. If the results do not pass the validation, 
the cause may be that temporal variations in the analyte sample gas 
concentration are fast relative to the interval between measurements. 
The difficulty may be avoided by: (1) Averaging the measurements over 
long sampling periods and using the averaged results in the statistical 
analysis, (2) modifying the sampling system to reduce TC by, for 
example, using a smaller volume cell or increasing the sample flow 
rate, (3) using two sample lines (4) use two analyzers to perform 
synchronized

[[Page 62148]]

measurements. This performance specification permits modifications in 
the sampling system to minimize TC if the other requirements of the 
validation sampling procedure are met.
    11.1.1.2  Validation With a Single Analyzer and Two Sampling Lines. 
An alternative sampling procedure uses two separate sample lines, one 
carrying spiked flue gas, the other carrying unspiked gas. A valve in 
the gas distribution manifold allows the operator to choose either 
sample. A short heated line connects the FTIR cell to the 3-way valve 
in the manifold. Both sampling lines are continuously purged. Each 
sample line has a rotameter and a bypass vent line after the rotameter, 
immediately upstream of the valve, so that the spike and unspiked 
sample flows can each be continuously monitored. Begin sampling by 
collecting spectra of 2 independent unspiked samples. Turn the sampling 
valve to close off the unspiked gas flow and allow the spiked flue gas 
to enter the FTIR cell. Isolate and evacuate the cell and fill with the 
spiked sample to ambient pressure. (While the evacuated cell is 
filling, prevent air leaks into the cell by making sure that the spike 
sample rotameter always indicates that a portion of the flow is 
directed out the by-pass vent.) Open the cell outlet valve to allow 
spiked sample to continuously flow through the cell. Measure spectra of 
2 independent spiked samples. Repeat this procedure until at least 24 
samples are collected.
    11.1.1.3  Synchronized Measurements With Two Analyzers. Use two 
FTIR analyzers, each with its own cell, to perform synchronized spiked 
and unspiked measurements. If possible, use a similar optical 
configuration for both systems. The optical configurations are compared 
by measuring the same CTS gas with both analyzers. Each FTIR system 
uses its own sampling system including a separate sampling probe and 
sampling line. A common gas distribution manifold can be used if the 
samples are never mixed. One sampling system and analyzer measures 
spiked effluent. The other sampling system and analyzer measures 
unspiked flue gas. The two systems are synchronized so that each 
measures spectra at approximately the same times. The sample flow rates 
are also synchronized so that both sampling rates are approximately the 
same (TC1  TC2 in equation 1). Start 
both systems at the same time. Collect spectra of at least 12 
independent samples with each (spiked and unspiked) system to obtain 
the minimum 24 measurements. Analyze the analytical results using 
Sections 12.1 and 12.2. Run averages can be used in the statistical 
analysis instead of individual measurements.
    11.1.1.4  Compare to a Reference Method (RM). Obtain EPA approval 
that the method qualifies as an RM for the analyte(s) and the source to 
be tested. Follow the published procedures for the RM in preparing and 
setting up equipment and sampling system, performing measurements, and 
reporting results. Since FTIR CEMS have multicomponent capability, it 
is possible to perform more than one RM simultaneously, one for each 
target analyte. Conduct at least 9 runs where the FTIR CEM and the RM 
are sampling simultaneously. Each Run is at least 30 minutes long and 
consists of spectra of at least 5 independent FTIR CEM samples and the 
corresponding RM measurements. If more than 9 runs are conducted, the 
analyst may eliminate up to 3 runs from the analysis if at least 9 runs 
are used.
    11.1.1.4.1  RMs Using Integrated Sampling. Perform the RM and FTIR 
CEM sampling simultaneously. The FTIR CEM can measure spectra as 
frequently as the analyst chooses (and should obtain measurements as 
frequently as possible) provided that the measurements include spectra 
of at least 5 independent measurements every 30 minutes. Concentration 
results from all of the FTIR CEM spectra within a run may be averaged 
for use in the statistical comparison even if all of the measurements 
are not independent. When averaging the FTIR CEM concentrations within 
a run, it is permitted to exclude some measurements from the average 
provided the minimum of 5 independent measurements every 30 minutes are 
included: The Run average of the FTIR CEM measurements depends on both 
the sample flow rate and the measurement frequency (MF). The run 
average of the RM using the integrated sampling method depends 
primarily on its sampling rate. If the target analyte concentration 
fluctuates significantly, the contribution to the run average of a 
large fluctuation depends on the sampling rate and measurement 
frequency, and on the duration and magnitude of the fluctuation. It is, 
therefore, important to carefully select the sampling rate for both the 
FTIR CEM and the RM and the measurement frequency for the FTIR CEM. The 
minimum of 9 run averages can be compared according to the relative 
accuracy test procedure in Performance Specification 2 for 
SO2 and NOx CEMs (40 CFR, Part 60, App. B).
    11.1.1.4.2  RMs Using a Grab Sampling Technique. Synchronize the RM 
and FTIR CEM measurements as closely as possible. For a grab sampling 
RM record the volume collected and the exact sampling period for each 
sample. Synchronize the FTIR CEM so that the FTIR measures a spectrum 
of a similar cell volume at the same time as the RM grab sample was 
collected. Measure at least 5 independent samples with both the FTIR 
CEM and the RM for each of the minimum 9 Runs. Compare the Run 
concentration averages by using the relative accuracy analysis 
procedure in 40 CFR, Part 60, App. B.
    11.1.1.4.3  Continuous Emission Monitors (CEMs) as RMs. If the RM 
is a CEM, synchronize the sampling flow rates of the RM and the FTIR 
CEM. Each run is at least 1-hour long and consists of at least 10 FTIR 
CEM measurements and the corresponding 10 RM measurements (or 
averages). For the statistical comparison use the relative accuracy 
analysis procedure in 40 CFR, Part 60, App. B. If the RM time constant 
is \1/2\ the FTIR CEM time constant, brief fluctuations in analyte 
concentrations which are not adequately measured with the slower FTIR 
CEM time constant can be excluded from the run average along with the 
corresponding RM measurements. However, the FTIR CEM run average must 
still include at least 10 measurements over a 1-hr period.

12.0  Calculations and Data Analysis

    12.1  Spike Dilution Ratio, Expected Concentration. The Method 301 
bias is calculated as follows.
[GRAPHIC] [TIFF OMITTED] TR17OC00.466

Where:

B = Bias at the spike level
Sm = Mean of the observed spiked sample concentrations
Mm = Mean of the observed unspiked sample concentrations
CS = Expected value of the spiked concentration.

    The CS is determined by comparing the SF6 tracer 
concentration in undiluted spike gas to the SF6 tracer 
concentrations in the spiked samples;
[GRAPHIC] [TIFF OMITTED] TR17OC00.467

The expected concentration (CS) is the measured concentration of the 
analyte in undiluted spike gas divided by the dilution factor
[GRAPHIC] [TIFF OMITTED] TR17OC00.468

Where:


[[Page 62149]]


[anal]dir=The analyte concentration in undiluted spike gas 
measured directly by filling the FTIR cell with the spike gas.

If the bias is statistically significant (Section 12.2), Method 301 
requires that a correction factor, CF, be multiplied by the analytical 
results, and that 0.7  CF  1.3.
[GRAPHIC] [TIFF OMITTED] TR17OC00.469

    12.2  Statistical Analysis of Validation Measurements. Arrange the 
independent measurements (or measurement averages) as in Table 1. More 
than 12 pairs of measurements can be analyzed. The statistical analysis 
follows EPA Method 301, Section 6.3. Section 12.1 of this performance 
specification shows the calculations for the bias, expected spike 
concentration, and correction factor. This Section shows the 
determination of the statistical significance of the bias. Determine 
the statistical significance of the bias at the 95 percent confidence 
level by calculating the t-value for the set of measurements. First, 
calculate the differences, di, for each pair of spiked and 
each pair of unspiked measurements. Then calculate the standard 
deviation of the spiked pairs of measurements.
[GRAPHIC] [TIFF OMITTED] TR17OC00.470

Where:

di = The differences between pairs of spiked measurements.
SDs = The standard deviation in the di values.
n = The number of spiked pairs, 2n=12 for the minimum of 12 spiked and 
12 unspiked measurements.

Calculate the relative standard deviation, RSD, using SDs 
and the mean of the spiked concentrations, Sm. The RSD must 
be 50%.
[GRAPHIC] [TIFF OMITTED] TR17OC00.471

Repeat the calculations in equations 7 and 8 to determine 
SDu and RSD, respectively, for the unspiked samples. 
Calculate the standard deviation of the mean using SDs and 
SDu from equation 7.
[GRAPHIC] [TIFF OMITTED] TR17OC00.472

The t-statistic is calculated as follows to test the bias for 
statistical significance;
[GRAPHIC] [TIFF OMITTED] TR17OC00.473

where the bias, B, and the correction factor, CF, are given in Section 
12.1. For 11 degrees of freedom, and a one-tailed distribution, Method 
301 requires that t 2.201. If the t-statistic indicates the 
bias is statistically significant, then analytical measurements must be 
multiplied by the correction factor. There is no limitation on the 
number of measurements, but there must be at least 12 independent 
spiked and 12 independent unspiked measurements. Refer to the t-
distribution (Table 2) at the 95 percent confidence level and 
appropriate degrees of freedom for the critical t-value.

16.0  References

    1. Method 318, 40 CFR, Part 63, Appendix A (Draft), 
``Measurement of Gaseous Formaldehyde, Phenol and Methanol Emissions 
by FTIR Spectroscopy,'' EPA Contract No. 68D20163, Work Assignment 
2-18, February, 1995.

[[Page 62150]]

    2. ``EPA Protocol for the Use of Extractive Fourier Transform 
Infrared (FTIR) Spectrometry in Analyses of Gaseous Emissions from 
Stationary Industrial Sources,'' February, 1995.
    3. ``Measurement of Gaseous Organic and Inorganic Emissions by 
Extractive FTIR Spectroscopy,'' EPA Contract No. 68-D2-0165, Work 
Assignment 3-08.
    4. ``Method 301--Field Validation of Pollutant Measurement 
Methods from Various Waste Media,'' 40 CFR 63, App A.

17.0  Tables, Diagrams, Flowcharts, and Validation Data

                    Table 1.--Arrangement of Validation Measurements for Statistical Analysis
----------------------------------------------------------------------------------------------------------------
  Measurement  (or average)        Time        Spiked  (ppm)      di spiked     Unspiked  (ppm)    di unspiked
----------------------------------------------------------------------------------------------------------------
1...........................                              S1                                U1
--------------------------------------------------------------                 -----------------
2...........................                              S2            S2-S1               U2            U2-U1
----------------------------------------------------------------------------------------------------------------
3...........................                              S3                                U3
--------------------------------------------------------------                 -----------------
4...........................                              S4            S4-S3               U4            U4-U3
----------------------------------------------------------------------------------------------------------------
5...........................                              S5                                U5
--------------------------------------------------------------                 -----------------
6...........................                              S6            S6-S5               U6            U6-U5
----------------------------------------------------------------------------------------------------------------
7...........................                              S7                                U7
--------------------------------------------------------------                 -----------------
8...........................                              S8            S8-S7               U8            U8-U7
----------------------------------------------------------------------------------------------------------------
9...........................                              S9                                U9
--------------------------------------------------------------                 -----------------
10..........................                             S10           S10-S9              U10           U10-U9
----------------------------------------------------------------------------------------------------------------
11..........................                             S11                               U11
--------------------------------------------------------------                 -----------------
12..........................                             S12          S12-S11              U12          U12-U11
----------------------------------------------------------------------------------------------------------------
Average ->..................                              Sm                                Mm
----------------------------------------------------------------------------------------------------------------


                                                                   Table 2.--t=Values
--------------------------------------------------------------------------------------------------------------------------------------------------------
       n-1a              t-value              n-1a              t-value              n-1a              t-value              n-1a             t-value
--------------------------------------------------------------------------------------------------------------------------------------------------------
              11              2.201                  17              2.110                  23              2.069                  29             2.045
              12              2.179                  18              2.101                  24              2.064                  30             2.042
              13              2.160                  19              2.093                  25              2.060                  40             2.021
              14              2.145                  20              2.086                  26              2.056                  60             2.000
              15              2.131                  21              2.080                  27              2.052                 120             1.980
              16              2.120                  22              2.074                  28              2.048                   8            1.960
--------------------------------------------------------------------------------------------------------------------------------------------------------
(a)n is the number of independent pairs of measurements (a pair consists of one spiked and its corresponding unspiked measurement). Either discreet
  (independent) measurements in a single run, or run averages can be used.

* * * * *

PART 61--NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS

    1. The authority citation for Part 61 continues to read as follows: 
42 U.S.C. 7401, 7412, 7413, 7414, 7416, 7601, and 7602.

    2. In Sec. 61.18, paragraph (a) is revised to read as follows:


Sec. 61.18  Incorporation by reference.

* * * * *
    (a) The following materials are available for purchase from at 
least one of the following addresses: American Society for Testing and 
Materials (ASTM), 1916 Race Street, Philadelphia, PA 19103; or 
University Microfilms International, 300 North Zeeb Road, Ann Arbor, MI 
48106.
    (1) ASTM D737-75, Standard Test Method for Air Permeability of 
Textile Fabrics, incorporation by reference (IBR) approved January 27, 
1983 for Sec. 61.23(a).
    (2) ASTM D835-85, Standard Specification for Refined Benzene-485, 
IBR approved September 14, 1989 for Sec. 61.270(a).
    (3) ASTM D836-84, Standard Specification for Industrial Grade 
Benzene, IBR approved September 14, 1989 for Sec. 61.270(a).
    (4) ASTM D1193-77, 91, Standard Specification for Reagent Water, 
IBR approved for Appendix B: Method 101, Section 7.1.1; Method 101A, 
Section 7.1.1; and Method 104, Section 7.1; Method 108, Section 7.1.3; 
Method 108A, Section 7.1.1; Method 108B, Section 7.1.1; Method 108C, 
Section 7.1.1; and Method 111, Section 7.3.
    (5) ASTM D2267-68, 78, 88, Aromatics in Light Naphthas and Aviation 
Gasoline by Gas Chromatography, IBR approved September 30, 1986, for 
Sec. 61.67(h)(1).
    (6) ASTM D2359-85a, 93, Standard Specification for Refined Benzene-
535, IBR approved September 14, 1989 for Sec. 61.270(a).
    (7) ASTM D2382-76, 88, Heat of Combustion of Hydrocarbon Fuels by 
Bomb Calorimeter (High-Precision Method), IBR approved June 6, 1984 for 
Sec. 61.245(e)(3).
    (8) ASTM D2504-67, 77, 88, 93, Noncondensable Gases in 
C3 and Lighter Hydrocarbon Products by Gas

[[Page 62151]]

Chromatography, IBR approved June 6, 1984 for Sec. 61.245(e)(3).
    (9) ASTM D2986-71, 78, 95a, Standard Method for Evaluation of Air, 
Assay Media by the Monodisperse DOP (Dioctyl Phthalate) Smoke Test, IBR 
approved for Appendix B: Method 103, Section 6.1.3.
    (10) ASTM D4420-94, Standard Test Method for Determination of 
Aromatics in Finished Gasoline by Gas Chromatography, IBR approved for 
Sec. 61.67(h)(1).
    (11) ASTM D4734-87, 96, Standard Specification for Refined Benzene-
545, IBR approved September 14, 1989 for Sec. 61.270(a).
    (12) ASTM D4809-95, Standard Test Method for Heat of Combustion of 
Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision Method), IBR 
approved for Sec. 61.245(e)(3).
    (13) ASTM E50-82, 86, 90 (Reapproved 1995), Standard Practices for 
Apparatus Reagents, and Safety Precautions for Chemical Analysis of 
Metals, IBR approved for Appendix B: Method 108C, Section 6.1.4.
* * * * *


Sec. 61.20  [Amended]

    3. Amend Sec. 61.20 as follows:
    a. Paragraph (a) is amended by revising the words ``100,000 tons'' 
to read ``90,720 megagrams (Mg) (100,000 tons).''
    b. Paragraph (b) is amended by revising the words ``10,000 tons'' 
to read ``9,072 Mg (10,000 tons).''
    c. Paragraph (b) is amended by revising the words ``100,000 tons'' 
to read ``90,720 Mg (100,000 tons).''


61.21  [Amended]

    4. In Sec. 61.21(b), the words ``Effective dose equivalent means 
the sum of the products of absorbed dose and appropriate factors to 
account for differences in biological effectiveness due to the quality 
of radiation and its distribution in the body of reference man'' are 
revised to read ``Effective dose equivalent means the sum of the 
products of the absorbed dose and appropriate effectiveness factors. 
These factors account for differences in biological effectiveness due 
to the quality of radiation and its distribution in the body of 
reference man.''


Sec. 61.23  [Amended]

    5. Amend Sec. 61.23 as follows:
    a. In paragraph (a), the first sentence is amended by revising the 
abbreviation ``EPA'' to read ``U.S. Environmental Protection Agency 
(EPA).''
    b. In paragraph (a), the second sentence is amended by revising the 
word ``Appendix'' to read ``appendix.''


Sec. 61.24  [Amended]

    6. Amend Sec. 61.24 as follows:
    a. In paragraph (a), the first sentence is amended by revising the 
words ``used in making the calculation'' to read ``used in making the 
calculations.''
    b. In paragraph (a), the second sentence is amended by revising the 
words ``Such report shall'' to read ``This report shall.''


Sec. 61.30  [Amended]

    7. In Sec. 61.30, paragraph (a) is amended by revising the words 
``Extraction plans'' to read ``Extraction plants.''


Sec. 61.32  [Amended]

    8. Amend Sec. 61.32 as follows:
    a. Paragraph (a) is amended by revising the words ``10 grams'' to 
read ``10 grams (0.022 lb).''
    b. Paragraphs (b) and (b)(1)(i) are amended by revising the words 
``0.01 g/m \3\'' to read ``0.01 g/m \3\ 
(4.37x10-6 gr/ft \3\)'' wherever they occur.


Sec. 61.42  [Amended]

    9. Amend Sec. 61.42 as follows:
    a. Paragraph (a) is amended by revising the words ``75 microgram 
minutes per cubic meter of air'' to read ``75 microgram minutes per 
cubic meter (g-min/m \3\) (4.68 pound minutes per cubic foot 
(lb-min/ft \3\)) of air.''
    b. Paragraph (b) is amended by revising the words ``2 grams per 
hour'' to read ``2.0 g/hr (0.0044 lb/hr).''
    c. Paragraph (b) is amended by revising the words ``10 grams per 
day'' to read ``10 g/day (0.022 lb/day).''


Sec. 61.52  [Amended]

    10. Amend Sec. 61.52 as follows:
    a. Paragraph (a) is amended by revising the words ``2300 grams'' to 
read ``2.3 kg (5.1 lb).''
    b. Paragraph (b) is amended by revising the words ``3200 grams'' to 
read ``3.2 kg (7.1 lb).''


Sec. 61.53  [Amended]

    11. In Sec. 61.53, paragraph (c) is amended by revising the words 
``1,300 gms/day'' to read ``1.3 kg/day (2.9 lb/day).''


Sec. 61.55  [Amended]

    12. Amend Sec. 61.55 as follows:
    a. In paragraph (a), the second sentence is amended by revising the 
words ``1,600 g'' to read ``1.6 kg (3.5 lb).''
    b. Paragraph (b)(1) is amended by revising the words ``Reference 
Method'' to read ``Method'' wherever they occur.
    c. Paragraph (c)(4) is amended by revising the words ``established 
in 2'' to read ``established in paragraph (c)(2) of this section.''


Sec. 61.61  [Amended]

    13. Amend Sec. 61.61 as follows:
    a. Paragraph (c) is amended by revising the words ``polyvinyl 
chloride plant'' to read ``polyvinyl chloride (PVC) plant.''
    b. In paragraph (l), the first sentence is amended by revising the 
words ``a least'' to read ``at least.''
    c. Paragraph (w)(3) is amended by revising the words ``Test Method 
21'' to read ``Method 21.''


Sec. 61.62  [Amended]

    14. In Sec. 61.62, paragraph (b) is amended by revising the words 
``0.2 g/kg (0.0002 lb/lb)'' to read ``0.2 g/kg (0.4 lb/ton).''


Sec. 61.64  [Amended]

    15. Amend Sec. 61.64 as follows:
    a. In paragraph (a)(2), the first sentence is amended by revising 
the words ``0.02 g vinyl chloride/kg (0.00002 lb vinyl chloride/lb)'' 
to read ``0.02 g vinyl chloride/kg (0.04 lb vinyl chloride/ton).''
    b. Paragraph (e)(2)(i) is amended by revising the words ``2 g/kg 
(0.002 lb/lb)'' to read ``2 g/kg (4 lb/ton).''
    c. Paragraph (e)(2)(ii) is amended by revising the words ``0.4 g/kg 
(0.0004 lb/lb)'' to read ``0.4 g/kg (0.8 lb/ton).''
    d. Paragraph (f)(2)(i) is amended by revising the words ``2.02 g/kg 
(0.00202 lb/lb)'' to read ``2.02 g/kg (4.04 lb/ton).''
    e. Paragraph (f)(2)(ii) is amended by revising the words ``0.42 g/
kg (0.00042 lb/lb)'' to read ``0.42 g/kg (0.84 lb/ton).''


Sec. 61.65  [Amended]

    16. Amend Sec. 61.65 as follows:
    a. In paragraph (a), the first sentence is amended by revising the 
words ``Relief valve discharge'' to read ``Relief valve discharge 
(RVD).''
    b. Paragraph (b)(8)(i)(D)(1) is amended by revising the words 
``sections 5.2.1. and 5.2.2. of Test Method 106 and in accordance with 
section 7.1 of Test Method 106'' to read ``sections 7.2.1 and 7.2.2 of 
Method 106 and in accordance with section 10.1 of Method 106.''
    c. In paragraph (b)(8)(i)(D)(2), the fourth sentence is amended by 
revising the words ``maximum self life'' to read ``maximum shelf 
life.''
    d. In paragraph (b)(8)(i)(D)(2), the fifth sentence is amended by 
revising the words ``section 7.3 of Test Method 106. The requirements 
in section 5.2.3.1. and 5.2.3.2. of Test Method 106'' to read 
``Sections 8.1 and 9.2 of Method 106. The requirements in Sections 
7.2.3.1 and 7.2.3.2 of Method 106.''
    e. In paragraph (c), the second sentence is amended by revising the

[[Page 62152]]

words ``Test Method'' to read ``Method 106.''

    17. Amend Sec. 61.67 by:
    a. Revising Sec. 61.67(g).
    b. In paragraph (h)(1) by revising ``ASTM Method D-2267'' to read 
``ASTM D2267-68, 78, or 88 or D4420-94.''
    The revisions read as follows:


Sec. 61.67  Emission tests.

* * * * *
    (g) Unless otherwise specified, the owner or operator shall use the 
test methods in Appendix B to this part for each test as required by 
paragraphs (g)(1), (g)(2), (g)(3), (g)(4), and (g)(5) of this section, 
unless an alternative method has been approved by the Administrator. If 
the Administrator finds reasonable grounds to dispute the results 
obtained by an alternative method, he may require the use of a 
reference method. If the results of the reference and alternative 
methods do not agree, the results obtained by the reference method 
prevail, and the Administrator may notify the owner or operator that 
approval of the method previously considered to be alternative is 
withdrawn. Whenever Method 107 is specified, and the conditions in 
Section 1.2, ``Applicability'' of Method 107A are met, Method 107A may 
be used.
    (1) Method 106 is to be used to determine the vinyl chloride 
emissions from any source for which an emission limit is prescribed in 
Sec. 61.62(a) or (b), Sec. 61.63(a), or Sec. 61.64(a)(1), (b), (c), or 
(d), or from any control system to which reactor emissions are required 
to be ducted in Sec. 61.64(a)(2) or to which fugitive emissions are 
required to be ducted in Sec. 61.65(b)(1)(ii), (b)(2), (b)(5), 
(b)(6)(ii), or (b)(9)(ii).
    (i) For each run, one sample is to be collected. The sampling site 
is to be at least two stack or duct diameters downstream and one half 
diameter upstream from any flow disturbance such as a bend, expansion, 
contraction, or visible flame. For a rectangular cross section, an 
equivalent diameter is to be determined from the following equation:
    Equivalent diameter = 2(length)(width)/(length + width)
    The sampling point in the duct is to be at the centroid of the 
cross section. The sample is to be extracted at a rate proportional to 
the gas velocity at the sampling point. The sample is to contain a 
minimum volume of 50 liters (1.8 ft3) corrected to standard 
conditions and is to be taken over a period as close to 1 hour as 
practicable.
    (ii) Each emission test is to consist of three runs. For the 
purpose of determining emissions, the average of results of all runs is 
to apply. The average is to be computed on a time weighted basis.
    (iii) For gas streams containing more that 10 percent oxygen, the 
concentration of vinyl chloride as determined by Method 106 is to be 
corrected to 10 percent oxygen (dry basis) for determination of 
emissions by using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.474

Where:

Cb(corrected) = The concentration of vinyl chloride in the 
exhaust gases, corrected to 10 percent oxygen.
Cb = The concentration of vinyl chloride as measured by 
Method 106.
20.9 = Percent oxygen in the ambient air at standard conditions.
10.9 = Percent oxygen in the ambient air at standard conditions, minus 
the 10.0 percent oxygen to which the correction is being made.
Percent O2 = Percent oxygen in the exhaust gas as measured 
by Method 3 of Appendix A of Part 60 of this chapter.

    (iv) For those emission sources where the emission limit is 
prescribed in terms of mass rather than concentration, mass emissions 
are to be determined using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.475

Where:

CBX = Vinyl chloride emissions, g/kg (lb/lb) product.
Cb = Concentration of vinyl chloride as measured by Test 
Method 106, ppmv.
DVC = Density of vinyl chloride at standard conditions, 2.60 
kg/m3 (0.162 lb/ft3).
Q = Volumetric flow rate as determined by Method 2 of Appendix A to 
Part 60 of this chapter, m3/hr (ft3/hr).
K = Unit conversion factor, 1,000 g/kg (1 lb/lb).
10-6 = Conversion factor for ppm.
Z = Production rate, kg/hr (lb/hr).

    (2) Method 107 or Method 601 (incorporated by reference as 
specified in Sec. 61.18) is to be used to determine the concentration 
of vinyl chloride in each inprocess wastewater stream for which an 
emission limit is prescribed in Sec. 61.65(b)(9)(i).
    (3) When a stripping operation is used to attain the emission 
limits in Sec. 61.64(e) and (f), emissions are to be determined using 
Method 107 as follows:
    (i) The number of strippers (or reactors used as strippers) and 
samples and the types and grades of resin to be sampled are to be 
determined by the Administrator for each individual plant at the time 
of the test based on the plant's operation.
    (ii) Each sample is to be taken immediately following the stripping 
operation.
    (iii) The corresponding quantity of material processed by each 
stripper (or reactor used as a stripper) is to be determined on a dry 
solids basis and by a method submitted to and approved by the 
Administrator.
    (iv) At the prior request of the Administrator, the owner or 
operator shall provide duplicates of the samples required in paragraph 
(g)(3)(i) of this section.
    (4) Where control technology other than or in addition to a 
stripping operation is used to attain the emission limit in 
Sec. 61.64(e), emissions are to be determined as follows:
    (i) Method 106 is to be used to determine atmospheric emissions 
from all of the process equipment simultaneously. The requirements of 
paragraph (g)(1) of this section are to be met.
    (ii) Method 107 is to be used to determine the concentration of 
vinyl chloride in each inprocess wastewater stream subject to the 
emission limit prescribed in Sec. 61.64(e). Vinyl chloride mass 
emissions are to be determined using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.476

Where:

CBX = Vinyl chloride emissions, g/kg (lb/lb) product in each 
inprocess wastewater stream.
Crvc = Concentration of vinyl chloride in wastewater, as 
measured by Method 107, ppmw.
Dwater = Density of wastewater, 1.0 kg/m3 (0.0624 
lb/ft3).
Qwater = Wastewater flow rate, determined in accordance with 
a method which has been submitted to and approved by the Administrator, 
m3/hr (ft3/hr).
K = Unit conversion factor, 1,000 g/kg (1 lb/lb).
10-6 = Conversion factor for ppm.
Z = Production rate, kg/hr (lb/hr), determined in accordance with a 
method which has been submitted to and approved by the Administrator.

    (5) The reactor opening loss for which an emission limit is 
prescribed in Sec. 61.64(a)(2) is to be determined. The number of 
reactors for which the determination is to be made is to be specified 
by the Administrator for each individual plant at the time of the

[[Page 62153]]

determination based on the plant's operation.
    (i) Except as provided in paragraph (g)(5)(ii) of this section, the 
reactor opening loss is to be determined using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.477

Where:

CBX = Vinyl chloride emissions, g/kg (lb/lb) product.
Cb = Concentration of vinyl chloride, in ppmv, as determined 
by Method 106 or a portable hydrocarbon detector which measures 
hydrocarbons with a sensitivity of at least 10 ppmv.
VR = Capacity of the reactor, m\3\ (ft\3\).
DVC = Density of vinyl chloride at standard conditions, 2.60 
kg/m\3\ (0.162 lb/ft\3\).
K = Unit conversion factor, 1,000 g/kg (1 lb/lb).
10-\6\ = Conversion factor for ppm.
Z = Production rate, kg/hr (lb/hr).

    (A) If Method 106 is used to determine the concentration of vinyl 
chloride (Cb), the sample is to be withdrawn at a constant 
rate with a probe of sufficient length to reach the vessel bottom from 
the manhole. Samples are to be taken for 5 minutes within 6 inches of 
the vessel bottom, 5 minutes near the vessel center, and 5 minutes near 
the vessel top.
    (B) If a portable hydrocarbon detector is used to determine the 
concentration of vinyl chloride (Cb), a probe of sufficient 
length to reach the vessel bottom from the manhole is to be used to 
make the measurements. One measurement will be made within 6 inches of 
the vessel bottom, one near the vessel center and one near the vessel 
top. Measurements are to be made at each location until the reading is 
stabilized. All hydrocarbons measured are to be assumed to be vinyl 
chloride.
    (C) The production rate of polyvinyl chloride (Z), which is the 
product of the average batch weight and the number of batches produced 
since the reactor was last opened to the atmosphere, is to be 
determined by a method submitted to and approved by the Administrator.
    (ii) A calculation based on the number of evacuations, the vacuum 
involved, and the volume of gas in the reactor is hereby approved by 
the Administrator as an alternative method for determining reactor 
opening loss for postpolymerization reactors in the manufacture of bulk 
resins. Calculation methods based on techniques other than repeated 
evacuation of the reactor may be approved by the Administrator for 
determining reactor opening loss for postpolymerization reactors in the 
manufacture of bulk resins.
    (6) For a reactor that is used as a stripper, the emissions of 
vinyl chloride from reactor opening loss and all sources following the 
reactor used as a stripper for which an emission limit is prescribed in 
Sec. 61.64(f) are to be determined. The number of reactors for which 
the determination is to be made is to be specified by the Administrator 
for each individual plant at the time of the determination based on the 
plant's operation.
    (i) For each batch stripped in the reactor, the following 
measurements are to be made:
    (A) The concentration of vinyl chloride in resin after stripping, 
measured according to paragraph (g)(3) of this section;
    (B) The reactor vacuum at end of strip from plant instrument; and
    (C) The reactor temperature at the end of strip from plant 
instrument.
    (ii) For each batch stripped in the reactor, the following 
information is to be determined:
    (A) The vapor pressure of water in the reactor at the end of strip 
from the following table:

                                                  Metric Units
----------------------------------------------------------------------------------------------------------------
  Reactor  vapor                         Reactor  vapor                        Reactor  vapor      H2O  vapor
  temperature  (        H2O vapor        temperature  (   H2O vapor pressure   temperature  (     pressure  (mm
      deg.C)        pressure  (mm Hg)        deg.C)             (mm Hg)            deg.C)              Hg)
----------------------------------------------------------------------------------------------------------------
              40               55.3                  62              163.8                 84             416.8
              41               58.3                  63              171.4                 85             433.6
              42               61.5                  64              179.3                 86             450.9
              43               64.8                  65              187.5                 87             468.7
              44               68.3                  66              196.1                 88             487.1
              45               71.9                  67              205.0                 89             506.1
              46               75.6                  68              214.2                 90             525.8
              47               79.6                  69              223.7                 91             546.0
              48               83.7                  70              233.7                 92             567.0
              49               88.0                  71              243.9                 93             588.6
              50               92.5                  72              254.6                 94             610.9
              51               97.2                  73              265.7                 95             633.9
              52              102.1                  74              277.2                 96             657.6
              53              107.2                  75              289.1                 97             682.1
              54              112.5                  76              301.4                 98             707.3
              55              118.0                  77              314.1                 99             733.2
              56              123.8                  78              327.3                100             760.0
              57              129.8                  79              341.0
              58              136.1                  80              355.1
              59              142.6                  81              369.7
              60              149.4                  82              384.9
              61              156.4                  83              400.6
----------------------------------------------------------------------------------------------------------------


[[Page 62154]]


                                                  English Units
----------------------------------------------------------------------------------------------------------------
  Reactor  vapor      H2O vapor      Reactor vapor                           Reactor  vapor
  temperature  (      pressure      temperature  (    H2O vapor  pressure    temperature  (        H2O vapor
      deg.F)           (psia)           deg.F)               (psia)              deg.F)         pressure  (psia)
----------------------------------------------------------------------------------------------------------------
             104        1.07                   144               3.167                  183               8.060
             106        1.13                   145               3.314                  185               8.384
             108        1.19                   147               3.467                  187               8.719
             109        1.25                   149               3.626                  189               9.063
             111        1.32                   151               3.792                  190               9.419
             113        1.39                   153               3.964                  192               9.786
             115        1.46                   154               4.142                  194              10.17
             117        1.54                   156               4.326                  196              10.56
             118        1.62                   158               4.519                  198              10.96
             120        1.70                   160               4.716                  199              11.38
             122        1.79                   162               4.923                  201              11.81
             124        1.88                   163               5.138                  203              12.26
             126       1.974                   165               5.360                  205              12.72
             127       2.073                   167               5.590                  207              13.19
             129       2.175                   169               5.828                  208              13.68
             131       2.282                   170               6.074                  210              14.18
             133       2.394                   172               6.329                  212              14.70
             135       2.510                   174               6.594
             136       2.632                   176               6.866
             138       2.757                   178               7.149
             140       2.889                   180               7.443
             142       3.024                   181               7.746
----------------------------------------------------------------------------------------------------------------

    (B) The partial pressure of vinyl chloride in reactor at end of 
strip from the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.478

Where:

PPVC = Partial pressure of vinyl chloride, mm Hg (psia)
PATM = Atmospheric pressure at 0  deg.C (32  deg.F), 760 mm 
Hg (14.7 psia)
PRV = Absolute pressure of reactor vacuum, mm Hg (psia)
PW = Vapor pressure of water, mm Hg (psia)


    (C) The reactor vapor space volume at the end of the strip from the 
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.479

Where:

VRVS = Reactor vapor space volume, m\3\ (ft\3\)
VR = Reactor capacity, m\3\ (ft\3\)
VW = Volume of water in reactor from recipe, m\3\ (ft\3\)
WPVC = Dry weight of polyvinyl chloride in reactor from 
recipe, kg (lb)
DPVC = Typical density of polyvinyl chloride, 1,400 kg/m\3\ 
(87.4 lb/ft\3\)

    (iii) For each batch stripped in the reactor, the combined reactor 
opening loss and emissions from all sources following the reactor used 
as a stripper is to be determined using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.480

Where:

CBX = Vinyl chloride emissions, g/kg (lb/lb) product.
PPMVC = Concentration of vinyl chloride in resin after 
stripping, ppmw
K1 = Conversion factor from ppmw to units of emission 
standard, 0.001 (metric units) = 0.002 (English units)
PPVC = Partial pressure of vinyl chloride determined 
according to paragraph (g)(6)(ii)(B) of this section, mm Hg (psia)
VRVS = Reactor vapor space volume determined according to 
paragraph (g)(6)(ii)(C) of this section, m\3\ (ft\3\)
RVC = Ideal gas constant for vinyl chloride, 1,002 g- deg.K/
(mm Hg-m\3\) [5.825 lb- deg.R/(psia-ft\3\)]
MPVC = Dry weight of polyvinyl chloride in reactor from 
recipe, kg (lb)
TR = Reactor temperature,  deg.C ( deg.F)
KT = Temperature conversion factor for  deg.C to  deg.K, 273 
( deg.F to  deg.R, 460)

    (h)(1) Each piece of equipment within a process unit that can 
reasonably contain equipment in vinyl chloride service is presumed to 
be in vinyl chloride service unless an owner or operator demonstrates 
that the piece of equipment is not in vinyl chloride service. For a 
piece of equipment to be considered not in vinyl chloride service, it 
must be determined that the percent vinyl chloride content can be 
reasonably expected not to exceed 10 percent by weight for liquid 
streams or contained liquid volumes and 10 percent by volume for gas 
streams or contained gas volumes, which also includes gas volumes above 
liquid streams or contained liquid volumes. For purposes of determining 
the percent vinyl chloride content of the process fluid that is 
contained in or contacts equipment, procedures that conform to the 
methods described in ASTM Method D-2267 (incorporated by

[[Page 62155]]

reference as specified in Sec. 61.18) shall be used.
    (2)(i) An owner or operator may use engineering judgment rather 
than the procedures in paragraph (h)(1) of this section to demonstrate 
that the percent vinyl chloride content does not exceed 10 percent by 
weight for liquid streams and 10 percent by volume for gas streams, 
provided that the engineering judgment demonstrates that the vinyl 
chloride content clearly does not exceed 10 percent. When an owner or 
operator and the Administrator do not agree on whether a piece of 
equipment is not in vinyl chloride service, however, the procedures in 
paragraph (h)(1) of this section shall be used to resolve the 
disagreement.
    (ii) If an owner or operator determines that a piece of equipment 
is in vinyl chloride service, the determination can be revised only 
after following the procedures in paragraph (h)(1) of this section.
    (3) Samples used in determining the percent vinyl chloride content 
shall be representative of the process fluid that is contained in or 
contacts the equipment.


Sec. 61.68  [Amended]

    18. Amend Sec. 61.68 as follows:
    a. Paragraph (c)(1) is amended by revising the words ``sections 
5.2.1. and 5.2.2. of Test Method 106 and in accordance with section 7.1 
of Test Method 106'' to read ``Sections 7.2.1 and 7.2.2 of Method 106 
and in accordance with Section 10.1 of Method 106.''
    b. In paragraph (c)(2), the fifth sentence is amended by revising 
the words ``section 7.3 of Test Method 106. The requirements in section 
5.2.3.1. and 5.2.3.2. of Test Method 106'' to read ``Sections 8.1 and 
9.2 of Method 106. The requirements in Sections 7.2.3.1 and 7.2.3.2 of 
Method 106.''

    19. Sec. 61.70(c) is revised as follows: 18440


Sec. 61.70  Reporting.

* * * * *
    (c) Unless otherwise specified, the owner or operator shall use the 
test methods in Appendix B to this part to conduct emission tests as 
required by paragraphs (c)(2) and (c)(3) of this section, unless an 
alternative method has been approved by the Administrator. If the 
Administrator finds reasonable grounds to dispute the results obtained 
by an alternative method, he may require the use of a reference method. 
If the results of the reference and alternative methods do not agree, 
the results obtained by the reference method prevail, and the 
Administrator may notify the owner or operator that approval of the 
method previously considered to be alternative is withdrawn.
    (1) The owner or operator shall include in the report a record of 
the vinyl chloride content of emissions for each 3-hour period during 
which average emissions are in excess of the emission limits in 
Sec. 61.62(a) or (b), Sec. 61.63(a), or Sec. 61.64(a)(1), (b), (c), or 
(d), or during which average emissions are in excess of the emission 
limits specified for any control system to which reactor emissions are 
required to be ducted in Sec. 61.64(a)(2) or to which fugitive 
emissions are required to be ducted in Sec. 61.65(b)(I)(ii), (b)(2), 
(b)(5), (b)(6)(ii), or (b)(9)(ii). The number of 3-hour periods for 
which average emissions were determined during the reporting period 
shall be reported. If emissions in excess of the emission limits are 
not detected, the report shall contain a statement that no excess 
emissions have been detected. The emissions are to be determined in 
accordance with Sec. 61.68(e).
    (2) In polyvinyl chloride plants for which a stripping operation is 
used to attain the emission level prescribed in Sec. 61.64(e), the 
owner or operator shall include in the report a record of the vinyl 
chloride content in the polyvinyl chloride resin.
    (i) If batch stripping is used, one representative sample of 
polyvinyl chloride resin is to be taken from each batch of each grade 
of resin immediately following the completion of the stripping 
operation, and identified by resin type and grade and the date and time 
the batch is completed. The corresponding quantity of material 
processed in each stripper batch is to be recorded and identified by 
resin type and grade and the date and time the batch is completed.
    (ii) If continuous stripping is used, one representative sample of 
polyvinyl chloride resin is to be taken for each grade of resin 
processed or at intervals of 8 hours for each grade of resin which is 
being processed, whichever is more frequent. The sample is to be taken 
as the resin flows out of the stripper and identified by resin type and 
grade and the date and time the sample was taken. The corresponding 
quantity of material processed by each stripper over the time period 
represented by the sample during the 8-hour period, is to be recorded 
and identified by resin type and grade and the date and time it 
represents.
    (iii) The vinyl chloride content in each sample is to be determined 
by Method 107 as prescribed in Sec. 61.67(g)(3).
    (iv) [Reserved]
    (v) The report to the Administrator by the owner or operator is to 
include a record of any 24-hour average resin vinyl chloride 
concentration, as determined in this paragraph, in excess of the limits 
prescribed in Sec. 61.64(e). The vinyl chloride content found in each 
sample required by paragraphs (c)(2)(i) and (c)(2)(ii) of this section 
shall be averaged separately for each type of resin, over each calendar 
day and weighted according to the quantity of each grade of resin 
processed by the stripper(s) that calendar day, according to the 
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.481

Where:

AT = 24-hour average concentration of type T resin in ppm 
(dry weight basis).
QT = Total production of type T resin over the 24-hour 
period, in kg (ton).
T = Type of resin.
MGi = Concentration of vinyl chloride in one sample of grade 
Gi resin in ppm.
PGi = Production of grade Gi resin represented by 
the sample, in kg (ton).
Gi = Grade of resin: e.g., G1, G2, 
G3.
n = Total number of grades of resin produced during the 24-hour period.

    The number of 24-hour average concentrations for each resin type 
determined during the reporting period shall be reported. If no 24-hour 
average resin vinyl chloride concentrations in excess of the limits 
prescribed in

[[Page 62156]]

Sec. 61.64(e) are measured, the report shall state that no excess resin 
vinyl chloride concentrations were measured.
    (vi) The owner or operator shall retain at the source and make 
available for inspection by the Administrator for a minimum of 3 years 
records of all data needed to furnish the information required by 
paragraph (c)(2)(v) of this section. The records are to contain the 
following information:
    (A) The vinyl chloride content found in all the samples required in 
paragraphs (c)(2)(i) and (c)(2)(ii) of this section, identified by the 
resin type and grade and the time and date of the sample, and
    (B) The corresponding quantity of polyvinyl chloride resin 
processed by the stripper(s), identified by the resin type and grade 
and the time and date it represents.
    (3) The owner or operator shall include in the report a record of 
any emissions from each reactor opening in excess of the emission 
limits prescribed in Sec. 61.64(a)(2). Emissions are to be determined 
in accordance with Sec. 61.67(g)(5), except that emissions for each 
reactor are to be determined. The number of reactor openings during the 
reporting period shall be reported. If emissions in excess of the 
emission limits are not detected, the report shall include a statement 
that excess emissions have not been detected.
    (4) In polyvinyl chloride plants for which stripping in the reactor 
is used to attain the emission level prescribed in Sec. 61.64(f), the 
owner or operator shall include in the report a record of the vinyl 
chloride emissions from reactor opening loss and all sources following 
the reactor used as a stripper.
    (i) One representative sample of polyvinyl chloride resin is to be 
taken from each batch of each grade of resin immediately following the 
completion of the stripping operation, and identified by resin type and 
grade and the date and time the batch is completed. The corresponding 
quantity of material processed in each stripper batch is to be recorded 
and identified by resin type and grade and the date and time the batch 
is completed.
    (ii) The vinyl chloride content in each sample is to be determined 
by Method 107 as prescribed in Sec. 61.67(g)(3).
    (iii) The combined emissions from reactor opening loss and all 
sources following the reactor used as a stripper are to be determined 
for each batch stripped in a reactor according to the procedure 
prescribed in Sec. 61.67(g)(6).
    (iv) The report to the Administrator by the owner or operator is to 
include a record of any 24-hour average combined reactor opening loss 
and emissions from all sources following the reactor used as a stripper 
as determined in this paragraph, in excess of the limits prescribed in 
Sec. 61.64(f). The combined reactor opening loss and emissions from all 
sources following the reactor used as a stripper associated with each 
batch are to be averaged separately for each type of resin, over each 
calendar day and weighted according to the quantity of each grade of 
resin stripped in reactors that calendar day as follows:
    For each type of resin (suspension, dispersion, latex, bulk, 
other), the following calculation is to be performed:
[GRAPHIC] [TIFF OMITTED] TR17OC00.482

Where:

AT = 24-hour average combined reactor opening loss and 
emissions from all sources following the reactor used as a stripper, in 
g vinyl chloride/kg (lb/ton) product (dry weight basis).
QT = Total production of resin in batches for which 
stripping is completed during the 24-hour period, in kg (ton).
T = Type of resin.
CGi = Average combined reactor opening loss and emissions 
from all sources following the reactor used as a stripper of all 
batches of grade Gi resin for which stripping is completed 
during the 24-hour period, in g vinyl chloride/kg (lb/ton) product (dry 
weight basis) (determined according to procedure prescribed in 
Sec. 61.67(g)(6)).
PGi = Production of grade Gi resin in the batches 
for which C is determined, in kg (ton).
Gi = Grade of resin: e.g., G1, G2, 
G3.
n = Total number of grades of resin in batches for which stripping is 
completed during the 24-hour period.

    The number of 24-hour average emissions determined during the 
reporting period shall be reported. If no 24-hour average combined 
reactor opening loss and emissions from all sources following the 
reactor used as a stripper in excess of the limits prescribed in 
Sec. 61.64(f) are determined, the report shall state that no excess 
vinyl chloride emissions were determined.
* * * * *


Sec. 61.93  [Amended]

    20. In Sec. 61.93, paragraphs (b)(1)(I), (b)(1)(ii), and (b)(2)(I) 
are amended by revising the words ``Reference Method'' to read 
``Method'' wherever they occur.


Sec. 61.107  [Amended]

    21. Amend Sec. 61.107 as follows:
    a. Paragraphs (b)(1)(I), (b)(1)(ii), and (b)(2)(I) are amended by 
revising the words ``Reference Method'' to read ``Method'' wherever 
they occur.
    b. Paragraphs (b)(2)(iv) and (b)(5)(v) are amended by revising the 
words ``method 114'' to read ``Method 114'' wherever they occur.
    c. Paragraph (b)(5)(iv) is amended by revising the words ``table 
2'' to read ``Table 2'', wherever they occur.


Sec. 61.110  [Amended]

    22. In Sec. 61.110, paragraph (c)(2) is amended by revising the 
words ``1,000 megagrams'' to read ``1,000 megagrams (1,102 tons).''


Sec. 61.123  [Amended]

    23. Amend Sec. 61.123 as follows:
    a. Paragraph (d) is amended by revising the words ``curies per 
metric ton'' to read ``curies per Mg or curies per ton'' wherever they 
occur.
    b. In paragraph (d), the fifth sentence is amended by revising the 
words ``in metric tons'' to read ``in Mg (tons).''


Sec. 61.125  [Amended]

    24. Amend Sec. 61.125 as follows:
    a. Paragraph (a)(1) is amended by revising the words ``Test Method 
1 of Appendix A'' to read ``Method 1 of Appendix A.''
    b. Paragraph (a)(2) is amended by revising the words ``Test Method 
2 of Appendix A'' to read ``Method 2 of Appendix A.''
    c. Paragraph (a)(3) is amended by revising the words ``Test Method 
3 of Appendix A'' to read ``Method 3 of Appendix A.''
    d. Paragraph (a)(4) is amended by revising the words ``Test Method 
5 of

[[Page 62157]]

Appendix A'' to read ``Method 5 of Appendix A.''
    e. Paragraph (a)(5) is amended by revising the words ``Test Method 
111 of Appendix B'' to read ``Method 111 of Appendix B.''


Sec. 61.132  [Amended]

    25. In Sec. 61.132, paragraphs (b) and (b)(1) are amended by 
revising the words ``Reference Method'' to read ``Method'' wherever 
they occur.


Sec. 61.133  [Amended]

    26. In Sec. 61.133, paragraphs (c) and (c)(1) are amended by 
revising the words ``Reference Method'' to read ``Method'' wherever 
they occur.

    27. Amend Sec. 61.139 as follows:
    a. In paragraph (c)(1), the equation definitions for 
``Qaj'' and ``Qbi'' are revised.
    b. Paragraph (d)(2)(ii) is amended by revising the words ``method 
21'' to read ``Method 21'' wherever they occur.
    c. In paragraph (g)(1)(vi), the second sentence is amended by 
revising the words ``Either follow section 7.1, ``Integrated Bag 
Sampling and Analysis,'' or section 7.2, ``Direct Interface Sampling 
and Analysis Procedure'''' to read ``Either the integrated bag sampling 
and analysis procedure or the direct interface procedure may be used.''
    d. Paragraph (g)(1)(vi)(A) is amended by revising the words 
``section 7.1'' to read ``the integrated bag sampling and analysis 
procedure.''
    e. In paragraph (g)(1)(vi)(B), the first sentence is amended by 
revising the words ``section 7.2'' to read ``the direct interface 
sampling and analysis procedure.''
    f. Paragraphs (h)(3), (h)(3)(ii), and (h)(4)(ii) are amended by 
revising the words ``method 18'' to read ``Method 18'' wherever they 
occur.
    The revisions read as follows:


Sec. 61.139  Provisions for alternative means for process vessels, 
storage tanks, and tar-intercepting sumps.

* * * * *
    (c) * * *
    (1) * * *

Qaj = volumetric flow rate in vents after the control 
device, standard cubic meters/minute (scm/min) [standard cubic feet/
minute (scf/min)].
Qbi = volumetric flow rate in vents before the control 
device, scm/min (scf/min).
* * * * *


61.155  [Amended]

    28. In Sec. 61.155, the section heading is amended by revising the 
words ``asbesto-containing'' to read ``asbestos-containing.''


Sec. 61.162  [Amended]

    29. Amend Sec. 61.162 as follows:
    a. Paragraph (a)(1) is amended by revising the words ``2.5 Mg per 
year'' to read ``2.5 Mg (2.7 ton) per year.''
    b. Paragraph (b)(1) is amended by revising the words ``0.4 Mg per 
year'' to read ``0.4 Mg (0.44 ton) per year.''

    30. Amend Sec. 61.164 as follows:
    a. Paragraph (c) is amended by revising the words ``8.0 Mg per 
year'' to read ``8.0 Mg (8.8 ton) per year.''
    b. Paragraph (c) is amended by revising the words ``1.0 Mg per 
year'' to read ``1.0 Mg (1.1 ton) per year.''
    c. In paragraph (c)(1), the first sentence is amended by revising 
the words ``grams of elemental arsenic per kilogram'' to read ``grams 
of elemental arsenic per kilogram (pounds per ton).''
    d. Paragraphs (c)(1) and (d)(3) are revised; the equation and 
definitions in paragraphs (c)(2) and (d)(5) are revised; and the 
definitions of the terms ``Ra'' and ``Ti'' in 
paragraph (d)(4) are revised.
    e. Paragraph (d) is amended by revising the words ``8.0 Mg per 
year'' to read ``8.0 Mg (8.8 ton) per year.''
    f. Paragraph (d) is amended by revising the words ``1.0 Mg per 
year'' to read ``1.0 Mg (1.1 ton) per year.''
    g. Paragraph (d)(2)(i) is amended by revising the words ``emission 
rate (g/h)'' to read ``emission rate, g/hr (lb/hr).''
    h. Paragraph (d)(2)(ii)(D) is amended by revising the words 
``Section 4 of Method 5D'' to read ``Section 8.0 of Method 5D.''
    i. Paragraph (e)(1)(ii)(D) is amended by revising the words 
``Section 4 of Method 5D'' to read ``Section 8.0 of Method 5D.''
    The revisions read as follows:


Sec. 61.164  Test methods and procedures.

* * * * *
    (c) * * *
    (1) Derive a theoretical uncontrolled arsenic emission factor (T), 
based on material balance calculations for each arsenic-containing 
glass type (i) produced during the 12-month period, as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.483

Where:

Ti = The theoretical uncontrolled arsenic emission factor 
for each glass type (i), g/kg (lb/ton).
Abi = Fraction by weight of elemental arsenic in the fresh 
batch for each glass type (I).
Wbi = Weight of fresh batch melted per unit weight of glass 
produced for each glass type (i), g/kg (lb/ton).
Aci = Fraction by weight of elemental arsenic in cullet for 
each glass type (i).
Wci = Weight of cullet melted per unit weight of glass 
produced for each glass type (i), g/kg (lb/ton).
Bgi = Weight of elemental arsenic per unit weight of glass 
produced for each glass type (i), g/kg (lb/ton).

    (2) * * *
    [GRAPHIC] [TIFF OMITTED] TR17OC00.484
    
Where:

Yi = Theoretical uncontrolled arsenic emission estimate for 
the 12-month period for each glass type, Mg/year (ton/year).
Ti = Theoretical uncontrolled arsenic emission factor for 
each type of glass (i) produced during the 12-month period as 
calculated in paragraph (c)(1) of this section, g/kg (lb/ton).
Gi = Quantity of each arsenic-containing glass type (i) 
produced during the 12-month period, kg/yr (ton/yr).
K = conversion factor for unit consistency, 106 g/Mg (2,000 
lb/ton).
* * * * *
    (d) * * *
    (3) Determine the actual uncontrolled arsenic emission factor 
(Ra) as follows:


[[Page 62158]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.485

Where:

Ra = Actual uncontrolled arsenic emission factor, g/kg (lb/
ton).
Ea = Actual uncontrolled arsenic emission rate from 
paragraph (d)(2) of this section, g/hr (lb/hr).
P = Rate of glass production, kg/hr (ton/hr), determined by dividing 
the weight of glass pulled from the furnace during the emission test by 
the number of hours taken to perform the test under paragraph (d)(2) of 
this section.

    (4) * * *

Ra = Actual uncontrolled arsenic emission factor, determined 
in paragraph (d)(3) of this section, g/kg (lb/ton).
Ti = Theoretical uncontrolled arsenic emission factor, g/kg 
(lb/ton), determined in paragraph (c)(1) of this section for the same 
glass type for which Ra was determined.

    (5) * * *
    [GRAPHIC] [TIFF OMITTED] TR17OC00.486
    
Where:

U = Uncontrolled arsenic emission rate for the 12-month period, Mg/yr 
(ton/yr).
Ti = Theoretical uncontrolled arsenic emission factor for 
each type of glass (i) produced during the 12-month period as 
calculated in paragraph (c)(1) of this section, g/kg (lb/ton).
F = The correction factor calculated in paragraph (d)(4) of this 
section.
Gi = Quantity of each arsenic-containing glass type (i) 
produced during the 12-month period, kg/yr (ton/yr).
n = Number of arsenic-containing glass types produced during the 12-
month period.
K = Conversion factor for unit consistency, 10\6\ g/Mg (2,000 lb/ton).
* * * * *


Sec. 61.165  [Amended]

    31. In Sec. 61.165, paragraph (a)(7) is amended by revising the 
words ``all records of maintenance'' at the beginning of the sentence 
to read ``All maintenance.''


Sec. 61.172  [Amended]

    32. Amend Sec. 61.172 as follows:
    a. Paragraph (a) is amended by revising the words ``75 kg/h'' to 
read ``75 kg/hr (165 lb/hr).''
    b. Paragraph (c) is amended by revising the words ``11.6 milligrams 
per dry standard cubic meter'' to read ``11.6 mg/dscm (0.0051 gr/
dscf).''


Sec. 61.174  [Amended]

    33. In Sec. 61.174, paragraph (f)(3)is amended by revising the 
equation definitions as follows:


Sec. 61.174  Test methods and procedures.

* * * * *
    (f) * * *
    (3) * * *

Rc is the converter arsenic charging rate, kg/hr (lb/hr).
Ac is the monthly average weight percent of arsenic in the 
copper matte charged during the month(%) as determined under paragraph 
(f)(2) of this section.
Al is the monthly average weight percent of arsenic in the 
lead matte charged during the month(%) as determined under paragraph 
(f)(2) of this section.
Wci is the total rate of copper matte charged to a copper 
converter during the month, kg (lb).
Wli is the total rate of lead matte charged to a copper 
converter during the month, kg (lb).
Hc is the total number of hours the copper converter 
department was in operation during the month (hr).
n is the number of copper converters in operation during the month.
* * * * *


Sec. 61.192  [Amended]

    34. In Sec. 61.192, the first sentence is amended by revising the 
words ``20 pCi/-m\2\-s'' to read ``20 picocuries per square meter per 
second (pCi/(m\2\-sec)) (1.9 pCi/(ft\2\-sec)).''


Sec. 61.202  [Amended]

    35. In Sec. 61.202, the third sentence is amended by revising the 
words ``20 pCi/m\2\-s'' to read ``20 pCi/(m\2\-sec) (1.9 pCi/(ft\2\-
sec)).''


Sec. 61.204  [Amended]

    36. In Sec. 61.204, paragraph (b) is amended by revising the words 
``10 picocuries per gram (pCi/g)'' to read ``10 pCi/g (4500 pCi/lb).''


Sec. 61.205  [Amended]

    37-38. In Sec. 61.205, paragraph (b)(2) is amended by revising the 
words ``7,000 pounds'' to read ``3182 kg (7,000 lb)'' wherever they 
occur.


Sec. 61.208  [Amended]

    39. Amend Sec. 61.208 as follows:
    a. Paragraph (a)(1)(iii) is amended by revising the words 
``quantity (in pounds) of phosphogypsum'' are revised to read 
``quantity of phosphogypsum, in kilograms or pounds.''
    b. Paragraph (a)(1)(vi) is amended by revising the words ``in pCi/
g'' to read ``in pCi/g (pCi/lb).''


Sec. 61.222  [Amended]

    40. In Sec. 61.222, paragraph (a) is amended by revising the words 
``20 pCi/m\2\-s'' to read ``20 pCi/(m\2\-sec) (1.9 pCi/(ft\2\-sec)).''


Sec. 61.241  [Amended]

    41. In Sec. 61.241, the definition of the term ``In vacuum 
service'' is amended by revising the words ``5 kilopascals (kPa) 
below'' to read ``5 kilopascals (kPa) (0.7 psia) below.''


Sec. 61.242-11  [Amended]

    42. In Sec. 61.242-11, paragraph (c) is amended by revising the 
words ``760  deg.C'' to read ``760  deg.C (1,400  deg.F).''


Sec. 61.243-2  [Amended]

    43. Amend Sec. 61.243-2 as follows:
    a. Paragraph (b)(2) is amended by revising the words ``skip 1 of 
the'' to read ``skip one of the.''
    b. Paragraph (b)(3) is amended by revising the words ``After 5 
consecutive'' to read ``After five consecutive.''
    c. Paragraph (b)(3) is amended by revising the words ``skip 3 of 
the quartely'' to read ``skip three of the quarterly.''


Sec. 61.244  [Amended]

    44. Amend Sec. 61.244 as follows:
    a. In paragraph (b)(1) by revising the words ``emission 
limitation.limitation to test data'' to read ``emission limitation to 
test data.''
    b. By redesignating paragraph (b)(3) as paragraph (b)(2).


Sec. 61.245  [Amended]

    45-46. Amend Sec. 61.245 as follows:
    a. Paragraphs (b)(2), (b)(3), (b)(5), (c)(2), (c)(3), (e)(3), and 
(e)(4) are amended by revising the words ``Reference Method'' to read 
``Method'' wherever they occur.
    b. In paragraph (e)(3), the definitions of the terms 
``HT'', ``K'', ``Ci'', and ``Hi'' are 
revised; and the equation and definitions in (e)(5) are revised as 
follows:

[[Page 62159]]

Sec. 61.245  Test methods and procedures.

* * * * *
    (e) * * *
    (3) * * *
HT = Net heating value of the sample, MJ/scm (BTU/scf); 
where the net enthalpy per mole of offgas is based on combustion at 25 
deg.C and 760 mm Hg (77  deg.F and 14.7 psi), but the standard 
temperature for determining the volume corresponding to one mole is 20 
deg.C (68  deg.F).
K = conversion constant, 1.740  x  10 \7\ (g-mole) (MJ)/(ppm-scm-kcal) 
(metric units); or 4.674  x  10\8\ ((g-mole) (Btu)/(ppm-scf-kcal)) 
(English units)
Ci = Concentration of sample component ``i'' in ppm, as measured by 
Method 18 of Appendix A to 40 CFR Part 60 and ASTM D2504-67, 77, or 88 
(Reapproved 1993) (incorporated by reference as specified in 
Sec. 61.18).
Hi = net heat of combustion of sample component ``i'' at 25 
deg.C and 760 mm Hg (77  deg.F and 14.7 psi), kcal/g-mole. The heats of 
combustion may be determined using ASTM D2382-76 or 88 or D4809-95 
(incorporated by reference as specified in Sec. 61.18) if published 
values are not available or cannot be calculated.
* * * * *
    (5) * * *
    [GRAPHIC] [TIFF OMITTED] TR17OC00.487
    
Where:

Vmax = Maximum permitted velocity, m/sec (ft/sec).
HT = Net heating value of the gas being combusted, as 
determined in paragraph (e)(3) of this section, MJ/scm (Btu/scf).
K1 = 8.706 m/sec (metric units)
    = 28.56 ft/sec (English units)
K2 = 0.7084 m4/(MJ-sec) (metric units)
    = 0.087 ft4/(Btu-sec) (English units)
* * * * *


Sec. 61.252  [Amended]

    47. In Sec. 61.252, paragraph (a) is amended by revising the words 
``20 pCi/m2-s'' to read 20 pCi/(m2-sec) (1.9 pCi/
(ft2-sec)).


Sec. 61.270  [Amended]

    48. Amend Sec. 61.270 as follows:
    a. Paragraph (a) is revised.
    b. Paragraph (e) is amended by revising the words ``204.9 kPa'' to 
read ``204.9 kPa (29.72 psia).''
    The revisions read as follows:


Sec. 61.270  Applicability and designation of sources.

    (a) The source to which this subpart applies is each storage vessel 
that is storing benzene having a specific gravity within the range of 
specific gravities specified in ASTM D836-84 for Industrial Grade 
Benzene, ASTM D835-85 for Refined Benzene-485, ASTM D2359-85a or 93 for 
Refined Benzene-535, and ASTM D4734-87 or 96 for Refined Benzene-545. 
These specifications are incorporated by reference as specified in 
Sec. 61.18. See Sec. 61.18 for acceptable versions of these methods.
* * * * *


Sec. 61.272  [Amended]

    49. Amend Sec. 61.272 as follows:
    a. In paragraph (c)(1)(i), the fourth sentence is amended by 
revising the words ``816  deg.C'' to read ``816  deg.C (1,500 
deg.F).''
    b. Paragraph (d) is amended by revising the letter ``O'' in the 
words ``40 CFR 6O.18(e)'' to read ``40 CFR 60.18(e).''


Sec. 61.301  [Amended]

    50. Amend Sec. 61.301 as follows:
    a. The definitions of the terms ``Leak'' and ``Vapor-tight marine 
vessel'' are amended by revising the words ``method 21'' to read 
``Method 21'' wherever they occur.
    b. In the definition of the terms ``Vapor-tight tank truck or 
vapor-tight railcar'', the second sentence is amended by revising the 
words ``method 27 of part 60, appendix A'' to read ``Method 27 of 
Appendix A to 40 CFR part 60.''


Sec. 61.302  [Amended]

    51. Amend Sec. 61.302 as follows:
    a. In paragraph (d)(1), the third sentence is amended by revising 
the words ``method 27 of part 60, appendix A'' to read ``Method 27 of 
Appendix A to 40 CFR Part 60.''
    b. In paragraph (e)(2), the second sentence is amended by revising 
the words ``method 21 of part 60, appendix A'' to read ``Method 21 of 
Appendix A to 40 CFR Part 60.''
    c. In paragraph (e)(2)(ii)(B), fourth sentence, the words ``method 
21'' are revised to read ``Method 21 of Appendix A to 40 CFR Part 60.''
    d. In paragraph (h), the first sentence is amended by revising the 
words ``method 27 of part 60, appendix A'' to read ``Method 27 of 
Appendix A to 40 CFR Part 60.''


Sec. 61.303  [Amended]

    52. In Sec. 61.303, paragraphs (c), (c)(1), and (c)(2) are amended 
by revising the words ``44 MW'' to read ``44 MW (150  x  106 
BTU/hr)'' wherever they occur.


Sec. 61.304  [Amended]

    53. Amend Sec. 61.304 as follows:
    a. Paragraph (a)(4)(iii) is amended by revising the word ``method'' 
to read ``Method.''
    b. In paragraph (a)(4)(iv), the first sentence is amended by 
revising the words ``method 25A or method 25B'' to read ``Method 25A or 
Method 25B.''
    c. Paragraph (b) is amended by revising the words ``a performance 
test according to method 22 of appendix A of this part, shall be 
performed to determine visible emissions. The observation period shall 
be at least 2 hours and shall be conducted according to method 22'' to 
read ``a performance test according to Method 22 of appendix A of 40 
CFR part 60 shall be performed to determine visible emissions. The 
observation period shall be at least 2 hours.''

    54. Amend Sec. 61.305 as follows:
    a. Paragraphs (a), (b)(3), and (d) are amended by revising the 
words ``44 MW'' to read ``44 MW (150  x  106 BTU/hr)'' 
wherever they occur.
    b. Paragraph (a)(3)(ii) is revised.
    c. Paragraphs (b)(1), (b)(2), and (b)(3) are amended by revising 
the words ``28  deg.C'' to read ``28  deg.C (50  deg.F)'' wherever they 
occur.
    The revisions read as follows:


Sec. 61.305  Reporting and recordkeeping.

    (a) * * *
    (3) * * *
    (ii) The average combustion temperature of the steam generating 
unit or process heater with a design heat input capacity of less than 
44 MW (150  x  106 BTU/hr), measured with the following 
frequency: at least every 2 minutes during a loading cycle if the total 
time period of the loading cycle is less than 3 hours, and every 15 
minutes if the total time period of the loading cycle is equal to or 
greater than 3 hours. The measured temperature shall be averaged over 
the loading cycle.
* * * * *


Sec. 61.342  [Amended]

    55. Amend Sec. 61.342 as follows:
    a. In paragraph (a), the first sentence, the words ``10 megagrams 
per year (Mg/yr)'' are revised to read ``10 megagrams per year (Mg/yr) 
(11 ton/yr).''
    b. Paragraphs (a)(3), (b), (c), (c)(3)(i), (d), and (e) are amended 
by revising the words ``10 Mg/yr'' to read ``10 Mg/yr (11 ton/yr).''
    c. Paragraph (c)(3)(i) is amended by revising the words ``0.02 
liters per minute'' to read ``0.02 liters per minute (0.005 gallons per 
minute).''
    d. Paragraph (c)(3)(ii)(B) is amended by revising the words ``2.0 
Mg/yr'' to read ``2.0 Mg/yr (2.2 ton/yr).''

[[Page 62160]]

    e. Paragraph (d)(2)(1) is redesignated as paragraph (d)(2)(i).
    f. In paragraph (d)(2)(i), the first sentence is amended by 
revising the words ``1 Mg/yr'' to read ``1 Mg/yr (1.1 ton/yr).''
    g. In paragraph (e)(2)(i), the first sentence is amended by 
revising the words ``6.0 Mg/yr'' to read ``6.0 Mg/yr (6.6 ton/yr).''


Sec. 61.348  [Amended]

    56. Amend Sec. 61.348 as follows:
    a. In paragraph (b)(2)(ii), the first sentence is amended by 
revising the words ``1 Mg/yr'' to read ``1 Mg/yr (1.1 ton/yr).''
    b. In paragraph (b)(2)(ii)(B), by revising the third sentence.
    The revision reads as follows:


Sec. 61.348  Standards: Treatment processes.

    (b) * * *
    (2) * * *
    (ii) * * *
    (B) * * * An enhanced biodegradation unit typically operates at a 
food-to-microorganism ratio in the range of 0.05 to 1.0 kg of 
biological oxygen demand per kg of biomass per day, a mixed liquor 
suspended solids ratio in the range of 1 to 8 grams per liter (0.008 to 
0.7 pounds per liter), and a residence time in the range of 3 to 36 
hours.
* * * * *


Sec. 61.349  [Amended]

    57. In Sec. 61.349, paragraph (a)(2)(i)(C) is amended by revising 
the words ``760  deg.C'' to read ``760  deg.C (1,400  deg.F).''


Sec. 61.354  [Amended]

    58. In Sec. 61.354, paragraph (c)(4) is amended by revising the 
words ``44 megawatts (MW)'' to read ``44 MW (150  x  106 
BTU/hr).''

    58a. In paragraph (c)(5), ``44 MW'' is revised to read ``44 MW (150 
 x  106 BTU/hr).''


Sec. 61.355  [Amended]

    59. Amend Sec. 61.355 as follows:
    a. Paragraphs (a)(3), (a)(4), (a)(4)(ii) are amended by revising 
the words ``10 Mg/yr'' to read ``10 Mg/yr (11 ton/yr)'' wherever they 
occur.
    b. Paragraphs (a)(4), (a)(5), and (a)(5)(ii) are amended by 
revising the words ``1 Mg/yr'' to read ``1 Mg/yr (1.1 ton/yr)'' 
wherever they occur.
    c. Paragraphs (c)(3)(ii)(F) and (c)(3)(ii)(H) are amended by 
revising the words ``10  deg.C'' to read ``10  deg.C (50  deg.F)'' 
wherever they occur.
    d. Paragraph (c)(3)(v) is amended by revising the words ``kg/yr'' 
to read ``kg/yr (lb/yr)'' wherever they occur.
    e. Paragraphs (e)(3), (e)(4), (f)(3), (f)(4)(iv), (f)(5), 
(i)(3)(iv), and (i)(4) are amended by revising the definitions of the 
terms used in the equations; and (f)(4)(iii) and (i)(3)(iii) are 
amended by revising the equation and definitions of terms used in the 
equations.
    f. Paragraphs (f)(4)(ii)(B), (f)(4)(ii)(C), (h)(1), (h)(2), (h)(3), 
(h)(5), (h)(6), (i)(2), (i)(3)(ii)(B), and (i)(3)(ii)(C) are amended by 
revising the word ``method'' to read ``Method'' wherever it occurs.
    g. Paragraph (k)(7) is amended by revising the words ``6.0 Mg/yr'' 
to read ``6.0 Mg/yr (6.6 ton/yr).''
    The revisions read as follows:


Sec. 61.355  Test methods, procedures, and compliance provisions.

* * * * *
    (e) * * *
    (3) * * *

Eb = Mass flow rate of benzene entering the treatment 
process, kg/hr (lb/hr).
K = Density of the waste stream, kg/m\3\ (lb/ft\3\).
Vi = Average volume flow rate of waste entering the 
treatment process during each run i, m\3\/hr (ft\3\/hr).
Ci = Average concentration of benzene in the waste stream 
entering the treatment process during each run i, ppmw.
n = Number of runs.
106 = Conversion factor for ppmw.

    (4) * * *
Ea = Mass flow rate of benzene exiting the treatment 
process, kg/hr (lb/hr).
K = Density of the waste stream, kg/m3 (lb/ft3).
Vi = Average volume flow rate of waste exiting the treatment 
process during each run i, m3/hr (ft3/hr).
Ci = Average concentration of benzene in the waste stream 
exiting the treatment process during each run i, ppmw.
n = Number of runs.
106 = Conversion factor for ppmw.

    (f) * * *
    (3) * * *

Eb = Mass flow rate of benzene entering the combustion unit, 
kg/hr (lb/hr).
K = Density of the waste stream, kg/m3 (lb/ft3).
Vi = Average volume flow rate of waste entering the 
combustion unit during each run i, m3/hr (ft3/
hr).
Ci = Average concentration of benzene in the waste stream 
entering the combustion unit during each run i, ppmw.
n = Number of runs.
106 = Conversion factor for ppmw.

    (4) * * *
    (iii) * * *
    [GRAPHIC] [TIFF OMITTED] TR17OC00.488
    
Where:

Mi = Mass of benzene emitted during run i, kg (lb).
V = Volume of air-vapor mixture exhausted at standard conditions, 
m3 (ft3).
C = Concentration of benzene measured in the exhaust, ppmv.
Db = Density of benzene, 3.24 kg/m3 (0.202 lb/
ft3).
106 = Conversion factor for ppmv.
    (iv) * * *
Ea = Mass flow rate of benzene emitted from the combustion 
unit, kg/hr (lb/hr).
Mi = Mass of benzene emitted from the combustion unit during 
run i, kg (lb).
T = Total time of all runs, hr.
n = Number of runs.

    (5) * * *

R = Benzene destruction efficiency for the combustion unit, percent.
Eb = Mass flow rate of benzene entering the combustion unit, 
kg/hr (lb/hr).
Ea = Mass flow rate of benzene emitted from the combustion 
unit, kg/hr (lb/hr).
* * * * *
    (i) * * *
    (3) * * *
    (iii) * * *
    [GRAPHIC] [TIFF OMITTED] TR17OC00.489
    
    [GRAPHIC] [TIFF OMITTED] TR17OC00.490
    
Maj = Mass of organics or benzene in the vent stream 
entering the control device during run j, kg (lb).
Mbj = Mass of organics or benzene in the vent stream exiting 
the control device during run j, kg (lb).
Vaj = Volume of vent stream entering the control device 
during run j, at standard conditions, m3 (ft3).
Vbj = Volume of vent stream exiting the control device 
during run j, at standard conditions, m3 (ft3).
Cai = Organic concentration of compound i or the benzene 
concentration measured in the vent stream entering the control device 
as determined by Method 18, ppm by volume on a dry basis.
Cbi = Organic concentration of compound i or the benzene 
concentration measured in the vent stream exiting the control device as 
determined by Method 18, ppm by volume on a dry basis.
MWi = Molecular weight of organic compound i in the vent 
stream, or the molecular weight of benzene, kg/kg-mol (lb/lb-mole).

[[Page 62161]]

n = Number of organic compounds in the vent stream; if benzene 
reduction efficiency is being demonstrated, then n=1.
K1 = Conversion factor for molar volume at standard 
conditions (293 K and 760 mm Hg (527 R and 14.7 psia))
    = 0.0416 kg-mol/m3 (0.00118 lb-mol/ft3)
10-6=Conversion factor for ppmv.

    (iv) * * *

Ea = Mass flow rate of organics or benzene entering the 
control device, kg/hr (lb/hr).
Eb = Mass flow rate of organics or benzene exiting the 
control device, kg/hr (lb/hr).
Maj = Mass of organics or benzene in the vent stream 
entering the control device during run j, kg (lb).
M bj = Mass of organics or benzene in the vent stream 
exiting the control device during run j, kg (lb).
T = Total time of all runs, hr.
n = Number of runs.
(4) * * *
R = Total organic reduction of efficiency or benzene reduction 
efficiency for the control device, percent.
Eb = Mass flow rate of organics or benzene entering the 
control device, kg/hr (lb/hr).
Ea = Mass flow rate of organic or benzene emitted from the 
control device, kg/hr (lb/hr).
* * * * *


Sec. 61.356  [Amended]

    60. Amend Sec. 61.356 as follows:
    a. Paragraph (b)(2)(i) is amended by revising the words ``0.02 
liters per minute'' to read ``0.02 liters (0.005 gallons) per minute.''
    b. Paragraph (b)(2)(i) is amended by revising the words ``10 Mg/
yr'' to read ``10 Mg/yr (11 ton/yr).''
    c. Paragraph (b)(2)(ii) is amended by revising the words ``2.0 Mg/
yr'' to read ``2.0 Mg/yr (2.2 ton/yr).''
    d. Paragraph (b)(4) is amended by revising the words ``6.0 Mg/yr'' 
to read ``6.0 Mg/yr (6.6 ton/yr).''
    e. Paragraphs (j)(4), (j)(5), and (j)(6) are amended by revising 
the words ``28  deg.C'' to read ``28  deg.C (50  deg.F)'' wherever they 
occur.
    f. Paragraph (j)(6) is amended by revising the words ``44 MW'' to 
read ``44 MW (150  x  106 BTU/hr)'' wherever they occur.
    g. Paragraph (j)(8) is amended by revising the words ``6  deg.C'' 
to read ``6  deg.C (11  deg.F)'' wherever they occur.


Sec. 61.357  [Amended]

    61. Amend Sec. 61.357 as follows:
    a. Paragraphs (b) and (c) are amended by revising the words ``1 Mg/
yr'' to read ``1 Mg/yr (1.1 ton/yr)'' wherever they occur.
    b. Paragraphs (c) and (d) are amended by revising the words ``10 
Mg/yr'' to read ``10 Mg/yr (11 ton/yr)'' wherever they occur.
    c. Paragraphs (d)(7)(iv)(A), (d)(7)(iv)(B), and (d)(7)(iv)(C) are 
amended by revising the words ``28  deg.C'' to read ``28  deg.C (50 
deg.F)'' wherever they occur.
    d. Paragraph (d)(7)(iv)(C) is amended by revising the words ``44 
MW'' to read ``44 MW (150  x  106 BTU/hr).''
    e. Paragraph (d)(7)(iv)(E) is amended by revising the words ``6 
deg.C'' to read ``6  deg.C (11  deg.F).''

    62. In Part 61, Appendix B is amended by revising Methods 101, 
101A, 102, 103, 104, 105, 106, 107, 107A, 108, 108A, 108B, 108C, and 
111 to read as follows:

Method 101--Determination of Particulate and Gaseous Mercury 
Emissions From Chlor-Alkali Plants (Air Streams)

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from methods in Appendix A to 40 CFR Part 
60. Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of at least the following 
additional test methods: Method 1, Method 2, Method 3, and Method 5.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
              Analyte                   CAS No.          Sensitivity
------------------------------------------------------------------------
Mercury (Hg)......................       7439-97-6  Dependent upon
                                                     recorder and
                                                     spectrophotometer.
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of Hg emissions, including both particulate and gaseous Hg, from chlor-
alkali plants and other sources (as specified in the regulations) where 
the carrier-gas stream in the duct or stack is principally air.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    Particulate and gaseous Hg emissions are withdrawn isokinetically 
from the source and collected in acidic iodine monochloride (ICl) 
solution. The Hg collected (in the mercuric form) is reduced to 
elemental Hg, which is then aerated from the solution into an optical 
cell and measured by atomic absorption spectrophotometry.

3.0  Definitions [Reserved]

4.0  Interferences

    4.1  Sample Collection. Sulfur dioxide (SO2) reduces ICl 
and causes premature depletion of the ICl solution.
    4.2  Sample Analysis.
    4.2.1  ICl concentrations greater than 10-4 molar 
inhibit the reduction of the Hg (II) ion in the aeration cell.
    4.2.2  Condensation of water vapor on the optical cell windows 
causes a positive interference.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method does not purport to address 
all of the safety problems associated with its use. It is the 
responsibility of the user of this test method to establish appropriate 
safety and health practices and determine the applicability of 
regulatory limitations prior to performing this test method.
    5.2  Corrosive Reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water for at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burn as thermal burn.
    5.2.1  Hydrochloric Acid (HCl). Highly toxic and corrosive. Causes 
severe damage to tissues. Vapors are highly irritating to eyes, skin, 
nose, and lungs, causing severe damage. May cause bronchitis, 
pneumonia, or edema of lungs. Exposure to concentrations of 0.13 to 0.2 
percent can be lethal to humans in a few minutes. Provide ventilation 
to limit exposure. Reacts with metals, producing hydrogen gas.
    5.2.2  Nitric Acid (HNO3). Highly corrosive to eyes, 
skin, nose, and lungs. Vapors cause bronchitis, pneumonia, or edema of 
lungs. Reaction to inhalation may be delayed as long as 30 hours and

[[Page 62162]]

still be fatal. Provide ventilation to limit exposure. Strong oxidizer. 
Hazardous reaction may occur with organic materials such as solvents.
    5.2.3  Sulfuric Acid (H2SO4). Rapidly 
destructive to body tissue. Will cause third degree burns. Eye damage 
may result in blindness. Inhalation may be fatal from spasm of the 
larynx, usually within 30 minutes. 3 mg/m3 will cause lung 
damage. 1 mg/m\3\ for 8 hours will cause lung damage or, in higher 
concentrations, death. Provide ventilation to limit inhalation. Reacts 
violently with metals and organics.

6.0  Equipment and Supplies.

    6.1  Sample Collection. A schematic of the sampling train used in 
performing this method is shown in Figure 101-1; it is similar to the 
Method 5 sampling train. The following items are required for sample 
collection:
    6.1.1  Probe Nozzle, Pitot Tube, Differential Pressure Gauge, 
Metering System, Barometer, and Gas Density Determination Equipment. 
Same as Method 5, Sections 6.1.1.1, 6.1.1.3, 6.1.1.4, 6.1.1.9, 6.1.2, 
and 6.1.3, respectively.
    6.1.2  Probe Liner. Borosilicate or quartz glass tubing. A heating 
system capable of maintaining a gas temperature of 120  14 
deg.C (248  25  deg.F) at the probe exit during sampling 
may be used to prevent water condensation.


    Note: Do not use metal probe liners.


    6.1.3  Impingers. Four Greenburg-Smith impingers connected in 
series with leak-free ground glass fittings or any similar leak-free 
noncontaminating fittings. For the first, third, and fourth impingers, 
impingers that are modified by replacing the tip with a 13-mm ID (0.5-
in.) glass tube extending to 13 mm (0.5 in.) from the bottom of the 
flask may be used.
    6.1.4  Acid Trap. Mine Safety Appliances air line filter, Catalog 
number 81857, with acid absorbing cartridge and suitable connections, 
or equivalent.
    6.2  Sample Recovery. The following items are needed for sample 
recovery:
    6.2.1  Glass Sample Bottles. Leakless, with Teflon-lined caps, 
1000- and 100-ml.
    6.2.2  Graduated Cylinder. 250-ml.
    6.2.3  Funnel and Rubber Policeman. To aid in transfer of silica 
gel to container; not necessary if silica gel is weighed in the field.
    6.2.4  Funnel. Glass, to aid in sample recovery.
    6.3  Sample Preparation and Analysis. The following items are 
needed for sample preparation and analysis:
    6.3.1  Atomic Absorption Spectrophotometer. Perkin-Elmer 303, or 
equivalent, containing a hollow-cathode mercury lamp and the optical 
cell described in Section 6.3.2.
    6.3.2  Optical Cell. Cylindrical shape with quartz end windows and 
having the dimensions shown in Figure 101-2. Wind the cell with 
approximately 2 meters (6 ft) of 24-gauge Nichrome wire, or equivalent, 
and wrap with fiberglass insulation tape, or equivalent; do not let the 
wires touch each other.
    6.3.3  Aeration Cell. Constructed according to the specifications 
in Figure 101-3. Do not use a glass frit as a substitute for the blown 
glass bubbler tip shown in Figure 101-3.
    6.3.4  Recorder. Matched to output of the spectrophotometer 
described in Section 6.3.1.
    6.3.5  Variable Transformer. To vary the voltage on the optical 
cell from 0 to 40 volts.
    6.3.6  Hood. For venting optical cell exhaust.
    6.3.7  Flow Metering Valve.
    6.3.8  Rate Meter. Rotameter, or equivalent, capable of measuring 
to within 2 percent a gas flow of 1.5 liters/min (0.053 cfm).
    6.3.9  Aeration Gas Cylinder. Nitrogen or dry, Hg-free air, 
equipped with a single-stage regulator.
    6.3.10  Tubing. For making connections. Use glass tubing (ungreased 
ball and socket connections are recommended) for all tubing connections 
between the solution cell and the optical cell; do not use Tygon 
tubing, other types of flexible tubing, or metal tubing as substitutes. 
Teflon, steel, or copper tubing may be used between the nitrogen tank 
and flow metering valve (Section 6.3.7), and Tygon, gum, or rubber 
tubing between the flow metering valve and the aeration cell.
    6.3.11  Flow Rate Calibration Equipment. Bubble flow meter or wet-
test meter for measuring a gas flow rate of 1.5  0.1 
liters/min (0.053  0.0035 cfm).
    6.3.12  Volumetric Flasks. Class A with penny head standard taper 
stoppers; 100-, 250-, 500-, and 1000-ml.
    6.3.13  Volumetric Pipets. Class A; 1-, 2-, 3-, 4-, and 5-ml.
    6.3.14  Graduated Cylinder. 50-ml.
    6.3.15  Magnetic Stirrer. General-purpose laboratory type.
    6.3.16  Magnetic Stirring Bar. Teflon-coated.
    6.3.17  Balance. Capable of weighing to  0.5 g.
    6.3.18  Alternative Analytical Apparatus. Alternative systems are 
allowable as long as they meet the following criteria:
    6.3.18.1  A linear calibration curve is generated and two 
consecutive samples of the same aliquot size and concentration agree 
within 3 percent of their average.
    6.3.18.2  A minimum of 95 percent of the spike is recovered when an 
aliquot of a source sample is spiked with a known concentration of Hg 
(II) compound.
    6.3.18.3  The reducing agent should be added after the aeration 
cell is closed.
    6.3.18.4  The aeration bottle bubbler should not contain a frit.
    6.3.18.5  Any Tygon tubing used should be as short as possible and 
conditioned prior to use until blanks and standards yield linear and 
reproducible results.
    6.3.18.6  If manual stirring is done before aeration, it should be 
done with the aeration cell closed.
    6.3.18.7  A drying tube should not be used unless it is conditioned 
as the Tygon tubing above.

7.0  Reagents and Standards

    Unless otherwise indicated, all reagents must conform to the 
specifications established by the Committee on Analytical Reagents of 
the American Chemical Society; where such specifications are not 
available, use the best available grade.
    7.1  Sample Collection. The following reagents are required for 
sample collection:
    7.1.1  Water. Deionized distilled, to conform to ASTM D 1193-77 or 
91 (incorporated by reference--see Sec. 61.18), Type 1. If high 
concentrations of organic matter are not expected to be present, the 
analyst may eliminate the KMnO4 test for oxidizable organic 
matter. Use this water in all dilutions and solution preparations.
    7.1.2  Nitric Acid, 50 Percent (v/v). Mix equal volumes of 
concentrated HNO3 and water, being careful to add the acid 
to the water slowly.
    7.1.3  Silica Gel. Indicating type, 6- to 16-mesh. If previously 
used, dry at 175  deg.C (350  deg.F) for 2 hours. The tester may use 
new silica gel as received.
    7.1.4  Potassium Iodide (KI) Solution, 25 Percent. Dissolve 250 g 
of KI in water, and dilute to 1 liter.
    7.1.5  Iodine Monochloride Stock Solution, 1.0 M. To 800 ml of 25 
percent KI solution, add 800 ml of concentrated HCl. Cool to room 
temperature. With vigorous stirring, slowly add 135 g of potassium 
iodate (KIO3), and stir until all free iodine has dissolved. 
A clear orange-red solution occurs when all the KIO3 has 
been added. Cool to room temperature, and dilute to 1800 ml with

[[Page 62163]]

water. Keep the solution in amber glass bottles to prevent degradation.
    7.1.6  Absorbing Solution, 0.1 M ICl. Dilute 100 ml of the 1.0 M 
ICl stock solution to 1 liter with water. Keep the solution in amber 
glass bottles and in darkness to prevent degradation. This reagent is 
stable for at least two months.
    7.2  Sample Preparation and Analysis. The following reagents and 
standards are required for sample preparation and analysis:
    7.2.1  Reagents.
    7.2.1.1  Tin (II) Solution. Prepare fresh daily, and keep sealed 
when not being used. Completely dissolve 20 g of tin (II) chloride (or 
25 g of tin (II) sulfate) crystals (Baker Analyzed reagent grade or any 
other brand that will give a clear solution) in 25 ml of concentrated 
HCl. Dilute to 250 ml with water. Do not substitute HNO3, 
H2SO4, or other strong acids for the HCl.
    7.2.1.2  Sulfuric Acid, 5 Percent (v/v). Dilute 25 ml of 
concentrated H2SO4 to 500 ml with water.
    7.2.2  Standards
    7.2.2.1  Hg Stock Solution, 1 mg Hg/ml. Prepare and store all Hg 
standard solutions in borosilicate glass containers. Completely 
dissolve 0.1354 g of Hg (II) chloride in 75 ml of water in a 100-ml 
glass volumetric flask. Add 10 ml of concentrated HNO3, and 
adjust the volume to exactly 100 ml with water. Mix thoroughly. This 
solution is stable for at least one month.
    7.2.2.2  Intermediate Hg Standard Solution, 10 g Hg/ml. 
Prepare fresh weekly. Pipet 5.0 ml of the Hg stock solution (Section 
7.2.2.1) into a 500-ml glass volumetric flask, and add 20 ml of the 5 
percent H2SO4 solution. Dilute to exactly 500 ml 
with water. Thoroughly mix the solution.
    7.2.2.3  Working Hg Standard Solution, 200 ng Hg/ml. Prepare fresh 
daily. Pipet 5.0 ml of the intermediate Hg standard solution (Section 
7.2.2.2) into a 250-ml volumetric glass flask. Add 10 ml of the 5 
percent H2SO4 and 2 ml of the 0.1 M ICl absorbing 
solution taken as a blank (Section 8.7.4.3), and dilute to 250 ml with 
water. Mix thoroughly.

8.0  Sample Collection, Preservation, Transport, and Storage

    Because of the complexity of this method, testers should be trained 
and experienced with the test procedures to ensure reliable results. 
Since the amount of Hg that is collected generally is small, the method 
must be carefully applied to prevent contamination or loss of sample.
    8.1  Pretest Preparation. Follow the general procedure outlined in 
Method 5, Section 8.1, except omit Sections 8.1.2 and 8.1.3.
    8.2  Preliminary Determinations. Follow the general procedure 
outlined in Method 5, Section 8.2, with the exception of the following:
    8.2.1  Select a nozzle size based on the range of velocity heads to 
assure that it is not necessary to change the nozzle size in order to 
maintain isokinetic sampling rates below 28 liters/min (1.0 cfm).
    8.2.2  Perform test runs such that samples are obtained over a 
period or periods that accurately determine the maximum emissions that 
occur in a 24-hour period. In the case of cyclic operations, run 
sufficient tests for the accurate determination of the emissions that 
occur over the duration of the cycle. A minimum sample time of 2 hours 
is recommended. In some instances, high Hg or high SO2 
concentrations make it impossible to sample for the desired minimum 
time. This is indicated by reddening (liberation of free iodine) in the 
first impinger. In these cases, the sample run may be divided into two 
or more subruns to ensure that the absorbing solution is not depleted.
    8.3  Preparation of Sampling Train.
    8.3.1  Clean all glassware (probe, impingers, and connectors) by 
rinsing with 50 percent HNO3, tap water, 0.1 M ICl, tap 
water, and finally deionized distilled water. Place 100 ml of 0.1 M ICl 
in each of the first three impingers. Take care to prevent the 
absorbing solution from contacting any greased surfaces. Place 
approximately 200 g of preweighed silica gel in the fourth impinger. 
More silica gel may be used, but care should be taken to ensure that it 
is not entrained and carried out from the impinger during sampling. 
Place the silica gel container in a clean place for later use in the 
sample recovery. Alternatively, determine and record the weight of the 
silica gel plus impinger to the nearest 0.5 g.
    8.3.2  Install the selected nozzle using a Viton A O-ring when 
stack temperatures are less than 260  deg.C (500  deg.F). Use a 
fiberglass string gasket if temperatures are higher. See APTD-0576 
(Reference 3 in Method 5) for details. Other connecting systems using 
either 316 stainless steel or Teflon ferrules may be used. Mark the 
probe with heat-resistant tape or by some other method to denote the 
proper distance into the stack or duct for each sampling point.
    8.3.3  Assemble the train as shown in Figure 101-1, using (if 
necessary) a very light coat of silicone grease on all ground glass 
joints. Grease only the outer portion (see APTD-0576) to avoid the 
possibility of contamination by the silicone grease.


    Note: An empty impinger may be inserted between the third 
impinger and the silica gel to remove excess moisture from the 
sample stream.

    8.3.4  After the sampling train has been assembled, turn on and set 
the probe heating system, if applicable, at the desired operating 
temperature. Allow time for the temperatures to stabilize. Place 
crushed ice around the impingers.
    8.4  Leak-Check Procedures. Follow the leak-check procedures 
outlined in Method 5, Section 8.4.
    8.5  Sampling Train Operation. Follow the general procedure 
outlined in Method 5, Section 8.5. For each run, record the data 
required on a data sheet such as the one shown in Figure 101-4.
    8.6  Calculation of Percent Isokinetic. Same as Method 5, Section 
8.6.
    8.7  Sample Recovery. Begin proper cleanup procedure as soon as the 
probe is removed from the stack at the end of the sampling period.
    8.7.1  Allow the probe to cool. When it can be safely handled, wipe 
off any external particulate matter near the tip of the probe nozzle, 
and place a cap over it. Do not cap off the probe tip tightly while the 
sampling train is cooling. Capping would create a vacuum and draw 
liquid out from the impingers.
    8.7.2  Before moving the sampling train to the cleanup site, remove 
the probe from the train, wipe off the silicone grease, and cap the 
open outlet of the probe. Be careful not to lose any condensate that 
might be present. Wipe off the silicone grease from the impinger. Use 
either ground-glass stoppers, plastic caps, or serum caps to close 
these openings.
    8.7.3  Transfer the probe and impinger assembly to a cleanup area 
that is clean, protected from the wind, and free of Hg contamination. 
The ambient air in laboratories located in the immediate vicinity of 
Hg-using facilities is not normally free of Hg contamination.
    8.7.4  Inspect the train before and during disassembly, and note 
any abnormal conditions. Treat the samples as follows.
    8.7.4.1  Container No. 1 (Impingers and Probe).
    8.7.4.1.1  Using a graduated cylinder, measure the liquid in the 
first three impingers to within 1 ml. Record the volume of liquid 
present (e.g., see Figure 5-6 of Method 5). This information is needed 
to calculate the moisture content of the effluent gas.

[[Page 62164]]

(Use only glass storage bottles and graduated cylinders that have been 
precleaned as in Section 8.3.1) Place the contents of the first three 
impingers into a 1000-ml glass sample bottle.
    8.7.4.1.2  Taking care that dust on the outside of the probe or 
other exterior surfaces does not get into the sample, quantitatively 
recover the Hg (and any condensate) from the probe nozzle, probe 
fitting, and probe liner as follows: Rinse these components with two 
50-ml portions of 0.1 M ICl. Next, rinse the probe nozzle, fitting and 
liner, and each piece of connecting glassware between the probe liner 
and the back half of the third impinger with a maximum of 400 ml of 
water. Add all washings to the 1000-ml glass sample bottle containing 
the liquid from the first three impingers.
    8.7.4.1.3  After all washings have been collected in the sample 
container, tighten the lid on the container to prevent leakage during 
shipment to the laboratory. Mark the height of the liquid to determine 
later whether leakage occurred during transport. Label the container to 
identify clearly its contents.
    8.7.4.2  Container No. 2 (Silica Gel). Same as Method 5, Section 
8.7.6.3.
    8.7.4.3  Container No. 3 (Absorbing Solution Blank). Place 50 ml of 
the 0.1 M ICl absorbing solution in a 100-ml sample bottle. Seal the 
container. Use this blank to prepare the working Hg standard solution 
(Section 7.2.2.3).

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.4 10.2......................  Sampling           Ensure accuracy and
                                 equipment leak-    precision of
                                 checks and         sampling
                                 calibration.       measurements.
10.5, 10.6....................  Spectrophotometer  Ensure linearity of
                                 calibration.       spectrophotometer
                                                    response to
                                                    standards.
11.3.3........................  Check for matrix   Eliminate matrix
                                 effects.           effects.
------------------------------------------------------------------------

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

10.0  Calibration and Standardizations

    Note: Maintain a laboratory log of all calibrations.

    10.1  Before use, clean all glassware, both new and used, as 
follows: brush with soap and tap water, liberally rinse with tap water, 
soak for 1 hour in 50 percent HNO3, and then rinse with 
deionized distilled water.
    10.2  Sampling Equipment. Calibrate the sampling equipment 
according to the procedures outlined in the following sections of 
Method 5: Section 10.1 (Probe Nozzle), Section 10.2 (Pitot Tube 
Assembly), Section 10.3 (Metering System), Section 10.5 (Temperature 
Sensors), Section 10.6 (Barometer).
    10.3  Aeration System Flow Rate Meter. Assemble the aeration system 
as shown in Figure 101-5. Set the outlet pressure on the aeration gas 
cylinder regulator to a minimum pressure of 500 mm Hg (10 psi), and use 
the flow metering valve and a bubble flowmeter or wet-test meter to 
obtain a flow rate of 1.5  0.1 liters/min (0.053 
 0.0035 cfm) through the aeration cell. After the 
calibration of the aeration system flow rate meter is complete, remove 
the bubble flowmeter from the system.
    10.4  Optical Cell Heating System. Using a 50-ml graduated 
cylinder, add 50 ml of water to the bottle section of the aeration 
cell, and attach the bottle section to the bubbler section of the cell. 
Attach the aeration cell to the optical cell and while aerating at 1.5 
 0.1 liters/min (0.053  0.0035 cfm), determine 
the minimum variable transformer setting necessary to prevent 
condensation of moisture in the optical cell and in the connecting 
tubing. (This setting should not exceed 20 volts.)
    10.5  Spectrophotometer and Recorder.
    10.5.1  The Hg response may be measured by either peak height or 
peak area.

    Note: The temperature of the solution affects the rate at which 
elemental Hg is released from a solution and, consequently, it 
affects the shape of the absorption curve (area) and the point of 
maximum absorbance (peak height). Therefore, to obtain reproducible 
results, bring all solutions to room temperature before use.


    10.5.2  Set the spectrophotometer wavelength at 253.7 nm, and make 
certain the optical cell is at the minimum temperature that will 
prevent water condensation. Then set the recorder scale as follows: 
Using a 50-ml graduated cylinder, add 50 ml of water to the aeration 
cell bottle. Add three drops of Antifoam B to the bottle, and then 
pipet 5.0 ml of the working Hg standard solution into the aeration 
cell.


    Note: Always add the Hg-containing solution to the aeration cell 
after the 50 ml of water.

    10.5.3  Place a Teflon-coated stirring bar in the bottle. Before 
attaching the bottle section to the bubbler section of the aeration 
cell, make certain that (1) the aeration cell exit arm stopcock (Figure 
101-3) is closed (so that Hg will not prematurely enter the optical 
cell when the reducing agent is being added) and (2) there is no flow 
through the bubbler. If conditions (1) and (2) are met, attach the 
bottle section to the bubbler section of the aeration cell. Pipet 5 ml 
of tin (II) reducing solution into the aeration cell through the side 
arm, and immediately stopper the side arm. Stir the solution for 15 
seconds, turn on the recorder, open the aeration cell exit arm 
stopcock, and immediately initiate aeration with continued stirring. 
Determine the maximum absorbance of the standard, and set this value to 
read 90 percent of the recorder full scale.
    10.6  Calibration Curve.
    10.6.1  After setting the recorder scale, repeat the procedure in 
Section 10.5 using 0.0-, 1.0-, 2.0-, 3.0-, 4.0-, and 5.0-ml aliquots of 
the working standard solution (final amount of Hg in the aeration cell 
is 0, 200, 400, 600, 800, and 1000 ng, respectively). Repeat this 
procedure on each aliquot size until two consecutive peaks agree within 
3 percent of their average value.


    Note: To prevent Hg carryover from one sample to another, do not 
close the aeration cell from the optical cell until the recorder pen 
has returned to the baseline.)


    10.6.2  It should not be necessary to disconnect the aeration gas 
inlet line from the aeration cell when changing samples. After 
separating the bottle and bubbler sections of the aeration cell, place 
the bubbler section into a 600-ml beaker containing approximately 400 
ml of water. Rinse the bottle section of the aeration cell with a 
stream of water to remove all traces of the tin (II) reducing agent. 
Also, to prevent the loss of Hg before aeration, remove all traces of 
the reducing agent between samples by washing with water. It will be 
necessary, however, to wash the aeration cell parts with concentrated 
HCl if any of the following conditions occur: (1) A white film appears 
on any inside surface of the aeration cell, (2) the calibration curve 
changes suddenly, or (3) the replicate samples do not yield 
reproducible results.
    10.6.3  Subtract the average peak height (or peak area) of the 
blank (0.0-ml aliquot)--which must be less than 2 percent of recorder 
full scale--from the averaged peak heights of the 1.0-, 2.0-, 3.0-, 
4.0-, and 5.0-ml aliquot standards. If the blank absorbance is greater 
than 2 percent of full-scale, the probable

[[Page 62165]]

cause is Hg contamination of a reagent or carry-over of Hg from a 
previous sample. Prepare the calibration curve by plotting the 
corrected peak height of each standard solution versus the 
corresponding final total Hg weight in the aeration cell (in ng), and 
draw the best fit straight line. This line should either pass through 
the origin or pass through a point no further from the origin than 
 2 percent of the recorder full scale. If the line does not 
pass through or very near to the origin, check for nonlinearity of the 
curve and for incorrectly prepared standards.

11.0  Analytical Procedure

    11.1  Sample Loss Check. Check the liquid level in each container 
to see whether liquid was lost during transport. If a noticeable amount 
of leakage occurred, either void the sample or use methods subject to 
the approval of the Administrator to account for the losses.
    11.2  Sample Preparation. Treat each sample as follows:
    11.2.1  Container No. 1 (Impingers and Probe). Carefully transfer 
the contents of Container No. 1 into a 1000-ml volumetric flask, and 
adjust the volume to exactly 1000 ml with water.
    11.2.2  Dilutions. Pipet a 2-ml aliquot from the diluted sample 
from Section 11.2.1 into a 250-ml volumetric flask. Add 10 ml of 5 
percent H2SO4, and adjust the volume to exactly 
250 ml with water. This solution is stable for at least 72 hours.


    Note: The dilution factor will be 250/2 for this solution.


    11.3  Analysis. Calibrate the analytical equipment and develop a 
calibration curve as outlined in Sections 10.3 through 10.6.
    11.3.1  Mercury Samples. Repeat the procedure used to establish the 
calibration curve with an appropriately sized aliquot (1 to 5 ml) of 
the diluted sample (from Section 11.2.2) until two consecutive peak 
heights agree within 3 percent of their average value. The peak maximum 
of an aliquot (except the 5-ml aliquot) must be greater than 10 percent 
of the recorder full scale. If the peak maximum of a 1.0-ml aliquot is 
off scale on the recorder, further dilute the original source sample to 
bring the Hg concentration into the calibration range of the 
spectrophotometer.
    11.3.2  Run a blank and standard at least after every five samples 
to check the spectrophotometer calibration. The peak height of the 
blank must pass through a point no further from the origin than 
2 percent of the recorder full scale. The difference 
between the measured concentration of the standard (the product of the 
corrected peak height and the reciprocal of the least squares slope) 
and the actual concentration of the standard must be less than 7 
percent, or recalibration of the analyzer is required.
    11.3.3  Check for Matrix Effects (optional). Use the Method of 
Standard Additions as follows to check at least one sample from each 
source for matrix effects on the Hg results. The Method of Standard 
Additions procedures described on pages 9-4 and 9-5 of the section 
entitled ``General Information'' of the Perkin Elmer Corporation Atomic 
Absorption Spectrophotometry Manual, Number 303-0152 (Reference 16 in 
Section 16.0) are recommended. If the results of the Method of Standard 
Additions procedure used on the single source sample do not agree to 
within 5 percent of the value obtained by the routine 
atomic absorption analysis, then reanalyze all samples from the source 
using the Method of Standard Additions procedure.
    11.4  Container No. 2 (Silica Gel). Weigh the spent silica gel (or 
silica gel plus impinger) to the nearest 0.5 g using a balance. (This 
step may be conducted in the field.)

12.0  Data Analysis and Calculations

    Carry out calculations, retaining at least one extra decimal 
significant figure beyond that of the acquired data. Round off figures 
only after the final calculation. Other forms of the equations may be 
used as long as they give equivalent results.
    12.1  Average Dry Gas Meter Temperature and Average Orifice 
Pressure Drop, Dry Gas Volume, Volume of Water Vapor Condensed, 
Moisture Content, and Isokinetic Variation. Same as Method 5, Sections 
12.2 through 12.5 and 12.11, respectively.
    12.2  Stack Gas Velocity. Using the data from this test and 
Equation 2-9 of Method 2, calculate the average stack gas velocity 
vs.
    12.3  Total Mercury.
    12.3.1  For each source sample, correct the average maximum 
absorbance of the two consecutive samples whose peak heights agree 
within 3 percent of their average for the contribution of the solution 
blank (see Section 10.6.3). Use the calibration curve and these 
corrected averages to determine the final total weight of Hg in ng in 
the aeration cell for each source sample.
    12.3.2  Correct for any dilutions made to bring the sample into the 
working range of the spectrophotometer. Then calculate the Hg in the 
original solution, mHg, as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.491

Where:

CHg(AC) = Total ng of Hg in aliquot analyzed (reagent blank 
subtracted).
DF = Dilution factor for the Hg-containing solution (before adding to 
the aeration cell; e.g., DF = 250/2 if the source samples were diluted 
as described in Section 11.2.2).
Vf = Solution volume of original sample, 1000 ml for samples 
diluted as described in Section 11.2.1.
10-\3\ = Conversion factor, g/ng.
S = Aliquot volume added to aeration cell, ml.

    12.4  Mercury Emission Rate. Calculate the daily Hg emission rate, 
R, using Equation 101-2. For continuous operations, the operating time 
is equal to 86,400 seconds per day. For cyclic operations, use only the 
time per day each stack is in operation. The total Hg emission rate 
from a source will be the summation of results from all stacks.
[GRAPHIC] [TIFF OMITTED] TR17OC00.492

Where:

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

[[Page 62166]]

K3 = 10-6 g/g for metric units.
     = 2.2046 ``  x  10-9 lb/g for English units.
Ps = Absolute stack gas pressure, mm Hg (in. Hg).
t = Daily operating time, sec/day.
Ts = Absolute average stack gas temperature,  deg.K 
( deg.R).
Vm(std) = Dry gas sample volume at standard conditions, scm 
(scf).
Vw(std) = Volume of water vapor at standard conditions, scm 
(scf).

    12.5  Determination of Compliance. Each performance test consists 
of three repetitions of the applicable test method. For the purpose of 
determining compliance with an applicable national emission standard, 
use the average of the results of all repetitions.

13.0  Method Performance

    The following estimates are based on collaborative tests, wherein 
13 laboratories performed duplicate analyses on two Hg-containing 
samples from a chlor-alkali plant and on one laboratory-prepared sample 
of known Hg concentration. The sample concentrations ranged from 2 to 
65 g Hg/ml.
    13.1  Precision. The estimated intra-laboratory and inter-
laboratory standard deviations are 1.6 and 1.8 g Hg/ml, 
respectively.
    13.2  Accuracy. The participating laboratories that analyzed a 64.3 
g Hg/ml (in 0.1 M ICl) standard obtained a mean of 63.7 
g Hg/ml.
    13.3  Analytical Range. After initial dilution, the range of this 
method is 0.5 to 120 g Hg/ml. The upper limit can be extended 
by further dilution of the sample.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    Same as Method 5, Section 17.0, References 1-3, 5, and 6, with the 
addition of the following:

    1. Determining Dust Concentration in a Gas Stream. ASME 
Performance Test Code No. 27. New York, NY. 1957.
    2. DeVorkin, Howard, et al. Air Pollution Source Testing Manual. 
Air Pollution Control District. Los Angeles, CA. November 1963.
    3. Hatch, W.R., and W.I. Ott. Determination of Sub-Microgram 
Quantities of Mercury by Atomic Absorption Spectrophotometry. Anal. 
Chem. 40:2085-87. 1968.
    4. Mark, L.S. Mechanical Engineers' Handbook. McGraw-Hill Book 
Co., Inc. New York, NY. 1951.
    5. Western Precipitation Division of Joy Manufacturing Co. 
Methods for Determination of Velocity, Volume, Dust and Mist Content 
of Gases. Bulletin WP-50. Los Angeles, CA. 1968.
    6. Perry, J.H. Chemical Engineers' Handbook. McGraw-Hill Book 
Co., Inc. New York, NY. 1960.
    7. Shigehara, R.T., W.F. Todd, and W.S. Smith. Significance of 
Errors in Stack Sampling Measurements. Stack Sampling News. 1(3):6-
18. September 1973.
    8. Smith, W.S., R.T. Shigehara, and W.F. Todd. A Method of 
Interpreting Stack Sampling Data. Stack Sampling News. 1(2):8-17. 
August 1973.
    9. Standard Method for Sampling Stacks for Particulate Matter. 
In: 1971 Annual Book of ASTM Standards, Part 23. ASTM Designation D 
2928-71. Philadelphia, PA 1971.
    10. Vennard, J.K. Elementary Fluid Mechanics. John Wiley and 
Sons, Inc. New York. 1947.
    11. Mitchell, W.J. and M.R. Midgett. Improved Procedure for 
Determining Mercury Emissions from Mercury Cell Chlor-Alkali Plants. 
J. APCA. 26:674-677. July 1976.
    12. Shigehara, R.T. Adjustments in the EPA Nomograph for 
Different Pitot Tube Coefficients and Dry Molecular Weights. Stack 
Sampling News. 2:4-11. October 1974.
    13. Vollaro, R.F. Recommended Procedure for Sample Traverses in 
Ducts Smaller than 12 Inches in Diameter. U.S. Environmental 
Protection Agency, Emission Measurement Branch. Research Triangle 
Park, NC. November 1976.
    14. Klein, R. and C. Hach. Standard Additions: Uses and 
Limitation in Spectrophotometric Measurements. Amer. Lab. 9:21. 
1977.
    15. Perkin Elmer Corporation. Analytical Methods for Atomic 
Absorption Spectrophotometry. Norwalk, Connecticut. September 1976.
BILLING CODE 6560-50-P

[[Page 62167]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.493


[[Page 62168]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.494


[[Page 62169]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.495


[[Page 62170]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.496


[[Page 62171]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.497


[[Page 62172]]



Method 101A--Determination of Particulate and Gaseous Mercury 
Emissions From Sewage Sludge Incinerators

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from methods in Appendix A to 40 CFR Part 
60 and in this part. Therefore, to obtain reliable results, persons 
using this method should also have a thorough knowledge of at least 
the following additional test methods: Methods 1, Method 2, Method 
3, and Method 5 of Part 60 (Appendix A), and Method 101 Part 61 
(Appendix B).

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.            Sensitivity
------------------------------------------------------------------------
Mercury (Hg)...................       7439-97-6   Dependent upon
                                                   spectrophotometer and
                                                   recorder.
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of Hg emissions from sewage sludge incinerators and other sources as 
specified in an applicable subpart of the regulations.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  Particulate and gaseous Hg emissions are withdrawn 
isokinetically from the source and are collected in acidic potassium 
permanganate (KMnO4) solution. The Hg collected (in the 
mercuric form) is reduced to elemental Hg, which is then aerated from 
the solution into an optical cell and measured by atomic absorption 
spectrophotometry.

3.0  Definitions. [Reserved]

4.0  Interferences

    4.1  Sample Collection. Excessive oxidizable organic matter in the 
stack gas prematurely depletes the KMnO4 solution and 
thereby prevents further collection of Hg.
    4.2  Analysis. Condensation of water vapor on the optical cell 
windows causes a positive interference.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Corrosive Reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water for at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burns as thermal 
burns.
    5.2.1  Hydrochloric Acid (HCl). Highly toxic. Vapors are highly 
irritating to eyes, skin, nose, and lungs, causing severe damage. May 
cause bronchitis, pneumonia, or edema of lungs. Exposure to 
concentrations of 0.13 to 0.2 percent can be lethal to humans in a few 
minutes. Provide ventilation to limit exposure. Reacts with metals, 
producing hydrogen gas.
    5.2.2  Nitric Acid (HNO3). Highly corrosive to eyes, 
skin, nose, and lungs. Vapors cause bronchitis, pneumonia, or edema of 
lungs. Reaction to inhalation may be delayed as long as 30 hours and 
still be fatal. Provide ventilation to limit exposure. Strong oxidizer. 
Hazardous reaction may occur with organic materials such as solvents.
    5.2.3  Sulfuric acid (H2SO4). Rapidly 
destructive to body tissue. Will cause third degree burns. Eye damage 
may result in blindness. Inhalation may be fatal from spasm of the 
larynx, usually within 30 minutes. May cause lung tissue damage with 
edema. 3 mg/m\3\ will cause lung damage in uninitiated. 1 mg/m\3\ for 8 
hours will cause lung damage or, in higher concentrations, death. 
Provide ventilation to limit inhalation. Reacts violently with metals 
and organics.
    5.3  Chlorine Evolution. Hydrochloric acid reacts with 
KMnO4 to liberate chlorine gas. Although this is a minimal 
concern when small quantities of HCl (5-10 ml) are used in the impinger 
rinse, a potential safety hazard may still exist. At sources that emit 
higher concentrations of oxidizable materials (e.g., power plants), 
more HCl may be required to remove the larger amounts of brown deposit 
formed in the impingers. In such cases, the potential safety hazards 
due to sample container pressurization are greater, because of the 
larger volume of HCl rinse added to the recovered sample. These hazards 
are eliminated by storing and analyzing the HCl impinger wash 
separately from the permanganate impinger sample.

6.0  Equipment and Supplies

    6.1  Sample Collection and Sample Recovery. Same as Method 101, 
Sections 6.1 and 6.2, respectively, with the following exceptions:
    6.1.1  Probe Liner. Same as in Method 101, Section 6.1.2, except 
that if a filter is used ahead of the impingers, the probe heating 
system must be used to minimize the condensation of gaseous Hg.
    6.1.2  Filter Holder (Optional). Borosilicate glass with a rigid 
stainless-steel wire-screen filter support (do not use glass frit 
supports) and a silicone rubber or Teflon gasket, designed to provide a 
positive seal against leakage from outside or around the filter. The 
filter holder must be equipped with a filter heating system capable of 
maintaining a temperature around the filter holder of 120  
14  deg.C (248  25  deg.F) during sampling to minimize both 
water and gaseous Hg condensation. A filter may also be used in cases 
where the stream contains large quantities of particulate matter.
    6.2  Sample Analysis. Same as Method 101, Section 6.3, with the 
following additions and exceptions:
    6.2.1  Volumetric Pipets. Class A; 1-, 2-, 3-, 4-, 5-, 10-, and 20-
ml.
    6.2.2  Graduated Cylinder. 25-ml.
    6.2.3  Steam Bath.
    6.2.4  Atomic Absorption Spectrophotometer or Equivalent. Any 
atomic absorption unit with an open sample presentation area in which 
to mount the optical cell is suitable. Instrument settings recommended 
by the particular manufacturer should be followed. Instruments designed 
specifically for the measurement of mercury using the cold-vapor 
technique are commercially available and may be substituted for the 
atomic absorption spectrophotometer.
    6.2.5  Optical Cell. Alternatively, a heat lamp mounted above the 
cell or a moisture trap installed upstream of the cell may be used.
    6.2.6  Aeration Cell. Alternatively, aeration cells available with 
commercial cold vapor instrumentation may be used.
    6.2.7  Aeration Gas Cylinder. Nitrogen, argon, or dry, Hg-free air, 
equipped with a single-stage regulator. Alternatively, aeration may be 
provided

[[Page 62173]]

by a peristaltic metering pump. If a commercial cold vapor instrument 
is used, follow the manufacturer's recommendations.

7.0  Reagents and Standards

    Unless otherwise indicated, it is intended that all reagents 
conform to the specifications established by the Committee on 
Analytical Reagents of the American Chemical Society, where such 
specifications are available; otherwise, use the best available grade.
    7.1  Sample Collection and Recovery. The following reagents are 
required for sample collection and recovery:
    7.1.1  Water. Deionized distilled, to conform to ASTM D 1193-77 or 
91 Type 1. If high concentrations of organic matter are not expected to 
be present, the analyst may eliminate the KMnO4 test for 
oxidizable organic matter. Use this water in all dilutions and solution 
preparations.
    7.1.2  Nitric Acid, 50 Percent (V/V). Mix equal volumes of 
concentrated HNO3 and water, being careful to add the acid 
to the water slowly.
    7.1.3  Silica Gel. Indicating type, 6 to 16 mesh. If previously 
used, dry at 175  deg.C (350  deg.F) for 2 hours. New silica gel may be 
used as received.
    7.1.4  Filter (Optional). Glass fiber filter, without organic 
binder, exhibiting at least 99.95 percent efficiency on 0.3-m 
dioctyl phthalate smoke particles. The filter in cases where the gas 
stream contains large quantities of particulate matter, but blank 
filters should be analyzed for Hg content.
    7.1.5  Sulfuric Acid, 10 Percent (V/V). Carefully add and mix 100 
ml of concentrated H2SO4 to 900 ml of water.
    7.1.6  Absorbing Solution, 4 Percent KMnO4 (W/V). 
Prepare fresh daily. Dissolve 40 g of KMnO4 in sufficient 10 
percent H2SO4 to make 1 liter. Prepare and store 
in glass bottles to prevent degradation.
    7.1.7  Hydrochloric Acid, 8 N. Carefully add and mix 67 ml of 
concentrated HCl to 33 ml of water.
    7.2  Sample Analysis. The following reagents and standards are 
required for sample analysis:
    7.2.1  Water. Same as in Section 7.1.1.
    7.2.2  Tin (II) Solution. Prepare fresh daily, and keep sealed when 
not being used. Completely dissolve 20 g of tin (II) chloride (or 25 g 
of tin (II) sulfate) crystals (Baker Analyzed reagent grade or any 
other brand that will give a clear solution) in 25 ml of concentrated 
HCl. Dilute to 250 ml with water. Do not substitute HNO3, 
H2SO4, or other strong acids for the HCl.
    7.2.3  Sodium Chloride-Hydroxylamine Solution. Dissolve 12 g of 
sodium chloride and 12 g of hydroxylamine sulfate (or 12 g of 
hydroxylamine hydrochloride) in water and dilute to 100 ml.
    7.2.4  Hydrochloric Acid, 8 N. Same as Section 7.1.7.
    7.2.5  Nitric Acid, 15 Percent (V/V). Carefully add 15 ml 
HNO3 to 85 ml of water.
    7.2.6  Antifoam B Silicon Emulsion. J.T. Baker Company (or 
equivalent).
    7.2.7  Mercury Stock Solution, 1 mg Hg/ml. Prepare and store all Hg 
standard solutions in borosilicate glass containers. Completely 
dissolve 0.1354 g of Hg (II) chloride in 75 ml of water. Add 10 ml of 
concentrated HNO3, and adjust the volume to exactly 100 ml 
with water. Mix thoroughly. This solution is stable for at least one 
month.
    7.2.8  Intermediate Hg Standard Solution, 10 g/ml. Prepare 
fresh weekly. Pipet 5.0 ml of the Hg stock solution (Section 7.2.7) 
into a 500 ml volumetric flask, and add 20 ml of 15 percent 
HNO3 solution. Adjust the volume to exactly 500 ml with 
water. Thoroughly mix the solution.
    7.2.9  Working Hg Standard Solution, 200 ng Hg/ml. Prepare fresh 
daily. Pipet 5.0 ml from the ``Intermediate Hg Standard Solution'' 
(Section 7.2.8) into a 250-ml volumetric flask. Add 5 ml of 4 percent 
KMnO4 absorbing solution and 5 ml of 15 percent 
HNO3. Adjust the volume to exactly 250 ml with water. Mix 
thoroughly.
    7.2.10  Potassium Permanganate, 5 Percent (W/V). Dissolve 5 g of 
KMnO4 in water and dilute to 100 ml.
    7.2.11  Filter. Whatman No. 40, or equivalent.

8.0  Sample Collection, Preservation, Transport, and Storage

    Same as Method 101, Section 8.0, with the exception of the 
following:
    8.1  Preliminary Determinations. Same as Method 101, Section 8.2, 
except that the liberation of free iodine in the first impinger due to 
high Hg or sulfur dioxide concentrations is not applicable. In this 
method, high oxidizable organic content may make it impossible to 
sample for the desired minimum time. This problem is indicated by the 
complete bleaching of the purple color of the KMnO4 
solution. In cases where an excess of water condensation is 
encountered, collect two runs to make one sample, or add an extra 
impinger in front of the first impinger (also containing acidified 
KMnO4 solution).
    8.2  Preparation of Sampling Train. Same as Method 101, Section 
8.3, with the exception of the following:
    8.2.1  In this method, clean all the glass components by rinsing 
with 50 percent HNO3, tap water, 8 N HCl, tap water, and 
finally with deionized distilled water. Then place 50 ml of absorbing 
solution in the first impinger and 100 ml in each of the second and 
third impingers.
    8.2.2  If a filter is used, use a pair of tweezers to place the 
filter in the filter holder. Be sure to center the filter, and place 
the gasket in the proper position to prevent the sample gas stream from 
bypassing the filter. Check the filter for tears after assembly is 
completed. Be sure also to set the filter heating system at the desired 
operating temperature after the sampling train has been assembled.
    8.3  Sampling Train Operation. In addition to the procedure 
outlined in Method 101, Section 8.5, maintain a temperature around the 
filter (if applicable) of 120  14  deg.C (248  
25  deg.F).
    8.4  Sample Recovery. Same as Method 101, Section 8.7, with the 
exception of the following:
    8.4.1  Transfer the probe, impinger assembly, and (if applicable) 
filter assembly to the cleanup area.
    8.4.2  Treat the sample as follows:
    8.4.2.1  Container No. 1 (Impinger, Probe, and Filter Holder) and, 
if applicable, Container No. 1A (HCl rinse).
    8.4.2.1.1  Using a graduated cylinder, measure the liquid in the 
first three impingers to within 1 ml. Record the volume of liquid 
present (e.g., see Figure 5-6 of Method 5). This information is needed 
to calculate the moisture content of the effluent gas. (Use only 
graduated cylinder and glass storage bottles that have been precleaned 
as in Section 8.2.1.) Place the contents of the first three impingers 
(four if an extra impinger was added as described in Section 8.1) into 
a 1000-ml glass sample bottle labeled Container No. 1.


    Note: If a filter is used, remove the filter from its holder as 
outlined under Section 8.4.3.


    8.4.2.1.2  Taking care that dust on the outside of the probe or 
other exterior surfaces does not get into the sample, quantitatively 
recover the Hg (and any condensate) from the probe nozzle, probe 
fitting, probe liner, front half of the filter holder (if applicable), 
and impingers as follows: Rinse these components with a total of 400 ml 
(350 ml if an extra impinger was added as described in Section 8.1) of 
fresh absorbing solution, carefully assuring removal of all loose 
particulate matter from the impingers; add all washings to the 1000 ml 
glass sample bottle. To remove any residual brown deposits on the 
glassware following the

[[Page 62174]]

permanganate rinse, rinse with approximately 100 ml of water, carefully 
assuring removal of all loose particulate matter from the impingers. 
Add this rinse to Container No. 1.
    8.4.2.1.3  If no visible deposits remain after this water rinse, do 
not rinse with 8 N HCl. If deposits do remain on the glassware after 
the water rinse, wash impinger walls and stems with 25 ml of 8 N HCl, 
and place the wash in a separate container labeled Container No. 1A as 
follows: Place 200 ml of water in a sample container labeled Container 
No. 1A. Wash the impinger walls and stem with the HCl by turning the 
impinger on its side and rotating it so that the HCl contacts all 
inside surfaces. Pour the HCl wash carefully with stirring into 
Container No. 1A.
    8.4.2.1.4  After all washings have been collected in the 
appropriate sample container(s), tighten the lid(s) on the container(s) 
to prevent leakage during shipment to the laboratory. Mark the height 
of the fluid level to allow subsequent determination of whether leakage 
has occurred during transport. Label each container to identify its 
contents clearly.
    8.4.3  Container No. 2 (Silica Gel). Same as Method 5, Section 
8.7.6.3.
    8.4.4  Container No. 3 (Filter). If a filter was used, carefully 
remove it from the filter holder, place it in a 100-ml glass sample 
bottle, and add 20 to 40 ml of absorbing solution. If it is necessary 
to fold the filter, be sure that the particulate cake is inside the 
fold. Carefully transfer to the 100-ml sample bottle any particulate 
matter and filter fibers that adhere to the filter holder gasket by 
using a dry Nylon bristle brush and a sharp-edged blade. Seal the 
container. Label the container to identify its contents clearly. Mark 
the height of the fluid level to allow subsequent determination of 
whether leakage has occurred during transport.
    8.4.5  Container No. 4 (Filter Blank). If a filter was used, treat 
an unused filter from the same filter lot as that used for sampling 
according to the procedures outlined in Section 8.4.4.
    8.4.6  Container No. 5 (Absorbing Solution Blank). Place 650 ml of 
4 percent KMnO4 absorbing solution in a 1000-ml sample 
bottle. Seal the container.
    8.4.7  Container No. 6 (HCl Rinse Blank). Place 200 ml of water in 
a 1000-ml sample bottle, and add 25 ml of 8 N HCl carefully with 
stirring. Seal the container. Only one blank sample per 3 runs is 
required.

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.0, 10.0.....................  Sampling           Ensure accuracy and
                                 equipment leak-    precision of
                                 checks and         sampling
                                 calibration.       measurements.
10.2..........................  Spectrophotometer  Ensure linearity of
                                 calibration.       spectrophotometer
                                                    response to
                                                    standards.
11.3.3........................  Check for matrix   Eliminate matrix
                                 effects.           effects.
------------------------------------------------------------------------

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

10.0  Calibration and Standardization

    Same as Method 101, Section 10.0, with the following exceptions:
    10.1  Optical Cell Heating System Calibration. Same as in Method 
101, Section 10.4, except use a-25 ml graduated cylinder to add 25 ml 
of water to the bottle section of the aeration cell.
    10.2  Spectrophotometer and Recorder Calibration.
    10.2.1  The Hg response may be measured by either peak height or 
peak area.


    Note: The temperature of the solution affects the rate at which 
elemental Hg is released from a solution and, consequently, it 
affects the shape of the absorption curve (area) and the point of 
maximum absorbance (peak height). To obtain reproducible results, 
all solutions must be brought to room temperature before use.


    10.2.2  Set the spectrophotometer wave length at 253.7 nm, and make 
certain the optical cell is at the minimum temperature that will 
prevent water condensation. Then set the recorder scale as follows: 
Using a 25-ml graduated cylinder, add 25 ml of water to the aeration 
cell bottle. Add three drops of Antifoam B to the bottle, and then 
pipet 5.0 ml of the working Hg standard solution into the aeration 
cell.


    Note: Always add the Hg-containing solution to the aeration cell 
after the 25 ml of water.

    10.2.3  Place a Teflon-coated stirring bar in the bottle. Add 5 ml 
of absorbing solution to the aeration bottle, and mix well. Before 
attaching the bottle section to the bubbler section of the aeration 
cell, make certain that (1) the aeration cell exit arm stopcock (Figure 
101-3 of Method 101) is closed (so that Hg will not prematurely enter 
the optical cell when the reducing agent is being added) and (2) there 
is no flow through the bubbler. If conditions (1) and (2) are met, 
attach the bottle section to the bubbler section of the aeration cell. 
Add sodium chloride-hydroxylamine in 1 ml increments until the solution 
is colorless. Now add 5 ml of tin (II) solution to the aeration bottle 
through the side arm, and immediately stopper the side arm. Stir the 
solution for 15 seconds, turn on the recorder, open the aeration cell 
exit arm stopcock, and immediately initiate aeration with continued 
stirring. Determine the maximum absorbance of the standard, and set 
this value to read 90 percent of the recorder full scale.

11.0  Analytical Procedure

    11.1  Sample Loss Check. Check the liquid level in each container 
to see if liquid was lost during transport. If a noticeable amount of 
leakage occurred, either void the sample or use methods subject to the 
approval of the Administrator to account for the losses.
    11.2  Sample Preparation. Treat sample containers as follows:
    11.2.1  Containers No. 3 and No. 4 (Filter and Filter Blank).
    11.2.1.1  If a filter is used, place the contents, including the 
filter, of Containers No. 3 and No. 4 in separate 250-ml beakers, and 
heat the beakers on a steam bath until most of the liquid has 
evaporated. Do not heat to dryness. Add 20 ml of concentrated 
HNO3 to the beakers, cover them with a watch glass, and heat 
on a hot plate at 70  deg.C (160  deg.F) for 2 hours. Remove from the 
hot plate.
    11.2.1.2  Filter the solution from digestion of the Container No. 3 
contents through Whatman No. 40 filter paper, and save the filtrate for 
addition to the Container No. 1 filtrate as described in Section 
11.2.2. Discard the filter paper.
    11.2.1.3  Filter the solution from digestion of the Container No. 4 
contents through Whatman No. 40 filter paper, and save the filtrate for 
addition to Container No. 5 filtrate as described in Section 11.2.3 
below. Discard the filter paper.
    11.2.2  Container No. 1 (Impingers, Probe, and Filter Holder) and, 
if applicable, No. 1A (HCl rinse).
    11.2.2.1  Filter the contents of Container No. 1 through Whatman 
No. 40 filter paper into a 1 liter volumetric flask to remove the brown 
manganese

[[Page 62175]]

dioxide (MnO2) precipitate. Save the filter for digestion of 
the brown MnO2 precipitate. Add the sample filtrate from 
Container No. 3 to the 1-liter volumetric flask, and dilute to volume 
with water. If the combined filtrates are greater than 1000 ml, 
determine the volume to the nearest ml and make the appropriate 
corrections for blank subtractions. Mix thoroughly. Mark the filtrate 
as analysis Sample No. A.1 and analyze for Hg within 48 hr of the 
filtration step. Place the saved filter, which was used to remove the 
brown MnO2 precipitate, into an appropriate sized container. 
In a laboratory hood, add 25 ml of 8 N HCl to the filter and allow to 
digest for a minimum of 24 hours at room temperature.
    11.2.2.2  Filter the contents of Container 1A through Whatman No. 
40 filter paper into a 500-ml volumetric flask. Then filter the 
digestate of the brown MnO2 precipitate from Container No. 1 
through Whatman No. 40 filter paper into the same 500-ml volumetric 
flask, and dilute to volume with water. Mark this combined 500 ml 
dilute solution as analysis Sample No. A.2. Discard the filters.
    11.2.3  Container No. 5 (Absorbing Solution Blank) and No. 6 (HCl 
Rinse Blank).
    11.2.3.1  Treat Container No. 5 as Container No. 1 (as described in 
Section 11.2.2), except substitute the filter blank filtrate from 
Container No. 4 for the sample filtrate from Container No. 3, and mark 
as Sample A.1 Blank.
    11.2.3.2  Treat Container No. 6 as Container No. 1A, (as described 
in Section 11.2.2, except substitute the filtrate from the digested 
blank MnO2 precipitate for the filtrate from the digested 
sample MnO2 precipitate, and mark as Sample No. A.2 Blank.


    Note: When analyzing samples A.1 Blank and HCl A.2 Blank, always 
begin with 10 ml aliquots. This applies specifically to blank 
samples.


    11.3  Analysis. Calibrate the analytical equipment and develop a 
calibration curve as outlined in Section 10.0.
    11.3.1  Mercury Samples. Then repeat the procedure used to 
establish the calibration curve with appropriately sized aliquots (1 to 
10 ml) of the samples (from Sections 11.2.2 and 11.2.3) until two 
consecutive peak heights agree within 3 percent of their average value. 
If the 10 ml sample is below the detectable limit, use a larger aliquot 
(up to 20 ml), but decrease the volume of water added to the aeration 
cell accordingly to prevent the solution volume from exceeding the 
capacity of the aeration bottle. If the peak maximum of a 1.0 ml 
aliquot is off scale, further dilute the original sample to bring the 
Hg concentration into the calibration range of the spectrophotometer. 
If the Hg content of the absorbing solution and filter blank is below 
the working range of the analytical method, use zero for the blank.
    11.3.2  Run a blank and standard at least after every five samples 
to check the spectrophotometer calibration; recalibrate as necessary.
    11.3.3  Check for Matrix Effects (optional). Same as Method 101, 
Section 11.3.3.

12.0  Data Analysis and Calculations

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


    12.1  Nomenclature.

C(fltr)Hg = Total ng of Hg in aliquot of KMnO4 
filtrate and HNO3 digestion of filter analyzed (aliquot of 
analysis Sample No. A.1).
C(fltr blk)Hg = Total ng of Hg in aliquot of 
KMnO4 blank and HNO3 digestion of blank filter 
analyzed (aliquot of analysis Sample No. A.1 blank).
C(HC1 blk)Hg = Total ng of Hg analyzed in aliquot of the 
500-ml analysis Sample No. HCl A.2 blank.
C(HCl)Hg = Total ng of Hg analyzed in the aliquot from the 
500-ml analysis Sample No. HCl A.2.
DF = Dilution factor for the HCl-digested Hg-containing solution, 
Analysis Sample No. ``HCl A.2.''
DFblk = Dilution factor for the HCl-digested Hg containing 
solution, Analysis Sample No. ``HCl A.2 blank.'' (Refer to sample No. 
``HCl A.2'' dilution factor above.)
m(fltr)Hg = Total blank corrected g of Hg in 
KMnO4 filtrate and HNO3 digestion of filter 
sample.
m(HCl)Hg = Total blank corrected g of Hg in HCl 
rinse and HCl digestate of filter sample.
mHg = Total blank corrected Hg content in each sample, 
g.
S = Aliquot volume of sample added to aeration cell, ml.
Sblk = Aliquot volume of blank added to aeration cell, ml.
Vf(blk) = Solution volume of blank sample, 1000 ml for 
samples diluted as described in Section 11.2.2.
Vf(fltr) = Solution volume of original sample, normally 1000 
ml for samples diluted as described in Section 11.2.2.
Vf(HCl) = Solution volume of original sample, 500 ml for 
samples diluted as described in Section 11.2.1.
10-\3\ = Conversion factor, g/ng.

    12.2  Average Dry Gas Meter Temperature and Average Orifice 
Pressure Drop, Dry Gas Volume, Volume of Water Vapor Condensed, 
Moisture Content, Isokinetic Variation, and Stack Gas Velocity and 
Volumetric Flow Rate. Same as Method 5, Sections 12.2 through 12.5, 
12.11, and 12.12, respectively.
    12.3  Total Mercury.
    12.3.1  For each source sample, correct the average maximum 
absorbance of the two consecutive samples whose peak heights agree 
within 3 percent of their average for the contribution of the blank. 
Use the calibration curve and these corrected averages to determine the 
final total weight of Hg in ng in the aeration cell for each source 
sample.
    12.3.2  Correct for any dilutions made to bring the sample into the 
working range of the spectrophotometer.
[GRAPHIC] [TIFF OMITTED] TR17OC00.498


    Note: This dilution factor applies only to the intermediate 
dilution steps, since the original sample volume 
[(Vf)HCL] of ``HCl A.2'' has been factored out 
in the equation along with the sample aliquot (S). In Eq. 101A-1, 
the sample aliquot, S, is introduced directly into the aeration cell 
for analysis according to the procedure outlined in Section 11.3.1. 
A dilution factor is required only if it is necessary to bring the 
sample into the analytical instrument's calibration range.


    Note: The maximum allowable blank subtraction for the HCl is the 
lesser of the two following values: (1) the actual blank measured 
value (analysis Sample No. HCl A.2 blank), or (2) 5% of the Hg 
content in the combined HCl rinse and digested sample (analysis 
Sample No. HCl A.2).


[[Page 62176]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.499


    Note: The maximum allowable blank subtraction for the HCl is the 
lesser of the two following values: (1) the actual blank measured 
value (analysis Sample No. ``A.1 blank''), or (2) 5% of the Hg 
content in the filtrate (analysis Sample No. ``A.1'').

[GRAPHIC] [TIFF OMITTED] TR17OC00.500

    12.3  Mercury Emission Rate. Same as Method 101, Section 12.3.
    12.4  Determination of Compliance. Same as Method 101, Section 
12.4.

13.0  Method Performance

    13.1  Precision. Based on eight paired-train tests, the intra-
laboratory standard deviation was estimated to be 4.8 g/ml in 
the concentration range of 50 to 130 g/m3.
    13.2  Bias. [Reserved]
    13.3  Range. After initial dilution, the range of this method is 20 
to 800 ng Hg/ml. The upper limit can be extended by further dilution of 
the sample.

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

    Same as Section 16.0 of Method 101, with the addition of the 
following:

    1. Mitchell, W.J., et al. Test Methods to Determine the Mercury 
Emissions from Sludge Incineration Plants. U.S. Environmental 
Protection Agency. Research Triangle Park, NC. Publication No. EPA-
600/4-79-058. September 1979.
    2. Wilshire, Frank W., et al. Reliability Study of the U.S. 
EPA's Method 101A--Determination of Particulate and Gaseous Mercury 
Emissions. U.S. Environmental Protection Agency. Research Triangle 
Park, NC. Report No. 600/D-31/219 AREAL 367, NTIS Acc No. PB91-
233361.
    3. Memorandum from William J. Mitchell to Roger T. Shigehara 
discussing the potential safety hazard in Section 7.2 of Method 
101A. February 28, 1990.

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

Method 102--Determination of Particulate and Gaseous Mercury 
Emissions From Chlor-Alkali Plants (Hydrogen Streams)

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in this part and in 
Appendix A to 40 CFR Part 60. Therefore, to obtain reliable results, 
persons using this method should have a thorough knowledge of at 
least the following additional test methods: Method 1, Method 2, 
Method 3, Method 5, and Method 101.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.           Sensitivity
------------------------------------------------------------------------
Mercury (Hg)...................       7439-97-6  Dependent upon recorder
                                                  and spectrophotometer.
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of Hg emissions, including both particulate and gaseous Hg, from chlor-
alkali plants and other sources (as specified in the regulations) where 
the carrier-gas stream in the duct or stack is principally hydrogen.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  Particulate and gaseous Hg emissions are withdrawn 
isokinetically from the source and collected in acidic iodine 
monochloride (ICl) solution. The Hg collected (in the mercuric form) is 
reduced to elemental Hg, which is then aerated from the solution into 
an optical cell and measured by atomic absorption spectrophotometry.

3.0  Definitions [Reserved]

4.0  Interferences

    Same as Method 101, Section 4.2.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Corrosive Reagents. Same as Method 101, Section 5.2.
    5.3  Explosive Mixtures. The sampler must conduct the source test 
under conditions of utmost safety because hydrogen and air mixtures are 
explosive. Since the sampling train essentially is leakless, attention 
to safe operation can be concentrated at the inlet and outlet. If a 
leak does occur, however, remove the meter box cover to avoid a 
possible explosive mixture. The following specific precautions are 
recommended:
    5.3.1  Operate only the vacuum pump during the test. The other 
electrical equipment, e.g., heaters, fans, and timers, normally are not 
essential to the success of a hydrogen stream test.
    5.3.2  Seal the sample port to minimize leakage of hydrogen from 
the stack.
    5.3.3  Vent sampled hydrogen at least 3 m (10 ft) away from the 
train. This can be accomplished by attaching a 13-mm (0.50-in.) ID 
Tygon tube to the exhaust from the orifice meter.


    Note: A smaller ID tubing may cause the orifice meter 
calibration to be erroneous. Take care to ensure that the exhaust 
line is not bent or pinched.

6.0  Equipment and Supplies

    Same as Method 101, Section 6.0, with the exception of the 
following:
    6.1  Probe Heating System. Do not use, unless otherwise specified.
    6.2  Glass Fiber Filter. Do not use, unless otherwise specified.

7.0  Reagents and Standards

    Same as Method 101, Section 7.0.

[[Page 62177]]

8.0  Sample Collection, Preservation, Transport, and Storage

    Same as Method 101, Section 8.0, with the exception of the 
following:
    8.1  Setting of Isokinetic Rates.
    8.1.1  If a nomograph is used, take special care in the calculation 
of the molecular weight of the stack gas and in the setting of the 
nomograph to maintain isokinetic conditions during sampling (Sections 
8.1.1.1 through 8.1.1.3 below).
    8.1.1.1  Calibrate the meter box orifice. Use the techniques 
described in APTD-0576 (see Reference 9 in Section 17.0 of Method 5). 
Calibration of the orifice meter at flow conditions that simulate the 
conditions at the source is suggested. Calibration should either be 
done with hydrogen or with some other gas having similar Reynolds 
Number so that there is similarity between the Reynolds Numbers during 
calibration and during sampling.
    8.1.1.2  The nomograph described in APTD-0576 cannot be used to 
calculate the C factor because the nomograph is designed for use when 
the stack gas dry molecular weight is 29  4. Instead, the 
following calculation should be made to determine the proper C factor:
[GRAPHIC] [TIFF OMITTED] TR17OC00.501

Where:

Bws = Fraction by volume of water vapor in the stack gas.
Cp = Pitot tube calibration coefficient, dimensionless.
Md = Dry molecular weight of stack gas, lb/lb-mole.
Ps = Absolute pressure of stack gas, in. Hg.
Pm = Absolute pressure of gas at the meter, in. Hg.
Tm = Absolute temperature of gas at the orifice,  deg.R.
H@ = Meter box calibration factor obtained in 
Section 8.1.1.1, in. H2O.
0.00154 = (in. H2O/ deg.R).


    Note: This calculation is left in English units, and is not 
converted to metric units because nomographs are based on English 
units.


    8.1.1.3  Set the calculated C factor on the operating nomograph, 
and select the proper nozzle diameter and K factor as specified in 
APTD-0576. If the C factor obtained in Section 8.1.1.2 exceeds the 
values specified on the existing operating nomograph, expand the C 
scale logarithmically so that the values can be properly located.
    8.1.2  If a calculator is used to set isokinetic rates, it is 
suggested that the isokinetic equation presented in Reference 13 in 
Section 17.0 of Method 101 be consulted.
    8.2  Sampling in Small (12-in. Diameter) Stacks. When the stack 
diameter (or equivalent diameter) is less than 12 inches, conventional 
pitot tube-probe assemblies should not be used. For sampling 
guidelines, see Reference 14 in Section 17.0 of Method 101.

9.0  Quality Control

    Same as Method 101, Section 9.0.

10.0  Calibration and Standardizations

    Same as Method 101, Section 10.0.

11.0  Analytical Procedure

    Same as Method 101, Section 11.0.

12.0  Data Analysis and Calculations

    Same as Method 101, Section 12.0.

13.0  Method Performance

    Same as Method 101, Section 13.0.
    13.1  Analytical Range. After initial dilution, the range of this 
method is 0.5 to 120 g Hg/ml. The upper limit can be extended 
by further dilution of the sample.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    Same as Method 101, Section 16.0.

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

Method 103--Beryllium Screening Method

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.            Sensitivity
------------------------------------------------------------------------
Beryllium (Be).................       7440-41-7   Dependent upon
                                                   analytical procedure
                                                   used.
------------------------------------------------------------------------

    1.2  Applicability. This procedure details guidelines and 
requirements for methods acceptable for use in determining Be emissions 
in ducts or stacks at stationary sources.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  Particulate Be emissions are withdrawn isokinetically from 
three points in a duct or stack and are collected on a filter. The 
collected sample is analyzed for Be using an appropriate technique.

3.0  Definitions. [Reserved]

4.0  Interferences. [Reserved]

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Hydrochloric Acid (HCl). Highly corrosive and toxic. Vapors 
are highly irritating to eyes, skin, nose, and lungs, causing severe 
damage. May cause bronchitis, pneumonia, or edema of lungs. Exposure to 
concentrations of 0.13 to 0.2 percent can be lethal to humans in a few 
minutes. Provide ventilation to limit exposure. Reacts with metals, 
producing hydrogen gas. Personal protective equipment and safe 
procedures are useful in preventing chemical splashes. If contact 
occurs, immediately flush with copious amounts of water at least 15 
minutes. Remove clothing under shower and decontaminate. Treat residual 
chemical burn as thermal burn.

6.0  Equipment and Supplies

    6.1  Sample Collection. A schematic of the required sampling train 
configuration is shown in Figure 103-1 in Section 17.0. The essential 
components of the train are as follows:

[[Page 62178]]

    6.1.1  Nozzle. Stainless steel, or equivalent, with sharp, tapered 
leading edge.
    6.1.2  Probe. Sheathed borosilicate or quartz glass tubing.
    6.1.3  Filter. Millipore AA, or equivalent, with appropriate filter 
holder that provides a positive seal against leakage from outside or 
around the filter. It is suggested that a Whatman 41, or equivalent, be 
placed immediately against the back side of the Millipore filter as a 
guard against breakage of the Millipore. Include the backup filter in 
the analysis. To be equivalent, other filters shall exhibit at least 
99.95 percent efficiency (0.05 percent penetration) on 0.3 micron 
dioctyl phthalate smoke particles, and be amenable to the Be analysis 
procedure. The filter efficiency tests shall be conducted in accordance 
with ASTM D 2986-71, 78, 95a (incorporated by reference--see 
Sec. 61.18). Test data from the supplier's quality control program are 
sufficient for this purpose.
    6.1.4  Meter-Pump System. Any system that will maintain isokinetic 
sampling rate, determine sample volume, and is capable of a sampling 
rate of greater than 14 lpm (0.5 cfm).
    6.2  Measurement of Stack Conditions. The following equipment is 
used to measure stack conditions:
    6.2.1  Pitot Tube. Type S, or equivalent, with a constant 
coefficient (5 percent) over the working range.
    6.2.2  Inclined Manometer, or Equivalent. To measure velocity head 
to 10 percent of the minimum value.
    6.2.3  Temperature Measuring Device. To measure stack temperature 
to 1.5 percent of the minimum absolute stack temperature.
    6.2.4  Pressure Measuring Device. To measure stack pressure to 
2.5 mm Hg (0.1 in. Hg).
    6.2.5  Barometer. To measure atmospheric pressure to 
2.5 mm Hg (0.1 in. Hg).
    6.2.6  Wet and Dry Bulb Thermometers, Drying Tubes, Condensers, or 
Equivalent. To determine stack gas moisture content to 1 
percent.
    6.3  Sample Recovery.
    6.3.1  Probe Cleaning Equipment. Probe brush or cleaning rod at 
least as long as probe, or equivalent. Clean cotton balls, or 
equivalent, should be used with the rod.
    6.3.2  Leakless Glass Sample Bottles. To contain sample.
    6.4  Analysis. All equipment necessary to perform an atomic 
absorption, spectrographic, fluorometric, chromatographic, or 
equivalent analysis.

7.0  Reagents and Standards

    7.1  Sample Recovery.
    7.1.1  Water. Deionized distilled, to conform to ASTM D 1193-77, 91 
(incorporated by reference--see Sec. 61.18), Type 3.
    7.1.2  Acetone. Reagent grade.
    7.1.3  Wash Acid, 50 Percent (V/V) Hydrochloric Acid (HCl). Mix 
equal volumes of concentrated HCl and water, being careful to add the 
acid slowly to the water.
    7.2  Analysis. Reagents and standards as necessary for the selected 
analytical procedure.

8.0  Sample Collection, Preservation, Transport, and Storage

    Guidelines for source testing are detailed in the following 
sections. These guidelines are generally applicable; however, most 
sample sites differ to some degree and temporary alterations such as 
stack extensions or expansions often are required to insure the best 
possible sample site. Further, since Be is hazardous, care should be 
taken to minimize exposure. Finally, since the total quantity of Be to 
be collected is quite small, the test must be carefully conducted to 
prevent contamination or loss of sample.
    8.1  Selection of a Sampling Site and Number of Sample Runs. Select 
a suitable sample site that is as close as practicable to the point of 
atmospheric emission. If possible, stacks smaller than one foot in 
diameter should not be sampled.
    8.1.1  Ideal Sampling Site. The ideal sampling site is at least 
eight stack or duct diameters downstream and two diameters upstream 
from any flow disturbance such as a bend, expansion or contraction. For 
rectangular cross sections, use Equation 103-1 in Section 12.2 to 
determine an equivalent diameter, De.
    8.1.2  Alternate Sampling Site. Some sampling situations may render 
the above sampling site criteria impractical. In such cases, select an 
alternate site no less than two diameters downstream and one-half 
diameter upstream from any point of flow disturbance. Additional sample 
runs are recommended at any sample site not meeting the criteria of 
Section 8.1.1.
    8.1.3  Number of Sample Runs Per Test. Three sample runs constitute 
a test. Conduct each run at one of three different points. Select three 
points that proportionately divide the diameter, or are located at 25, 
50, and 75 percent of the diameter from the inside wall. For horizontal 
ducts, sample on a vertical line through the centroid. For rectangular 
ducts, sample on a line through the centroid and parallel to a side. If 
additional sample runs are performed per Section 8.1.2, proportionately 
divide the duct to accommodate the total number of runs.
    8.2  Measurement of Stack Conditions. Using the equipment described 
in Section 6.2, measure the stack gas pressure, moisture, and 
temperature to determine the molecular weight of the stack gas. Sound 
engineering estimates may be made in lieu of direct measurements. 
Describe the basis for such estimates in the test report.
    8.3  Preparation of Sampling Train.
    8.3.1  Assemble the sampling train as shown in Figure 103-1. It is 
recommended that all glassware be precleaned by soaking in wash acid 
for two hours.
    8.3.2  Leak check the sampling train at the sampling site. The 
leakage rate should not be in excess of 1 percent of the desired sample 
rate.
    8.4  Sampling Train Operation.
    8.4.1  For each run, measure the velocity at the selected sampling 
point. Determine the isokinetic sampling rate. Record the velocity head 
and the required sampling rate. Place the nozzle at the sampling point 
with the tip pointing directly into the gas stream. Immediately start 
the pump and adjust the flow to isokinetic conditions. At the 
conclusion of the test, record the sampling rate. Again measure the 
velocity head at the sampling point. The required isokinetic rate at 
the end of the period should not have deviated more than 20 percent 
from that originally calculated. Describe the reason for any deviation 
beyond 20 percent in the test report.
    8.4.2  Sample at a minimum rate of 14 liters/min (0.5 cfm). Obtain 
samples over such a period or periods of time as are necessary to 
determine the maximum emissions which would occur in a 24-hour period. 
In the case of cyclic operations, perform sufficient sample runs so as 
to allow determination or calculation of the emissions that occur over 
the duration of the cycle. A minimum sampling time of two hours per run 
is recommended.
    8.5  Sample Recovery.
    8.5.1  It is recommended that all glassware be precleaned as in 
Section 8.3. Sample recovery should also be performed in an area free 
of possible Be contamination. When the sampling train is moved, 
exercise care to prevent breakage and contamination. Set aside a 
portion of the acetone used in the sample recovery as a blank for 
analysis. The total amount of acetone used should be measured for 
accurate blank correction. Blanks can be eliminated if

[[Page 62179]]

prior analysis shows negligible amounts.
    8.5.2  Remove the filter (and backup filter, if used) and any loose 
particulate matter from filter holder, and place in a container.
    8.5.3  Clean the probe with acetone and a brush or long rod and 
cotton balls. Wash into the container with the filter. Wash out the 
filter holder with acetone, and add to the same container.

9.0  Quality Control. [Reserved]

10.0  Calibration and Standardization

    10.1  Sampling Train. As a procedural check, compare the sampling 
rate regulation with a dry gas meter, spirometer, rotameter (calibrated 
for prevailing atmospheric conditions), or equivalent, attached to the 
nozzle inlet of the complete sampling train.
    10.2  Analysis. Perform the analysis standardization as suggested 
by the manufacturer of the instrument, or the procedures for the 
analytical method in use.

11.0  Analytical Procedure

    Make the necessary preparation of samples and analyze for Be. Any 
currently acceptable method (e.g., atomic absorption, spectrographic, 
fluorometric, chromatographic) may be used.

12.0  Data Analysis and Calculations

    12.1  Nomenclature.

As(avg) = Stack area, m\2\ (ft\2\).
L = Length.
R = Be emission rate, g/day.
Vs(avg) = Average stack gas velocity, m/sec (ft/sec).
Vtotal = Total volume of gas sampled, m\3\ (ft\3\).
W = Width.
Wt = Total weight of Be collected, mg.
10-6 = Conversion factor, g/g.
86,400 = Conversion factor, sec/day.

    12.2  Calculate the equivalent diameter, De, for a rectangular 
cross section as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.502

    12.3  Calculate the Be emission rate, R, in g/day for each stack 
using Equation 103-2. For cyclic operations, use only the time per day 
each stack is in operation. The total Be emission rate from a source is 
the summation of results from all stacks.
[GRAPHIC] [TIFF OMITTED] TR17OC00.503

    12.4  Test Report. Prepare a test report that includes as a 
minimum: A detailed description of the sampling train used, results of 
the procedural check described in Section 10.1 with all data and 
calculations made, all pertinent data taken during the test, the basis 
for any estimates made, isokinetic sampling calculations, and emission 
results. Include a description of the test site, with a block diagram 
and brief description of the process, location of the sample points in 
the stack cross section, and stack dimensions and distances from any 
point of disturbance.

13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References. [Reserved]

BILLING CODE 6560-50-P

[[Page 62180]]

17.0  Tables, Diagrams, Flow Charts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.504

BILLING CODE 6560-50-C

[[Page 62181]]

Method 104--Determination of Beryllium Emissions From Stationary 
Sources

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from methods in Appendix A to 40 CFR part 
60. Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of at least the following 
additional test methods: Method 1, Method 2, Method 3, and Method 5 
in Appendix A, Part 60.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.            Sensitivity
------------------------------------------------------------------------
Beryllium (Be).................       7440-41-7   Dependent upon
                                                   recorder and
                                                   spectrophotometer.
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of Be emissions in ducts or stacks at stationary sources. Unless 
otherwise specified, this method is not intended to apply to gas 
streams other than those emitted directly to the atmosphere without 
further processing.
    1.3  Data Quality Objectives. Adherences to the requirements of 
this method will enhance the quality of the data obtained from air 
pollutant sampling methods.

2.0  Summary of Method

    2.1  Particulate and gaseous Be emissions are withdrawn 
isokinetically from the source and are collected on a glass fiber 
filter and in water. The collected sample is digested in an acid 
solution and is analyzed by atomic absorption spectrophotometry.

3.0  Definitions [Reserved]

4.0  Interferences

    4.1  Matrix Effects. Analysis for Be by flame atomic absorption 
spectrophotometry is sensitive to the chemical composition and to the 
physical properties (e.g., viscosity, pH) of the sample. Aluminum and 
silicon in particular are known to interfere when present in 
appreciable quantities. The analytical procedure includes (optionally) 
the use of the Method of Standard Additions to check for these matrix 
effects, and sample analysis using the Method of Standard Additions if 
significant matrix effects are found to be present (see Reference 2 in 
Section 16.0).

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Corrosive reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burn as thermal burn.
    5.2.1  Hydrochloric Acid (HCl). Highly toxic. Vapors are 
highly irritating to eyes, skin, nose, and lungs, causing severe 
damage. May cause bronchitis, pneumonia, or edema of lungs. Exposure to 
concentrations of 0.13 to 0.2 percent can be lethal to humans in a few 
minutes. Provide ventilation to limit exposure. Reacts with metals, 
producing hydrogen gas.
    5.2.2  Hydrogen Peroxide (H2O2). Irritating 
to eyes, skin, nose, and lungs.
    5.2.3  Nitric Acid (HNO3). Highly corrosive to eyes, 
skin, nose, and lungs. Vapors cause bronchitis, pneumonia, or edema of 
lungs. Reaction to inhalation may be delayed as long as 30 hours and 
still be fatal. Provide ventilation to limit exposure. Strong oxidizer. 
Hazardous reaction may occur with organic materials such as solvents.
    5.2.4  Sodium Hydroxide (NaOH). Causes severe damage to eyes and 
skin. Inhalation causes irritation to nose, throat, and lungs. Reacts 
exothermically with limited amounts of water.
    5.3  Beryllium is hazardous, and precautions should be taken to 
minimize exposure.

6.0  Equipment and Supplies

    6.1  Sample Collection. Same as Method 5, Section 6.1, with the 
exception of the following:
    6.1.1  Sampling Train. Same as Method 5, Section 6.1.1, with the 
exception of the following:
    6.1.2  Probe Liner. Borosilicate or quartz glass tubing. A heating 
system capable of maintaining a gas temperature of 120  14 
deg.C (248  25  deg.F) at the probe exit during sampling to 
prevent water condensation may be used.


    Note: Do not use metal probe liners.


    6.1.3  Filter Holder. Borosilicate glass, with a glass frit filter 
support and a silicone rubber gasket. Other materials of construction 
(e.g., stainless steel, Teflon, Viton) may be used, subject to the 
approval of the Administrator. The holder design shall provide a 
positive seal against leakage from the outside or around the filter. 
The holder shall be attached immediately at the outlet of the probe. A 
heating system capable of maintaining the filter at a minimum 
temperature in the range of the stack temperature may be used to 
prevent condensation from occurring.
    6.1.4  Impingers. Four Greenburg-Smith impingers connected in 
series with leak-free ground glass fittings or any similar leak-free 
noncontaminating fittings. For the first, third, and fourth impingers, 
use impingers that are modified by replacing the tip with a 13 mm-ID 
(0.5 in.) glass tube extending to 13 mm (0.5 in.) from the bottom of 
the flask may be used.
    6.2  Sample Recovery. The following items are needed for sample 
recovery:
    6.2.1  Probe Cleaning Rod. At least as long as probe.
    6.2.2  Glass Sample Bottles. Leakless, with Teflon-lined caps, 1000 
ml.
    6.2.3  Petri Dishes. For filter samples, glass or polyethylene, 
unless otherwise specified by the Administrator.
    6.2.4  Graduated Cylinder. 250 ml.
    6.2.5  Funnel and Rubber Policeman. To aid in transfer of silica 
gel to container; not necessary if silica gel is weighed in the field.
    6.2.6  Funnel. Glass, to aid in sample recovery.
    6.2.7  Plastic Jar. Approximately 300 ml.
    6.3  Analysis. The following items are needed for sample analysis:
    6.3.1  Atomic Absorption Spectrophotometer. Perkin-Elmer 303, or 
equivalent, with nitrous oxide/acetylene burner.
    6.3.2  Hot Plate.
    6.3.3  Perchloric Acid Fume Hood.

7.0  Reagents and Standards

    Note: Unless otherwise indicated, it is intended that all 
reagents conform to the specifications established by the Committee 
on Analytical Reagents of the American Chemical Society, where such 
specifications are available; otherwise, use the best available 
grade.


[[Page 62182]]


    7.1  Sample Collection. Same as Method 5, Section 7.1, including 
deionized distilled water conforming to ASTM D 1193-77 or 91 
(incorporated by reference--see Sec. 61.18), Type 3. The Millipore AA 
filter is recommended.
    7.2  Sample Recovery. Same as Method 5 in Appendix A, Part 60, 
Section 7.2, with the addition of the following:
    7.2.1  Wash Acid, 50 Percent (V/V) Hydrochloric Acid (HCl). Mix 
equal volumes of concentrated HCl and water, being careful to add the 
acid slowly to the water.
    7.3  Sample Preparation and Analysis. The following reagents and 
standards and standards are needed for sample preparation and analysis:
    7.3.1  Water. Same as in Section 7.1.
    7.3.2.  Perchloric Acid (HClO4). Concentrated (70 
percent V/V).
    7.3.3  Nitric Acid (HNO3). Concentrated.
    7.3.4  Beryllium Powder. Minimum purity 98 percent.
    7.3.5  Sulfuric Acid (H2SO4) Solution, 12 N. 
Dilute 33 ml of concentrated H2SO4 to 1 liter 
with water.
    7.3.6  Hydrochloric Acid Solution, 25 Percent HCl (V/V).
    7.3.7  Stock Beryllium Standard Solution, 10 g Be/ml. 
Dissolve 10.0 mg of Be in 80 ml of 12 N H2SO4 in 
a 1000-ml volumetric flask. Dilute to volume with water. This solution 
is stable for at least one month. Equivalent strength Be stock 
solutions may be prepared from Be salts such as BeCl2 and 
Be(NO3)2 (98 percent minimum purity).
    7.3.8  Working Beryllium Standard Solution, 1 g Be/ml. 
Dilute a 10 ml aliquot of the stock beryllium standard solution to 100 
ml with 25 percent HCl solution to give a concentration of 1 mg/ml. 
Prepare this dilute stock solution fresh daily.

8.0  Sample Collection, Preservation, Transport, and Storage

    The amount of Be that is collected is generally small, therefore, 
it is necessary to exercise particular care to prevent contamination or 
loss of sample.
    8.1  Pretest Preparation. Same as Method 5, Section 8.1, except 
omit Section 8.1.3.
    8.2  Preliminary Determinations. Same as Method 5, Section 8.2, 
with the exception of the following:
    8.2.1  Select a nozzle size based on the range of velocity heads to 
assure that it is not necessary to change the nozzle size in order to 
maintain isokinetic sampling rates below 28 liters/min (1.0 cfm).
    8.2.2  Obtain samples over a period or periods of time that 
accurately determine the maximum emissions that occur in a 24-hour 
period. In the case of cyclic operations, perform sufficient sample 
runs for the accurate determination of the emissions that occur over 
the duration of the cycle. A minimum sample time of 2 hours per run is 
recommended.
    8.3  Preparation of Sampling Train. Same as Method 5, Section 8.3, 
with the exception of the following:
    8.3.1  Prior to assembly, clean all glassware (probe, impingers, 
and connectors) by first soaking in wash acid for 2 hours, followed by 
rinsing with water.
    8.3.2  Save a portion of the water for a blank analysis.
    8.3.3  Procedures relating to the use of metal probe liners are not 
applicable.
    8.3.4  Probe and filter heating systems are needed only if water 
condensation is a problem. If this is the case, adjust the heaters to 
provide a temperature at or above the stack temperature. However, 
membrane filters such as the Millipore AA are limited to about 107 
deg.C (225  deg.F). If the stack gas is in excess of about 93  deg.C 
(200  deg.F), consideration should be given to an alternate procedure 
such as moving the filter holder downstream of the first impinger to 
insure that the filter does not exceed its temperature limit. After the 
sampling train has been assembled, turn on and set the probe heating 
system, if applicable, at the desired operating temperature. Allow time 
for the temperatures to stabilize. Place crushed ice around the 
impingers.


    Note: An empty impinger may be inserted between the third 
impinger and the silica gel to remove excess moisture from the 
sample stream.


    8.4  Leak Check Procedures, Sampling Train Operation, and 
Calculation of Percent Isokinetic. Same as Method 5, Sections 8.4, 8.5, 
and 8.6, respectively.
    8.5  Sample Recovery. Same as Method 5, Section 8.7, except treat 
the sample as follows: Transfer the probe and impinger assembly to a 
cleanup area that is clean, protected from the wind, and free of Be 
contamination. Inspect the train before and during this assembly, and 
note any abnormal conditions. Treat the sample as follows: Disconnect 
the probe from the impinger train.
    8.5.1  Container No. 1. Same as Method 5, Section 8.7.6.1.
    8.5.2  Container No. 2. Place the contents (measured to 1 ml) of 
the first three impingers into a glass sample bottle. Use the 
procedures outlined in Section 8.7.6.2 of Method 5, where applicable, 
to rinse the probe nozzle, probe fitting, probe liner, filter holder, 
and all glassware between the filter holder and the back half of the 
third impinger with water. Repeat this procedure with acetone. Place 
both water and acetone rinse solutions in the sample bottle with the 
contents of the impingers.
    8.5.3  Container No. 3. Same as Method 5, Section 8.7.6.3.
    8.6  Blanks.
    8.6.1  Water Blank. Save a portion of the water as a blank. Take 
200 ml directly from the wash bottle being used and place it in a 
plastic sample container labeled ``H2O blank.''
    8.6.2  Filter. Save two filters from each lot of filters used in 
sampling. Place these filters in a container labeled ``filter blank.''
    8.7  Post-test Glassware Rinsing. If an additional test is desired, 
the glassware can be carefully double rinsed with water and 
reassembled. However, if the glassware is out of use more than 2 days, 
repeat the initial acid wash procedure.

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.4, 10.1.....................  Sampling           Ensure accuracy and
                                 equipment leak     precision of
                                 checks and         sampling
                                 calibration.       measurements.
10.2..........................  Spectrophotometer  Ensure linearity of
                                 calibration.       spectrophotometer
                                                    response to
                                                    standards.
11.5..........................  Check for matrix   Eliminate matrix
                                 effects.           effects.
11.6..........................  Audit sample       Evaluate analyst's
                                 analysis.          technique and
                                                    standards
                                                    preparation.
------------------------------------------------------------------------


[[Page 62183]]

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

10.0  Calibration and Standardization

    Note: Maintain a laboratory log of all calibrations.

    10.1  Sampling Equipment. Same as Method 5, Section 10.0.
    10.2  Preparation of Standard Solutions. Pipet 1, 3, 5, 8, and 10 
ml of the 1.0 g Be/ml working standard solution into separate 
100 ml volumetric flasks, and dilute to the mark with water. The total 
amounts of Be in these standards are 1, 3, 5, 8, and 10 g, 
respectively.
    10.3  Spectrophotometer and Recorder. The Be response may be 
measured by either peak height or peak area. Analyze an aliquot of the 
10-g standard at 234.8 nm using a nitrous oxide/acetylene 
flame. Determine the maximum absorbance of the standard, and set this 
value to read 90 percent of the recorder full scale.
    10.4  Calibration Curve.
    10.4.1  After setting the recorder scale, analyze an appropriately 
sized aliquot of each standard and the BLANK (see Section 11) until two 
consecutive peaks agree within 3 percent of their average value.
    10.4.3  Subtract the average peak height (or peak area) of the 
blank--which must be less than 2 percent of recorder full scale--from 
the averaged peak heights of the standards. If the blank absorbance is 
greater than 2 percent of full-scale, the probable cause is Be 
contamination of a reagent or carry-over of Be from a previous sample. 
Prepare the calibration curve by plotting the corrected peak height of 
each standard solution versus the corresponding total Be weight in the 
standard (in g).
    10.5  Spectrophotometer Calibration Quality Control. Calculate the 
least squares slope of the calibration curve. The line must pass 
through the origin or through a point no further from the origin than 
2 percent of the recorder full scale. Multiply the 
corrected peak height by the reciprocal of the least squares slope to 
determine the distance each calibration point lies from the theoretical 
calibration line. The difference between the calculated concentration 
values and the actual concentrations (i.e., 1, 3, 5, 8, and 10 
g Be) must be less than 7 percent for all standards.

11.0  Analytical Procedure

    11.1  Sample Loss Check. Prior to analysis, check the liquid level 
in Container No. 2. Note on the analytical data sheet whether leakage 
occurred during transport. If a noticeable amount of leakage occurred, 
either void the sample or take steps, subject to the approval of the 
Administrator, to adjust the final results.
    11.2  Glassware Cleaning. Before use, clean all glassware according 
to the procedure of Section 8.3.1.
    11.3  Sample Preparation. The digestion of Be samples is 
accomplished in part in concentrated HClO4.


    Note: The sample must be heated to light brown fumes after the 
initial HNO3 addition; otherwise, dangerous perchlorates may result 
from the subsequent HClO4 digestion. HClO4 
should be used only under a hood.

    11.3.1  Container No. 1. Transfer the filter and any loose 
particulate matter from Container No. 1 to a 150-ml beaker. Add 35 ml 
concentrated HNO3. To oxidize all organic matter, heat on a 
hotplate until light brown fumes are evident. Cool to room temperature, 
and add 5 ml 12 N H2SO4 and 5 ml concentrated 
HClO4.
    11.3.2  Container No. 2. Place a portion of the water and acetone 
sample into a 150 ml beaker, and put on a hotplate. Add portions of the 
remainder as evaporation proceeds and evaporate to dryness. Cool the 
residue, and add 35 ml concentrated HNO3. To oxidize all 
organic matter, heat on a hotplate until light brown fumes are evident. 
Cool to room temperature, and add 5 ml 12 N H2SO4 
and 5 ml concentrated HClO4. Then proceed with step 11.3.4.
    11.3.3  Final Sample Preparation. Add the sample from Section 
11.3.2 to the 150-ml beaker from Section 11.3.1. Replace on a hotplate, 
and evaporate to dryness in a HClO4 hood. Cool the residue 
to room temperature, add 10.0 ml of 25 percent V/V HCl, and mix to 
dissolve the residue.
    11.3.4  Filter and Water Blanks. Cut each filter into strips, and 
treat each filter individually as directed in Section 11.3.1. Treat the 
200-ml water blank as directed in Section 11.3.2. Combine and treat 
these blanks as directed in Section 11.3.3.
    11.4  Spectrophotometer Preparation. Turn on the power; set the 
wavelength, slit width, and lamp current; and adjust the background 
corrector as instructed by the manufacturer's manual for the particular 
atomic absorption spectrophotometer. Adjust the burner and flame 
characteristics as necessary.
    11.5  Analysis. Calibrate the analytical equipment and develop a 
calibration curve as outlined in Sections 10.4 and 10.5.
    11.5.1  Beryllium Samples. Repeat the procedure used to establish 
the calibration curve with an appropriately sized aliquot of each 
sample (from Section 11.3.3) until two consecutive peak heights agree 
within 3 percent of their average value. The peak height of each sample 
must be greater than 10 percent of the recorder full scale. If the peak 
height of the sample is off scale on the recorder, further dilute the 
original source sample to bring the Be concentration into the 
calibration range of the spectrophotometer.
    11.5.2  Run a blank and standard at least after every five samples 
to check the spectrophotometer calibration. The peak height of the 
blank must pass through a point no further from the origin than 
2 percent of the recorder full scale. The difference 
between the measured concentration of the standard (the product of the 
corrected peak height and the reciprocal of the least squares slope) 
and the actual concentration of the standard must be less than 7 
percent, or recalibration of the analyzer is required.
    11.5.3  Check for Matrix Effects (optional). Use the Method of 
Standard Additions (see Reference 2 in Section 16.0) to check at least 
one sample from each source for matrix effects on the Be results. If 
the results of the Method of Standard Additions procedure used on the 
single source sample do not agree to within 5 percent of the value 
obtained by the routine atomic absorption analysis, then reanalyze all 
samples from the source using the Method of Standard Additions 
procedure.
    11.6  Container No. 2 (Silica Gel). Weigh the spent silica gel (or 
silica gel plus impinger) to the nearest 0.5 g using a balance. (This 
step may be conducted in the field.)

12.0  Data Analysis and Calculations

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

K1 = 0.3858  deg.K/mm Hg for metric units.
    = 17.64  deg.R/in. Hg for English units.
K3 = 10-\6\ g/g for metric units.
     = 2.2046  x  10-\9\ lb/g for English units.
mBe = Total weight of beryllium in the source sample.
Ps = Absolute stack gas pressure, mm Hg (in. Hg).
t = Daily operating time, sec/day.
Ts = Absolute average stack gas temperature,  deg.K 
( deg.R).
Vm(std) = Dry gas sample volume at standard conditions, scm 
(scf).
Vw(std) = Volume of water vapor at standard conditions, scm 
(scf).

    12.2  Average Dry Gas Meter Temperature and Average Orifice

[[Page 62184]]

Pressure Drop, Dry Gas Volume, Volume of Water Vapor Condensed, 
Moisture Content, Isokinetic Variation, and Stack Gas Velocity and 
Volumetric Flow Rate. Same as Method 5, Sections 12.2 through 12.5, 
12.11, and 12.12, respectively.
    12.3  Total Beryllium. For each source sample, correct the average 
maximum absorbance of the two consecutive samples whose peak heights 
agree within 3 percent of their average for the contribution of the 
solution blank (see Sections 11.3.4 and 11.5.2). Correcting for any 
dilutions if necessary, use the calibration curve and these corrected 
averages to determine the total weight of Be in each source sample.
    12.4  Beryllium Emission Rate. Calculate the daily Hg emission 
rate, R, using Equation 104-1. For continuous operations, the operating 
time is equal to 86,400 seconds per day. For cyclic operations, use 
only the time per day each stack is in operation. The total Hg emission 
rate from a source will be the summation of results from all stacks.
[GRAPHIC] [TIFF OMITTED] TR17OC00.505

    12.5  Determination of Compliance. Each performance test consists 
of three sample runs. For the purpose of determining compliance with an 
applicable national emission standard, use the average of the results 
of all sample runs.

13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    Same as References 1, 2, and 4-11 of Section 16.0 of Method 101 
with the addition of the following:

    1. Amos, M.D., and J.B. Willis. Use of High-Temperature Pre-
Mixed Flames in Atomic Absorption Spectroscopy. Spectrochim. Acta. 
22:1325. 1966.
    2. Fleet, B., K.V. Liberty, and T. S. West. A Study of Some 
Matrix Effects in the Determination of Beryllium by Atomic 
Absorption Spectroscopy in the Nitrous Oxide-Acetylene Flame. 
Talanta 17:203. 1970.

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

Method 105--Determination of Mercury in Wastewater Treatment Plant 
Sewage Sludges

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in this part. 
Therefore, to obtain reliable results, persons using this method 
should also have a thorough knowledge of at least the following 
additional test methods: Method 101 and Method 101A.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.            Sensitivity
------------------------------------------------------------------------
Mercury (Hg)...................       7439-97-6   Dependent upon
                                                   spectrophotometer and
                                                   recorder.
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of total organic and inorganic Hg content in sewage sludges.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  Time-composite sludge samples are withdrawn from the conveyor 
belt subsequent to dewatering and before incineration or drying. A 
weighed portion of the sludge is digested in aqua regia and is oxidized 
by potassium permanganate (KMnO4). Mercury in the digested 
sample is then measured by the conventional spectrophotometric cold-
vapor technique.

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Corrosive Reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burn as thermal burn.
    5.2.1  Hydrochloric Acid (HCl). Highly toxic. Vapors are highly 
irritating to eyes, skin, nose, and lungs, causing severe damage. May 
cause bronchitis, pneumonia, or edema of lungs. Exposure to 
concentrations of 0.13 to 0.2 percent can be lethal to humans in a few 
minutes. Provide ventilation to limit exposure. Reacts with metals, 
producing hydrogen gas.
    5.2.2  Nitric Acid (HNO3). Highly corrosive to eyes, 
skin, nose, and lungs. Vapors cause bronchitis, pneumonia, or edema of 
lungs. Reaction to inhalation may be delayed as long as 30 hours and 
still be fatal. Provide ventilation to limit exposure. Strong oxidizer. 
Hazardous reaction may occur with organic materials such as solvents.

6.0  Equipment and Supplies

    6.1  Sample Collection and Mixing. The following items are required 
for collection and mixing of the sludge samples:
    6.1.1  Container. Plastic, 50-liter.
    6.1.2  Scoop. To remove 950-ml (1 quart.) sludge sample.
    6.1.3  Mixer. Mortar mixer, wheelbarrow-type, 57-liter (or 
equivalent) with electricity-driven motor.
    6.1.4  Blender. Waring-type, 2-liter.
    6.1.5  Scoop. To remove 100-ml and 20-ml samples of blended sludge.
    6.1.6  Erlenmeyer Flasks. Four, 125-ml.

[[Page 62185]]

    6.1.7  Beakers. Glass beakers in the following sizes: 50 ml (1), 
200 ml (1), 400 ml (2).
    6.2  Sample Preparation and Analysis. Same as Method 101, Section 
6.3, with the addition of the following:
    6.2.1  Hot Plate.
    6.2.2  Desiccator.
    6.2.3  Filter Paper. S and S No. 588 (or equivalent).
    6.2.4  Beakers. Glass beakers, 200 ml and 400 ml (2 each).

7.0  Reagents and Standards

    Note: Unless otherwise indicated, it is intended that all 
reagents conform to the specifications established by the Committee 
on Analytical Reagents of the American Chemical Society, where such 
specifications are available; otherwise, use the best available 
grade.

    7.1  Sample Analysis. Same as Method 101A, Section 7.2, with the 
following additions and exceptions:
    7.1.1  Hydrochloric Acid. The concentrated HCl specified in Method 
101A, Section 7.2.4, is not required.
    7.1.2  Aqua Regia. Prepare immediately before use. Carefully add 
one volume of concentrated HNO3 to three volumes of 
concentrated HCl.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Sludge Sampling. Withdraw equal volume increments of sludge 
[for a total of at least 15 liters (16 quarts)] at intervals of 30 min 
over an 8-hr period, and combine in a rigid plastic container.
    8.2  Sludge Mixing. Transfer the entire 15-liter sample to a mortar 
mixer. Mix the sample for a minimum of 30 min at 30 rpm. Take six 100-
ml portions of sludge, and combine in a 2-liter blender. Blend sludge 
for 5 min; add water as necessary to give a fluid consistency. 
Immediately after stopping the blender, withdraw four 20-ml portions of 
blended sludge, and place them in separate, tared 125-ml Erlenmeyer 
flasks. Reweigh each flask to determine the exact amount of sludge 
added.
    8.3  Sample Holding Time. Samples shall be analyzed within the time 
specified in the applicable subpart of the regulations.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
10.0..........................  Spectrophotometer  Ensure linearity of
                                 calibration.       spectrophotometer
                                                    response to
                                                    standards.
11.0..........................  Check for matrix   Eliminate matrix
                                 effects.           effects.
------------------------------------------------------------------------

10.0  Calibration and Standardization

    Same as Method 101A, Section 10.2.

11.0  Analytical Procedures

    11.1  Solids Content of Blended Sludge. Dry one of the 20-ml 
blended samples from Section 8.2 in an oven at 105  deg.C (221  deg.F) 
to constant weight. Cool in a desiccator, weigh and record the dry 
weight of the sample.
    11.2  Aqua Regia Digestion of Blended Samples.
    11.2.1  To each of the three remaining 20-ml samples from Section 
8.2 add 25 ml of aqua regia, and digest the on a hot plate at low heat 
(do not boil) for 30 min, or until samples are a pale yellow-brown 
color and are void of the dark brown color characteristic of organic 
matter. Remove from hotplate and allow to cool.
    11.2.2  Filter each digested sample separately through an S and S 
No. 588 filter or equivalent, and rinse the filter contents with 50 ml 
of water. Transfer the filtrate and filter washing to a 100-ml 
volumetric flask, and carefully dilute to volume with water.
    11.3  Solids Content of the Sludge Before Blending. Remove two 100-
ml portions of mixed sludge from the mortar mixer and place in 
separate, tared 400-ml beakers. Reweigh each beaker to determine the 
exact amount of sludge added. Dry in oven at 105  deg.C (221  deg.F) 
and cool in a desiccator to constant weight.
    11.4  Analysis for Mercury. Analyze the three aqua regia-digested 
samples using the procedures outlined in Method 101A, Section 11.0.

12.0  Data Analysis and Calculations

    12.1  Nomenclature.

Cm = Concentration of Hg in the digested sample, g/
g.
Fsb = Weight fraction of solids in the blended sludge.
Fsm = Weight fraction of solids in the collected sludge 
after mixing.
M = Hg content of the sewage sludge (on a dry basis), g/g.
m = Mass of Hg in the aliquot of digested sample analyzed, g.
n = number of digested samples (specified in Section 11.2 as three).
Va = Volume of digested sample analyzed, ml.
Vs = Volume of digested sample, ml.
Wb = Weight of empty sample beaker, g.
Wbs = Weight of sample beaker and sample, g.
Wbd = Weight of sample beaker and sample after drying, g.
Wf = Weight of empty sample flask, g.
Wfd = Weight of sample flask and sample after drying, g.
Wfs = Weight of sample flask and sample, g.

    12.2  Mercury Content of Digested Sample (Wet Basis).
    12.2.1  For each sample analyzed for Hg content, calculate the 
arithmetic mean maximum absorbance of the two consecutive samples whose 
peak heights agree 3 percent of their average. Correct this 
average value for the contribution of the blank. Use the calibration 
curve and these corrected averages to determine the final Hg 
concentration in the solution cell for each sludge sample.
    12.2.2  Calculate the average Hg concentration of the digested 
samples by correcting for any dilutions made to bring the sample into 
the working range of the spectrophotometer and for the weight of the 
sludge portion digested, using Equation 105-1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.506

    12.3  Solids Content of Blended Sludge. Determine the solids 
content of the blended sludge using Equation 105-2.

[[Page 62186]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.507

    12.4  Solids Content of Bulk Sample (before blending but, after 
mixing in mortar mixer). Determine the solids content of each 100 ml 
aliquot (Section 11.3), and average the results.
[GRAPHIC] [TIFF OMITTED] TR17OC00.508

    12.5  Mercury Content of Bulk Sample (Dry Basis). Average the 
results from the three samples from each 8-hr composite sample, and 
calculate the Hg concentration of the composite sample on a dry basis.
[GRAPHIC] [TIFF OMITTED] TR17OC00.509

13.0  Method Performance

    13.1  Range. The range of this method is 0.2 to 5 micrograms per 
gram; it may be extended by increasing or decreasing sample size.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    1. Bishop, J.N. Mercury in Sediments. Ontario Water Resources 
Commission. Toronto, Ontario, Canada. 1971.
    2. Salma, M. Private Communication. EPA California/Nevada Basin 
Office. Alameda, California.
    3. Hatch, W.R. and W.L. Ott. Determination of Sub-Microgram 
Quantities of Mercury by Atomic Absorption Spectrophotometry. 
Analytical Chemistry. 40:2085. 1968.
    4. Bradenberger, H., and H. Bader. The Determination of Nanogram 
Levels of Mercury in Solution by a Flameless Atomic Absorption 
Technique. Atomic Absorption Newsletter. 6:101. 1967.
    5. Analytical Quality Control Laboratory (AQCL). Mercury in 
Sediment (Cold Vapor Technique) (Provisional Method). U.S. 
Environmental Protection Agency. Cincinnati, Ohio. April 1972.
    6. Kopp, J.F., M.C. Longbottom, and L.B. Lobring. ``Cold Vapor'' 
Method for Determining Mercury. Journal AWWA. 64(1):20-25. 1972.
    7. Manual of Methods for Chemical Analysis of Water and Wastes. 
U.S. Environmental Protection Agency. Cincinnati, Ohio. Publication 
No. EPA-624/2-74-003. December 1974. pp. 118-138.
    8. Mitchell, W.J., M.R. Midgett, J. Suggs, R.J. Velton, and D. 
Albrink. Sampling and Homogenizing Sewage for Analysis. 
Environmental Monitoring and Support Laboratory, Office of Research 
and Development, U.S. Environmental Protection Agency. Research 
Triangle Park, N.C. March 1979. p. 7.

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

Method 106--Determination of Vinyl Chloride Emissions From 
Stationary Sources

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.            Sensitivity
------------------------------------------------------------------------
Vinyl Chloride (CH2:CHCl)......         75-01-4   Dependent upon
                                                   analytical equipment.
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of vinyl chloride emissions from ethylene dichloride, vinyl chloride, 
and polyvinyl chloride manufacturing processes. This method does not 
measure vinyl chloride contained in particulate matter.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  An integrated bag sample of stack gas containing vinyl 
chloride is subjected to GC analysis using a flame ionization detector 
(FID).

3.0  Definitions. [Reserved]

4.0  Interferences

    4.1  Resolution interferences of vinyl chloride may be encountered 
on some sources. Therefore, the chromatograph operator should select 
the column and operating parameters best suited to the particular 
analysis requirements. The selection made is subject to approval of the 
Administrator. Approval is automatic, provided that confirming data are 
produced through an adequate supplemental analytical technique, and 
that the data are available for review by the Administrator. An example 
of this would be analysis with a different column or GC/mass 
spectroscopy.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Toxic Analyte. Care must be exercised to prevent exposure of 
sampling personnel to vinyl chloride, which is a carcinogen.

6.0  Equipment and Supplies

    6.1  Sample Collection (see Figure 106-1). The sampling train 
consists of the following components:
    6.1.1  Probe. Stainless steel, borosilicate glass, Teflon tubing 
(as stack temperature permits), or equivalent, equipped with a glass 
wool plug to remove particulate matter.

[[Page 62187]]

    6.1.2  Sample Lines. Teflon, 6.4-mm outside diameter, of sufficient 
length to connect probe to bag. Use a new unused piece for each series 
of bag samples that constitutes an emission test, and discard upon 
completion of the test.
    6.1.3  Quick Connects. Stainless steel, male (2) and female (2), 
with ball checks (one pair without), located as shown in Figure 106-1.
    6.1.4  Tedlar Bags. 50- to 100-liter capacity, to contain sample. 
Aluminized Mylar bags may be used if the samples are analyzed within 24 
hours of collection.
    6.1.5  Bag Containers. Rigid leak-proof containers for sample bags, 
with covering to protect contents from sunlight.
    6.1.6  Needle Valve. To adjust sample flow rates.
    6.1.7  Pump. Leak-free, with minimum of 2-liter/min capacity.
    6.1.8  Charcoal Tube. To prevent admission of vinyl chloride and 
other organics to the atmosphere in the vicinity of samplers.
    6.1.9  Flowmeter. For observing sampling flow rate; capable of 
measuring a flow range from 0.10 to 1.00 liter/min.
    6.1.10  Connecting Tubing. Teflon, 6.4-mm outside diameter, to 
assemble sampling train (Figure 106-1).
    6.1.11  Tubing Fittings and Connectors. Teflon or stainless steel, 
to assemble sampling training.
    6.2  Sample Recovery. Teflon tubing, 6.4-mm outside diameter, to 
connect bag to GC sample loop. Use a new unused piece for each series 
of bag samples that constitutes an emission test, and discard upon 
conclusion of analysis of those bags.
    6.3  Analysis. The following equipment is required:
    6.3.1  Gas Chromatograph. With FID potentiometric strip chart 
recorder and 1.0 to 5.0-ml heated sampling loop in automatic sample 
valve. The chromatographic system shall be capable of producing a 
response to 0.1-ppmv vinyl chloride that is at least as great as the 
average noise level. (Response is measured from the average value of 
the base line to the maximum of the wave form, while standard operating 
conditions are in use.)
    6.3.2  Chromatographic Columns. Columns as listed below. Other 
columns may be used provided that the precision and accuracy of the 
analysis of vinyl chloride standards are not impaired and that 
information is available for review confirming that there is adequate 
resolution of vinyl chloride peak. (Adequate resolution is defined as 
an area overlap of not more than 10 percent of the vinyl chloride peak 
by an interferent peak. Calculation of area overlap is explained in 
Procedure 1 of appendix C to this part: ``Determination of Adequate 
Chromatographic Peak Resolution.'')
    6.3.2.1  Column A. Stainless steel, 2.0 m by 3.2 mm, containing 80/
100-mesh Chromasorb 102.
    6.3.2.2  Column B. Stainless steel, 2.0 m by 3.2 mm, containing 20 
percent GE SF-96 on 60/ip-mesh Chromasorb P AW; or stainless steel, 1.0 
m by 3.2 mm containing 80/100-mesh Porapak T. Column B is required as a 
secondary column if acetaldehyde is present. If used, column B is 
placed after column A. The combined columns should be operated at 120 
deg.C (250  deg.F).
    6.3.3  Rate Meters (2). Rotameter , or equivalent, 100-ml/min 
capacity, with flow control valves.
    6.3.4  Gas Regulators. For required gas cylinders.
    6.3.5  Temperature Sensor. Accurate to 1  deg.C 
(2  deg.F), to measure temperature of heated sample loop at 
time of sample injection.
    6.3.6  Barometer. Accurate to 5 mm Hg, to measure 
atmospheric pressure around GC during sample analysis.
    6.3.7  Pump. Leak-free, with minimum of 100-ml/min capacity.
    6.3.8  Recorder. Strip chart type, optionally equipped with either 
disc or electronic integrator.
    6.3.9  Planimeter. Optional, in place of disc or electronic 
integrator on recorder, to measure chromatograph peak areas.
    6.4  Calibration and Standardization.
    6.4.1  Tubing. Teflon, 6.4-mm outside diameter, separate pieces 
marked for each calibration concentration.

    Note: The following items are required only if the optional 
standard gas preparation procedures (Section 10.1) are followed.


    6.4.2  Tedlar Bags. Sixteen-inch-square size, with valve; separate 
bag marked for each calibration concentration.
    6.4.3  Syringes. 0.5-ml and 50-l, gas tight, individually 
calibrated to dispense gaseous vinyl chloride.
    6.4.4  Dry Gas Meter with Temperature and Pressure Gauges. Singer 
Model DTM-115 with 802 index, or equivalent, to meter nitrogen in 
preparation of standard gas mixtures, calibrated at the flow rate used 
to prepare standards.

7.0  Reagents and Standards

    7.1  Analysis. The following reagents are required for analysis.
    7.1.1  Helium or Nitrogen. Purity 99.9995 percent or greater, for 
chromatographic carrier gas.
    7.1.2  Hydrogen. Purity 99.9995 percent or greater.
    7.1.3  Oxygen or Air. Either oxygen (purity 99.99 percent or 
greater) or air (less than 0.1 ppmv total hydrocarbon content), as 
required by detector.
    7.2  Calibration. Use one of the following options: either Sections 
7.2.1 and 7.2.2, or Section 7.2.3.
    7.2.1  Vinyl Chloride. Pure vinyl chloride gas certified by the 
manufacturer to contain a minimum of 99.9 percent vinyl chloride. If 
the gas manufacturer maintains a bulk cylinder supply of 99.9+ percent 
vinyl chloride, the certification analysis may have been performed on 
this supply, rather than on each gas cylinder prepared from this bulk 
supply. The date of gas cylinder preparation and the certified analysis 
must have been affixed to the cylinder before shipment from the gas 
manufacturer to the buyer.
    7.2.2  Nitrogen. Same as described in Section 7.1.1.
    7.2.3  Cylinder Standards. Gas mixture standards (50-,10-, and 5 
ppmv vinyl chloride) in nitrogen cylinders may be used to directly 
prepare a chromatograph calibration curve as described in Section 10.3 
if the following conditions are met: (a) The manufacturer certifies the 
gas composition with an accuracy of 3 percent or better. 
(b) The manufacturer recommends a maximum shelf life over which the gas 
concentration does not change by greater than 5 percent 
from the certified value. (c) The manufacturer affixes the date of gas 
cylinder preparation, certified vinyl chloride concentration, and 
recommended maximum shelf to the cylinder before shipment to the buyer.
    7.2.3.1  Cylinder Standards Certification. The manufacturer shall 
certify the concentration of vinyl chloride in nitrogen in each 
cylinder by (a) directly analyzing each cylinder and (b) calibrating 
his analytical procedure on the day of cylinder analysis. To calibrate 
his analytical procedure, the manufacturer shall use as a minimum, a 
three point calibration curve. It is recommended that the manufacturer 
maintain (1) a high concentration calibration standard (between 50 and 
100 ppmv) to prepare his calibration curve by an appropriate dilution 
technique and (2) a low-concentration calibration standard (between 5 
and 10 ppmv) to verify the dilution technique used. If the difference 
between the apparent concentration read from the calibration curve and 
the true concentration assigned to the low-concentration calibration 
standard exceeds 5 percent of the true concentration, the manufacturer 
shall

[[Page 62188]]

determine the source of error and correct it, then repeat the three-
point calibration.
    7.2.3.2  Verification of Manufacturer's Calibration Standards. 
Before using a standard, the manufacturer shall verify each calibration 
standard (a) by comparing it to gas mixtures prepared (with 99 mole 
percent vinyl chloride) in accordance with the procedure described in 
Section 7.2.1 or (b) calibrating it against vinyl chloride cylinder 
Standard Reference Materials (SRM's) prepared by the National Institute 
of Standards and Technology, if such SRM's are available. The agreement 
between the initially determined concentration value and the 
verification concentration value must be 5 percent. The 
manufacturer must reverify all calibration standards on a time interval 
consistent with the shelf life of the cylinder standards sold.
    7.2.4  Audit Cylinder Standards.
    7.2.4.1  Gas mixture standards with concentrations known only to 
the person supervising the analysis of samples. The concentrations of 
the audit cylinders should be: one low-concentration cylinder in the 
range of 5 to 20 ppmv vinyl chloride and one high-concentration 
cylinder in the range of 20 to 50 ppmv. When available, obtain audit 
samples from the appropriate EPA Regional Office or from the 
responsible enforcement authority.


    Note: The responsible enforcement agency should be notified at 
least 30 days prior to the test date to allow sufficient time for 
sample delivery.


    7.2.4.2  Alternatively, audit cylinders obtained from a commercial 
gas manufacturer may be used provided: (a) the gas meets the conditions 
described in Section 7.2.3, (b) the gas manufacturer certifies the 
audit cylinder as described in Section 7.2.3.1, and (c) the gas 
manufacturer obtains an independent analysis of the audit cylinders to 
verify this analysis. Independent analysis is defined here to mean 
analysis performed by an individual different than the individual who 
performs the gas manufacturer's analysis, while using calibration 
standards and analysis equipment different from those used for the gas 
manufacturer's analysis. Verification is complete and acceptable when 
the independent analysis concentration is within 5 percent of the gas 
manufacturer's concentration.

8.0  Sample Collection, Preservation, Storage, and Transport

    Note: Performance of this method should not be attempted by 
persons unfamiliar with the operation of a gas chromatograph (GC) 
nor by those who are unfamiliar with source sampling, because 
knowledge beyond the scope of this presentation is required.


    8.1  Bag Leak-Check. The following leak-check procedure is 
recommended, but not required, prior to sample collection. The post-
test leak-check procedure is mandatory. Connect a water manometer and 
pressurize the bag to 5 to 10 cm H2O (2 to 4 in. 
H2O). Allow to stand for 10 min. Any displacement in the 
water manometer indicates a leak. Also, check the rigid container for 
leaks in this manner.


    Note: An alternative leak-check method is to pressurize the bag 
to 5 to 10 cm H2O and allow it to stand overnight. A deflated bag 
indicates a leak. For each sample bag in its rigid container, place 
a rotameter in line between the bag and the pump inlet. Evacuate the 
bag. Failure of the rotameter to register zero flow when the bag 
appears to be empty indicates a leak.


    8.2  Sample Collection. Assemble the sample train as shown in 
Figure 106-1. Join the quick connects as illustrated, and determine 
that all connection between the bag and the probe are tight. Place the 
end of the probe at the centroid of the stack and start the pump with 
the needle valve adjusted to yield a flow that will fill over 50 
percent of bag volume in the specific sample period. After allowing 
sufficient time to purge the line several times, change the vacuum line 
from the container to the bag and evacuate the bag until the rotameter 
indicates no flow. Then reposition the sample and vacuum lines and 
begin the actual sampling, keeping the rate proportional to the stack 
velocity. At all times, direct the gas exiting the rotameter away from 
sampling personnel. At the end of the sample period, shut off the pump, 
disconnect the sample line from the bag, and disconnect the vacuum line 
from the bag container. Protect the bag container from sunlight.
    8.3  Sample Storage. Keep the sample bags out of direct sunlight. 
When at all possible, analysis is to be performed within 24 hours, but 
in no case in excess of 72 hours of sample collection. Aluminized Mylar 
bag samples must be analyzed within 24 hours.
    8.4  Post-test Bag Leak-Check. Subsequent to recovery and analysis 
of the sample, leak-check the sample bag according to the procedure 
outlined in Section 8.1.

9.0  Quality Control

    9.1  Miscellaneous Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
10.3..........................  Chromatograph      Ensure precision and
                                 calibration.       accuracy of
                                                    chromatograph.
11.1..........................  Audit sample       Evaluate analytical
                                 analysis.          technique and
                                                    standards
                                                    preparation.
------------------------------------------------------------------------

    9.2  Immediately after the preparation of the calibration curve and 
prior to the sample analyses, perform the analysis audit described in 
Appendix C, Procedure 2: ``Procedure for Field Auditing GC Analysis.''

10.0  Calibration and Standardization

    Note: Maintain a laboratory log of all calibrations.


    10.1  Preparation of Vinyl Chloride Standard Gas Mixtures. 
(Optional Procedure-delete if cylinder standards are used.) Evacuate a 
16-inch square Tedlar bag that has passed a leak-check (described in 
Section 8.1) and meter in 5.0 liters of nitrogen. While the bag is 
filling, use the 0.5-ml syringe to inject 250 l of 99.9+ 
percent vinyl chloride gas through the wall of the bag. Upon 
withdrawing the syringe, immediately cover the resulting hole with a 
piece of adhesive tape. The bag now contains a vinyl chloride 
concentration of 50 ppmv. In a like manner use the 50 l 
syringe to prepare gas mixtures having 10-and 5-ppmv vinyl chloride 
concentrations. Place each bag on a smooth surface and alternately 
depress opposite sides of the bag 50 times to further mix the gases. 
These gas mixture standards may be used for 10 days from the date of 
preparation, after which time new gas mixtures must be prepared. 
(Caution: Contamination may be a problem when a bag is reused if the 
new gas mixture standard is a lower concentration than the previous gas 
mixture standard.)
    10.2  Determination of Vinyl Chloride Retention Time. (This section 
can be performed simultaneously with Section 10.3.) Establish 
chromatograph conditions identical with those in Section 11.3. 
Determine proper attenuator position. Flush the sampling loop with 
helium or nitrogen and activate the sample valve. Record the injection 
time, sample loop temperature, column temperature, carrier gas flow

[[Page 62189]]

rate, chart speed, and attenuator setting. Record peaks and detector 
responses that occur in the absence of vinyl chloride. Maintain 
conditions with the equipment plumbing arranged identically to Section 
11.2, and flush the sample loop for 30 seconds at the rate of 100 ml/
min with one of the vinyl chloride calibration mixtures. Then activate 
the sample valve. Record the injection time. Select the peak that 
corresponds to vinyl chloride. Measure the distance on the chart from 
the injection time to the time at which the peak maximum occurs. This 
quantity divided by the chart speed is defined as the retention time. 
Since other organics may be present in the sample, positive 
identification of the vinyl chloride peak must be made.
    10.3  Preparation of Chromatograph Calibration Curve. Make a GC 
measurement of each gas mixture standard (described in Section 7.2.3 or 
10.1) using conditions identical to those listed in Sections 11.2 and 
11.3. Flush the sampling loop for 30 seconds at the rate of 100 ml/min 
with one of the standard mixtures, and activate the sample valve. 
Record the concentration of vinyl chloride injected (Cc), 
attenuator setting, chart speed, peak area, sample loop temperature, 
column temperature, carrier gas flow rate, and retention time. Record 
the barometric pressure. Calculate Ac, the peak area 
multiplied by the attenuator setting. Repeat until two consecutive 
injection areas are within 5 percent, then plot the average of those 
two values versus Cc. When the other standard gas mixtures 
have been similarly analyzed and plotted, draw a straight line through 
the points derived by the least squares method. Perform calibration 
daily, or before and after the analysis of each emission test set of 
bag samples, whichever is more frequent. For each group of sample 
analyses, use the average of the two calibration curves which bracket 
that group to determine the respective sample concentrations. If the 
two calibration curves differ by more than 5 percent from their mean 
value, then report the final results by both calibration curves.

11.0  Analytical Procedure

    11.1  Audit Sample Analysis. Immediately after the preparation of 
the calibration curve and prior to the sample analyses, perform the 
analysis audit described in Procedure 2 of appendix C to this part: 
``Procedure for Field Auditing GC Analysis.''
    11.2  Sample Recovery. With a new piece of Teflon tubing identified 
for that bag, connect a bag inlet valve to the gas chromatograph sample 
valve. Switch the valve to receive gas from the bag through the sample 
loop. Arrange the equipment so the sample gas passes from the sample 
valve to 100-ml/min rotameter with flow control valve followed by a 
charcoal tube and a 1-in. H2O pressure gauge. Maintain the 
sample flow either by a vacuum pump or container pressurization if the 
collection bag remains in the rigid container. After sample loop 
purging is ceased, allow the pressure gauge to return to zero before 
activating the gas sampling valve.
    11.3  Analysis.
    11.3.1  Set the column temperature to 100  deg.C (210  deg.F) and 
the detector temperature to 150  deg.C (300  deg.F). When optimum 
hydrogen and oxygen (or air) flow rates have been determined, verify 
and maintain these flow rates during all chromatography operations. 
Using helium or nitrogen as the carrier gas, establish a flow rate in 
the range consistent with the manufacturer's requirements for 
satisfactory detector operation. A flow rate of approximately 40 ml/min 
should produce adequate separations. Observe the base line periodically 
and determine that the noise level has stabilized and that base line 
drift has ceased. Purge the sample loop for 30 seconds at the rate of 
100 ml/min, shut off flow, allow the sample loop pressure to reach 
atmospheric pressure as indicated by the H2O manometer, then 
activate the sample valve. Record the injection time (the position of 
the pen on the chart at the time of sample injection), sample number, 
sample loop temperature, column temperature, carrier gas flow rate, 
chart speed, and attenuator setting. Record the barometric pressure. 
From the chart, note the peak having the retention time corresponding 
to vinyl chloride as determined in Section 10.2. Measure the vinyl 
chloride peak area, Am, by use of a disc integrator, 
electronic integrator, or a planimeter. Measure and record the peak 
heights, Hm. Record Am and retention time. Repeat 
the injection at least two times or until two consecutive values for 
the total area of the vinyl chloride peak agree within 5 percent of 
their average. Use the average value for these two total areas to 
compute the bag concentration.
    11.3.2  Compare the ratio of Hm to Am for the 
vinyl chloride sample with the same ratio for the standard peak that is 
closest in height. If these ratios differ by more than 10 percent, the 
vinyl chloride peak may not be pure (possibly acetaldehyde is present) 
and the secondary column should be employed (see Section 6.3.2.2).
    11.4  Determination of Bag Water Vapor Content. Measure the ambient 
temperature and barometric pressure near the bag. From a water 
saturation vapor pressure table, determine and record the water vapor 
content of the bag, Bwb, as a decimal figure. (Assume the 
relative humidity to be 100 percent unless a lesser value is known.)

12.0  Calculations and Data Analysis

    12.1  Nomenclature.

Am = Measured peak area.
Af = Attenuation factor.
Bwb = Water vapor content of the bag sample, as analyzed, 
volume fraction.
Cb = Concentration of vinyl chloride in the bag, ppmv.
Cc = Concentration of vinyl chloride in the standard sample, 
ppmv.
Pi = Laboratory pressure at time of analysis, mm Hg.
Pr = Reference pressure, the laboratory pressure recorded 
during calibration, mm Hg.
Ti = Absolute sample loop temperature at the time of 
analysis,  deg.K ( deg.R).
Tr = Reference temperature, the sample loop temperature 
recorded during calibration,  deg.K ( deg.R).

    12.2  Sample Peak Area. Determine the sample peak area, 
Ac, as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.510

    12.3  Vinyl Chloride Concentration. From the calibration curves 
prepared in Section 10.3, determine the average concentration value of 
vinyl chloride, Cc, that corresponds to Ac, the 
sample peak area. Calculate the concentration of vinyl chloride in the 
bag, Cb, as follows:

[[Page 62190]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.511

13.0  Method Performance

    13.1  Analytical Range. This method is designed for the 0.1 to 50 
parts per million by volume (ppmv) range. However, common gas 
chromatograph (GC) instruments are capable of detecting 0.02 ppmv vinyl 
chloride. With proper calibration, the upper limit may be extended as 
needed.

14.0  Pollution Prevention, [Reserved]

15.0  Waste Management, [Reserved]

16.0  References

    1. Brown D.W., E.W. Loy, and M.H. Stephenson. Vinyl Chloride 
Monitoring Near the B. F. Goodrich Chemical Company in Louisville, 
KY. Region IV, U.S. Environmental Protection Agency, Surveillance 
and Analysis Division, Athens, GA. June 24, 1974.
    2. G.D. Clayton and Associates. Evaluation of a Collection and 
Analytical Procedure for Vinyl Chloride in Air. U.S. Environmental 
Protection Agency, Research Triangle Park, N.C. EPA Contract No. 68-
02-1408, Task Order No. 2, EPA Report No. 75-VCL-1. December 13, 
1974.
    3. Midwest Research Institute. Standardization of Stationary 
Source Emission Method for Vinyl Chloride. U.S. Environmental 
Protection Agency, Research Triangle Park, N.C. Publication No. EPA-
600/4-77-026. May 1977.
    4. Scheil, G. and M.C. Sharp. Collaborative Testing of EPA 
Method 106 (Vinyl Chloride) that Will Provide for a Standardized 
Stationary Source Emission Measurement Method. U.S. Environmental 
Protection Agency, Research Triangle Park, N.C. Publication No. EPA 
600/4-78-058. October 1978.

17.0 Tables, Diagrams Flowcharts, and Validation Data.

BILLING CODE 6560-50-P

[[Page 62191]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.512

BILLING CODE 6560-50-C

[[Page 62192]]

Method 107--Determination of Vinyl Chloride Content of In-Process 
Wastewater Samples, and Vinyl Chloride Content of Polyvinyl 
Chloride Resin Slurry, Wet Cake, and Latex Samples

    Note: Performance of this method should not be attempted by 
persons unfamiliar with the operation of a gas chromatograph (GC) 
nor by those who are unfamiliar with source sampling, because 
knowledge beyond the scope of this presentation is required. This 
method does not include all of the specifications (e.g., equipment 
and supplies) and procedures (e.g., sampling and analytical) 
essential to its performance. Some material is incorporated by 
reference from other methods in this part. Therefore, to obtain 
reliable results, persons using this method should have a thorough 
knowledge of at least the following additional test methods: Method 
106.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.            Sensitivity
------------------------------------------------------------------------
Vinyl Chloride (CH2:CHCl)......         75-01-4   Dependent upon
                                                   analytical equipment.
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of the vinyl chloride monomer (VCM) content of in-process wastewater 
samples, and the residual vinyl chloride monomer (RCVM) content of 
polyvinyl chloride (PVC) resins, wet, cake, slurry, and latex samples. 
It cannot be used for polymer in fused forms, such as sheet or cubes. 
This method is not acceptable where methods from section 304(h) of the 
Clean Water Act, 33 U.S.C. 1251 et seq. (the Federal Water Pollution 
Control Amendments of 1972 as amended by the Clean Water Act of 1977) 
are required.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  The basis for this method relates to the vapor equilibrium 
that is established at a constant known temperature in a closed system 
between RVCM, PVC resin, water, and air. The RVCM in a PVC resin will 
equilibrate rapidly in a closed vessel, provided that the temperature 
of the PVC resin is maintained above the glass transition temperature 
of that specific resin.
    2.2  A sample of PVC or in-process wastewater is collected in a 
vial or bottle and is conditioned. The headspace in the vial or bottle 
is then analyzed for vinyl chloride using gas chromatography with a 
flame ionization detector.

3.0  Definitions [Reserved]

4.0  Interferences

    4.1  The chromatograph columns and the corresponding operating 
parameters herein described normally provide an adequate resolution of 
vinyl chloride; however, resolution interferences may be encountered on 
some sources. Therefore, the chromatograph operator shall select the 
column and operating parameters best suited to his particular analysis 
requirements, subject to the approval of the Administrator. Approval is 
automatic provided that confirming data are produced through an 
adequate supplemental analytical technique, such as analysis with a 
different column or GC/mass spectroscopy, and that these data are made 
available for review by the Administrator.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Toxic Analyte. Care must be exercised to prevent exposure of 
sampling personnel to vinyl chloride, which is a carcinogen. Do not 
release vinyl chloride to the laboratory atmosphere during preparation 
of standards. Venting or purging with VCM/air mixtures must be held to 
a minimum. When they are required, the vapor must be routed to outside 
air. Vinyl chloride, even at low ppm levels, must never be vented 
inside the laboratory. After vials have been analyzed, the gas must be 
vented prior to removal of the vial from the instrument turntable. 
Vials must be vented through a hypodermic needle connected to an 
activated charcoal tube to prevent release of vinyl chloride into the 
laboratory atmosphere. The charcoal must be replaced prior to vinyl 
chloride breakthrough.

6.0  Equipment and Supplies

    6.1  Sample Collection. The following equipment is required:
    6.1.1  Glass bottles. 60-ml (2-oz) capacity, with wax-lined screw-
on tops, for PVC samples.
    6.1.2  Glass Vials. Headspace vials, with Teflon-faced butyl rubber 
sealing discs, for water samples.
    6.1.3  Adhesive Tape. To prevent loosening of bottle tops.
    6.2  Sample Recovery. The following equipment is required:
    6.2.1  Glass Vials. Headspace vials, with butyl rubber septa and 
aluminum caps. Silicone rubber is not acceptable.
    6.2.2  Analytical Balance. Capable of determining sample weight 
within an accuracy of 1 percent.
    6.2.3  Vial Sealer. To seal headspace vials.
    6.2.4  Syringe. 100-ml capacity.
    6.3  Analysis. The following equipment is required:
    6.3.1  Headspace Sampler and Chromatograph. Capable of sampling and 
analyzing a constant amount of headspace gas from a sealed vial, while 
maintaining that vial at a temperature of 90  deg.C  0.5 
deg.C (194  deg.F  0.9  deg.F). The chromatograph shall be 
equipped with a flame ionization detector (FID). Perkin-Elmer 
Corporation Models F-40, F-42, F-45, HS-6, and HS-100, and Hewlett-
Packard Corporation Model 19395A have been found satisfactory. 
Chromatograph backflush capability may be required.
    6.3.2  Chromatographic Columns. Stainless steel 1 m by 3.2 mm and 2 
m by 3.2 mm, both containing 50/80-mesh Porapak Q. Other columns may be 
used provided that the precision and accuracy of the analysis of vinyl 
chloride standards are not impaired and information confirming that 
there is adequate resolution of the vinyl chloride peak are available 
for review. (Adequate resolution is defined as an area overlap of not 
more than 10 percent of the vinyl chloride peak by an interferant peak. 
Calculation of area overlap is explained in Procedure 1 of appendix C 
to this part: ``Determination of Adequate Chromatographic Peak 
Resolution.'') Two 1.83 m columns, each containing 1 percent Carbowax 
1500 on Carbopak B, have been found satisfactory for samples containing 
acetaldehyde.
    6.3.3  Temperature Sensor. Range 0 to 100  deg.C (32 to 212  deg.F) 
accurate to 0.1 deg.C.
    6.3.4  Integrator-Recorder. To record chromatograms.
    6.3.5  Barometer. Accurate to 1 mm Hg.

[[Page 62193]]

    6.3.6  Regulators. For required gas cylinders.
    6.3.7  Headspace Vial Pre-Pressurizer. Nitrogen pressurized 
hypodermic needle inside protective shield.

7.0  Reagents and Standards

    7.1  Analysis. Same as Method 106, Section 7.1, with the addition 
of the following:
    7.1.1  Water. Interference-free.
    7.2  Calibration. The following items are required for calibration:
    7.2.1  Cylinder Standards (4). Gas mixture standards (50-, 500-, 
2000- and 4000-ppm vinyl chloride in nitrogen cylinders). Cylinder 
standards may be used directly to prepare a chromatograph calibration 
curve as described in Section 10.3, if the following conditions are 
met: (a) The manufacturer certifies the gas composition with an 
accuracy of 3 percent or better (see Section 7.2.1.1). (b) 
The manufacturer recommends a maximum shelf life over which the gas 
concentration does not change by greater than 5 percent 
from the certified value. (c) The manufacturer affixes the date of gas 
cylinder preparation, certified vinyl chloride concentration, and 
recommended maximum shelf life to the cylinder before shipment to the 
buyer.
    7.2.1.1  Cylinder Standards Certification. The manufacturer shall 
certify the concentration of vinyl chloride in nitrogen in each 
cylinder by (a) directly analyzing each cylinder and (b) calibrating 
the analytical procedure on the day of cylinder analysis. To calibrate 
the analytical procedure, the manufacturer shall use, as a minimum, a 
3-point calibration curve. It is recommended that the manufacturer 
maintain (1) a high-concentration calibration standard (between 4000 
and 8000 ppm) to prepare the calibration curve by an appropriate 
dilution technique and (2) a low-concentration calibration standard 
(between 50 and 500 ppm) to verify the dilution technique used. If the 
difference between the apparent concentration read from the calibration 
curve and the true concentration assigned to the low-concentration 
calibration standard exceeds 5 percent of the true concentration, the 
manufacturer shall determine the source of error and correct it, then 
repeat the 3-point calibration.
    7.2.1.2  Verification of Manufacturer's Calibration Standards. 
Before using, the manufacturer shall verify each calibration standard 
by (a) comparing it to gas mixtures prepared (with 99 mole percent 
vinyl chloride) in accordance with the procedure described in Section 
10.1 of Method 106 or by (b) calibrating it against vinyl chloride 
cylinder Standard Reference Materials (SRMs) prepared by the National 
Institute of Standards and Technology, if such SRMs are available. The 
agreement between the initially determined concentration value and the 
verification concentration value must be within 5 percent. The 
manufacturer must reverify all calibration standards on a time interval 
consistent with the shelf life of the cylinder standards sold.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Sample Collection.
    8.1.1  PVC Sampling. Allow the resin or slurry to flow from a tap 
on the tank or silo until the tap line has been well purged. Extend and 
fill a 60-ml sample bottle under the tap, and immediately tighten a cap 
on the bottle. Wrap adhesive tape around the cap and bottle to prevent 
the cap from loosening. Place an identifying label on each bottle, and 
record the date, time, and sample location both on the bottles and in a 
log book.
    8.1.2  Water Sampling. At the sampling location fill the vials 
bubble-free to overflowing so that a convex meniscus forms at the top. 
The excess water is displaced as the sealing disc is carefully placed, 
with the Teflon side down, on the opening of the vial. Place the 
aluminum seal over the disc and the neck of the vial, and crimp into 
place. Affix an identifying label on the bottle, and record the date, 
time, and sample location both on the vials and in a log book.
    8.2  Sample Storage. All samples must be analyzed within 24 hours 
of collection, and must be refrigerated during this period.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
10.3..........................  Chromatograph      Ensure precision and
                                 calibration.       accuracy of
                                                    chromatograph.
------------------------------------------------------------------------

10.0  Calibration and Standardization

    Note: Maintain a laboratory log of all calibrations.

    10.1  Preparation of Standards. Calibration standards are prepared 
as follows: Place 100 l or about two equal drops of distilled 
water in the sample vial, then fill the vial with the VCM/nitrogen 
standard, rapidly seat the septum, and seal with the aluminum cap. Use 
a \1/8\-in. stainless steel line from the cylinder to the vial. Do not 
use rubber or Tygon tubing. The sample line from the cylinder must be 
purged (into a properly vented hood) for several minutes prior to 
filling the vials. After purging, reduce the flow rate to between 500 
and 1000 cc/min. Place end of tubing into vial (near bottom). Position 
a septum on top of the vial, pressing it against the \1/8\-in. filling 
tube to minimize the size of the vent opening. This is necessary to 
minimize mixing air with the standard in the vial. Each vial is to be 
purged with standard for 90 seconds, during which time the filling tube 
is gradually slid to the top of the vial. After the 90 seconds, the 
tube is removed with the septum, simultaneously sealing the vial. 
Practice will be necessary to develop good technique. Rubber gloves 
should be worn during the above operations. The sealed vial must then 
be pressurized for 60 seconds using the vial prepressurizer. Test the 
vial for leakage by placing a drop of water on the septum at the needle 
hole. Prepressurization of standards is not required unless samples 
have been prepressurized.
    10.2  Analyzer Calibration. Calibration is to be performed each 8-
hour period the chromatograph is used. Alternatively, calibration with 
duplicate 50-, 500-, 2,000-, and 4,000-ppm standards (hereafter 
described as a four-point calibration) may be performed on a monthly 
basis, provided that a calibration confirmation test consisting of 
duplicate analyses of an appropriate standard is performed once per 
plant shift, or once per chromatograph carrousel operation (if the 
chromatograph operation is less frequent than once per shift). The 
criterion for acceptance of each calibration confirmation test is that 
both analyses of 500-ppm standards [2,000-ppm standards if dispersion 
resin (excluding latex resin) samples are being analyzed] must be 
within 5 percent of the most recent four-point calibration curve. If 
this criterion is not met, then a complete four-point calibration must 
be performed before sample analyses can proceed.

[[Page 62194]]

    10.3  Preparation of Chromatograph Calibration Curve. Prepare two 
vials each of 50-, 500-, 2,000-, and 4,000-ppm standards. Run the 
calibration samples in exactly the same manner as regular samples. Plot 
As, the integrator area counts for each standard sample, 
versus Cc, the concentration of vinyl chloride in each 
standard sample. Draw a straight line through the points derived by the 
least squares method.

11.0  Analytical Procedure

    11.1  Preparation of Equipment. Install the chromatographic column 
and condition overnight at 160  deg.C (320  deg.F). In the first 
operation, Porapak columns must be purged for 1 hour at 230  deg.C (450 
 deg.F).
    Do not connect the exit end of the column to the detector while 
conditioning. Hydrogen and air to the detector must be turned off while 
the column is disconnected.
    11.2  Flow Rate Adjustments. Adjust flow rates as follows:
    11.2.1.  Nitrogen Carrier Gas. Set regulator on cylinder to read 50 
psig. Set regulator on chromatograph to produce a flow rate of 30.0 cc/
min. Accurately measure the flow rate at the exit end of the column 
using the soap film flowmeter and a stopwatch, with the oven and column 
at the analysis temperature. After the instrument program advances to 
the ``B'' (backflush) mode, adjust the nitrogen pressure regulator to 
exactly balance the nitrogen flow rate at the detector as was obtained 
in the ``A'' mode.
    11.2.2.  Vial Prepressurizer Nitrogen.
    11.2.2.1  After the nitrogen carrier is set, solve the following 
equation and adjust the pressure on the vial prepressurizer 
accordingly.
[GRAPHIC] [TIFF OMITTED] TR17OC00.599

Where:

T1 = Ambient temperature,  deg.K ( deg.R).
T2 = Conditioning bath temperature,  deg.K ( deg.R).
P1 = Gas chromatograph absolute dosing pressure (analysis 
mode), k Pa.
Pw1 = Water vapor pressure 525.8 mm Hg @ 90  deg.C.
Pw2 = Water vapor pressure 19.8 mm Hg @ 22  deg.C.
7.50 = mm Hg per k Pa.
10 kPa = Factor to adjust the prepressurized pressure to slightly less 
than the dosing pressure.

    11.2.2.2  Because of gauge errors, the apparatus may over-
pressurize the vial. If the vial pressure is at or higher than the 
dosing pressure, an audible double injection will occur. If the vial 
pressure is too low, errors will occur on resin samples because of 
inadequate time for head-space gas equilibrium. This condition can be 
avoided by running several standard gas samples at various pressures 
around the calculated pressure, and then selecting the highest pressure 
that does not produce a double injection. All samples and standards 
must be pressurized for 60 seconds using the vial prepressurizer. The 
vial is then placed into the 90  deg.C conditioning bath and tested for 
leakage by placing a drop of water on the septum at the needle hole. A 
clean, burr-free needle is mandatory.
    11.2.3.  Burner Air Supply. Set regulator on cylinder to read 50 
psig. Set regulator on chromatograph to supply air to burner at a rate 
between 250 and 300 cc/min. Check with bubble flowmeter.
    11.2.4.  Hydrogen Supply. Set regulator on cylinder to read 30 
psig. Set regulator on chromatograph to supply approximately 35 
 5 cc/min. Optimize hydrogen flow to yield the most 
sensitive detector response without extinguishing the flame. Check flow 
with bubble meter and record this flow.
    11.3  Temperature Adjustments. Set temperatures as follows:
    11.3.1.  Oven (chromatograph column), 140  deg.C (280  deg.F).
    11.3.2.  Dosing Line, 150  deg.C (300  deg.F).
    11.3.3.  Injection Block, 170  deg.C (340  deg.F).
    11.3.4.  Sample Chamber, Water Temperature, 90  deg.C  
1.0  deg.C (194  deg.F  1.8  deg.F).
    11.4  Ignition of Flame Ionization Detector. Ignite the detector 
according to the manufacturer's instructions.
    11.5  Amplifier Balance. Balance the amplifier according to the 
manufacturer's instructions.
    11.6  Programming the Chromatograph. Program the chromatograph as 
follows:
    11.6.1.  I -- Dosing or Injection Time. The normal setting is 2 
seconds.
    11.6.2.  A -- Analysis Time. The normal setting is approximately 70 
percent of the VCM retention time. When this timer terminates, the 
programmer initiates backflushing of the first column.
    11.6.3.  B -- Backflushing Time. The normal setting is double the 
analysis time.
    11.6.4.  W -- Stabilization Time. The normal setting is 0.5 min to 
1.0 min.
    11.6.5.  X -- Number of Analyses Per Sample. The normal setting is 
one.
    11.7.  Sample Treatment. All samples must be recovered and analyzed 
within 24 hours after collection.
    11.7.1  Resin Samples. The weight of the resin used must be between 
0.1 and 4.5 grams. An exact weight must be obtained (within 
1 percent) for each sample. In the case of suspension 
resins, a volumetric cup can be prepared for holding the required 
amount of sample. When the cup is used, open the sample bottle, and add 
the cup volume of resin to the tared sample vial (tared, including 
septum and aluminum cap). Obtain the exact sample weight, add 100 ml or 
about two equal drops of water, and immediately seal the vial. Report 
this value on the data sheet; it is required for calculation of RVCM. 
In the case of dispersion resins, the cup cannot be used. Weigh the 
sample in an aluminum dish, transfer the sample to the tared vial, and 
accurately weigh it in the vial. After prepressurization of the 
samples, condition them for a minimum of 1 hour in the 90  deg.C (190 
deg.F) bath. Do not exceed 5 hours. Prepressurization is not required 
if the sample weight, as analyzed, does not exceed 0.2 gram. It is also 
not required if solution of the prepressurization equation yields an 
absolute prepressurization value that is within 30 percent of the 
atmospheric pressure.


    Note: Some aluminum vial caps have a center section that must be 
removed prior to placing into sample tray. If the cap is not 
removed, the injection needle will be damaged.


    11.7.2  Suspension Resin Slurry and Wet Cake Samples. Decant the 
water from a wet cake sample, and turn the sample bottle upside down 
onto a paper towel. Wait for the water to drain, place approximately 
0.2 to 4.0 grams of the wet cake sample in a tared vial (tared, 
including septum and aluminum cap) and seal immediately. Then determine 
the sample weight (1 percent). All samples weighing over 0.2 gram, must 
be prepressurized prior to conditioning for 1 hour at 90  deg.C (190 
deg.F), except as noted in Section 11.7.1. A sample of wet cake is used 
to determine total solids (TS). This is required for calculating the 
RVCM.
    11.7.3  Dispersion Resin Slurry and Geon Latex Samples. The 
materials

[[Page 62195]]

should not be filtered. Sample must be thoroughly mixed. Using a tared 
vial (tared, including septum and aluminum cap) add approximately eight 
drops (0.25 to 0.35 g) of slurry or latex using a medicine dropper. 
This should be done immediately after mixing. Seal the vial as soon as 
possible. Determine sample weight (1 percent). Condition the vial for 1 
hour at 90  deg.C (190  deg.F) in the analyzer bath. Determine the TS 
on the slurry sample (Section 11.10).
    11.7.4  In-process Wastewater Samples. Using a tared vial (tared, 
including septum and aluminum cap) quickly add approximately 1 cc of 
water using a medicine dropper. Seal the vial as soon as possible. 
Determine sample weight (1 percent). Condition the vial for 1 hour at 
90  deg.C (190  deg.F) in the analyzer bath.
    11.8  Preparation of Sample Turntable.
    11.8.1  Before placing any sample into turntable, be certain that 
the center section of the aluminum cap has been removed. The numbered 
sample vials should be placed in the corresponding numbered positions 
in the turntable. Insert samples in the following order:
    11.8.1.1  Positions 1 and 2. Old 2000-ppm standards for 
conditioning. These are necessary only after the analyzer has not been 
used for 24 hours or longer.
    11.8.1.2  Position 3. 50-ppm standard, freshly prepared.
    11.8.1.3  Position 4. 500-ppm standard, freshly prepared.
    11.8.1.4  Position 5. 2000-ppm standard, freshly prepared.
    11.8.1.5  Position 6. 4000-ppm standard, freshly prepared.
    11.8.1.6  Position 7. Sample No. 7 (This is the first sample of the 
day, but is given as 7 to be consistent with the turntable and the 
integrator printout.)
    11.8.2  After all samples have been positioned, insert the second 
set of 
50-, 500-, 2000-, and 4000-ppm standards. Samples, including standards, 
must be conditioned in the bath of 90  deg.C (190  deg.F) for a minimum 
of one hour and a maximum of five hours.
    11.9  Start Chromatograph Program. When all samples, including 
standards, have been conditioned at 90  deg.C (190  deg.F) for at least 
one hour, start the analysis program according to the manufacturer's 
instructions. These instructions must be carefully followed when 
starting and stopping a program to prevent damage to the dosing 
assembly.
    11.10  Determination of Total Solids. For wet cake, slurry, resin 
solution, and PVC latex samples, determine TS for each sample by 
accurately weighing approximately 3 to 4 grams of sample in an aluminum 
pan before and after placing in a draft oven (105 to 110  deg.C (221 to 
230  deg.F)). Samples must be dried to constant weight. After first 
weighing, return the pan to the oven for a short period of time, and 
then reweigh to verify complete dryness. The TS are then calculated as 
the final sample weight divided by initial sample weight.

12.0  Calculations and Data Analysis

    12.1  Nomenclature.

As = Chromatogram area counts of vinyl chloride for the 
sample, area counts.
As = Chromatogram area counts of vinyl chloride for the 
sample.
Cc = Concentration of vinyl chloride in the standard sample, 
ppm.
Kp = Henry's Law Constant for VCM in PVC 90  deg.C, 6.52  x  
10-\6\ g/g/mm Hg.
Kw = Henry's Law Constant for VCM in water 90  deg.C, 7  x  
10-\7\ g/g/mm Hg.
Mv = Molecular weight of VCM, 62.5 g/mole.
m = Sample weight, g.
Pa = Ambient atmospheric pressure, mm Hg.
R = Gas constant, (62360 \3\ ml) (mm Hg)/(mole)( deg.K).
Rf = Response factor in area counts per ppm VCM.
Rs = Response factor, area counts/ppm.
Tl = Ambient laboratory temperature,  deg.K.
TS = Total solids expressed as a decimal fraction.
T2 = Equilibrium temperature,  deg.K.
Vg = Volume of vapor phase, ml.
[GRAPHIC] [TIFF OMITTED] TR17OC00.513

Vv = Vial volume,\3\ ml.
1.36 = Density of PVC at 90  deg.C, g/\3\ ml.
0.9653 = Density of water at 90  deg.C, 
g/\3\ ml.

    12.2  Response Factor. If the calibration curve described in 
Section 10.3 passes through zero, an average response factor, 
Rf, may be used to facilitate computation of vinyl chloride 
sample concentrations.
    12.2.1  To compute Rf, first compute a response factor, 
Rs, for each sample as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.514

    12.2.2  Sum the individual response factors, and calculate 
Rf. If the calibration curve does not pass through zero, use 
the calibration curve to determine each sample concentration.
    12.3  Residual Vinyl Chloride Monomer Concentration, 
(Crvc) or Vinyl Chloride Monomer Concentration. Calculate 
Crvc in ppm or mg/kg as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.515


    Note: Results calculated using these equations represent 
concentration based on the total sample. To obtain results based on 
dry PVC content, divide by TS.

13.0  Method Performance

    13.1  Range and Sensitivity. The lower limit of detection of vinyl 
chloride will vary according to the sampling and chromatographic 
system. The system should be capable of producing a measurement for a 
50-ppm vinyl chloride standard that is at least

[[Page 62196]]

10 times the standard deviation of the system background noise level.
    13.2  An interlaboratory comparison between seven laboratories of 
three resin samples, each split into three parts, yielded a standard 
deviation of 2.63 percent for a sample with a mean of 2.09 ppm, 4.16 
percent for a sample with a mean of 1.66 ppm, and 5.29 percent for a 
sample with a mean of 62.66 ppm.

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

    1. B.F. Goodrich, Residual Vinyl Chloride Monomer Content of 
Polyvinyl Chloride Resins, Latex, Wet Cake, Slurry and Water 
Samples. B.F. Goodrich Chemical Group Standard Test Procedure No. 
1005-E. B.F. Goodrich Technical Center, Avon Lake, Ohio. October 8, 
1979.
    2. Berens, A.R. The Diffusion of Vinyl Chloride in Polyvinyl 
Chloride. ACS-Division of Polymer Chemistry, Polymer Preprints 15 
(2):197. 1974.
    3. Berens, A.R. The Diffusion of Vinyl Chloride in Polyvinyl 
Chloride. ACS-Division of Polymer Chemistry, Polymer Preprints 15 
(2):203. 1974.
    4. Berens, A.R., et. al. Analysis for Vinyl Chloride in PVC 
Powders by Head-Space Gas Chromatography. Journal of Applied Polymer 
Science. 19:3169-3172. 1975.
    5. Mansfield, R.A. The Evaluation of Henry's Law Constant (Kp) 
and Water Enhancement in the Perkin-Elmer Multifract F-40 Gas 
Chromatograph. B.F. Goodrich. Avon Lake, Ohio. February 10, 1978.

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

Method 108--Determination of Particulate and Gaseous Arsenic 
Emissions

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in Appendix A to 40 CFR 
Part 60. Therefore, to obtain reliable results, persons using this 
method should have a thorough knowledge of at least the following 
additional test methods: Method 1, Method 2, Method 3, Method 5, and 
Method 12.

1.0  Scope and Application.

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.            Sensitivity
------------------------------------------------------------------------
Arsenic compounds as arsenic          7440-38-2   Lower limit 10 g/ml or less.
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of inorganic As emissions from stationary sources as specified in an 
applicable subpart of the regulations.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    Particulate and gaseous As emissions are withdrawn isokinetically 
from the source and are collected on a glass mat filter and in water. 
The collected arsenic is then analyzed by means of atomic absorption 
spectrophotometry (AAS).

3.0  Definitions. [Reserved]

4.0  Interferences

    Analysis for As by flame AAS is sensitive to the chemical 
composition and to the physical properties (e.g., viscosity, pH) of the 
sample. The analytical procedure includes a check for matrix effects 
(Section 11.5).

5.0  Safety

    5.1  This method may involve hazardous materials, operations, and 
equipment. This test method may not address all of the safety problems 
associated with its use. It is the responsibility of the user to 
establish appropriate safety and health practices and determine the 
applicability of regulatory limitations prior to performing this test 
method.
    5.2  Corrosive reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures that prevent chemical 
splashes are recommended. If contact occurs, immediately flush with 
copious amounts of water for at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burns as thermal 
burns.
    5.2.1  Hydrochloric Acid (HCl). Highly corrosive liquid with toxic 
vapors. Vapors are highly irritating to eyes, skin, nose, and lungs, 
causing severe damage. May cause bronchitis, pneumonia, or edema of 
lungs. Exposure to concentrations of 0.13 to 0.2 percent can be lethal 
to humans in a few minutes. Provide ventilation to limit exposure. 
Reacts with metals, producing hydrogen gas.
    5.2.2  Hydrogen Peroxide (H2O2). Very harmful 
to eyes. 30% H2O2 can burn skin, nose, and lungs.
    5.2.3  Nitric Acid (HNO3). Highly corrosive to eyes, 
skin, nose, and lungs. Vapors are highly toxic and can cause 
bronchitis, pneumonia, or edema of lungs. Reaction to inhalation may be 
delayed as long as 30 hours and still be fatal. Provide ventilation to 
limit exposure. Strong oxidizer. Hazardous reaction may occur with 
organic materials such as solvents.
    5.2.4  Sodium Hydroxide (NaOH). Causes severe damage to eyes and 
skin. Inhalation causes irritation to nose, throat, and lungs. Reacts 
exothermically with small amounts of water.

6.0  Equipment and Supplies

    6.1  Sample Collection. A schematic of the sampling train used in 
performing this method is shown in Figure 108-1; it is similar to the 
Method 5 sampling train of 40 CFR Part 60, Appendix A. The following 
items are required for sample collection:
    6.1.1  Probe Nozzle, Probe Liner, Pitot Tube, Differential Pressure 
Gauge, Filter Holder, Filter Heating System, Temperature Sensor, 
Metering System, Barometer, and Gas Density Determination Equipment. 
Same as Method 5, Sections 6.1.1.1 to 6.1.1.7, 6.1.1.9, 6.1.2, and 
6.1.3, respectively.
    6.1.2  Impingers. Four impingers connected in series with leak-free 
ground-glass fittings or any similar leak-free noncontaminating 
fittings. For the first, third, and fourth impingers, use the 
Greenburg-Smith design, modified by replacing the tip with a 1.3-cm ID 
(0.5-in.) glass tube extending to about 1.3 cm (0.5 in.) from the 
bottom of the flask. For the second impinger, use the Greenburg-Smith 
design with the standard tip. Modifications (e.g., flexible connections 
between the impingers, materials other than glass, or flexible vacuum 
lines to connect the filter holder to the condenser) are subject to the 
approval of the Administrator.
    6.1.3  Temperature Sensor. Place a temperature sensor, capable of 
measuring temperature to within 1  deg.C (2  deg.F), at the outlet of 
the fourth impinger for monitoring purposes.
    6.2  Sample Recovery. The following items are required for sample 
recovery:
    6.2.1  Probe-Liner and Probe-Nozzle Brushes, Petri Dishes, 
Graduated Cylinder and/or Balance, Plastic Storage Containers, and 
Funnel and Rubber Policeman. Same as Method 5, Sections 6.2.1 and 6.2.4 
to 6.2.8, respectively.
    6.2.2  Wash Bottles. Polyethylene (2).
    6.2.3  Sample Storage Containers. Chemically resistant, 
polyethylene or

[[Page 62197]]

polypropylene for glassware washes, 500- or 1000-ml.
    6.3  Analysis. The following items are required for analysis:
    6.3.1  Spectrophotometer. Equipped with an electrodeless discharge 
lamp and a background corrector to measure absorbance at 193.7 
nanometers (nm). For measuring samples having less than 10 g 
As/ml, use a vapor generator accessory or a graphite furnace.
    6.3.2  Recorder. To match the output of the spectrophotometer.
    6.3.3  Beakers. 150 ml.
    6.3.4  Volumetric Flasks. Glass 50-, 100-, 200-, 500-, and 1000-ml; 
and polypropylene, 50-ml.
    6.3.5  Balance. To measure within 0.5 g.
    6.3.6  Volumetric Pipets. 1-, 2-, 3-, 
5-, 8-, and 10-ml.
    6.3.7  Oven.
    6.3.8  Hot Plate.

7.0  Reagents and Standards

    Unless otherwise indicated, it is intended that all reagents 
conform to the specifications established by the Committee on 
Analytical Reagents of the American Chemical Society, where such 
specifications are available; otherwise, use the best available grade.
    7.1  The following reagents are required for sample collection:
    7.1.1  Filters. Same as Method 5, Section 7.1.1, except that the 
filters need not be unreactive to SO2.
    7.1.2  Silica Gel, Crushed Ice, and Stopcock Grease. Same as Method 
5, Sections 7.1.2, 7.1.4, and 7.1.5, respectively.
    7.1.3  Water. Deionized distilled to meet ASTM D 1193-77 or 91 
(incorporated by reference-see Sec. 61.18), Type 3. When high 
concentrations of organic matter are not expected to be present, the 
KMnO4 test for oxidizable organic matter may be omitted.
    7.2  Sample Recovery.
    7.2.1  0.1 N NaOH. Dissolve 4.00 g of NaOH in about 500 ml of water 
in a 1-liter volumetric flask. Then, dilute to exactly 1.0 liter with 
water.
    7.3  Analysis. The following reagents and standards are required 
for analysis:
    7.3.1  Water. Same as Section 7.1.3.
    7.3.2  Sodium Hydroxide, 0.1 N. Same as in Section 7.2.1.
    7.3.3  Sodium Borohydride (NaBH4), 5 Percent Weight by 
Volume (W/V). Dissolve 50.0 g of NaBH4 in about 500 ml of 
0.1 N NaOH in a 1-liter volumetric flask. Then, dilute to exactly 1.0 
liter with 0.1 N NaOH.
    7.3.4  Hydrochloric Acid, Concentrated.
    7.3.5  Potassium Iodide (KI), 30 Percent (W/V). Dissolve 300 g of 
KI in 500 ml of water in a 1 liter volumetric flask. Then, dilute to 
exactly 1.0 liter with water.
    7.3.6  Nitric Acid, Concentrated.
    7.3.7  Nitric Acid, 0.8 N. Dilute 52 ml of concentrated 
HNO3 to exactly 1.0 liter with water.
    7.3.8  Nitric Acid, 50 Percent by Volume (V/V). Add 50 ml 
concentrated HNO3 to 50 ml water.
    7.3.9  Stock Arsenic Standard, 1 mg As/ml. Dissolve 1.3203 g of 
primary standard grade As2O3 in 20 ml of 0.1 N 
NaOH in a 150 ml beaker. Slowly add 30 ml of concentrated 
HNO3. Heat the resulting solution and evaporate just to 
dryness. Transfer the residue quantitatively to a 1-liter volumetric 
flask, and dilute to 1.0 liter with water.
    7.3.10  Arsenic Working Solution, 1.0 g As/ml. Pipet 
exactly 1.0 ml of stock arsenic standard into an acid-cleaned, 
appropriately labeled 1-liter volumetric flask containing about 500 ml 
of water and 5 ml of concentrated HNO3. Dilute to exactly 
1.0 liter with water.
    7.3.11  Air. Suitable quality for AAS analysis.
    7.3.12  Acetylene. Suitable quality for AAS analysis.
    7.3.13  Nickel Nitrate, 5 Percent Ni (W/V). Dissolve 24.780 g of 
nickel nitrate hexahydrate 
[Ni(NO3)26H2O] in water in a 100-ml 
volumetric flask, and dilute to 100 ml with water.
    7.3.14  Nickel Nitrate, 1 Percent Ni (W/V). Pipet 20 ml of 5 
percent nickel nitrate solution into a 100-ml volumetric flask, and 
dilute to exactly 100 ml with water.
    7.3.15  Hydrogen Peroxide, 3 Percent by Volume. Pipet 50 ml of 30 
percent H2O2 into a 500-ml volumetric flask, and 
dilute to exactly 500 ml with water.
    7.3.16  Quality Assurance Audit Samples. When making compliance 
determinations, and upon availability, audit samples may be obtained 
from the appropriate EPA regional Office or from the responsible 
enforcement authority.


    Note: The responsible enforcement authority should be notified 
at least 30 days prior to the test date to allow sufficient time for 
sample delivery.

8.0  Sample Collection, Preservation, Transport, and Storage

    8.1  Pretest Preparation. Follow the general procedure given in 
Method 5, Section 8.1, except the filter need not be weighed, and the 
200 ml of 0.1N NaOH and Container 4 should be tared to within 0.5 g.
    8.2  Preliminary Determinations. Follow the general procedure given 
in Method 5, Section 8.2, except select the nozzle size to maintain 
isokinetic sampling rates below 28 liters/min (1.0 cfm).
    8.3  Preparation of Sampling Train. Follow the general procedure 
given in Method 5, Section 8.3.
    8.4  Leak-Check Procedures. Same as Method 5, Section 8.4.
    8.5  Sampling Train Operation. Follow the general procedure given 
in Method 5, Section 8.5, except maintain isokinetic sampling flow 
rates below 28 liters/min (1.0 cfm). For each run, record the data 
required on a data sheet similar to the one shown in Figure 108-2.
    8.6  Calculation of Percent Isokinetic. Same as Method 5, Section 
8.6.
    8.7  Sample Recovery. Same as Method 5, Section 8.7, except that 
0.1 N NaOH is used as the cleanup solvent instead of acetone and that 
the impinger water is treated as follows:
    8.7.1  Container Number 4 (Impinger Water). Clean each of the first 
three impingers and connecting glassware in the following manner:
    8.7.1.1  Wipe the impinger ball joints free of silicone grease, and 
cap the joints.
    8.7.1.2  Rotate and agitate each of the first two impingers, using 
the impinger contents as a rinse solution.
    8.7.1.3  Transfer the liquid from the first three impingers to 
Container Number 4. Remove the outlet ball-joint cap, and drain the 
contents through this opening. Do not separate the impinger parts 
(inner and outer tubes) while transferring their contents to the 
container.
    8.7.1.4  Weigh the contents of Container No. 4 to within 0.5 g. 
Record in the log the weight of liquid along with a notation of any 
color or film observed in the impinger catch. The weight of liquid is 
needed along with the silica gel data to calculate the stack gas 
moisture content.

    Note: Measure and record the total amount of 0.1 N NaOH used for 
rinsing under Sections 8.7.1.5 and 8.7.1.6.

    8.7.1.5  Pour approximately 30 ml of 0.1 NaOH into each of the 
first two impingers, and agitate the impingers. Drain the 0.1 N NaOH 
through the outlet arm of each impinger into Container Number 4. Repeat 
this operation a second time; inspect the impingers for any abnormal 
conditions.
    8.7.1.6  Wipe the ball joints of the glassware connecting the 
impingers and the back half of the filter holder free of silicone 
grease, and rinse each piece of glassware twice with 0.1 N NaOH; 
transfer this rinse into Container Number 4. (DO NOT RINSE or brush the 
glass-fritted filter support.) Mark the height of the fluid level to 
determine whether leakage occurs during transport. Label the container 
to identify clearly its contents.

[[Page 62198]]

    8.8  Blanks.
    8.8.1  Sodium Hydroxide. Save a portion of the 0.1 N NaOH used for 
cleanup as a blank. Take 200 ml of this solution directly from the wash 
bottle being used and place it in a plastic sample container labeled 
``NaOH blank.''
    8.8.2  Water. Save a sample of the water, and place it in a 
container labeled ``H2O blank.''
    8.8.3  Filter. Save two filters from each lot of filters used in 
sampling. Place these filters in a container labeled ``filter blank.''

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.4, 10.1.....................  Sampling           Ensures accuracy and
                                 equipment leak-    precision of
                                 checks and         sampling
                                 calibration.       measurements.
10.4..........................  Spectrophotometer  Ensures linearity of
                                 calibration.       spectrophotometer
                                                    response to
                                                    standards.
11.5..........................  Check for matrix   Eliminates matrix
                                 effects.           effects.
11.6..........................  Audit sample       Evaluates analyst's
                                 analysis.          technique and
                                                    standards
                                                    preparation.
------------------------------------------------------------------------

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

10.0  Calibration and Standardization

    Note: Maintain a laboratory log of all calibrations.

    10.1  Sampling Equipment. Same as Method 5, Section 10.0.
    10.2  Preparation of Standard Solutions.
    10.2.1  For the high level procedure, pipet 1, 3, 5, 8, and 10 ml 
of the 1.0 mg As/ml stock solution into separate 100 ml volumetric 
flasks, each containing 5 ml of concentrated HNO3. Dilute to 
the mark with water.
    10.2.2  For the low level vapor generator procedure, pipet 1, 2, 3, 
and 5 ml of 1.0 g As/ml standard solution into separate 
reaction tubes. Dilute to the mark with water.
    10.2.3  For the low level graphite furnace procedure, pipet 1, 5, 
10 and 15 ml of 1.0 g As/ml standard solution into separate 
flasks along with 2 ml of the 5 percent nickel nitrate solution and 10 
ml of the 3 percent H2O2 solution. Dilute to the 
mark with water.
    10.3  Calibration Curve. Analyze a 0.8 N HNO3 blank and 
each standard solution according to the procedures outlined in section 
11.4.1. Repeat this procedure on each standard solution until two 
consecutive peaks agree within 3 percent of their average value. 
Subtract the average peak height (or peak area) of the blank--which 
must be less than 2 percent of recorder full scale--from the averaged 
peak height of each standard solution. If the blank absorbance is 
greater than 2 percent of full-scale, the probable cause is As 
contamination of a reagent or carry-over of As from a previous sample. 
Prepare the calibration curve by plotting the corrected peak height of 
each standard solution versus the corresponding final total As weight 
in the solution.
    10.4  Spectrophotometer Calibration Quality Control. Calculate the 
least squares slope of the calibration curve. The line must pass 
through the origin or through a point no further from the origin than 
2 percent of the recorder full scale. Multiply the 
corrected peak height by the reciprocal of the least squares slope to 
determine the distance each calibration point lies from the theoretical 
calibration line. The difference between the calculated concentration 
values and the actual concentrations (e.g., 1, 3, 5, 8, and 10 mg As 
for the high-level procedure) must be less than 7 percent for all 
standards.

    Note: For instruments equipped with direct concentration readout 
devices, preparation of a standard curve will not be necessary. In 
all cases, follow calibration and operational procedures in the 
manufacturers' instruction manual.

11.0  Analytical Procedure

    11.1  Sample Loss Check. Prior to analysis, check the liquid level 
in Containers Number 2 and Number 4. Note on the analytical data sheet 
whether leakage occurred during transport. If a noticeable amount of 
leakage occurred, either void the sample or take steps, subject to the 
approval of the Administrator, to adjust the final results.
    11.2  Sample Preparation.
    11.2.1  Container Number 1 (Filter). Place the filter and loose 
particulate matter in a 150 ml beaker. Also, add the filtered solid 
material from Container Number 2 (see Section 11.2.2). Add 50 ml of 0.1 
N NaOH. Then stir and warm on a hot plate at low heat (do not boil) for 
about 15 minutes. Add 10 ml of concentrated HNO3, bring to a 
boil, then simmer for about 15 minutes. Filter the solution through a 
glass fiber filter. Wash with hot water, and catch the filtrate in a 
clean 150 ml beaker. Boil the filtrate, and evaporate to dryness. Cool, 
add 5 ml of 50 percent HNO3, and then warm and stir. Allow 
to cool. Transfer to a 50-ml volumetric flask, dilute to volume with 
water, and mix well.
    11.2.2  Container Number 2 (Probe Wash).
    11.2.2.1  Filter (using a glass fiber filter) the contents of 
Container Number 2 into a 200 ml volumetric flask. Combine the filtered 
(solid) material with the contents of Container Number 1 (Filter).
    11.2.2.2  Dilute the filtrate to exactly 200 ml with water. Then 
pipet 50 ml into a 150 ml beaker. Add 10 ml of concentrated 
HNO3, bring to a boil, and evaporate to dryness. Allow to 
cool, add 5 ml of 50 percent HNO3, and then warm and stir. 
Allow the solution to cool, transfer to a 50-ml volumetric flask, 
dilute to volume with water, and mix well.
    11.2.3  Container Number 4 (Impinger Solution). Transfer the 
contents of Container Number 4 to a 500 ml volumetric flask, and dilute 
to exactly 500-ml with water. Pipet 50 ml of the solution into a 150-ml 
beaker. Add 10 ml of concentrated HNO3, bring to a boil, and 
evaporate to dryness. Allow to cool, add 5 ml of 50 percent 
HNO3, and then warm and stir. Allow the solution to cool, 
transfer to a 50-ml volumetric flask, dilute to volume with water, and 
mix well.
    11.2.4  Filter Blank. Cut each filter into strips, and treat each 
filter individually as directed in Section 11.2.1, beginning with the 
sentence, ``Add 50 ml of 0.1 N NaOH.''
    11.2.5  Sodium Hydroxide and Water Blanks. Treat separately 50 ml 
of 0.1 N NaOH and 50 ml water, as directed under Section 11.2.3, 
beginning with the sentence, ``Pipet 50 ml of the solution into a 150-
ml beaker.''
    11.3  Spectrophotometer Preparation. Turn on the power; set the 
wavelength, slit width, and lamp current. Adjust the background 
corrector as instructed by the manufacturer's manual for the particular 
atomic absorption spectrophotometer. Adjust the burner and flame 
characteristics as necessary.
    11.4  Analysis. Calibrate the analytical equipment and develop a 
calibration curve as outlined in Sections 10.2 through 10.4.
    11.4.1  Arsenic Samples. Analyze an appropriately sized aliquot of 
each diluted sample (from Sections 11.2.1

[[Page 62199]]

through 11.2.3) until two consecutive peak heights agree within 3 
percent of their average value. If applicable, follow the procedures 
outlined in Section 11.4.1.1. If the sample concentration falls outside 
the range of the calibration curve, make an appropriate dilution with 
0.8 N HNO3 so that the final concentration falls within the 
range of the curve. Using the calibration curve, determine the arsenic 
concentration in each sample fraction.


    Note: Because instruments vary between manufacturers, no 
detailed operating instructions will be given here. Instead, the 
instrument manufacturer's detailed operating instructions should be 
followed.


    11.4.1.1  Arsenic Determination at Low Concentration. The lower 
limit of flame AAS is 10 g As/ml. If the arsenic concentration 
of any sample is at a lower level, use the graphite furnace or vapor 
generator which is available as an accessory component. Flame, graphite 
furnace, or vapor generators may be used for samples whose 
concentrations are between 10 and 30 g/ml. Follow the 
manufacturer's instructions in the use of such equipment.
    11.4.1.1.1  Vapor Generator Procedure. Place a sample containing 
between 0 and 5 g of arsenic in the reaction tube, and dilute 
to 15 ml with water. Since there is some trial and error involved in 
this procedure, it may be necessary to screen the samples by 
conventional atomic absorption until an approximate concentration is 
determined. After determining the approximate concentration, adjust the 
volume of the sample accordingly. Pipet 15 ml of concentrated HCl into 
each tube. Add 1 ml of 30 percent KI solution. Place the reaction tube 
into a 50  deg.C (120  deg.F) water bath for 5 minutes. Cool to room 
temperature. Connect the reaction tube to the vapor generator assembly. 
When the instrument response has returned to baseline, inject 5.0 ml of 
5 percent NaBH4, and integrate the resulting 
spectrophotometer signal over a 30-second time period.
    11.4.1.1.2  Graphite Furnace Procedure. Dilute the digested sample 
so that a 5 ml aliquot contains less than 1.5 g of arsenic. 
Pipet 5 ml of this digested solution into a 10-ml volumetric flask. Add 
1 ml of the 1 percent nickel nitrate solution, 0.5 ml of 50 percent 
HNO3, and 1 ml of the 3 percent hydrogen peroxide and dilute 
to 10 ml with water. The sample is now ready for analysis.
    11.4.1.2  Run a blank (0.8 N HNO3) and standard at least 
after every five samples to check the spectrophotometer calibration. 
The peak height of the blank must pass through a point no further from 
the origin than 2 percent of the recorder full scale. The 
difference between the measured concentration of the standard (the 
product of the corrected average peak height and the reciprocal of the 
least squares slope) and the actual concentration of the standard must 
be less than 7 percent, or recalibration of the analyzer is required.
    11.4.1.3  Determine the arsenic concentration in the filter blank 
(i.e., the average of the two blank values from each lot).
    11.4.2  Container Number 3 (Silica Gel). This step may be conducted 
in the field. Weigh the spent silica gel (or silica gel plus impinger) 
to the nearest 0.5 g; record this weight.
    11.5  Check for matrix effects on the arsenic results. Same as 
Method 12, Section 11.5.
    11.6  Audit Sample Analysis.
    11.6.1  When the method is used to analyze samples to demonstrate 
compliance with a source emission regulation, a set of EPA audit 
samples must be analyzed, subject to availability.
    11.6.2  Concurrently analyze the audit samples and the compliance 
samples in the same manner to evaluate the technique of the analyst and 
the standards preparation.

    Note: It is recommended that known quality control samples be 
analyzed prior to the compliance and audit sample analyses to 
optimize the system accuracy and precision. These quality control 
samples may be obtained by contacting the appropriate EPA regional 
Office or the responsible enforcement authority.


    11.6.3  The same analyst, analytical reagents, and analytical 
system shall be used for the compliance samples and the EPA audit 
samples. If this condition is met, duplicate auditing of subsequent 
compliance analyses for the same enforcement agency within a 30-day 
period is waived. An audit sample set may not be used to validate 
different sets of compliance samples under the jurisdiction of separate 
enforcement agencies, unless prior arrangements have been made with 
both enforcement agencies.
    11.7  Audit Sample Results.
    11.7.1  Calculate the audit sample concentrations in g/
m3 and submit results using the instructions provided with 
the audit samples.
    11.7.2  Report the results of the audit samples and the compliance 
determination samples along with their identification numbers, and the 
analyst's name to the responsible enforcement authority. Include this 
information with reports of any subsequent compliance analyses for the 
same enforcement authority during the 30-day period.
    11.7.3  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 and 
audit samples, and include initial and reanalysis values in the test 
report.
    11.7.4  Failure to meet the 10 percent specification may require 
retests until the audit problems are resolved. However, if the audit 
results do not affect the compliance or noncompliance status of the 
affected facility, the Administrator may waive the reanalysis 
requirement, further audits, or retests and accept the results of the 
compliance test. While steps are being taken to resolve audit analysis 
problems, the Administrator may also choose to use the data to 
determine the compliance or noncompliance status of the affected 
facility.

12.0  Data Analysis and Calculations

12.1  Nomenclature.

Bws = Water in the gas stream, proportion by volume.
Ca = Concentration of arsenic as read from the standard 
curve, g/ml.
Cc = Actual audit concentration, g/m3.
Cd, = Determined audit concentration, g/m3.
Cs = Arsenic concentration in stack gas, dry basis, 
converted to standard conditions, g/dsm3 (gr/dscf).
Ea = Arsenic mass emission rate, g/hr (lb/hr).
Fd = Dilution factor (equals 1 if the sample has not been 
diluted).
I = Percent of isokinetic sampling.
mbi = Total mass of all four impingers and contents before 
sampling, g.
mfi = Total mass of all four impingers and contents after 
sampling, g.
mn = Total mass of arsenic collected in a specific part of 
the sampling train, g.
mt = Total mass of arsenic collected in the sampling train, 
g.
Tm = Absolute average dry gas meter temperature (see Figure 
108-2),  deg.K ( deg.R).
Vm = Volume of gas sample as measured by the dry gas meter, 
dry basis, m3 (ft3).
Vm(std) = Volume of gas sample as measured by the dry gas 
meter, corrected to standard conditions, m3 
(ft3).
Vn = Volume of solution in which the arsenic is contained, 
ml.
Vw(std) = Volume of water vapor collected in the sampling 
train, corrected to standard conditions, m3 
(ft3).
H = Average pressure differential across the orifice meter 
(see Figure 108-2), mm H2O (in. H2O).


[[Page 62200]]


    12.2  Average Dry Gas Meter Temperatures (Tm) and 
Average Orifice Pressure Drop (H). See data sheet (Figure 108-
2).
    12.3  Dry Gas Volume. Using data from this test, calculate 
Vm(std) according to the procedures outlined in Method 5, 
Section 12.3.
    12.4  Volume of Water Vapor.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.516
    
Where:

K2 = 0.001334 m\3\/g for metric units.
    = 0.047012 ft\3\/g for English units.

    12.5 Moisture Content.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.517
    
    12.6  Amount of Arsenic Collected.
    12.6.1  Calculate the amount of arsenic collected in each part of 
the sampling train, as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.518

    12.6.2  Calculate the total amount of arsenic collected in the 
sampling train as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.519

    12.7  Calculate the arsenic concentration in the stack gas (dry 
basis, adjusted to standard conditions) as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.520

Where:

K3 = 10-\6\ g/g for metric units
= 1.54  x  10-\5\ gr/g for English units

    12.8  Stack Gas Velocity and Volumetric Flow Rate. Calculate the 
average stack gas velocity and volumetric flow rate using data obtained 
in this method and the equations in Sections 12.2 and 12.3 of Method 2.
    12.9  Pollutant Mass Rate. Calculate the arsenic mass emission rate 
as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.521

    12.10  Isokinetic Variation. Same as Method 5, Section 12.11.

13.0  Method Performance

    13.1  Sensitivity. The lower limit of flame AAS 10 g As/
ml. The analytical procedure includes provisions for the use of a 
graphite furnace or vapor generator for samples with a lower arsenic 
concentration.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References.

    Same as References 1 through 9 of Method 5, Section 17.0, with the 
addition of the following:

    1. Perkin Elmer Corporation. Analytical Methods for Atomic 
Absorption Spectrophotometry. 303-0152. Norwalk, Connecticut. 
September 1976. pp. 5-6.
    2. Standard Specification for Reagent Water. In: Annual Book of 
American Society for Testing and Materials Standards. Part 31: 
Water, Atmospheric Analysis. American Society for Testing and 
Materials. Philadelphia, PA. 1974. pp. 40-42.
    3. Stack Sampling Safety Manual (Draft). U.S. Environmental 
Protection Agency, Office of Air Quality Planning and Standard, 
Research Triangle Park, NC. September 1978.

[[Page 62201]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.522


[[Page 62202]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.523

BILLING CODE 6560-50-C

[[Page 62203]]

Method 108A--Determination of Arsenic Content in Ore Samples From 
Nonferrous Smelters

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in Appendix A to 40 CFR 
part 60. Therefore, to obtain reliable results, persons using this 
method should have a thorough knowledge of Method 12.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.            Sensitivity
------------------------------------------------------------------------
Arsenic compounds as arsenic    7440-38-2........  Lower limit 10 g/ml or less.
------------------------------------------------------------------------

    1.2  Applicability. This method applies to the determination of 
inorganic As content of process ore and reverberatory matte samples 
from nonferrous smelters and other sources as specified in an 
applicable subpart of the regulations.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    Arsenic bound in ore samples is liberated by acid digestion and 
analyzed by flame atomic absorption spectrophotometry (AAS).

3.0  Definitions [Reserved]

4.0  Interferences

    Analysis for As by flame AAS is sensitive to the chemical 
composition and to the physical properties (e.g., viscosity, pH) of the 
sample. The analytical procedure includes a check for matrix effects 
(section 11.5).

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user to establish appropriate safety and health practices and 
determine the applicability of regulatory limitations prior to 
performing this test method.
    5.2  Corrosive Reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures that prevent chemical 
splashes are recommended. If contact occurs, immediately flush with 
copious amounts of water for at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burns as thermal 
burns.
    5.2.1  Hydrochloric Acid (HCl). Highly corrosive liquid with toxic 
vapors. Vapors are highly irritating to eyes, skin, nose, and lungs, 
causing severe damage. May cause bronchitis, pneumonia, or edema of 
lungs. Exposure to concentrations of 0.13 to 0.2 percent can be lethal 
to humans in a few minutes. Provide ventilation to limit exposure. 
Reacts with metals, producing hydrogen gas.
    5.2.2  Hydrofluoric Acid (HF). Highly corrosive to eyes, skin, 
nose, throat, and lungs. Reaction to exposure may be delayed by 24 
hours or more. Provide ventilation to limit exposure.
    5.2.3  Hydrogen Peroxide (H2O2). Very harmful 
to eyes. 30% H2O2 can burn skin, nose, and lungs.
    5.2.4  Nitric Acid (HNO3). Highly corrosive to eyes, 
skin, nose, and lungs. Vapors are highly toxic and can cause 
bronchitis, pneumonia, or edema of lungs. Reaction to inhalation may be 
delayed as long as 30 hours and still be fatal. Provide ventilation to 
limit exposure. Strong oxidizer. Hazardous reaction may occur with 
organic materials such as solvents.
    5.2.5  Sodium Hydroxide (NaOH). Causes severe damage to eyes and 
skin. Inhalation causes irritation to nose, throat, and lungs. Reacts 
exothermically with limited amounts of water.

6.0  Equipment and Supplies

    6.1  Sample Collection and Preparation. The following items are 
required for sample collection and preparation:
    6.1.1  Parr Acid Digestion Bomb. Stainless steel with vapor-tight 
Teflon cup and cover.
    6.1.2  Volumetric Pipets. 2- and 5-ml sizes.
    6.1.3  Volumetric Flask. 50-ml polypropylene with screw caps, (one 
needed per standard).
    6.1.4  Funnel. Polyethylene or polypropylene.
    6.1.5  Oven. Capable of maintaining a temperature of approximately 
105  deg.C (221  deg.F).
    6.1.6  Analytical Balance. To measure to within 0.1 mg.
    6.2  Analysis. The following items are required for analysis:
    6.2.1  Spectrophotometer and Recorder. Equipped with an 
electrodeless discharge lamp and a background corrector to measure 
absorbance at 193.7 nm. For measuring samples having less than 10 
g As/ml, use a graphite furnace or vapor generator accessory. 
The recorder shall match the output of the spectrophotometer.
    6.2.2  Volumetric Flasks. Class A, 50-ml (one needed per sample and 
blank), 500-ml, and 1-liter.
    6.2.3  Volumetric Pipets. Class A, 
1-, 5-, 10-, and 25-ml sizes.

7.0  Reagents and Standards.

    Unless otherwise indicated, it is intended that all reagents 
conform to the specifications established by the Committee on 
Analytical Reagents of the American Chemical Society, where such 
specifications are available; otherwise, use the best available grade.
    7.1  Sample Collection and Preparation. The following reagents are 
required for sample collection and preparation:
    7.1.1  Water. Deionized distilled to meet ASTM D 1193-77 or 91 Type 
3 (incorporated by reference--See Sec. 61.18). When high concentrations 
of organic matter are not expected to be present, the KMnO4 
test for oxidizable organic matter may be omitted. Use in all dilutions 
requiring water.
    7.1.2  Nitric Acid Concentrated.
    7.1.3  Nitric Acid, 0.5 N. In a 1-liter volumetric flask containing 
water, add 32 ml of concentrated HNO3 and dilute to volume 
with water.
    7.1.4  Hydrofluoric Acid, Concentrated.
    7.1.5  Potassium Chloride (KCl) Solution, 10 percent weight by 
volume (W/V). Dissolve 10 g KCl in water, add 3 ml concentrated 
HNO3, and dilute to 100 ml.
    7.1.6  Filter. Teflon filters, 3-micron porosity, 47-mm size. 
(Available from Millipore Co., type FS, Catalog Number FSLW04700.)
    7.1.7  Sodium Borohydride (NaBH4), 5 Percent (W/V). 
Dissolve 50.0 g of NaBH4 in about 500 ml of 0.1 N NaOH in a 
1-liter volumetric flask. Then, dilute to exactly 1.0 liter with 0.1 N 
NaOH.
    7.1.8  Nickel Nitrate, 5 Percent Ni (W/V). Dissolve 24.780 g of 
nickel nitrate hexahydrate [Ni(NO3)2 
6H2O] in water in a 100-ml volumetric flask, and dilute to 
100 ml with water.

[[Page 62204]]

    7.1.9  Nickel Nitrate, 1 Percent Ni (W/V). Pipet 20 ml of 5 percent 
nickel nitrate solution into a 100-ml volumetric flask, and dilute to 
100 ml with water.
    7.2  Analysis. The following reagents and standards are required 
for analysis:
    7.2.1  Water. Same as in Section 7.1.1.
    7.2.2  Sodium Hydroxide, 0.1 N. Dissolve 2.00 g of NaOH in water in 
a 500-ml volumetric flask. Dilute to volume with water.
    7.2.3  Nitric Acid, 0.5 N. Same as in Section 7.1.3.
    7.2.4  Potassium Chloride Solution, 10 percent. Same as in Section 
7.1.5.
    7.2.5  Hydrochloric Acid, Concentrated.
    7.2.6  Potassium Iodide (KI), 30 Percent (W/V). Dissolve 300 g of 
KI in about 500 ml of water in a 1-liter volumetric flask. Then, dilute 
to exactly 1.0 liter with water.
    7.2.7  Hydrogen Peroxide, 3 Percent by Volume. Pipet 50 ml of 30 
percent H2O2 into a 500-ml volumetric flask, and 
dilute to exactly 500 ml with water.
    7.2.8  Stock Arsenic Standard, 1 mg As/ml. Dissolve 1.3203 g of 
primary grade As2O3 in 20 ml of 0.1 N NaOH. 
Slowly add 30 ml of concentrated HNO3, and heat in an oven 
at 105  deg.C (221  deg.F) for 2 hours. Allow to cool, and dilute to 1 
liter with deionized distilled water.
    7.2.9  Nitrous Oxide. Suitable quality for AAS analysis.
    7.2.10  Acetylene. Suitable quality for AAS analysis.
    7.2.11  Quality Assurance Audit Samples. When making compliance 
determinations, and upon availability, audit samples may be obtained 
from the appropriate EPA regional Office or from the responsible 
enforcement authority.

    Note: The responsible enforcement authority should be notified 
at least 30 days prior to the test date to allow sufficient time for 
sample delivery.

8.0  Sample Collection, Preservation, Transport, and Storage

    8.1  Sample Collection. A sample that is representative of the ore 
lot to be tested must be taken prior to analysis. (A portion of the 
samples routinely collected for metals analysis may be used provided 
the sample is representative of the ore being tested.)
    8.2  Sample Preparation. The sample must be ground into a finely 
pulverized state.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
10.2..........................  Spectrophotometer  Ensure linearity of
                                 calibration.       spectrophotometer
                                                    response to
                                                    standards.
11.5..........................  Check for matrix   Eliminate matrix
                                 effects.           effects
11.6..........................  Audit sample       Evaluate analyst's
                                 analysis.          technique and
                                                    standards
                                                    preparation.
------------------------------------------------------------------------

10.0  Calibration and Standardizations

    Note: Maintain a laboratory log of all calibrations.

    10.1  Preparation of Standard Solutions. Pipet 1, 5, 10, and 25 ml 
of the stock As solution into separate 100-ml volumetric flasks. Add 10 
ml KCl solution and dilute to the mark with 0.5 N HNO3. This 
will give standard concentrations of 10, 50, 100, and 250 g 
As/ml. For low-level arsenic samples that require the use of a graphite 
furnace or vapor generator, follow the procedures in Section 11.3:1. 
Dilute 10 ml of KCl solution to 100 ml with 0.5 N HNO3 and 
use as a reagent blank.
    10.2  Calibration Curve. Analyze the reagent blank and each 
standard solution according to the procedures outlined in Section 11.3. 
Repeat this procedure on each standard solution until two consecutive 
peaks agree within 3 percent of their average value. Subtract the 
average peak height (or peak area) of the blank--which must be less 
than 2 percent of recorder full scale--from the averaged peak heights 
of each standard solution. If the blank absorbance is greater than 2 
percent of full-scale, the probable cause is Hg contamination of a 
reagent or carry-over of As from a previous sample. Prepare the 
calibration curve by plotting the corrected peak height of each 
standard solution versus the corresponding final total As weight in the 
solution.
    10.3  Spectrophotometer Calibration Quality Control. Calculate the 
least squares slope of the calibration curve. The line must pass 
through the origin or through a point no further from the origin than 
2 percent of the recorder full scale. Multiply the 
corrected peak height by the reciprocal of the least squares slope to 
determine the distance each calibration point lies from the theoretical 
calibration line. The difference between the calculated concentration 
values and the actual concentrations must be less than 7 percent for 
all standards.

    Note: For instruments equipped with direct concentration readout 
devices, preparation of a standard curve will not be necessary. In 
all cases, follow calibration and operational procedures in the 
manufacturer's instruction manual.

11.0  Analytical Procedure

    11.1  Sample Preparation. Weigh 50 to 500 mg of finely pulverized 
sample to the nearest 0.1 mg. Transfer the sample into the Teflon cup 
of the digestion bomb, and add 2 ml each of concentrated 
HNO3 and HF. Seal the bomb immediately to prevent the loss 
of any volatile arsenic compounds that may form. Heat in an oven at 105 
 deg.C (221  deg.F) for 2 hours. Remove the bomb from the oven and 
allow to cool. Using a Teflon filter, quantitatively filter the 
digested sample into a 50-ml polypropylene volumetric flask. Rinse the 
bomb three times with small portions of 0.5 N HNO3, and 
filter the rinses into the flask. Add 5 ml of KCl solution to the 
flask, and dilute to 50 ml with 0.5 N HNO3.
    11.2  Spectrophotometer Preparation.
    11.2.1  Turn on the power; set the wavelength, slit width, and lamp 
current. Adjust the background corrector as instructed by the 
manufacturer's manual for the particular atomic absorption 
spectrophotometer. Adjust the burner and flame characteristics as 
necessary.
    11.2.2  Develop a spectrophotometer calibration curve as outlined 
in Sections 10.2 and 10.3.
    11.3  Arsenic Determination. Analyze an appropriately sized aliquot 
of each diluted sample (from Section 11.1) until two consecutive peak 
heights agree within 3 percent of their average value. If applicable, 
follow the procedures outlined in Section 11.3.1. If the sample 
concentration falls outside the range of the calibration curve, make an 
appropriate dilution with 0.5 N HNO3 so that the final 
concentration falls within the range of the curve. Using the 
calibration curve, determine the As concentration in each sample.

    Note: Because instruments vary between manufacturers, no 
detailed operating instructions will be given here. Instead, the 
instrument manufacturer's detailed operating instructions should be 
followed.

    11.3.1  Arsenic Determination at Low Concentration. The lower limit 
of flame AAS is 10 g As/ml. If the arsenic concentration of 
any sample is at a lower level, use the vapor generator or graphite 
furnace which is available as

[[Page 62205]]

an accessory component. Flame, graphite furnace, or vapor generators 
may be used for samples whose concentrations are between 10 and 30 
g/ml. Follow the manufacturer's instructions in the use of 
such equipment.
    11.3.1.1  Vapor Generator Procedure. Place a sample containing 
between 0 and 5 g of arsenic in the reaction tube, and dilute 
to 15 ml with water. Since there is some trial and error involved in 
this procedure, it may be necessary to screen the samples by 
conventional AAS until an approximate concentration is determined. 
After determining the approximate concentration, adjust the volume of 
the sample accordingly. Pipet 15 ml of concentrated HCl into each tube. 
Add 1 ml of 30 percent KI solution. Place the reaction tube into a 50 
deg.C (120  deg.F) water bath for 5 minutes. Cool to room temperature. 
Connect the reaction tube to the vapor generator assembly. When the 
instrument response has returned to baseline, inject 5.0 ml of 5 
percent NaBH4 and integrate the resulting spectrophotometer 
signal over a 30-second time period.
    11.3.1.2  Graphite Furnace Procedure. Pipet 5 ml of the digested 
solution into a 10-ml volumetric flask. Add 1 ml of the 1 percent 
nickel nitrate solution, 0.5 ml of 50 percent HNO3, and 1 ml 
of the 3 percent H2O2, and dilute to 10 ml with 
water. The sample is now ready to inject in the furnace for analysis.
    11.4  Run a blank and standard at least after every five samples to 
check the spectrophotometer calibration. The peak height of the blank 
must pass through a point no further from the origin than 2 
percent of the recorder full scale. The difference between the measured 
concentration of the standard (the product of the corrected average 
peak height and the reciprocal of the least squares slope) and the 
actual concentration of the standard must be less than 7 percent, or 
recalibration of the analyzer is required.
    11.5  Mandatory Check for Matrix Effects on the Arsenic Results. 
Same as Method 12, Section 11.5.
    11.6  Audit Sample Analysis.
    11.6.1  When the method is used to analyze samples to demonstrate 
compliance with a source emission regulation, a set of EPA audit 
samples must be analyzed, subject to availability.
    11.6.2  Concurrently analyze the audit samples and the compliance 
samples in the same manner to evaluate the technique of the analyst and 
the standards preparation.


    Note: It is recommended that known quality control samples be 
analyzed prior to the compliance and audit sample analyses to 
optimize the system accuracy and precision. These quality control 
samples may be obtained by contacting the appropriate EPA regional 
Office or the responsible enforcement authority.


    11.6.3  The same analyst, analytical reagents, and analytical 
system shall be used for the compliance samples and the EPA audit 
samples. If this condition is met, duplicate auditing of subsequent 
compliance analyses for the same enforcement agency within a 30-day 
period is waived. An audit sample set may not be used to validate 
different sets of compliance samples under the jurisdiction of separate 
enforcement agencies, unless prior arrangements have been made with 
both enforcement agencies.
    11.7  Audit Sample Results.
    11.7.1  Calculate the audit sample concentrations in g/m\3\ and 
submit results using the instructions provided with the audit samples.
    11.7.2  Report the results of the audit samples and the compliance 
determination samples along with their identification numbers, and the 
analyst's name to the responsible enforcement authority. Include this 
information with reports of any subsequent compliance analyses for the 
same enforcement authority during the 30-day period.
    11.7.3  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 and 
audit samples, and include initial and reanalysis values in the test 
report.
    11.7.4  Failure to meet the 10 percent specification may require 
retests until the audit problems are resolved. However, if the audit 
results do not affect the compliance or noncompliance status of the 
affected facility, the Administrator may waive the reanalysis 
requirement, further audits, or retests and accept the results of the 
compliance test. While steps are being taken to resolve audit analysis 
problems, the Administrator may also choose to use the data to 
determine the compliance or noncompliance status of the affected 
facility.

12.0  Data Analysis and Calculations

    12.1  Calculate the percent arsenic in the ore sample as follows:
    [GRAPHIC] [TIFF OMITTED] TR17OC00.524
    
Where:

Ca = Concentration of As as read from the standard curve, 
g/ml.
Fd = Dilution factor (equals to 1 if the sample has not been 
diluted).
W = Weight of ore sample analyzed, mg.
5 = (50 ml sample `` 100)/(103 g/mg).

13.0  Method Performance

    13.1  Sensitivity. The lower limit of flame AAS is 10 g 
As/ml. The analytical procedure includes provisions for the use of a 
graphite furnace or vapor generator for samples with a lower arsenic 
concentration.

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    Same as References 1 through 9 of Section 17.0 of Method 5, with 
the addition of the following:

    1. Perkin Elmer Corporation. Analytical Methods of Atomic 
Absorption Spectrophotometry. 303-0152. Norwalk, Connecticut. 
September 1976. pp 5-6.
    2. Ringwald, D. Arsenic Determination on Process Materials from 
ASARCO's Copper Smelter in Tacoma, Washington. Unpublished Report. 
Prepared for Emission Measurement Branch, Emission Standards and 
Engineering Division, U.S. Environmental Protection Agency, Research 
Triangle Park, North Carolina. August 1980. 35 pp.
    3. Stack Sampling Safety Manual (Draft). U.S. Environmental 
Protection Agency, Office of Air Quality Planning and Standard, 
Research Triangle Park, NC. September 1978.

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

Method 108B--Determination of Arsenic Content in Ore Samples From 
Nonferrous Smelters

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in this appendix and in 
Appendix A to 40 CFR Part 60. Therefore, to

[[Page 62206]]

obtain reliable results, persons using this method should have a 
thorough knowledge of at least the following additional test 
methods: Method 12 and Method 108A.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.            Sensitivity
------------------------------------------------------------------------
Arsenic compounds as arsenic    7440-38-2........  Lower limit 10 g/ml.
------------------------------------------------------------------------

    1.2  Applicability. This method applies to the determination of 
inorganic As content of process ore and reverberatory matte samples 
from nonferrous smelters and other sources as specified in an 
applicable subpart of the regulations. Samples resulting in an 
analytical concentration greater than 10 g As/ml may be 
analyzed by this method. For lower level arsenic samples, Method 108C 
should be used.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    Arsenic bound in ore samples is liberated by acid digestion and 
analyzed by flame atomic absorption spectrophotometry (AAS).

3.0  Definitions [Reserved]

4.0  Interferences

    Analysis for As by flame AAS is sensitive to the chemical 
composition and to the physical properties (e.g., viscosity, pH) of the 
sample. The analytical procedure includes a check for matrix effects 
(Section 11.4).

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user to establish appropriate safety and health practices and 
determine the applicability of regulatory limitations prior to 
performing this test method.
    5.2  Corrosive Reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures that prevent chemical 
splashes are recommended. If contact occurs, immediately flush with 
copious amounts of water for at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burns as thermal 
burns.
    5.2.1  Hydrochloric acid (HCl). Highly corrosive liquid with toxic 
vapors. Vapors are highly irritating to eyes, skin, nose, and lungs, 
causing severe damage. May cause bronchitis, pneumonia, or edema of 
lungs. Exposure to concentrations of 0.13 to 0.2 percent can be lethal 
to humans in a few minutes. Provide ventilation to limit exposure. 
Reacts with metals, producing hydrogen gas.
    5.2.2  Hydrofluoric Acid (HF). Highly corrosive to eyes, skin, 
nose, throat, and lungs. Reaction to exposure may be delayed by 24 
hours or more. Provide ventilation to limit exposure.
    5.2.3  Nitric Acid (HNO3). Highly corrosive to eyes, 
skin, nose, and lungs. Vapors are highly toxic and can cause 
bronchitis, pneumonia, or edema of lungs. Reaction to inhalation may be 
delayed as long as 30 hours and still be fatal. Provide ventilation to 
limit exposure. Strong oxidizer. Hazardous reaction may occur with 
organic materials such as solvents.
    5.2.4  Perchloric Acid (HClO4). Corrosive to eyes, skin, 
nose, and throat. Provide ventilation to limit exposure. Very strong 
oxidizer. Keep separate from water and oxidizable materials to prevent 
vigorous evolution of heat, spontaneous combustion, or explosion. Heat 
solutions containing HClO4 only in hoods specifically 
designed for HClO4.

6.0  Equipment and Supplies

    6.1  Sample Preparation. The following items are required for 
sample preparation:
    6.1.1  Teflon Beakers. 150-ml.
    6.1.2  Graduated Pipets. 5-ml disposable.
    6.1.3  Graduated Cylinder. 50-ml.
    6.1.4  Volumetric Flask. 100-ml.
    6.1.5  Analytical Balance. To measure within 0.1 mg.
    6.1.6  Hot Plate.
    6.1.7  Perchloric Acid Fume Hood.
    6.2  Analysis. The following items are required for analysis:
    6.2.1  Spectrophotometer. Equipped with an electrodeless discharge 
lamp and a background corrector to measure absorbance at 193.7 nm.
    6.2.2  Beaker and Watch Glass. 400-ml.
    6.2.3  Volumetric Flask. 1-liter.
    6.2.4  Volumetric Pipets. 1-, 5-, 10-, and 25-ml.

7.0  Reagents and Standards

    Unless otherwise indicated, it is intended that all reagents 
conform to the specifications established by the Committee on 
Analytical Reagents of the American Chemical Society, where such 
specifications are available; otherwise, use the best available grade.
    7.1  Sample Preparation. The following reagents are required for 
sample preparation:
    7.1.1  Water. Deionized distilled to meet ASTM D 1193-77 or 91 Type 
3 (incorporated by reference--see Sec. 61.18).
    7.1.2  Nitric Acid, Concentrated.
    7.1.3  Hydrofluoric Acid, Concentrated.
    7.1.4  Perchloric Acid, 70 Percent.
    7.1.5  Hydrochloric Acid, Concentrated.
    7.2  Analysis. The following reagents and standards are required 
for analysis:
    7.2.1  Water. Same as in Section 7.1.1.
    7.2.2  Stock Arsenic Standard, 1.0 mg As/ml. Dissolve 1.3203 g of 
primary grade As203 [dried at 105  deg.C (221 
deg.F)] in a 400-ml beaker with 10 ml of HNO3 and 5 ml of 
HCl. Cover with a watch glass, and heat gently until dissolution is 
complete. Add 10 ml of HNO3 and 25 ml of HClO4, 
evaporate to strong fumes of HClO4, and reduce to about 20 
ml volume. Cool, add 100 ml of water and 100 ml of HCl, and transfer 
quantitatively to a 1-liter volumetric flask. Dilute to volume with 
water and mix.
    7.2.3  Acetylene. Suitable quality for AAS analysis.
    7.2.4  Air. Suitable quality for AAS analysis.
    7.2.5  Quality Assurance Audit Samples. Same as in Method 108A, 
Section 7.2.11.

8.0  Sample Collection, Preservation, Transport, and Storage

    Same as in Method 108A, Sections 8.1 and 8.2.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
10.2..........................  Spectrophotometer  Ensure linearity of
                                 calibration.       spectrophotometer
                                                    response to
                                                    standards.

[[Page 62207]]

 
11.4..........................  Check for matrix   Eliminate matrix
                                 effects.           effects.
11.5..........................  Audit sample       Evaluate analyst's
                                 analysis.          technique and
                                                    standards
                                                    preparation.
------------------------------------------------------------------------

10.0  Calibration and Standardization

    Note: Maintain a laboratory log of all calibrations.

    10.1  Preparation of Standard Solutions. Pipet 1, 5, 10, and 25 ml 
of the stock As solution into separate 100-ml volumetric flasks. Add 2 
ml of HClO4, 10 ml of HCl, and dilute to the mark with 
water. This will provide standard concentrations of 10, 50, 100, and 
250 g As/ml.
    10.2  Calibration Curve and Spectrophotometer Calibration Quality 
Control. Same as Method 108A, Sections 10.2 and 10.3

11.0  Analytical Procedure

    11.1  Sample Preparation. Weigh 100 to 1000 mg of finely pulverized 
sample to the nearest 0.1 mg. Transfer the sample to a 150-ml Teflon 
beaker. Dissolve the sample by adding 15 ml of HNO3, 10 ml 
of HCl, 10 ml of HF, and 10 ml of HClO4 in the exact order 
as described, and let stand for 10 minutes. In a HClO4 fume 
hood, heat on a hot plate until 2-3 ml of HClO4 remain, then 
cool. Add 20 ml of water and 10 ml of HCl. Cover and warm until the 
soluble salts are in solution. Cool, and transfer quantitatively to a 
100-ml volumetric flask. Dilute to the mark with water.
    11.2  Spectrophotometer Preparation. Same as in Method 108A, 
Section 11.2.
    11.3  Arsenic Determination. If the sample concentration falls 
outside the range of the calibration curve, make an appropriate 
dilution with 2 percent HClO4/10 percent HCl (prepared by 
diluting 2 ml concentrated HClO4 and 10 ml concentrated HCl 
to 100 ml with water) so that the final concentration falls within the 
range of the curve. Using the calibration curve, determine the As 
concentration in each sample.

    Note: Because instruments vary between manufacturers, no 
detailed operating instructions will be given here. Instead, the 
instrument manufacturer's detailed operating instructions should be 
followed.

    Run a blank and standard at least after every five samples to check 
the spectrophotometer calibration. The peak height of the blank must 
pass through a point no further from the origin than 2 
percent of the recorder full scale. The difference between the measured 
concentration of the standard (the product of the corrected average 
peak height and the reciprocal of the least squares slope) and the 
actual concentration of the standard must be less than 7 percent, or 
recalibration of the analyzer is required.
    11.4  Mandatory Check for Matrix Effects on the Arsenic Results. 
Same as Method 12, Section 11.5.
    11.5  Audit Sample Analysis. Same as in Method 108A, Section 11.6.

12.0  Data Analysis and Calculations

    Same as in Method 108A, Section 12.0.

13.0  Method Performance

    13.1  Sensitivity. The lower limit of flame AAS is 10 g 
As/ml.

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References

    Same as in Method 108A, Section 16.0.

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

Method 108C--Determination of Arsenic Content in Ore Samples From 
Nonferrous Smelters (Molybdenum Blue Photometric Procedure)

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in this part. 
Therefore, to obtain reliable results, persons using this method 
should have a thorough knowledge of at least Method 108A.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.            Sensitivity
------------------------------------------------------------------------
Arsenic compounds as arsenic    7440-38-2........  Lower limit 0.0002
 (As).                                              percent As by
                                                    weight.
------------------------------------------------------------------------

    1.2  Applicability. This method applies to the determination of 
inorganic As content of process ore and reverberatory matte samples 
from nonferrous smelters and other sources as specified in an 
applicable subpart of the regulations.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    Arsenic bound in ore samples is liberated by acid digestion and 
analyzed by the molybdenum blue photometric procedure.

3.0  Definitions. [Reserved]

4.0  Interferences. [Reserved]

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user to establish appropriate safety and health practices and 
determine the applicability of regulatory limitations prior to 
performing this test method.
    5.2  Corrosive Reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures that prevent chemical 
splashes are recommended. If contact occurs, immediately flush with 
copious amounts of water for at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burns as thermal 
burns.
    5.2.1  Hydrochloric Acid (HCl). Highly corrosive liquid with toxic 
vapors. Vapors are highly irritating to eyes, skin, nose, and lungs, 
causing severe damage. May cause bronchitis, pneumonia, or edema of 
lungs. Exposure to concentrations of 0.13 to 0.2 percent can be lethal 
to humans in a few minutes. Provide ventilation to limit exposure. 
Reacts with metals, producing hydrogen gas.
    5.2.2  Hydrofluoric Acid (HF). Highly corrosive to eyes, skin, 
nose, throat, and lungs. Reaction to exposure may be delayed by 24 
hours or more. Provide ventilation to limit exposure.

[[Page 62208]]

    5.2.3  Nitric Acid (HNO4). Highly corrosive to eyes, 
skin, nose, and lungs. Vapors are highly toxic and can cause 
bronchitis, pneumonia, or edema of lungs. Reaction to inhalation may be 
delayed as long as 30 hours and still be fatal. Provide ventilation to 
limit exposure. Strong oxidizer. Hazardous reaction may occur with 
organic materials such as solvents.
    5.2.4  Perchloric Acid (HClO4). Corrosive to eyes, skin, 
nose, and throat. Provide ventilation to limit exposure. Very strong 
oxidizer. Keep separate from water and oxidizable materials to prevent 
vigorous evolution of heat, spontaneous combustion, or explosion. Heat 
solutions containing HClO4 only in hoods specifically 
designed for HClO4.
    5.2.5  Sulfuric acid (H2SO4). Rapidly 
destructive to body tissue. Will cause third degree burns. Eye damage 
may result in blindness. Inhalation may be fatal from spasm of the 
larynx, usually within 30 minutes. May cause lung tissue damage with 
edema. 3 mg/m\3\ will cause lung damage in uninitiated. 1 mg/m\3\ for 8 
hours will cause lung damage or, in higher concentrations, death. 
Provide ventilation to limit inhalation. Reacts violently with metals 
and organics.

6.0  Equipment and Supplies

    6.1  Sample Preparation. The following items are required for 
sample preparation:
    6.1.1  Analytical Balance. To measure to within 0.1 mg.
    6.1.2  Erlenmeyer Flask. 300-ml.
    6.1.3  Hot Plate.
    6.1.4  Distillation Apparatus. No. 6, in ASTM E 50-82, 86, or 90 
(Reapproved 1995)(incorporated by reference--see Sec. 61.18); detailed 
in Figure 108C-1.
    6.1.5  Graduated Cylinder. 50-ml.
    6.1.6  Perchloric Acid Fume Hood.
    6.2  Analysis. The following items are required for analysis:
    6.2.1  Spectrophotometer. Capable of measuring at 660 nm.

6.2.2  Volumetric Flasks. 50- and 100-ml.

7.0  Reagents and Standards

    Unless otherwise indicated, it is intended that all reagents 
conform to the specifications established by the Committee on 
Analytical Reagents of the American Chemical Society, where such 
specifications are available; otherwise, use the best available grade.
    7.1  Sample Preparation. The following reagents are required for 
sample preparation:
    7.1.1  Water. Deionized distilled to meet ASTM D 1193-77 or 91 Type 
3 (incorporated by reference--see Sec. 61.18). When high concentrations 
of organic matter are not expected to be present, the KMnO4 
test for oxidizable organic matter may be omitted. Use in all dilutions 
requiring water.
    7.1.2  Nitric Acid, Concentrated.
    7.1.3  Hydrofluoric Acid, Concentrated.
    7.1.4  Sulfuric Acid, Concentrated.
    7.1.5  Perchloric Acid, 70 Percent.
    7.1.6  Hydrochloric Acid, Concentrated.
    7.1.7  Dilute Hydrochloric Acid. Add one part concentrated HCl to 
nine parts water.
    7.1.8  Hydrazine Sulfate 
((NH2)2H2SO4).
    7.1.9  Potassium Bromide (KBr).
    7.1.10  Bromine Water, Saturated.
    7.2  Analysis. The following reagents and standards are required 
for analysis:
    7.2.1  Water. Same as in Section 7.1.1.
    7.2.2  Methyl Orange Solution, 1 g/liter.
    7.2.3  Ammonium Molybdate Solution, 5 g/liter. Dissolve 0.5 g 
(NH4)Mo7O244H2O 
in water in a 100-ml volumetric flask, and dilute to the mark. This 
solution must be freshly prepared.
    7.2.4  Standard Arsenic Solution, 10 g As/ml. Dissolve 
0.13203 g of As2O3 in 100 ml HCl in a 1-liter 
volumetric flask. Add 200 ml of water, cool, dilute to the mark with 
water, and mix. Transfer 100 ml of this solution to a 1-liter 
volumetric flask, add 40 ml HCl, cool, dilute to the mark, and mix.
    7.2.5  Hydrazine Sulfate Solution, 1 g/liter. Dissolve 0.1 g of 
[(NH2)2H2SO4] in 
water, and dilute to 100 ml in a volumetric flask. This solution must 
be freshly prepared.
    7.2.6  Potassium Bromate (KBrO3) Solution, 0.03 Percent 
Weight by Volume (W/V). Dissolve 0.3 g KBrO3 in water, and 
dilute to 1 liter with water.
    7.2.7  Ammonium Hydroxide (NH4OH), Concentrated.
    7.2.8  Boiling Granules.
    7.2.9  Hydrochloric Acid, 50 percent by volume. Dilute equal parts 
concentrated HCl with water.
    7.2.10  Quality Assurance Audit Samples. Same as in Method 108A, 
Section 7.2.11.

8.0  Sample Collection, Preservation, Transport, and Storage

    Same as in Method 108A, Sections 8.1 and 8.2.

9.0  Quality Control

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
10.2..........................  Calibration curve  Ensure linearity of
                                 preparation.       spectrophotometric
                                                    analysis of
                                                    standards.
11.3..........................  Audit sample       Evaluate analyst's
                                 analysis.          technique and
                                                    standards
                                                    preparation.
------------------------------------------------------------------------

10.0  Calibration and Standardizations

    Note: Maintain a laboratory log of all calibrations.

    10.1  Preparation of Standard Solutions. Transfer 1.0, 2.0, 4.0, 
8.0, 12.0, 16.0, and 20.0 ml of standard arsenic solution (10 
g/ml) to each of seven 50-ml volumetric flasks. Dilute to 20 
ml with dilute HCl. Add one drop of methyl orange solution and 
neutralize to the yellow color with dropwise addition of 
NH4OH. Just bring back to the red color by dropwise addition 
of dilute HCl, and add 10 ml in excess. Proceed with the color 
development as described in Section 11.2.
    10.2  Calibration Curve. Plot the spectrophotometric readings of 
the calibration solutions against g As per 50 ml of solution. 
Use this curve to determine the As concentration of each sample.
    10.3  Spectrophotometer Calibration Quality Control. Calculate the 
least squares slope of the calibration curve. The line must pass 
through the origin or through a point no further from the origin than 
2 percent of the recorder full scale. Multiply the 
corrected peak height by the reciprocal of the least squares slope to 
determine the distance each calibration point lies from the theoretical 
calibration line. The difference between the calculated concentration 
values and the actual concentrations must be less than 7 percent for 
all standards.

11.0  Analytical Procedure

    11.1  Sample Preparation.
    11.1.1  Weigh 1.0 g of finely pulverized sample to the nearest 0.1 
mg. Transfer the sample to a 300 ml Erlenmeyer flask and add 15 ml of 
HNO3, 4 ml HCl, 2 ml HF, 3 ml HClO4, and 15 ml 
H2SO4, in the order listed. In a HClO4 
fume hood, heat on a hot plate to decompose the sample. Then heat while 
swirling over an open flame until dense white fumes evolve. Cool, add 
15

[[Page 62209]]

ml of water, swirl to hydrate the H2SO4 
completely, and add several boiling granules. Cool to room temperature.
    11.1.2  Add 1 g of KBr, 1 g hydrazine sulfate, and 50 ml HCl. 
Immediately attach the distillation head with thermometer and dip the 
side arm into a 50-ml graduated cylinder containing 25 ml of water and 
2 ml of bromine water. Keep the graduated cylinder immersed in a beaker 
of cold water during distillation. Distill until the temperature of the 
vapor in the flask reaches 107  deg.C (225  deg.F). When distillation 
is complete, remove the flask from the hot plate, and simultaneously 
wash down the side arm with water as it is removed from the cylinder.
    11.1.3  If the expected arsenic content is in the range of 0.0020 
to 0.10 percent, dilute the distillate to the 50-ml mark of the 
cylinder with water, stopper, and mix. Transfer a 5.0-ml aliquot to a 
50-ml volumetric flask. Add 10 ml of water and a boiling granule. Place 
the flask on a hot plate, and heat gently until the bromine is expelled 
and the color of methyl orange indicator persists upon the addition of 
1 to 2 drops. Cool the flask to room temperature. Neutralize just to 
the yellow color of the indicator with dropwise additions of 
NH4OH. Bring back to the red color by dropwise addition of 
dilute HCl, and add 10 ml excess. Proceed with the molybdenum blue 
color development as described in Section 11.2.
    11.1.4  If the expected arsenic content is in the range of 0.0002 
to 0.0010 percent As, transfer either the entire initial distillate or 
the measured remaining distillate from Section 11.1.2 to a 250-ml 
beaker. Wash the cylinder with two successive portions of concentrated 
HNO3, adding each portion to the distillate in the beaker. 
Add 4 ml of concentrated HClO4, a boiling granule, and cover 
with a flat watch glass placed slightly to one side. Boil gently on a 
hot plate until the volume is reduced to approximately 10 ml. Add 3 ml 
of HNO3, and continue the evaporation until HClO4 
is refluxing on the beaker cover. Cool briefly, rinse the underside of 
the watch glass and the inside of the beaker with about 3-5 ml of 
water, cover, and continue the evaporation to expel all but 2 ml of the 
HClO4.

    Note: If the solution appears cloudy due to a small amount of 
antimony distilling over, add 4 ml of 50 percent HCl and 5 ml of 
water, cover, and warm gently until clear. If cloudiness persists, 
add 5 ml of HNO3 and 2 ml H2SO4. 
Continue the evaporation of volatile acids to solubilize the 
antimony until dense white fumes of H2SO4 
appear. Retain at least 1 ml of the H2SO4.

    11.1.5  To the 2 ml of HClO4 solution or 1 ml of 
H2SO4 solution, add 15 ml of water, boil gently 
for 2 minutes, and then cool. Proceed with the molybdenum blue color 
development by neutralizing the solution directly in the beaker just to 
the yellow indicator color by dropwise addition of NH4OH. 
Obtain the red color by dropwise addition of dilute HCl. Transfer the 
solution to a 50-ml volumetric flask. Rinse the beaker successively 
with 10 ml of dilute HCl, followed by several small portions of water. 
At this point the volume of solution in the flask should be no more 
than 40 ml. Continue with the color development as described in Section 
11.2.
    11.2  Analysis.
    11.2.1  Add 1 ml of KBrO3 solution to the flask and heat 
on a low-temperature hot plate to about 50  deg.C (122  deg.F) to 
oxidize the arsenic and methyl orange. Add 5.0 ml of ammonium molybdate 
solution to the warm solution and mix. Add 2.0 ml of hydrazine sulfate 
solution, dilute until the solution comes within the neck of the flask, 
and mix. Place the flask in a 400 ml beaker, 80 percent full of boiling 
water, for 10 minutes. Enough heat must be supplied to prevent the 
water bath from cooling much below the boiling point upon inserting the 
volumetric flask. Remove the flask, cool to room temperature, dilute to 
the mark, and mix.
    11.2.2  Transfer a suitable portion of the reference solution to an 
absorption cell, and adjust the spectrophotometer to the initial 
setting using a light band centered at 660 nm. While maintaining this 
spectrophotometer adjustment, take the readings of the calibration 
solutions followed by the samples.
    11.3  Audit Sample Analysis. Same as in Method 108A, Section 11.6.

12.0  Data Analysis and Calculations

    Same as in Method 108A, Section 12.0.

13.0  Method Performance. [Reserved]

14.0   Pollution Prevention. [Reserved]

15.0 Waste  Management. [Reserved]

16.0  References

    1. Ringwald, D. Arsenic Determination on Process Materials from 
ASARCO's Copper Smelter in Tacoma, Washington. Unpublished Report. 
Prepared for the Emission Measurement Branch, Technical Support 
Division, U.S. Environmental Protection Agency, Research Triangle 
Park, North Carolina. August 1980. 35 pp.
BILLING CODE 6560-50-P

[[Page 62210]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.525

BILLING CODE 6560-50-C

Method 111--Determination of Polonium-210 Emissions From Stationary 
Sources

    Note: This method does not include all of the specifications (e.g., 
equipment and supplies) and procedures (e.g., sampling and analytical) 
essential to its performance. Some material is incorporated by 
reference from methods in appendix A to 40 CFR Part 60. Therefore, to 
obtain reliable results, persons using this method should have a 
thorough knowledge of at least the following additional test methods: 
Method 1, Method 2, Method 3, and Method 5.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.            Sensitivity
------------------------------------------------------------------------
Polonium......................  7440-08-6........  Not specified.
------------------------------------------------------------------------

    1.2  Applicability. This method is applicable for the determination 
of the polonium-210 content of particulate matter samples collected 
from stationary source exhaust stacks, and for the use of these data to 
calculate polonium-210 emissions from individual sources and from all 
affected sources at a facility.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    A particulate matter sample, collected according to Method 5, is 
analyzed for polonium-210 content: the polonium-210 in the sample is 
put in solution, deposited on a metal disc, and the radioactive 
disintegration rate measured. Polonium in acid solution spontaneously 
deposits on surfaces of metals that are more electropositive than 
polonium. This principle is routinely used in the radiochemical 
analysis of polonium-210. Data reduction procedures are provided, 
allowing the calculation of polonium-210 emissions from individual 
sources

[[Page 62211]]

and from all affected sources at a facility, using data obtained from 
Methods 2 and 5 and from the analytical procedures herein.

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Corrosive Reagents. The following reagents are hazardous. 
Personal protective equipment and safe procedures are useful in 
preventing chemical splashes. If contact occurs, immediately flush with 
copious amounts of water at least 15 minutes. Remove clothing under 
shower and decontaminate. Treat residual chemical burns as thermal 
burns.
    5.2.1  Hydrochloric Acid (HCl). Highly corrosive liquid with toxic 
vapors. Vapors are highly irritating to eyes, skin, nose, and lungs, 
causing severe damage. May cause bronchitis, pneumonia, or edema of 
lungs. Exposure to concentrations of 0.13 to 0.2 percent can be lethal 
to humans in a few minutes. Provide ventilation to limit exposure. 
Reacts with metals, producing hydrogen gas.
    5.2.2  Hydrofluoric Acid (HF). Highly corrosive to eyes, skin, 
nose, throat, and lungs. Reaction to exposure may be delayed by 24 
hours or more. Provide ventilation to limit exposure.
    5.2.3  Nitric Acid (HNO3). Highly corrosive to eyes, 
skin, nose, and lungs. Vapors cause bronchitis, pneumonia, or edema of 
lungs. Reaction to inhalation may be delayed as long as 30 hours and 
still be fatal. Provide ventilation to limit exposure. Strong oxidizer. 
Hazardous reaction may occur with organic materials such as solvents.
    5.2.4  Perchloric Acid (HClO4). Corrosive to eyes, skin, 
nose, and throat. Provide ventilation to limit exposure. Keep separate 
from water and oxidizable materials to prevent vigorous evolution of 
heat, spontaneous combustion, or explosion. Heat solutions containing 
HClO4 only in hoods specifically designed for 
HClO4.

6.0  Equipment and Supplies

    6.1  Alpha Spectrometry System. Consisting of a multichannel 
analyzer, biasing electronics, silicon surface barrier detector, vacuum 
pump and chamber.
    6.2  Constant Temperature Bath at 85  deg.C (185  deg.F).
    6.3  Polished Silver Discs. 3.8 cm diameter, 0.4 mm thick with a 
small hole near the edge.
    6.4  Glass Beakers. 400 ml, 150 ml.
    6.5  Hot Plate, Electric.
    6.6  Fume Hood.
    6.7  Teflon Beakers, 150 ml.
    6.8  Magnetic Stirrer.
    6.9  Stirring Bar.
    6.10  Hooks. Plastic or glass, to suspend plating discs.
    6.11  Internal Proportional Counter. For measuring alpha particles.
    6.12  Nucleopore Filter Membranes. 25 mm diameter, 0.2 micrometer 
pore size or equivalent.
    6.13  Planchets. Stainless steel, 32 mm diameter with 1.5 mm lip.
    6.14  Transparent Plastic Tape. 2.5 cm wide with adhesive on both 
sides.
    6.15  Epoxy Spray Enamel.
    6.16  Suction Filter Apparatus. For 25 mm diameter filter.
    6.17  Wash Bottles, 250 ml capacity.
    6.18  Graduated Cylinder, plastic, 25 ml capacity.
    6.19  Volumetric Flasks, 100 ml, 250 ml.

7.0  Reagents and Standards

    Unless otherwise indicated, it is intended that all reagents 
conform to the specifications established by the Committee on 
Analytical Reagents of the American Chemical Society, where such 
specifications are available; otherwise, use the best available grade.
    7.1  Ascorbic Acid.
    7.2  Ammonium Hydroxide (NH4OH), 15 M.
    7.3  Water. Deionized distilled, to conform to ASTM D 1193-77 or 91 
(incorporated by reference--see Sec. 61.18), Type 3. Use in all 
dilutions requiring water.
    7.4  Ethanol (C2H5OH), 95 percent.
    7.5  Hydrochloric Acid, 12 M.
    7.6  Hydrochloric Acid, 1 M. Dilute 83 ml of the 12 M HCl to 1 
liter with distilled water.
    7.7  Hydrofluoric Acid, 29 M.
    7.8  Hydrofluoric Acid, 3 M. Dilute 52 ml of the 29 M HF to 500 ml 
with distilled water. Use a plastic graduated cylinder and storage 
bottle.
    7.9  Lanthanum Carrier, 0.1 mg La+3/ml. Dissolve 0.078 
gram lanthanum nitrate, 
La(NO3)36H2O in 250 ml of 1 
M HCl.
    7.10  Nitric Acid, 16 M.
    7.11  Perchloric Acid, 12 M.
    7.12  Polonium-209 Solution.
    7.13  Silver Cleaner. Any mild abrasive commercial silver cleaner.
    7.14  Degreaser.
    7.15  Standard Solution. Standardized solution of an alpha-emitting 
actinide element, such as plutonium-239 or americium-241.

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

9.0  Quality Control

    9.1  General Requirement.
    9.1.1  All analysts using this method are required to demonstrate 
their ability to use the method and to define their respective accuracy 
and precision criteria.
    9.2  Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
10.1..........................  Standardization    Ensure precision of
                                 of alpha           sample analyses.
                                 spectrometry
                                 system.
10.3..........................  Standardization    Ensure precise sizing
                                 of internal        of sample aliquot.
                                 proportional
                                 counter.
11.1, 11.2....................  Determination of   Minimize background
                                 procedure          effects.
                                 background and
                                 instrument
                                 background.
11.3..........................  Audit sample       Evaluate analyst's
                                 analysis.          technique.
------------------------------------------------------------------------

10.0  Calibration and Standardization

    10.1  Standardization of Alpha Spectrometry System.
    10.1.1  Add a quantity of the actinide standard solution to a 100 
ml volumetric flask so that the final concentration when diluted to a 
volume of 100 ml will be approximately 1 pCi/ml.
    10.1.2  Add 10 ml of 16 M HNO3 and dilute to 100 ml with 
water.
    10.1.3  Add 20 ml of 1 M HCl to each of six 150 ml beakers. Add 1.0 
ml of lanthanum carrier, 0.1 mg lanthanum per ml, to the acid solution 
in each beaker.
    10.1.4  Add 1.0 ml of the 1 pCi/ml working solution (from Section 
10.1.1)

[[Page 62212]]

to each beaker. Add 5.0 ml of 3 M HF to each beaker.
    10.1.5  Cover beakers and allow solutions to stand for a minimum of 
30 minutes. Filter the contents of each beaker through a separate 
filter membrane using the suction filter apparatus. After each 
filtration, wash the filter membrane with 10 ml of distilled water and 
5 ml of ethanol, and allow the filter membrane to air dry on the filter 
apparatus.
    10.1.6  Carefully remove the filter membrane and mount it, 
filtration side up, with double-side tape on the inner surface of a 
planchet. Place planchet in an alpha spectrometry system and count each 
planchet for 1000 minutes.
    10.1.7  Calculate the counting efficiency of the detector for each 
aliquot of the 1 pCi/ml actinide working solution using Eq. 111-1 in 
Section 12.2.
    10.1.8  Determine the average counting efficiency of the detector, 
Ec, by calculating the average of the six determinations.
    10.2  Preparation of Standardized Solution of Polonium-209.
    10.2.1  Add a quantity of the Po-209 solution to a 100 ml 
volumetric flask so that the final concentration when diluted to a 100 
ml volume will be approximately 1 pCi/ml.
    10.2.2  Follow the procedures outlined in Sections 10.1.2 through 
10.1.6, except substitute 1.0 ml of polonium-209 tracer solution 
(Section 10.2.1) and 3.0 ml of 15 M ammonium hydroxide for the 1 pCi/ml 
actinide working solution and the 3 M HF, respectively.
    10.2.3  Calculate the activity of each aliquot of the polonium-209 
tracer solution using Eq. 111-2 in Section 12.3.
    10.2.4  Determine the average activity of the polonium-209 tracer 
solution, F, by averaging the results of the six determinations.
    10.3  Standardization of Internal Proportional Counter
    10.3.1  Add a quantity of the actinide standard solution to a 100 
ml volumetric flask so that the final concentration when diluted to a 
100 ml volume will be approximately 100 pCi/ml.
    10.3.2  Follow the procedures outlined in Sections 10.1.2 through 
10.1.6, except substitute the 100 pCi/ml actinide working solution for 
the 1 pCi/ml solution, place the planchet in an internal proportional 
counter (instead of an alpha spectrometry system), and count for 100 
minutes (instead of 1000 minutes).
    10.3.3  Calculate the counting efficiency of the internal 
proportional counter for each aliquot of the 100 pCi/ml actinide 
working solution using Eq. 111-3 in 12.4.
    10.3.4  Determine the average counting efficiency of the internal 
proportional counter, EI, by averaging the results of the 
six determinations.

11.0  Analytical Procedure

    Note: Perform duplicate analyses of all samples, including 
background counts, quality assurance audit samples, and Method 5 
samples. Duplicate measurements are considered acceptable when the 
difference between them is less than two standard deviations as 
described in EPA 600/4-77-001 or subsequent revisions.

    11.1  Determination of Procedure Background. Background counts used 
in all equations are determined by performing the specific analysis 
required using the analytical reagents only. All procedure background 
counts and sample counts for the internal proportional counter should 
utilize a counting time of 100 minutes; for the alpha spectrometry 
system, 1000 minutes. These background counts should be performed no 
less frequently than once per 10 sample analyses.
    11.2  Determination of Instrument Background. Instrument 
backgrounds of the internal proportional counter and the alpha 
spectrometry system should be determined on a weekly basis. Instrument 
background should not exceed procedure background. If this occurs, it 
may be due to a malfunction or contamination, and should be corrected 
before use.
    11.3  Quality Assurance Audit Samples. An externally prepared 
performance evaluation sample shall be analyzed no less frequently than 
once per 10 sample analyses, and the results reported with the test 
results.
    11.4  Sample Preparation. Treat the Method 5 samples [i.e., the 
glass fiber filter (Container No. 1) and the acetone rinse (Container 
No. 2)] as follows:
    11.4.1  Container No. 1. Transfer the filter and any loose 
particulate matter from the sample container to a 150-ml Teflon beaker.
    11.4.2  Container No. 2. Note the level of liquid in the container, 
and confirm on the analysis sheet whether leakage occurred during 
transport. If a noticeable amount of leakage has occurred, either void 
the sample or use methods, subject to the approval of the 
Administrator, to correct the final results. Transfer the contents to a 
400-ml glass beaker. Add polonium-209 tracer solution to the glass 
beaker in an amount approximately equal to the amount of polonium-210 
expected in the total particulate sample. Record the activity of the 
tracer solution added. Add 16 M nitric acid to the beaker to digest and 
loosen the residue.
    11.4.3  Transfer the contents of the glass beaker to the Teflon 
beaker containing the glass fiber filter. Rinse the glass beaker with 
16 M HNO3. If necessary, reduce the volume in the beaker by 
evaporation until all of the nitric acid HNO3 from the glass 
beaker has been transferred to the Teflon beaker.
    11.4.4  Add 30 ml of 29 M HF to the Teflon beaker and evaporate to 
near dryness on a hot plate in a properly operating hood.


    Note: Do not allow the residue to go to dryness and overheat; 
this will result in loss of polonium.


    11.4.5  Repeat step 11.4.4 until the filter is dissolved.
    11.4.6  Add 100 ml of 16 M HNO3 to the residue in the 
Teflon beaker and evaporate to near dryness.


    Note: Do not allow the residue to go to dryness.


    11.4.7  Add 50 ml of 16 M HNO3 and 10 ml of 12 M 
perchloric acid to the Teflon beaker and heat until dense fumes of 
perchloric acid are evolved.
    11.4.8  Repeat steps 11.4.4 to 11.4.7 as necessary until sample is 
completely dissolved.
    11.4.9  Add 10 ml of 12 M HCl to the Teflon beaker and evaporate to 
dryness. Repeat additions and evaporations several times.
    11.4.10  Transfer the sample to a 250-ml volumetric flask and 
dilute to volume with 3 M HCl.
    11.5  Sample Screening. To avoid contamination of the alpha 
spectrometry system, check each sample as follows:
    11.5.1  Add 20 ml of 1 M HCl, 1 ml of the lanthanum carrier 
solution (0.1 mg La/ml), a 1 ml aliquot of the sample solution from 
Section 11.4.10, and 3 ml of 15 M ammonium hydroxide to a 250-ml beaker 
in the order listed. Allow this solution to stand for a minimum of 30 
minutes.
    11.5.2  Filter the solution through a filter membrane using the 
suction filter apparatus. Wash the filter membrane with 10 ml of water 
and 5 ml of ethanol, and allow the filter membrane to air dry on the 
filter apparatus.
    11.5.3  Carefully remove the filter membrane and mount it, 
filtration side up, with double-side tape on the inner surface of a 
planchet. Place the planchet in an internal proportional counter, and 
count for 100 minutes.
    11.5.4  Calculate the activity of the sample using Eq. 111-4 in 
Section 12.5.
    11.5.5  Determine the aliquot volume of the sample solution from 
Section 11.4.10 to be analyzed for polonium-210, such that the aliquot 
contains an

[[Page 62213]]

activity between 1 and 4 picocuries. Use Eq. 111-5 in Section 12.6.
    11.6  Preparation of Silver Disc for Spontaneous Electrodeposition.
    11.6.1  Clean both sides of the polished silver disc with silver 
cleaner and with degreaser.
    11.6.2  Place disc on absorbent paper and spray one side with epoxy 
spray enamel. This should be carried out in a well-ventilated area, 
with the disc lying flat to keep paint on one side only. Allow paint to 
dry for 24 hours before using disc for deposition.
    11.7  Sample Analysis.
    11.7.1  Add the aliquot of sample solution from Section 11.4.10 to 
be analyzed for polonium-210, the volume of which was determined in 
Section 11.5.5, to a suitable 200-ml container to be placed in a 
constant temperature bath.


    Note: Aliquot volume may require a larger container.


    11.7.2  If necessary, bring the volume to 100 ml with 1 M HCl. If 
the aliquot volume exceeds 100 ml, use total aliquot.
    11.7.3  Add 200 mg of ascorbic acid and heat solution to 85  deg.C 
(185  deg.F) in a constant temperature bath.
    11.7.4  Suspend a silver disc in the heated solution using a glass 
or plastic rod with a hook inserted through the hole in the disc. The 
disc should be totally immersed in the solution, and the solution must 
be stirred constantly, at all times during the plating operation. 
Maintain the disc in solution for 3 hours.
    11.7.5  Remove the silver disc, rinse with deionized distilled 
water, and allow to air dry at room temperature.
    11.7.6  Place the disc, with deposition side (unpainted side) up, 
on a planchet and secure with double-side plastic tape. Place the 
planchet with disc in alpha spectrometry system and count for 1000 
minutes.

12.0  Data Analysis and Calculations.

    12.1  Nomenclature.

A = Picocuries of polonium-210 in the Method 5 sample (from Section 
12.8).
AA = Picocuries of actinide added.
AL = Volume of sample aliquot used, in ml (specified in 
Section 11.5.1 as 1 ml).
AS = Aliquot to be analyzed, in ml.
BB = Procedure background counts measured in polonium-209 
spectral region.
BT = Polonium-209 tracer counts in sample.
CT = Total counts in polonium-210 spectral region.
D = Decay correction for time ``t'' (in days) from sample collection to 
sample counting, given by: D=e-0.005t
EC = Average counting efficiency of detector (from Section 
10.1.8), as counts per disintegration.
ECi = Counting efficiency of the detector for aliquot i of 
the actinide working solution, counts per disintegration.
EI = Average counting efficiency of the internal 
proportional counter, as determined in Section 10.3.4, counts per 
disintegration.
EIi = Counting efficiency of the internal proportional 
counter for aliquot i of the 100 pCi/ml actinide working solution, 
counts per disintegration.
EY = The fraction of polonium-209 recovered on the planchet 
(from Section 12.7).
F= Average activity of polonium-209 in sample (from Section 10.2.4), in 
pCi.
Fi = activity of aliquot i of the polonium-209 tracer 
solution, in pCi.
L = Dilution factor (unitless). This is the volume of sample solution 
prepared (specified as 250 ml in Section 11.1.10) divided by the volume 
of the aliquot of sample solution analyzed for polonium-210 (from 
Section 11.7.1).
Mi = Phosphorous rock processing rate of the source being 
tested, during run i, Mg/hr.
Mk = Phosphate rock processed annually by source k, in Mg/
yr.
n = Number of calciners at the elemental phosphorus plant.
P = Total activity of sample solution from Section 11.4.10, in pCi (see 
Eq. 111-4).
Qsd = Volumetric flow rate of effluent stream, as determined 
by Method 2, in dscm/hr.
S = Annual polonium-210 emissions from the entire facility, in curies/
yr.
Vm(std) = Volume of air sample, as determined by Method 5, 
in dscm.
Xk = Emission rate from source k, from Section 12.10, in 
curies/Mg.
10-12 = Curies per picocurie.
2.22 = Disintegrations per minute per picocurie.
250 = Volume of solution from Section 11.4.10, in ml.

    12.2  Counting Efficiency. Calculate the counting efficiency of the 
detector for each aliquot of the 1 pCi/ml actinide working solution 
using Eq. 111-1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.526

Where:

CB = Background counts in same peak area as CS.
CS = Gross counts in actinide peak.
T = Counting time in minutes, specified in Section 10.1.6 as 1000 
minutes.

    12.3  Polonium-209 Tracer Solution Activity. Calculate the activity 
of each aliquot of the polonium-209 tracer solution using Eq. 111-2.
[GRAPHIC] [TIFF OMITTED] TR17OC00.527

Where:

CB = Background counts in the 4.88 MeV region of spectrum 
the in the counting time T.
CS = Gross counts of polonium-209 in the 4.88 MeV region of 
the spectrum in the counting time T.
T = Counting time, specified in Section 10.1.6 as 1000 minutes.

    12.4 Control Efficiency of Internal Proportional Counter. Calculate 
the counting efficiency of the internal proportional counter for each 
aliquot of the 100 pCi/ml actinide working solution using Eq. 111-3.

[[Page 62214]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.528

Where:

CB = Gross counts of procedure background.
CS = Gross counts of standard.
T = Counting time in minutes, specified in Section 10.3.2 as 100 
minutes.

    12.5  Calculate the activity of the sample using Eq. 111-4.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.529
    
Where:

CB = Total counts of procedure background. (See Section 
11.1).
CS = Total counts of screening sample.
T = Counting time for sample and background (which must be equal), in 
minutes (specified in Section 11.5.3 as 100 minutes).

    12.6  Aliquot Volume. Determine the aliquot volume of the sample 
solution from Section 11.4.10 to be analyzed for polonium-210 , such 
that the aliquot contains an activity between 1 and 4 picocuries using 
Eq. 111-5.
[GRAPHIC] [TIFF OMITTED] TR17OC00.530

    12.7  Polonium-209 Recovery. Calculate the fraction of polonium-209 
recovered on the planchet, EY, using Eq. 111-6.
[GRAPHIC] [TIFF OMITTED] TR17OC00.531

Where:

T = Counting time, specified in Section 11.1 as 1000 minutes.

    12.8  Polonium-210 Activity. Calculate the activity of polonium-210 
in the Method 5 sample (including glass fiber filter and acetone rinse) 
using Eq. 111-7.
[GRAPHIC] [TIFF OMITTED] TR17OC00.532

Where:

CB = Procedure background counts in polonium-210 spectral 
region.
T = Counting time, specified in Section 11.1 as 1000 minutes for all 
alpha spectrometry sample and background counts.

    12.9  Emission Rate from Each Stack.
    12.9.1  For each test run, i, on a stack, calculate the measured 
polonium-210 emission rate, RSi, using Eq. 111-8.
[GRAPHIC] [TIFF OMITTED] TR17OC00.533

    12.9.2  Determine the average polonium-210 emission rate from the 
stack, RS, by taking the sum of the measured emission rates 
for all runs, and dividing by the number of runs performed.
    12.9.3  Repeat steps 12.9.1 and 12.9.2 for each stack of each 
calciner.
    12.10  Emission Rate from Each Source. Determine the total 
polonium-210 emission rate, Xk, from each source, k, by 
taking the sum of the average emission rates from all stacks to which 
the source exhausts.
    12.11  Annual Polonium-210 Emission Rate from Entire Facility. 
Determine the annual elemental phosphorus plant emissions of polonium-
210, S, using Eq. 111-9.
[GRAPHIC] [TIFF OMITTED] TR17OC00.534


[[Page 62215]]



13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    1. Blanchard, R.L. ``Rapid Determination of Lead-210 and 
Polonium-210 in Environmental Samples by Deposition on Nickel.'' 
Anal. Chem., 38:189, pp. 189-192. February 1966.

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

* * * * *

PART 63--NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS 
FOR SOURCE CATEGORIES

    1. The authority citation for Part 63 continues to read as follows:

    Authority: 42 U.S.C. 7401 et seq.


Sec. 63.7  [Amended]

    2. Amend Sec. 63.7 by revising paragraph (c)(4)(i) as follows:


Sec. 63.7  Performance testing requirements.

* * * * *
    (c) * * *
    (4)(i) Performance test method audit program. The owner or operator 
shall analyze performance audit (PA) samples during each performance 
test. The owner or operator shall request performance audit materials 
45 days prior to the test date. Cylinder audit gases, if available, 
must be obtained from the appropriate EPA Regional Office or from the 
responsible enforcement authority and analyzed in conjunction with the 
field samples.
* * * * *


Sec. 63.11  [Amended]

    3. Amend Sec. 63.11 as follows:
    a. The definition of ``Ci'' in paragraph (b)(6)(ii) is 
amended by revising ``D1946-77'' to read ``D1946-77 or 90 (Reapproved 
1994).''
    b. The definition of ``Hi'' in paragraph (b)(6)(ii) is 
amended by revising ``D2382-76'' to read ``D2382-76 or 88 or D4809-
95.''


Sec. 63.14  [Amended]

    4. In Sec. 63.14, by revising paragraph (b) to read as follows:


Sec. 63.14  Incorporation by reference.

* * * * *
    (b) The following materials are available for purchase from at 
least one of the following addresses: American Society for Testing and 
Materials (ASTM), 1916 Race Street, Philadelphia, PA 19103; or 
University Microfilms International, 300 North Zeeb Road, Ann Arbor, MI 
48106.
    (1) ASTM D523-89, Standard Test Method for Specular Gloss, IBR 
approved for Sec. 63.782.
    (2) ASTM D1193-77, 91, Standard Specification for Reagent Water, 
IBR approved for Appendix A: Method 306, Sections 7.1.1 and 7.4.2.
    (3) ASTM D1331-89, Standard Test Methods for Surface and 
Interfacial Tension of Solutions of Surface Active Agents, IBR approved 
for Appendix A: Method 306B, Sections 6.2, 11.1, and 12.2.2.
    (4) ASTM D1475-90, Standard Test Method for Density of Paint, 
Varnish Lacquer, and Related Products, IBR approved for Sec. 63.788, 
Appendix A.
    (5) ASTM D1946-77, 90, 94, Standard Method for Analysis of Reformed 
Gas by Gas Chromatography, IBR approved for Sec. 63.11(b)(6).
    (6) ASTM D2369-93, 95, Standard Test Method for Volatile Content of 
Coatings, IBR approved for Sec. 63.788, Appendix A.
    (7) ASTM D2382-76, 88, Heat of Combustion of Hydrocarbon Fuels by 
Bomb Calorimeter (High-Precision Method), IBR approved for 
Sec. 63.11(b)(6).
    (8) ASTM D2879-83, 96, Test Method for Vapor Pressure-Temperature 
Relationship and Initial Decomposition Temperature of Liquids by 
Isoteniscope, IBR approved for Sec. 63.111 of Subpart G.
    (9) ASTM D3257-93, Standard Test Methods for Aromatics in Mineral 
Spirits by Gas Chromatography, IBR approved for Sec. 63.786(b).
    (10) ASTM 3695-88, Standard Test Method for Volatile Alcohols in 
Water by Direct Aqueous-Injection Gas Chromatography, IBR approved for 
Sec. 63.365(e)(1) of Subpart O.
    (11) ASTM D3792-91, Standard Method for Water Content of Water-
Reducible Paints by Direct Injection into a Gas Chromatograph, IBR 
approved for Sec. 63.788, Appendix A.
    (12) ASTM D3912-80, Standard Test Method for Chemical Resistance of 
Coatings Used in Light-Water Nuclear Power Plants, IBR approved for 
Sec. 63.782.
    (13) ASTM D4017-90, 96a, Standard Test Method for Water in Paints 
and Paint Materials by the Karl Fischer Titration Method, IBR approved 
for Sec. 63.788, Appendix A.
    (14) ASTM D4082-89, Standard Test Method for Effects of Gamma 
Radiation on Coatings for Use in Light-Water Nuclear Power Plants, IBR 
approved for Sec. 63.782.
    (15) ASTM D4256-89, 94, Standard Test Method for Determination of 
the Decontaminability of Coatings Used in Light-Water Nuclear Power 
Plants, IBR approved for Sec. 63.782.
    (16) ASTM D4809-95, Standard Test Method for Heat of Combustion of 
Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision Method), IBR 
approved for Sec. 63.11(b)(6).
    (17) ASTM E180-93, Standard Practice for Determining the Precision 
of ASTM Methods for Analysis and Testing of Industrial Chemicals, IBR 
approved for Sec. 63.786(b).
    (18) ASTM E260-91, 96, General Practice for Packed Column Gas 
Chromatography, IBR approved for Secs. 63.750(b)(2) and 63.786(b)(5).


Sec. 63.111  [Amended]

    5. In Sec. 63.111, paragraph (3) of the definition of the term 
``Maximum true vapor pressure'' is amended by revising ``D2879-83'' to 
read ``D2879-83 or 96.''


Sec. 63.301  [Amended]

    6. Amend Sec. 63.301 as follows:
    a. The definition of the term ``Foundry coke producer'' is amended 
by revising the words ``1.25 million megagrams per year'' to read 
``1.25 million megagrams per year (1.38 million tons per year).''
    b. The definitions of the terms ``Short coke oven battery'' and 
``Tall coke oven battery'' are amended by revising the words ``6 
meters'' to read ``6 meters (20 feet)'' wherever they occur.


Sec. 63.304  [Amended]

    7. In Sec. 63.304, paragraph (b)(6)(iii) is amended by revising the 
words ``2.7 million Mg/yr'' to read ``2.7 million Mg/yr (3.0 million 
ton/yr).''


Sec. 63.750  [Amended]

    8. In Sec. 63.750, paragraph (b)(2) is amended by revising ``ASTM E 
260-91 (incorporated by reference as specified in Sec. 63.14 of subpart 
A of this part)'' to read ``ASTM E 260-91 or 96 (incorporated by 
reference--see Sec. 63.14 of Subpart A of this part).''


Sec. 63.782  [Amended]

    9. Amend Sec. 63.782 as follows:
    a. The definition for ``High-gloss specialty coating'' is amended 
by revising ``ASTM Method D523,'' to read ``ASTM D523-89.''
    b. The definition for Nuclear specialty coating is amended by 
revising ``ASTM D4256-89,'' to read ``ASTM D4256-89 or 94.''


Sec. 63.786  [Amended]

    10. In Sec. 63.786, paragraph (b)(5) is amended by revising ``ASTM 
Method E260-91'' to read ``ASTM E260-91 or 96.''

[[Page 62216]]

Sec. 63.788  [Amended]

    11. In Sec. 63.788, the Appendix A to Subpart II of Part 63-VOC 
Data Sheet is amended by revising ``ASTM Method D2369-93,'' and ``ASTM 
D4017-90'' to read ``ASTM D2369-93 or 95'' and ``ASTM D4017-81, 90, or 
96a'' respectively.

Appendix A--[Amended]

    12. Amend Method 310B in Appendix A as follows:
    a. Section 1.0 is amended by revising ``ethylidene norbornene 
(ENB)'' to read ``Applicable Termonomer.''
    b. Section 1.0 is amended by deleting ``16219-75-3.''
    c. In Section 5.0, correcting the section numbering from ``5.1, 
5.2, 5.3, 5.3, 5.4, 5.5, 5.6, and 5.7'' to ``5.1, 5.2, 5.3, 5.4, 5.5, 
5.6, 5.7, and 5.8.''
    d. Sections 5.3, 7.1, 7.2, 7.3, 7.5.6, 7.6, 7.6.1, 9.2, 10.1, 
10.2.2, 10.2.5, 10.2.8, 12.3, and 12.6 are amended by revising ``ENB'' 
to read ``termonomer'' wherever it appears.
    e. Sections 6.11, 7.5.1, 9.3.3, 11.1.2, and 12.5 are revised.
    f. The first sentence in Section 7.1 is amended by revising to read 
``Reagent toluene, EM Science Omnisolv (or equivalent).''
    g. Section 7.2 is amended by revising the first sentence to read 
``Reagent acetone, EM Science Omnisolv HR-GC (or equivalent).''
    h. Section 7.3 is amended by revising the first sentence to read 
``Reagent heptane, Aldrich Chemical Gold Label, Cat #15,487-3 (or 
equivalent).''
    i. Section 7.4.5 is amended by revising ``Section 5.4.4'' to read 
``7.4.4.''
    j. Section 9.3 is amended by revising the first sentence to read 
``Recovery efficiency must be determined for high ethylene 
concentration, low ethylene concentration, E-P terpolymer, or oil 
extended samples and whenever modifications are made to the method.''
    k. Section 13.1 is amended by revising the last sentence to read 
``Note: These values are examples; each sample type, as specified in 
Section 9.3, must be tested for sample recovery.''
    The revisions read as follows:

Method 310B-Determination of Residual Hexane Through Gas 
Chromatography

* * * * *

6.0  Equipment and Supplies * * *

    6.11  Crimp-top sample vials and HP p/n 5181-1211 crimp caps, or 
screw-top autosampler vials and screw tops.
* * * * *
    7.5.1  Preparation of Polymer Dissolving Solution. Fill a 4,000-ml 
volumetric flask about \3/4\ full with toluene.
* * * * *
    9.3.3  The precipitated polymer from the steps described above 
shall be redissolved using toluene as the solvent. No heptane shall be 
added to the sample in the second dissolving step. The toluene solvent 
and acetone precipitant shall be determined to be free of interfering 
compounds.
* * * * *
    11.1.2  Place crumb sample in bottle: RLA-3: 10 g (gives a dry wt. 
of 5.5 g).
* * * * *
    12.5  After obtaining the final dry weight of polymer used (Section 
11.1.10 of this method), record that result in a ``dry wt.'' column of 
the logbook (for oil extended polymer, the amount of oil extracted is 
added to the dry rubber weight).
* * * * *

    13.  Appendix A to Part 63 is amended by revising Methods 303, 
303A, 304A, 304B, 305, 306, 306A, and 306B to read as follows:

Method 303--Determination of Visible Emissions From By-Product Coke 
Oven Batteries

    Note: This method is not inclusive with respect to observer 
certification. Some material is incorporated by reference from other 
methods in appendix A to 40 CFR part 60. Therefore, to obtain 
reliable results, persons using this method should have a thorough 
knowledge of Method 9.

1.0  Scope and Application

    1.1  Applicability. This method is applicable for the determination 
of visible emissions (VE) from the following by-product coke oven 
battery sources: charging systems during charging; doors, topside port 
lids, and offtake systems on operating coke ovens; and collecting 
mains. This method is also applicable for qualifying observers for 
visually determining the presence of VE.

2.0  Summary of Method

    2.1  A certified observer visually determines the VE from coke oven 
battery sources. Certification procedures are presented. This method 
does not require that opacity of emissions be determined or that 
magnitude be differentiated.

3.0  Definitions

    3.1  Bench means the platform structure in front of the oven doors.
    3.2  By-product Coke Oven Battery means a source consisting of a 
group of ovens connected by common walls, where coal undergoes 
destructive distillation under positive pressure to produce coke and 
coke oven gas, from which by-products are recovered.
    3.3  Charge or charging period means the period of time that 
commences when coal begins to flow into an oven through a topside port 
and ends when the last charging port is recapped.
    3.4  Charging system means an apparatus used to charge coal to a 
coke oven (e.g., a larry car for wet coal charging systems).
    3.5  Coke oven door means each end enclosure on the push side and 
the coking side of an oven. The chuck, or leveler-bar, door is 
considered part of the push side door. The coke oven door area includes 
the entire area on the vertical face of a coke oven between the bench 
and the top of the battery between two adjacent buck stays.
    3.6  Coke side means the side of a battery from which the coke is 
discharged from ovens at the end of the coking cycle.
    3.7  Collecting main means any apparatus that is connected to one 
or more offtake systems and that provides a passage for conveying gases 
under positive pressure from the by-product coke oven battery to the 
by-product recovery system.
    3.8  Consecutive charges means charges observed successively, 
excluding any charge during which the observer's view of the charging 
system or topside ports is obscured.
    3.9  Damper-off means to close off the gas passage between the coke 
oven and the collecting main, with no flow of raw coke oven gas from 
the collecting main into the oven or into the oven's offtake system(s).
    3.10  Decarbonization period means the period of time for 
combusting oven carbon that commences when the oven lids are removed 
from an empty oven or when standpipe caps of an oven are opened. The 
period ends with the initiation of the next charging period for that 
oven.
    3.11  Larry car means an apparatus used to charge coal to a coke 
oven with a wet coal charging system.
    3.12  Log average means logarithmic average as calculated in 
Section 12.4.
    3.13  Offtake system means any individual oven apparatus that is 
stationary and provides a passage for gases from an oven to a coke oven 
battery collecting main or to another oven. Offtake system components 
include the standpipe and standpipe caps, goosenecks, stationary jumper 
pipes, mini-standpipes, and standpipe and gooseneck connections.
    3.14  Operating oven means any oven not out of operation for 
rebuild or maintenance work extensive enough to

[[Page 62217]]

require the oven to be skipped in the charging sequence.
    3.15  Oven means a chamber in the coke oven battery in which coal 
undergoes destructive distillation to produce coke.
    3.16  Push side means the side of the battery from which the coke 
is pushed from ovens at the end of the coking cycle.
    3.17  Run means the observation of visible emissions from topside 
port lids, offtake systems, coke oven doors, or the charging of a 
single oven in accordance with this method.
    3.18  Shed means an enclosure that covers the side of the coke oven 
battery, captures emissions from pushing operations and from leaking 
coke oven doors on the coke side or push side of the coke oven battery, 
and routes the emissions to a control device or system.
    3.19  Standpipe cap means An apparatus used to cover the opening in 
the gooseneck of an offtake system.
    3.20  Topside port lid means a cover, removed during charging or 
decarbonizing, that is placed over the opening through which coal can 
be charged into the oven of a by-product coke oven battery.
    3.21  Traverse time means accumulated time for a traverse as 
measured by a stopwatch. Traverse time includes time to stop and write 
down oven numbers but excludes time waiting for obstructions of view to 
clear or for time to walk around obstacles.
    3.22  Visible Emissions or VE means any emission seen by the 
unaided (except for corrective lenses) eye, excluding steam or 
condensing water.

4.0  Interferences [Reserved]

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Safety Training. Because coke oven batteries have hazardous 
environments, the training materials and the field training (Section 
10.0) shall cover the precautions required by the company to address 
health and safety hazards. Special emphasis shall be given to the 
Occupational Safety and Health Administration (OSHA) regulations 
pertaining to exposure of coke oven workers (see Reference 3 in Section 
16.0). In general, the regulation requires that special fire-retardant 
clothing and respirators be worn in certain restricted areas of the 
coke oven battery. The OSHA regulation also prohibits certain 
activities, such as chewing gum, smoking, and eating in these areas.

6.0  Equipment and Supplies [Reserved]

7.0  Reagents and Standards [Reserved]

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

9.0  Quality Control [Reserved]

10.0  Calibration and Standardization

    Observer certification and training requirements are as follows:
    10.1  Certification Procedures. This method requires only the 
determination of whether VE occur and does not require the 
determination of opacity levels; therefore, observer certification 
according to Method 9 in appendix A to part 60 of this chapter is not 
required to obtain certification under this method. However, in order 
to receive Method 303 observer certification, the first-time observer 
(trainee) shall have attended the lecture portion of the Method 9 
certification course. In addition, the trainee shall successfully 
complete the Method 303 training course, satisfy the field observation 
requirement, and demonstrate adequate performance and sufficient 
knowledge of Method 303. The Method 303 training course shall be 
conducted by or under the sanction of the EPA and shall consist of 
classroom instruction and field observations, and a proficiency test.
    10.1.1  The classroom instruction shall familiarize the trainees 
with Method 303 through lecture, written training materials, and a 
Method 303 demonstration video. A successful completion of the 
classroom portion of the Method 303 training course shall be 
demonstrated by a perfect score on a written test. If the trainee fails 
to answer all of the questions correctly, the trainee may review the 
appropriate portion of the training materials and retake the test.
    10.1.2  The field observations shall be a minimum of 12 hours and 
shall be completed before attending the Method 303 certification 
course. Trainees shall observe the operation of a coke oven battery as 
it pertains to Method 303, including topside operations, and shall also 
practice conducting Method 303 or similar methods. During the field 
observations, trainees unfamiliar with coke battery operations shall 
receive instruction from an experienced coke oven observer familiar 
with Method 303 or similar methods and with the operation of coke 
batteries. The trainee must verify completion of at least 12 hours of 
field observation prior to attending the Method 303 certification 
course.
    10.1.3  All trainees must demonstrate proficiency in the 
application of Method 303 to a panel of three certified Method 303 
observers, including an ability to differentiate coke oven emissions 
from condensing water vapor and smoldering coal. Each panel member 
shall have at least 120 days experience in reading visible emissions 
from coke ovens. The visible emissions inspections that will satisfy 
the experience requirement must be inspections of coke oven battery 
fugitive emissions from the emission points subject to emission 
standards under subpart L of this part (i.e., coke oven doors, topside 
port lids, offtake system(s), and charging operations), using either 
Method 303 or predecessor State or local test methods. A ``day's 
experience'' for a particular inspection is a day on which one complete 
inspection was performed for that emission point under Method 303 or a 
predecessor State or local method. A ``day's experience'' does not mean 
8 or 10 hours performing inspections, or any particular time expressed 
in minutes or hours that may have been spent performing them. Thus, it 
would be possible for an individual to qualify as a Method 303 panel 
member for some emission points, but not others (e.g., an individual 
might satisfy the experience requirement for coke oven doors, but not 
topside port lids). Until November 15, 1994, the EPA may waive the 
certification requirement (but not the experience requirement) for 
panel members. The composition of the panel shall be approved by the 
EPA. The panel shall observe the trainee in a series of training runs 
and a series of certification runs. There shall be a minimum of 1 
training run for doors, topside port lids, and offtake systems, and a 
minimum of 5 training runs (i.e., 5 charges) for charging. During 
training runs, the panel can advise the trainee on proper procedures. 
There shall be a minimum of 3 certification runs for doors, topside 
port lids, and offtake systems, and a minimum of 15 certification runs 
for charging (i.e., 15 charges). The certifications runs shall be 
unassisted. Following the certification test runs, the panel shall 
approve or disapprove certification based on the trainee's performance 
during the certification runs. To obtain certification, the trainee 
shall demonstrate to the satisfaction of the panel a high degree of 
proficiency in performing Method 303. To aid in evaluating the 
trainee's performance, a

[[Page 62218]]

checklist, provided by the EPA, will be used by the panel members.
    10.2  Observer Certification/Recertification. The coke oven 
observer certification is valid for 1 year from date of issue. The 
observer shall recertify annually by viewing the training video and 
answering all of the questions on the certification test correctly. 
Every 3 years, an observer shall be required to pass the proficiency 
test in Section 10.1.3 in order to be certified.
    10.3  The EPA (or applicable enforcement agency) shall maintain 
records reflecting a certified observer's successful completion of the 
proficiency test, which shall include the completed proficiency test 
checklists for the certification runs.
    10.4  An owner or operator of a coke oven battery subject to 
subpart L of this part may observe a training and certification program 
under this section.

11.0  Procedure

    11.1  Procedure for Determining VE from Charging Systems During 
Charging.
    11.1.1  Number of Oven Charges. Refer to Sec. 63.309(c)(1) of this 
part for the number of oven charges to observe. The observer shall 
observe consecutive charges. Charges that are nonconsecutive can only 
be observed when necessary to replace observations terminated prior to 
the completion of a charge because of visual interferences. (See 
Section 11.1.5).
    11.1.2  Data Records. Record all the information requested at the 
top of the charging system inspection sheet (Figure 303-1). For each 
charge, record the identification number of the oven being charged, the 
approximate beginning time of the charge, and the identification of the 
larry car used for the charge.
    11.1.3  Observer Position. Stand in an area or move to positions on 
the topside of the coke oven battery with an unobstructed view of the 
entire charging system. For wet coal charging systems or non-pipeline 
coal charging systems, the observer should have an unobstructed view of 
the emission points of the charging system, including larry car 
hoppers, drop sleeves, and the topside ports of the oven being charged. 
Some charging systems are configured so that all emission points can 
only be seen from a distance of five ovens. For other batteries, 
distances of 8 to 12 ovens are adequate.
    11.1.4  Observation. The charging period begins when coal begins to 
flow into the oven and ends when the last charging port is recapped. 
During the charging period, observe all of the potential sources of VE 
from the entire charging system. For wet coal charging systems or non-
pipeline coal charging systems, sources of VE typically include the 
larry car hoppers, drop sleeves, slide gates, and topside ports on the 
oven being charged. Any VE from an open standpipe cap on the oven being 
charged is included as charging VE.
    11.1.4.1  Using an accumulative-type stopwatch with unit divisions 
of at least 0.5 seconds, determine the total time VE are observed as 
follows. Upon observing any VE emerging from any part of the charging 
system, start the stopwatch. Stop the watch when VE are no longer 
observed emerging, and restart the watch when VE reemerges.
    11.1.4.2  When VE occur simultaneously from several points during a 
charge, consider the sources as one. Time overlapping VE as continuous 
VE. Time single puffs of VE only for the time it takes for the puff to 
emerge from the charging system. Continue to time VE in this manner for 
the entire charging period. Record the accumulated time to the nearest 
0.5 second under ``Visible emissions, seconds'' on Figure 303-1.
    11.1.5  Visual Interference. If fugitive VE from other sources at 
the coke oven battery site (e.g., door leaks or condensing water vapor 
from the coke oven wharf) prevent a clear view of the charging system 
during a charge, stop the stopwatch and make an appropriate notation 
under ``Comments'' on Figure 303-1. Label the observation an 
observation of an incomplete charge, and observe another charge to 
fulfill the requirements of Section 11.1.1.
    11.1.6  VE Exemptions. Do not time the following VE:
    11.1.6.1  The VE from burning or smoldering coal spilled on top of 
the oven, topside port lid, or larry car surfaces;

    Note: The VE from smoldering coal are generally white or gray. 
These VE generally have a plume of less than 1 meter long. If the 
observer cannot safely and with reasonable confidence determine that 
VE are from charging, do not count them as charging emissions.

    11.1.6.2  The VE from the coke oven doors or from the leveler bar; 
or
    11.1.6.3  The VE that drift from the top of a larry car hopper if 
the emissions had already been timed as VE from the drop sleeve.

    Note: When the slide gate on a larry car hopper closes after the 
coal has been added to the oven, the seal may not be airtight. On 
occasions, a puff of smoke observed at the drop sleeves is forced 
past the slide gate up into the larry car hopper and may drift from 
the top; time these VE either at the drop sleeves or the hopper. If 
the larry car hopper does not have a slide gate or the slide gate is 
left open or partially closed, VE may quickly pass through the larry 
car hopper without being observed at the drop sleeves and will 
appear as a strong surge of smoke; time these as charging VE.

    11.1.7  Total Time Record. Record the total time that VE were 
observed for each charging operation in the appropriate column on the 
charging system inspection sheet.
    11.1.8  Determination of Validity of a Set of Observations. Five 
charging observations (runs) obtained in accordance with this method 
shall be considered a valid set of observations for that day. No 
observation of an incomplete charge shall be included in a daily set of 
observations that is lower than the lowest reading for a complete 
charge. If both complete and incomplete charges have been observed, the 
daily set of observations shall include the five highest values 
observed. Four or three charging observations (runs) obtained in 
accordance with this method shall be considered a valid set of charging 
observations only where it is not possible to obtain five charging 
observations, because visual interferences (see Section 11.1.5) or 
inclement weather prevent a clear view of the charging system during 
charging. However, observations from three or four charges that satisfy 
these requirements shall not be considered a valid set of charging 
observations if use of such set of observations in a calculation under 
Section 12.4 would cause the value of A to be less than 145.
    11.1.9  Log Average. For each day on which a valid daily set of 
observations is obtained, calculate the daily 30-day rolling log 
average of seconds of visible emissions from the charging operation for 
each battery using these data and the 29 previous valid daily sets of 
observations, in accordance with Section 12.4.
    11.2.  Procedure for Determining VE from Coke Oven Door Areas. The 
intent of this procedure is to determine VE from coke oven door areas 
by carefully observing the door area from a standard distance while 
walking at a normal pace.
    11.2.1  Number of Runs. Refer to Sec. 63.309(c)(1) of this part for 
the appropriate number of runs.
    11.2.2  Battery Traverse. To conduct a battery traverse, walk the 
length of the battery on the outside of the pusher machine and quench 
car tracks at a steady, normal walking pace, pausing to make 
appropriate entries on the door area inspection sheet (Figure 303-2). A 
single test run consists of two timed traverses, one for the coke side 
and one for the push side. The walking pace shall be such that the 
duration of the traverse does not exceed an average of

[[Page 62219]]

4 seconds per oven door, excluding time spent moving around stationary 
obstructions or waiting for other obstructions to move from positions 
blocking the view of a series of doors. Extra time is allowed for each 
leak (a maximum of 10 additional seconds for each leaking door) for the 
observer to make the proper notation. A walking pace of 3 seconds per 
oven door has been found to be typical. Record the actual traverse time 
with a stopwatch.
    11.2.2.1  Include in the traverse time only the time spent 
observing the doors and recording door leaks. To measure actual 
traverse time, use an accumulative-type stopwatch with unit divisions 
of 0.5 seconds or less. Exclude interruptions to the traverse and time 
required for the observer to move to positions where the view of the 
battery is unobstructed, or for obstructions, such as the door machine, 
to move from positions blocking the view of a series of doors.
    11.2.2.2  Various situations may arise that will prevent the 
observer from viewing a door or a series of doors. Prior to the door 
inspection, the owner or operator may elect to temporarily suspend 
charging operations for the duration of the inspection, so that all of 
the doors can be viewed by the observer. The observer has two options 
for dealing with obstructions to view: (a) Stop the stopwatch and wait 
for the equipment to move or the fugitive emissions to dissipate before 
completing the traverse; or (b) stop the stopwatch, skip the affected 
ovens, and move to an unobstructed position to continue the traverse. 
Restart the stopwatch and continue the traverse. After the completion 
of the traverse, if the equipment has moved or the fugitive emissions 
have dissipated, inspect the affected doors. If the equipment is still 
preventing the observer from viewing the doors, then the affected doors 
may be counted as not observed. If option (b) is used because of doors 
blocked by machines during charging operations, then, of the affected 
doors, exclude the door from the most recently charged oven from the 
inspection. Record the oven numbers and make an appropriate notation 
under ``Comments'' on the door area inspection sheet (Figure 303-2).
    11.2.2.3  When batteries have sheds to control emissions, conduct 
the inspection from outside the shed unless the doors cannot be 
adequately viewed. In this case, conduct the inspection from the bench. 
Be aware of special safety considerations pertinent to walking on the 
bench and follow the instructions of company personnel on the required 
equipment and procedures. If possible, conduct the bench traverse 
whenever the bench is clear of the door machine and hot coke guide.
    11.2.3  Observations. Record all the information requested at the 
top of the door area inspection sheet (Figure 303-2), including the 
number of non-operating ovens. Record the clock time at the start of 
the traverse on each side of the battery. Record which side is being 
inspected (i.e., coke side or push side). Other information may be 
recorded at the discretion of the observer, such as the location of the 
leak (e.g., top of the door, chuck door, etc.), the reason for any 
interruption of the traverse, or the position of the sun relative to 
the battery and sky conditions (e.g., overcast, partly sunny, etc.).
    11.2.3.1  Begin the test run by starting the stopwatch and 
traversing either the coke side or the push side of the battery. After 
completing one side, stop the watch. Complete this procedure on the 
other side. If inspecting more than one battery, the observer may view 
the push sides and the coke sides sequentially.
    11.2.3.2  During the traverse, look around the entire perimeter of 
each oven door. The door is considered leaking if VE are detected in 
the coke oven door area. The coke oven door area includes the entire 
area on the vertical face of a coke oven between the bench and the top 
of the battery between two adjacent buck stays (e.g., the oven door, 
chuck door, between the masonry brick, buck stay or jamb, or other 
sources). Record the oven number and make the appropriate notation on 
the door area inspection sheet (Figure 303-2).


    Note: Multiple VE from the same door area (e.g., VE from both 
the chuck door and the push side door) are counted as only one 
emitting door, not as multiple emitting doors.


    11.2.3.3  Do not record the following sources as door area VE:
    11.2.3.3.1  VE from ovens with doors removed. Record the oven 
number and make an appropriate notation under ``Comments;''
    11.2.3.3.2  VE from ovens taken out of service. The owner or 
operator shall notify the observer as to which ovens are out of 
service. Record the oven number and make an appropriate notation under 
``Comments;'' or
    11.2.3.3.3  VE from hot coke that has been spilled on the bench as 
a result of pushing.
    11.2.4  Criteria for Acceptance. After completing the run, 
calculate the maximum time allowed to observe the ovens using the 
equation in Section 12.2. If the total traverse time exceeds T, void 
the run, and conduct another run to satisfy the requirements of 
Sec. 63.309(c)(1) of this part.
    11.2.5  Percent Leaking Doors. For each day on which a valid 
observation is obtained, calculate the daily 30-day rolling average for 
each battery using these data and the 29 previous valid daily 
observations, in accordance with Section 12.5.
    11.3  Procedure for Determining VE from Topside Port Lids and 
Offtake Systems.
    11.3.1  Number of Runs. Refer to Sec. 63.309(c)(1) of this part for 
the number of runs to be conducted. Simultaneous runs or separate runs 
for the topside port lids and offtake systems may be conducted.
    11.3.2  Battery Traverse. To conduct a topside traverse of the 
battery, walk the length of the battery at a steady, normal walking 
pace, pausing only to make appropriate entries on the topside 
inspection sheet (Figure 303-3). The walking pace shall not exceed an 
average rate of 4 seconds per oven, excluding time spent moving around 
stationary obstructions or waiting for other obstructions to move from 
positions blocking the view. Extra time is allowed for each leak for 
the observer to make the proper notation. A walking pace of 3 seconds 
per oven is typical. Record the actual traverse time with a stopwatch.
    11.3.3  Topside Port Lid Observations. To observe lids of the ovens 
involved in the charging operation, the observer shall wait to view the 
lids until approximately 5 minutes after the completion of the charge. 
Record all the information requested on the topside inspection sheet 
(Figure 303-3). Record the clock time when traverses begin and end. If 
the observer's view is obstructed during the traverse (e.g., steam from 
the coke wharf, larry car, etc.), follow the guidelines given in 
Section 11.2.2.2.
    11.3.3.1  To perform a test run, conduct a single traverse on the 
topside of the battery. The observer shall walk near the center of the 
battery but may deviate from this path to avoid safety hazards (such as 
open or closed charging ports, luting buckets, lid removal bars, and 
topside port lids that have been removed) and any other obstacles. Upon 
noting VE from the topside port lid(s) of an oven, record the oven 
number and port number, then resume the traverse. If any oven is 
dampered-off from the collecting main for decarbonization, note this 
under ``Comments'' for that particular oven.


    Note: Count the number of topside ports, not the number of 
points, exhibiting VE, i.e., if a topside port has several points of 
VE, count this as one port exhibiting VE.



[[Page 62220]]


    11.3.3.2  Do not count the following as topside port lid VE:
    11.3.3.2.1  VE from between the brickwork and oven lid casing or VE 
from cracks in the oven brickwork. Note these VE under ``Comments;''
    11.3.3.2.2  VE from topside ports involved in a charging operation. 
Record the oven number, and make an appropriate notation (e.g., not 
observed because ports open for charging) under ``Comments;''
    11.3.3.2.3  Topside ports having maintenance work done. Record the 
oven number and make an appropriate notation under ``Comments;'' or
    11.3.3.2.4  Condensing water from wet-sealing material. Ports with 
only visible condensing water from wet-sealing material are counted as 
observed but not as having VE.
    11.3.3.2.5  Visible emissions from the flue inspection ports and 
caps.
    11.3.4  Offtake Systems Observations. To perform a test run, 
traverse the battery as in Section 11.3.3.1. Look ahead and back two to 
four ovens to get a clear view of the entire offtake system for each 
oven. Consider visible emissions from the following points as offtake 
system VE: (a) the flange between the gooseneck and collecting main 
(``saddle''), (b) the junction point of the standpipe and oven 
(``standpipe base''), (c) the other parts of the offtake system (e.g., 
the standpipe cap), and (d) the junction points with ovens and flanges 
of jumper pipes.
    11.3.4.1  Do not stray from the traverse line in order to get a 
``closer look'' at any part of the offtake system unless it is to 
distinguish leaks from interferences from other sources or to avoid 
obstacles.
    11.3.4.2  If the centerline does not provide a clear view of the 
entire offtake system for each oven (e.g., when standpipes are longer 
than 15 feet), the observer may conduct the traverse farther from 
(rather than closer to) the offtake systems.
    11.3.4.3  Upon noting a leak from an offtake system during a 
traverse, record the oven number. Resume the traverse. If the oven is 
dampered-off from the collecting main for decarbonization and VE are 
observed, note this under ``Comments'' for that particular oven.
    11.3.4.4  If any part or parts of an offtake system have VE, count 
it as one emitting offtake system. Each stationary jumper pipe is 
considered a single offtake system.
    11.3.4.5  Do not count standpipe caps open for a decarbonization 
period or standpipes of an oven being charged as source of offtake 
system VE. Record the oven number and write ``Not observed'' and the 
reason (i.e., decarb or charging) under ``Comments.''


    Note: VE from open standpipes of an oven being charged count as 
charging emissions. All VE from closed standpipe caps count as 
offtake leaks.


    11.3.5  Criteria for Acceptance. After completing the run (allow 2 
traverses for batteries with double mains), calculate the maximum time 
allowed to observe the topside port lids and/or offtake systems using 
the equation in Section 12.3. If the total traverse time exceeds T, 
void the run and conduct another run to satisfy the requirements of 
Sec. 63.309(c)(1) of this part.
    11.3.6  In determining the percent leaking topside port lids and 
percent leaking offtake systems, do not include topside port lids or 
offtake systems with VE from the following ovens:
    11.3.6.1  Empty ovens, including ovens undergoing maintenance, 
which are properly dampered off from the main.
    11.3.6.2  Ovens being charged or being pushed.
    11.3.6.3  Up to 3 full ovens that have been dampered off from the 
main prior to pushing.
    11.3.6.4  Up to 3 additional full ovens in the pushing sequence 
that have been dampered off from the main for offtake system cleaning, 
for decarbonization, for safety reasons, or when a charging/pushing 
schedule involves widely separated ovens (e.g., a Marquard system); or 
that have been dampered off from the main for maintenance near the end 
of the coking cycle. Examples of reasons that ovens are dampered off 
for safety reasons are to avoid exposing workers in areas with 
insufficient clearance between standpipes and the larry car, or in 
areas where workers could be exposed to flames or hot gases from open 
standpipes, and to avoid the potential for removing a door on an oven 
that is not dampered off from the main.
    11.3.7  Percent Leaking Topside Port Lids and Offtake Systems. For 
each day on which a valid observation is obtained, calculate the daily 
30-day rolling average for each battery using these data and the 29 
previous valid daily observations, in accordance with Sections 12.6 and 
12.7.
    11.4  Procedure for Determining VE from Collecting Mains.
    11.4.1  Traverse. To perform a test run, traverse both the 
collecting main catwalk and the battery topside along the side closest 
to the collecting main. If the battery has a double main, conduct two 
sets of traverses for each run, i.e., one set for each main.
    11.4.2  Data Recording. Upon noting VE from any portion of a 
collection main, identify the source and approximate location of the 
source of VE and record the time under ``Collecting main'' on Figure 
303-3; then resume the traverse.
    11.4.3  Collecting Main Pressure Check. After the completion of the 
door traverse, the topside port lids, and offtake systems, compare the 
collecting main pressure during the inspection to the collecting main 
pressure during the previous 8 to 24 hours. Record the following: (a) 
the pressure during inspection, (b) presence of pressure deviation from 
normal operations, and (c) the explanation for any pressure deviation 
from normal operations, if any, offered by the operators. The owner or 
operator of the coke battery shall maintain the pressure recording 
equipment and conduct the quality assurance/quality control (QA/QC) 
necessary to ensure reliable pressure readings and shall keep the QA/QC 
records for at least 6 months. The observer may periodically check the 
QA/QC records to determine their completeness. The owner or operator 
shall provide access to the records within 1 hour of an observer's 
request.

12.0  Data Analysis and Calculations

    12.1  Nomenclature.

A = 150 or the number of valid observations (runs). The value of A 
shall not be less than 145, except for purposes of determinations under 
Sec. 63.306(c) (work practice plan implementation) or Sec. 63.306(d) 
(work practice plan revisions) of this part. No set of observations 
shall be considered valid for such a recalculation that otherwise would 
not be considered a valid set of observations for a calculation under 
this paragraph.
Di = Number of doors on non-operating ovens.
Dno = Number of doors not observed.
Dob = Total number of doors observed on operating ovens.
Dt = Total number of oven doors on the battery.
e = 2.72
J = Number of stationary jumper pipes.
L = Number of doors with VE.
Lb = Yard-equivalent reading.
Ls = Number of doors with VE observed from the bench under 
sheds.
Ly = Number of doors with VE observed from the yard.
Ly = Number of doors with VE observed from the yard on the 
push side.
ln = Natural logarithm.
N = Total number of ovens in the battery.
Ni = Total number of inoperable ovens.
PNO = Number of ports not observed.
Povn = Number of ports per oven.

[[Page 62221]]

PVE = Number of topside port lids with VE.
PLD = Percent leaking coke oven doors for the test run.
PLL = Percent leaking topside port lids for the run.
PLO = Percent leaking offtake systems.
T = Total time allowed for traverse, seconds.
Tovn = Number of offtake systems (excluding jumper pipes) 
per oven.
TNO = Number of offtake systems not observed.
TVE = Number of offtake systems with VE.
Xi = Seconds of VE during the ith charge.
Z = Number of topside port lids or offtake systems with VE.

    12.2  Criteria for Acceptance for VE Determinations from Coke Oven 
Door Areas. After completing the run, calculate the maximum time 
allowed to observe the ovens using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.535

    12.3  Criteria for Acceptance for VE Determinations from Topside 
Port Lids and Offtake Systems. After completing the run (allow 2 
traverses for batteries with double mains), calculate the maximum time 
allowed to observe the topside port lids and/or offtake systems by the 
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.536

    12.4  Average Duration of VE from Charging Operations. Use Equation 
303-3 to calculate the daily 30-day rolling log average of seconds of 
visible emissions from the charging operation for each battery using 
these current day's observations and the 29 previous valid daily sets 
of observations.
[GRAPHIC] [TIFF OMITTED] TR17OC00.537

    12.5  Percent Leaking Doors (PLD). Determine the total number of 
doors for which observations were made on the coke oven battery as 
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.538

    12.5.1  For each test run (one run includes both the coke side and 
the push side traverses), sum the number of doors with door area VE. 
For batteries subject to an approved alternative standard under 
Sec. 63.305 of this part, calculate the push side and the coke side PLD 
separately.
    12.5.2  Calculate percent leaking doors by using Equation 303-5:
    [GRAPHIC] [TIFF OMITTED] TR17OC00.539
    
    12.5.3  When traverses are conducted from the bench under sheds, 
calculate the coke side and the push side separately. Use Equation 303-
6 to calculate a yard-equivalent reading:
[GRAPHIC] [TIFF OMITTED] TR17OC00.540

If Lb is less than zero, use zero for Lb in 
Equation 303-7 in the calculation of PLD.
    12.5.3.1  Use Equation 303-7 to calculate PLD:
    [GRAPHIC] [TIFF OMITTED] TR17OC00.541
    
Round off PLD to the nearest hundredth of 1 percent and record as the 
percent leaking coke oven doors for the run.
    12.5.3.2  Average Percent Leaking Doors. Use Equation 303-8 to 
calculate the daily 30-day rolling average percent leaking doors for 
each battery using these current day's observations and the 29 previous 
valid daily sets of observations.
[GRAPHIC] [TIFF OMITTED] TR17OC00.542

    12.6  Topside Port Lids. Determine the percent leaking topside port 
lids for each run as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.543

    12.6.1  Round off this percentage to the nearest hundredth of 1 
percent and record this percentage as the percent leaking topside port 
lids for the run.
    12.6.2  Average Percent Leaking Topside Port Lids. Use Equation 
303-10 to calculate the daily 30-day rolling average percent leaking 
topside port lids for each battery using these current day's 
observations and the 29 previous valid daily sets of observations.

[[Page 62222]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.544

    12.7  Offtake Systems. Determine the percent leaking offtake 
systems for the run as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.545

    12.7.1  Round off this percentage to the nearest hundredth of 1 
percent and record this percentage as the percent leaking offtake 
systems for the run.
    12.7.2  Average Percent Leaking Offtake Systems. Use Equation 303-
12 to calculate the daily 30-day rolling average percent leaking 
offtake systems for each battery using these current day's observations 
and the 29 previous valid daily sets of observations.
[GRAPHIC] [TIFF OMITTED] TR17OC00.546

13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References.

    1. Missan, R., and A. Stein. Guidelines for Evaluation of 
Visible Emissions Certification, Field Procedures, Legal Aspects, 
and Background Material. U.S. Environmental Protection Agency. EPA 
Publication No. EPA-340/1-75-007. April 1975.
    2. Wohlschlegel, P., and D. E. Wagoner. Guideline for 
Development of a Quality Assurance Program: Volume IX--Visual 
Determination of Opacity Emission from Stationary Sources. U.S. 
Environmental Protection Agency. EPA Publication No. EPA-650/4-74-
005i. November 1975.
    3. U.S. Occupational Safety and Health Administration. Code of 
Federal Regulations. Title 29, Chapter XVII, Section 1910.1029(g). 
Washington, D.C. Government Printing Office. July 1, 1990.
    4. U.S. Environmental Protection Agency. National Emission 
Standards for Hazardous Air Pollutants; Coke Oven Emissions from 
Wet-Coal Charged By-Product Coke Oven Batteries; Proposed Rule and 
Notice of Public Hearing. Washington, D.C. Federal Register. Vol. 
52, No. 78 (13586). April 23, 1987.

17.0  Tables, Diagrams, Flowcharts, and Validation Data

Company name:----------------------------------------------------------
Battery no.: ______ Date: ______ Run no.: ______
City, State:-----------------------------------------------------------
Observer name:---------------------------------------------------------
Company representative(s):---------------------------------------------

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                                                                     Visible emissions,
           Charge No.                 Oven No.         Clock time          seconds               Comments
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[[Page 62223]]

 
 
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Figure 303-1. Charging System Inspection
Company name:---------------------------------------------------------
Battery no.:----------------------------------------------------------
Date:-----------------------------------------------------------------
City, State:----------------------------------------------------------
Total no. of ovens in battery:----------------------------------------
Observer name:--------------------------------------------------------
Certification expiration date:----------------------------------------
Inoperable ovens:-----------------------------------------------------
Company representative(s):--------------------------------------------
Traverse time CS:-----------------------------------------------------
Traverse time PS:-----------------------------------------------------
Valid run (Y or N):---------------------------------------------------

----------------------------------------------------------------------------------------------------------------
                                                                          Comments  (No. of blocked doors,
      Time traverse started/completed         PS/CS      Door No.         interruptions to traverse, etc.)
----------------------------------------------------------------------------------------------------------------
 
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Figure 303-2. Door Area Inspection.

[[Page 62224]]

Company name:---------------------------------------------------------
Battery no.:----------------------------------------------------------
Date:-----------------------------------------------------------------
City, State:----------------------------------------------------------
Total no. of ovens in battery:----------------------------------------
Observer name:--------------------------------------------------------
Certification expiration date:----------------------------------------
Inoperable ovens:-----------------------------------------------------
Company representative(s):--------------------------------------------
Total no. of lids:----------------------------------------------------
Total no. of offtakes:------------------------------------------------
Total no. of jumper pipes:--------------------------------------------
Ovens not observed:---------------------------------------------------
Total traverse time:--------------------------------------------------
Valid run (Y or N):---------------------------------------------------

----------------------------------------------------------------------------------------------------------------
                                    Type of Inspection
 Time traverse started/completed     (lids, offtakes,     Location of VE  (Oven #/Port #)         Comments
                                     collecting main)
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Figure 303-3. Topside Inspection

Method 303A--Determination of Visible Emissions From Nonrecovery 
Coke Oven Batteries

    Note: This method does not include all of the specifications 
pertaining to observer certification. Some material is incorporated 
by reference from other methods in this part and in appendix A to 40 
CFR Part 60. Therefore, to obtain reliable results, persons using 
this method should have a thorough knowledge of Method 9 and Method 
303.

1.0  Scope and Application

    1.1  Applicability. This method is applicable for the determination 
of visible emissions (VE) from leaking doors at nonrecovery coke oven 
batteries.

2.0  Summary of Method

    2.1  A certified observer visually determines the VE from coke oven 
battery sources while walking at a normal pace. This method does not 
require that opacity of emissions be determined or that magnitude be 
differentiated.

3.0  Definitions

    3.1  Bench means the platform structure in front of the oven doors.

[[Page 62225]]

    3.2  Coke oven door means each end enclosure on the push side and 
the coking side of an oven.
    3.3  Coke side means the side of a battery from which the coke is 
discharged from ovens at the end of the coking cycle.
    3.4  Nonrecovery coke oven battery means a source consisting of a 
group of ovens connected by common walls and operated as a unit, where 
coal undergoes destructive distillation under negative pressure to 
produce coke, and which is designed for the combustion of coke oven gas 
from which by-products are not recovered.
    3.5  Operating oven means any oven not out of operation for rebuild 
or maintenance work extensive enough to require the oven to be skipped 
in the charging sequence.
    3.6  Oven means a chamber in the coke oven battery in which coal 
undergoes destructive distillation to produce coke.
    3.7  Push side means the side of the battery from which the coke is 
pushed from ovens at the end of the coking cycle.
    3.8  Run means the observation of visible emissions from coke oven 
doors in accordance with this method.
    3.9  Shed means an enclosure that covers the side of the coke oven 
battery, captures emissions from pushing operations and from leaking 
coke oven doors on the coke side or push side of the coke oven battery, 
and routes the emissions to a control device or system.
    3.10  Traverse time means accumulated time for a traverse as 
measured by a stopwatch. Traverse time includes time to stop and write 
down oven numbers but excludes time waiting for obstructions of view to 
clear or for time to walk around obstacles.
    3.11  Visible Emissions or VE means any emission seen by the 
unaided (except for corrective lenses) eye, excluding steam or 
condensing water.

4.0  Interferences. [Reserved]

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user of this test method to establish appropriate safety and health 
practices and determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Safety Training. Because coke oven batteries have hazardous 
environments, the training materials and the field training (Section 
10.0) shall cover the precautions required by the company to address 
health and safety hazards. Special emphasis shall be given to the 
Occupational Safety and Health Administration (OSHA) regulations 
pertaining to exposure of coke oven workers (see Reference 3 in Section 
16.0). In general, the regulation requires that special fire-retardant 
clothing and respirators be worn in certain restricted areas of the 
coke oven battery. The OSHA regulation also prohibits certain 
activities, such as chewing gum, smoking, and eating in these areas.

6.0  Equipment and Supplies. [Reserved]

7.0  Reagents and Standards [Reserved]

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

9.0  Quality Control. [Reserved]

10.0  Calibration and Standardization.

    10.1  Training. This method requires only the determination of 
whether VE occur and does not require the determination of opacity 
levels; therefore, observer certification according to Method 9 in 
Appendix A to Part 60 is not required. However, the first-time observer 
(trainee) shall have attended the lecture portion of the Method 9 
certification course. Furthermore, before conducting any VE 
observations, an observer shall become familiar with nonrecovery coke 
oven battery operations and with this test method by observing for a 
minimum of 4 hours the operation of a nonrecovery coke oven battery in 
the presence of personnel experienced in performing Method 303 
assessments.

11.0  Procedure

    The intent of this procedure is to determine VE from coke oven door 
areas by carefully observing the door area while walking at a normal 
pace.
    11.1  Number of Runs. Refer to Sec. 63.309(c)(1) of this part for 
the appropriate number of runs.
    11.2  Battery Traverse. To conduct a battery traverse, walk the 
length of the battery on the outside of the pusher machine and quench 
car tracks at a steady, normal walking pace, pausing to make 
appropriate entries on the door area inspection sheet (Figure 303A-1). 
The walking pace shall be such that the duration of the traverse does 
not exceed an average of 4 seconds per oven door, excluding time spent 
moving around stationary obstructions or waiting for other obstructions 
to move from positions blocking the view of a series of doors. Extra 
time is allowed for each leak (a maximum of 10 additional seconds for 
each leaking door) for the observer to make the proper notation. A 
walking pace of 3 seconds per oven door has been found to be typical. 
Record the actual traverse time with a stopwatch. A single test run 
consists of two timed traverses, one for the coke side and one for the 
push side.
    11.2.1  Various situations may arise that will prevent the observer 
from viewing a door or a series of doors. The observer has two options 
for dealing with obstructions to view: (a) Wait for the equipment to 
move or the fugitive emissions to dissipate before completing the 
traverse; or (b) skip the affected ovens and move to an unobstructed 
position to continue the traverse. Continue the traverse. After the 
completion of the traverse, if the equipment has moved or the fugitive 
emissions have dissipated, complete the traverse by inspecting the 
affected doors. Record the oven numbers and make an appropriate 
notation under ``Comments'' on the door area inspection sheet (Figure 
303A-1).


    Note: Extra time incurred for handling obstructions is not 
counted in the traverse time.


    11.2.2  When batteries have sheds to control pushing emissions, 
conduct the inspection from outside the shed, if the shed allows such 
observations, or from the bench. Be aware of special safety 
considerations pertinent to walking on the bench and follow the 
instructions of company personnel on the required equipment and 
operations procedures. If possible, conduct the bench traverse whenever 
the bench is clear of the door machine and hot coke guide.
    11.3  Observations. Record all the information requested at the top 
of the door area inspection sheet (Figure 303A-1), including the number 
of non-operating ovens. Record which side is being inspected, i.e., 
coke side or push side. Other information may be recorded at the 
discretion of the observer, such as the location of the leak (e.g., top 
of the door), the reason for any interruption of the traverse, or the 
position of the sun relative to the battery and sky conditions (e.g., 
overcast, partly sunny, etc.).
    11.3.1  Begin the test run by traversing either the coke side or 
the push side of the battery. After completing one side, traverse the 
other side.
    11.3.2  During the traverse, look around the entire perimeter of 
each oven door. The door is considered leaking if VE are detected in 
the coke oven door area. The coke oven door area includes the entire 
area on the vertical face of a coke oven between the bench and the top 
of the battery and the

[[Page 62226]]

adjacent doors on both sides. Record the oven number and make the 
appropriate notation on the door area inspection sheet (Figure 303A-1).
    11.3.3  Do not record the following sources as door area VE:
    11.3.3.1  VE from ovens with doors removed. Record the oven number 
and make an appropriate notation under ``Comments'';
    11.3.3.2  VE from ovens where maintenance work is being conducted. 
Record the oven number and make an appropriate notation under 
``Comments''; or
    11.3.3.3  VE from hot coke that has been spilled on the bench as a 
result of pushing.

12.0  Data Analysis and Calculations

    Same as Method 303, Section 12.1, 12.2, 12.3, 12.4, and 12.5.

13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    Same as Method 303, Section 16.0.

17.0  Tables, Diagrams, Flowcharts, and Validation Data

Company name:---------------------------------------------------------
Battery no.:----------------------------------------------------------
Date:-----------------------------------------------------------------
City, State:----------------------------------------------------------
Total no. of ovens in battery:----------------------------------------
Observer name:--------------------------------------------------------
Certification expiration date:----------------------------------------
Inoperable ovens:-----------------------------------------------------
Company representative(s):--------------------------------------------
Traverse time CS:-----------------------------------------------------
Traverse time PS:-----------------------------------------------------
Valid run (Y or N):---------------------------------------------------

----------------------------------------------------------------------------------------------------------------
                                                                          Comments  (No. of blocked doors,
      Time traverse started/completed         PS/CS      Door No.         interruptions to traverse, etc.)
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Figure 303A-1. Door Area Inspection

[[Page 62227]]

Method 304A: Determination of Biodegradation Rates of Organic 
Compounds (Vent Option)

1.0  Scope and Application

    1.1  Applicability. This method is applicable for the determination 
of biodegradation rates of organic compounds in an activated sludge 
process. The test method is designed to evaluate the ability of an 
aerobic biological reaction system to degrade or destroy specific 
components in waste streams. The method may also be used to determine 
the effects of changes in wastewater composition on operation. The 
biodegradation rates determined by utilizing this method are not 
representative of a full-scale system. The rates measured by this 
method shall be used in conjunction with the procedures listed in 
appendix C of this part to calculate the fraction emitted to the air 
versus the fraction biodegraded.

2.0  Summary of Method

    2.1  A self-contained benchtop bioreactor system is assembled in 
the laboratory. A sample of mixed liquor is added and the waste stream 
is then fed continuously. The benchtop bioreactor is operated under 
conditions nearly identical to the target full-scale activated sludge 
process. Bioreactor temperature, dissolved oxygen concentration, 
average residence time in the reactor, waste composition, biomass 
concentration, and biomass composition of the full-scale process are 
the parameters which are duplicated in the benchtop bioreactor. Biomass 
shall be removed from the target full-scale activated sludge unit and 
held for no more than 4 hours prior to use in the benchtop bioreactor. 
If antifoaming agents are used in the full-scale system, they shall 
also be used in the benchtop bioreactor. The feed flowing into and the 
effluent exiting the benchtop bioreactor are analyzed to determine the 
biodegradation rates of the target compounds. The flow rate of the exit 
vent is used to calculate the concentration of target compounds 
(utilizing Henry's law) in the exit gas stream. If Henry's law 
constants for the compounds of interest are not known, this method 
cannot be used in the determination of the biodegradation rate and 
Method 304B is the suggested method. The choice of analytical 
methodology for measuring the compounds of interest at the inlet and 
outlet to the benchtop bioreactor are left to the discretion of the 
source, except where validated methods are available.

3.0  Definitions. [Reserved]

4.0  Interferences. [Reserved]

5.0  Safety

    5.1  If explosive gases are produced as a byproduct of 
biodegradation and could realistically pose a hazard, closely monitor 
headspace concentration of these gases to ensure laboratory safety. 
Placement of the benchtop bioreactor system inside a laboratory hood is 
recommended regardless of byproducts produced.

6.0.  Equipment and Supplies

    Note: Figure 304A-1 illustrates a typical laboratory apparatus 
used to measure biodegradation rates. While the following 
description refers to Figure 304A-1, the EPA recognizes that 
alternative reactor configurations, such as alternative reactor 
shapes and locations of probes and the feed inlet, will also meet 
the intent of this method. Ensure that the benchtop bioreactor 
system is self-contained and isolated from the atmosphere (except 
for the exit vent stream) by leak-checking fittings, tubing, etc.


    6.1  Benchtop Bioreactor. The biological reaction is conducted in a 
biological oxidation reactor of at least 6 liters capacity. The 
benchtop bioreactor is sealed and equipped with internal probes for 
controlling and monitoring dissolved oxygen and internal temperature. 
The top of the reactor is equipped for aerators, gas flow ports, and 
instrumentation (while ensuring that no leaks to the atmosphere exist 
around the fittings).
    6.2  Aeration gas. Aeration gas is added to the benchtop bioreactor 
through three diffusers, which are glass tubes that extend to the 
bottom fifth of the reactor depth. A pure oxygen pressurized cylinder 
is recommended in order to maintain the specified oxygen concentration. 
Install a blower (e.g., Diaphragm Type, 15 SCFH capacity) to blow the 
aeration gas into the reactor diffusers. Measure the aeration gas flow 
rate with a rotameter (e.g., 0-15 SCFH recommended). The aeration gas 
will rise through the benchtop bioreactor, dissolving oxygen into the 
mixture in the process. The aeration gas must provide sufficient 
agitation to keep the solids in suspension. Provide an exit for the 
aeration gas from the top flange of the benchtop bioreactor through a 
water-cooled (e.g., Allihn-type) vertical condenser. Install the 
condenser through a gas-tight fitting in the benchtop bioreactor 
closure. Install a splitter which directs a portion of the gas to an 
exit vent and the rest of the gas through an air recycle pump back to 
the benchtop bioreactor. Monitor and record the flow rate through the 
exit vent at least 3 times per day throughout the day.
    6.3  Wastewater Feed. Supply the wastewater feed to the benchtop 
bioreactor in a collapsible low-density polyethylene container or 
collapsible liner in a container (e.g., 20 L) equipped with a spigot 
cap (collapsible containers or liners of other material may be required 
due to the permeability of some volatile compounds through 
polyethylene). Obtain the wastewater feed by sampling the wastewater 
feed in the target process. A representative sample of wastewater shall 
be obtained from the piping leading to the aeration tank. This sample 
may be obtained from existing sampling valves at the discharge of the 
wastewater feed pump, or collected from a pipe discharging to the 
aeration tank, or by pumping from a well-mixed equalization tank 
upstream from the aeration tank. Alternatively, wastewater can be 
pumped continuously to the laboratory apparatus from a bleed stream 
taken from the equalization tank of the full-scale treatment system.
    6.3.1  Refrigeration System. Keep the wastewater feed cool by ice 
or by refrigeration to 4 deg.C. If using a bleed stream from the 
equalization tank, refrigeration is not required if the residence time 
in the bleed stream is less than five minutes.
    6.3.2  Wastewater Feed Pump. The wastewater is pumped from the 
refrigerated container using a variable-speed peristaltic pump drive 
equipped with a peristaltic pump head. Add the feed solution to the 
benchtop bioreactor through a fitting on the top flange. Determine the 
rate of feed addition to provide a retention time in the benchtop 
bioreactor that is numerically equivalent to the retention time in the 
full-scale system. The wastewater shall be fed at a rate sufficient to 
achieve 90 to 100 percent of the full-scale system residence time.
    6.3.3  Treated wastewater feed. The benchtop bioreactor effluent 
exits at the bottom of the reactor through a tube and proceeds to the 
clarifier.
    6.4  Clarifier. The effluent flows to a separate closed clarifier 
that allows separation of biomass and effluent (e.g., 2-liter pear-
shaped glass separatory funnel, modified by removing the stopcock and 
adding a 25-mm OD glass tube at the bottom). Benchtop bioreactor 
effluent enters the clarifier through a tube inserted to a depth of 
0.08 m (3 in.) through a stopper at the top of the

[[Page 62228]]

clarifier. System effluent flows from a tube inserted through the 
stopper at the top of the clarifier to a drain (or sample bottle when 
sampling). The underflow from the clarifier leaves from the glass tube 
at the bottom of the clarifier. Flexible tubing connects this fitting 
to the sludge recycle pump. This pump is coupled to a variable speed 
pump drive. The discharge from this pump is returned through a tube 
inserted in a port on the side of the benchtop bioreactor. An 
additional port is provided near the bottom of the benchtop bioreactor 
for sampling the reactor contents. The mixed liquor from the benchtop 
bioreactor flows into the center of the clarifier. The clarified system 
effluent separates from the biomass and flows through an exit near the 
top of the clarifier. There shall be no headspace in the clarifier.
    6.5  Temperature Control Apparatus. Capable of maintaining the 
system at a temperature equal to the temperature of the full-scale 
system. The average temperature should be maintained within 
2  deg.C of the set point.
    6.5.1  Temperature Monitoring Device. A resistance type temperature 
probe or a thermocouple connected to a temperature readout with a 
resolution of 0.1  deg.C or better.
    6.5.2  Benchtop Bioreactor Heater. The heater is connected to the 
temperature control device.
    6.6  Oxygen Control System. Maintain the dissolved oxygen 
concentration at the levels present in the full-scale system. Target 
full-scale activated sludge systems with dissolved oxygen concentration 
below 2 mg/L are required to maintain the dissolved oxygen 
concentration in the benchtop ioreactor within 0.5 mg/L of the target 
dissolved oxygen level. Target full-scale activated sludge systems with 
dissolved oxygen concentration above 2 mg/L are required to maintain 
the dissolved oxygen concentration in the benchtop bioreactor within 
1.5 mg/L of the target dissolved oxygen concentration; however, for 
target full-scale activated sludge systems with dissolved oxygen 
concentrations above 2 mg/L, the dissolved oxygen concentration in the 
benchtop bioreactor may not drop below 1.5 mg/L. If the benchtop 
bioreactor is outside the control range, the dissolved oxygen is noted 
and the reactor operation is adjusted.
    6.6.1  Dissolved Oxygen Monitor. Dissolved oxygen is monitored with 
a polarographic probe (gas permeable membrane) connected to a dissolved 
oxygen meter (e.g., 0 to 15 mg/L, 0 to 50  deg.C).
    6.6.2  Benchtop Bioreactor Pressure Monitor. The benchtop 
bioreactor pressure is monitored through a port in the top flange of 
the reactor. This is connected to a gauge control with a span of 13-cm 
water vacuum to 13-cm water pressure or better. A relay is activated 
when the vacuum exceeds an adjustable setpoint which opens a solenoid 
valve (normally closed), admitting oxygen to the system. The vacuum 
setpoint controlling oxygen addition to the system shall be set at 
approximately 2.5  0.5 cm water and maintained at this 
setting except during brief periods when the dissolved oxygen 
concentration is adjusted.
    6.7  Connecting Tubing. All connecting tubing shall be Teflon or 
equivalent in impermeability. The only exception to this specification 
is the tubing directly inside the pump head of the wastewater feed 
pump, which may be Viton, Silicone or another type of flexible tubing.

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

7.0  Reagents and Standards

    7.1  Wastewater. Obtain a representative sample of wastewater at 
the inlet to the full-scale treatment plant if there is an existing 
full-scale treatment plant (see section 6.3). If there is no existing 
full-scale treatment plant, obtain the wastewater sample as close to 
the point of determination as possible. Collect the sample by pumping 
the wastewater into the 20-L collapsible container. The loss of 
volatiles shall be minimized from the wastewater by collapsing the 
container before filling, by minimizing the time of filling, and by 
avoiding a headspace in the container after filling. If the wastewater 
requires the addition of nutrients to support the biomass growth and 
maintain biomass characteristics, those nutrients are added and mixed 
with the container contents after the container is filled.
    7.2  Biomass. Obtain the biomass or activated sludge used for rate 
constant determination in the bench-scale process from the existing 
full-scale process or from a representative biomass culture (e.g., 
biomass that has been developed for a future full-scale process). This 
biomass is preferentially obtained from a thickened acclimated mixed 
liquor sample. Collect the sample either by bailing from the mixed 
liquor in the aeration tank with a weighted container, or by collecting 
aeration tank effluent at the effluent overflow weir. Transport the 
sample to the laboratory within no more than 4 hours of collection. 
Maintain the biomass concentration in the benchtop bioreactor at the 
level of the full-scale system +10 percent throughout the sampling 
period of the test method.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Benchtop Bioreactor Operation. Charge the mixed liquor to the 
benchtop bioreactor, minimizing headspace over the liquid surface to 
minimize entrainment of mixed liquor in the circulating gas. Fasten the 
benchtop bioreactor headplate to the reactor over the liquid surface. 
Maintain the temperature of the contents of the benchtop bioreactor 
system at the temperature of the target full-scale system, 
2  deg.C, throughout the testing period. Monitor and record 
the temperature of the benchtop bioreactor contents at least to the 
nearest 0.1  deg.C.
    8.1.1  Wastewater Storage. Collect the wastewater sample in the 20-
L collapsible container. Store the container at 4  deg.C throughout the 
testing period. Connect the container to the benchtop bioreactor feed 
pump.
    8.1.2  Wastewater Flow Rate.
    8.1.2.1  The hydraulic residence time of the aeration tank is 
calculated as the ratio of the volume of the tank (L) to the flow rate 
(L/min). At the beginning of a test, the container shall be connected 
to the feed pump and solution shall be pumped to the benchtop 
bioreactor at the required flow rate to achieve the calculated 
hydraulic residence time of wastewater in the aeration tank.
[GRAPHIC] [TIFF OMITTED] TR17OC00.547

Where:

Qtest = wastewater flow rate (L/min)
Qfs = average flow rate of full-scale process (L/min)
Vfs = volume of full-scale aeration tank (L)

    8.1.2.2  The target flow rate in the test apparatus is the same as 
the flow rate in the target full-scale process

[[Page 62229]]

multiplied by the ratio of benchtop bioreactor volume (e.g., 6 L) to 
the volume of the full-scale aeration tank. The hydraulic residence 
time shall be maintained at 90 to 100 percent of the residence time 
maintained in the full-scale unit. A nominal flow rate is set on the 
pump based on a pump calibration. Changes in the elasticity of the 
tubing in the pump head and the accumulation of material in the tubing 
affect this calibration. The nominal pumping rate shall be changed as 
necessary based on volumetric flow measurements. Discharge the benchtop 
bioreactor effluent to a wastewater storage, treatment, or disposal 
facility, except during sampling or flow measurement periods.
    8.1.3  Sludge Recycle Rate. Set the sludge recycle rate at a rate 
sufficient to prevent accumulation in the bottom of the clarifier. Set 
the air circulation rate sufficient to maintain the biomass in 
suspension.
    8.1.4  Benchtop Bioreactor Operation and Maintenance. Temperature, 
dissolved oxygen concentration, exit vent flow rate, benchtop 
bioreactor effluent flow rate, and air circulation rate shall be 
measured and recorded three times throughout each day of benchtop 
bioreactor operation. If other parameters (such as pH) are measured and 
maintained in the target full-scale unit, these parameters, where 
appropriate, shall be monitored and maintained to target full-scale 
specifications in the benchtop bioreactor. At the beginning of each 
sampling period (Section 8.2), sample the benchtop bioreactor contents 
for suspended solids analysis. Take this sample by loosening a clamp on 
a length of tubing attached to the lower side port. Determine the 
suspended solids gravimetrically by the Gooch crucible/glass fiber 
filter method for total suspended solids, in accordance with Standard 
Methods\3\ or equivalent. When necessary, sludge shall be wasted from 
the lower side port of the benchtop bioreactor, and the volume that is 
wasted shall be replaced with an equal volume of the reactor effluent. 
Add thickened activated sludge mixed liquor as necessary to the 
benchtop bioreactor to increase the suspended solids concentration to 
the desired level. Pump this mixed liquor to the benchtop bioreactor 
through the upper side port (Item 24 in Figure 304A-1). Change the 
membrane on the dissolved oxygen probe before starting the test. 
Calibrate the oxygen probe immediately before the start of the test and 
each time the membrane is changed.
    8.1.5  Inspection and Correction Procedures. If the feed line 
tubing becomes clogged, replace with new tubing. If the feed flow rate 
is not within 5 percent of target flow any time the flow rate is 
measured, reset pump or check the flow measuring device and measure 
flow rate again until target flow rate is achieved.
    8.2  Test Sampling. At least two and one half hydraulic residence 
times after the system has reached the targeted specifications shall be 
permitted to elapse before the first sample is taken. Effluent samples 
of the clarifier discharge (Item 20 in Figure 304A-1) and the influent 
wastewater feed are collected in 40-mL septum vials to which two drops 
of 1:10 hydrochloric acid (HCl) in water have been added. Sample the 
clarifier discharge directly from the drain line. These samples will be 
composed of the entire flow from the system for a period of several 
minutes. Feed samples shall be taken from the feed pump suction line 
after temporarily stopping the benchtop bioreactor feed, removing a 
connector, and squeezing the collapsible feed container. Store both 
influent and effluent samples at 4  deg.C immediately after collection 
and analyze within 8 hours of collection.
    8.2.1  Frequency of Sampling. During the test, sample and analyze 
the wastewater feed and the clarifier effluent at least six times. The 
sampling intervals shall be separated by at least 8 hours. During any 
individual sampling interval, sample the wastewater feed simultaneously 
with or immediately after the effluent sample. Calculate the relative 
standard deviation (RSD) of the amount removed (i.e., effluent 
concentration--wastewater feed concentration). The RSD values shall be  
15 percent. If an RSD value is > 15 percent, continue sampling and 
analyzing influent and effluent sets of samples until the RSD values 
are within specifications.
    8.2.2  Sampling After Exposure of System to Atmosphere. If, after 
starting sampling procedures, the benchtop bioreactor system is exposed 
to the atmosphere (due to leaks, maintenance, etc.), allow at least one 
hydraulic residence time to elapse before resuming sampling.

9.0  Quality Control

    9.1  Dissolved Oxygen. Fluctuation in dissolved oxygen 
concentration may occur for numerous reasons, including undetected gas 
leaks, increases and decreases in mixed liquor suspended solids 
resulting from cell growth and solids loss in the effluent stream, 
changes in diffuser performance, cycling of effluent flow rate, and 
overcorrection due to faulty or sluggish dissolved oxygen probe 
response. Control the dissolved oxygen concentration in the benchtop 
bioreactor by changing the proportion of oxygen in the circulating 
aeration gas. Should the dissolved oxygen concentration drift below the 
designated experimental condition, bleed a small amount of aeration gas 
from the system on the pressure side (i.e., immediately upstream of one 
of the diffusers). This will create a vacuum in the system, triggering 
the pressure sensitive relay to open the solenoid valve and admit 
oxygen to the system. Should the dissolved oxygen concentration drift 
above the designated experimental condition, slow or stop the oxygen 
input to the system until the dissolved oxygen concentration approaches 
the correct level.
    9.2  Sludge Wasting.
    9.2.1  Determine the suspended solids concentration (section 8.1.4) 
at the beginning of a test, and once per day thereafter during the 
test. If the test is completed within a two day period, determine the 
suspended solids concentration after the final sample set is taken. If 
the suspended solids concentration exceeds the specified concentration, 
remove a fraction of the sludge from the benchtop bioreactor. The 
required volume of mixed liquor to remove is determined as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.548

Where:

Vw is the wasted volume (Liters),
Vr is the volume of the benchtop bioreactor (Liters),
Sm is the measured solids (g/L), and
Ss is the specified solids (g/L).

    9.2.2  Remove the mixed liquor from the benchtop bioreactor by 
loosening a clamp on the mixed liquor sampling tube and allowing the 
required volume to drain to a graduated flask. Clamp the tube when the 
correct volume has been

[[Page 62230]]

wasted. Replace the volume of the liquid wasted by pouring the same 
volume of effluent back into the benchtop bioreactor. Dispose of the 
waste sludge properly.
    9.3  Sludge Makeup. In the event that the suspended solids 
concentration is lower than the specifications, add makeup sludge back 
into the benchtop bioreactor. Determine the amount of sludge added by 
the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.549

Where:

Vw is the volume of sludge to add (Liters),
Vr is the volume of the benchtop bioreactor (Liters),
Sw is the solids in the makeup sludge (g/L),
Sm is the measured solids (g/L), and Ss is the 
specified solids (g/L).

10.0  Calibration and Standardization

    10.1  Wastewater Pump Calibration. Determine the wastewater flow 
rate by collecting the system effluent for a time period of at least 
one hour, and measuring the volume with a graduated cylinder. Record 
the collection time period and volume collected. Determine flow rate. 
Adjust the pump speed to deliver the specified flow rate.
    10.2  Calibration Standards. Prepare calibration standards from 
pure certified standards in an aqueous medium. Prepare and analyze 
three concentrations of calibration standards for each target component 
(or for a mixture of components) in triplicate daily throughout the 
analyses of the test samples. At each concentration level, a single 
calibration shall be within 5 percent of the average of the three 
calibration results. The low and medium calibration standards shall 
bracket the expected concentration of the effluent (treated) 
wastewater. The medium and high standards shall bracket the expected 
influent concentration.

11.0  Analytical Procedures

    11.1  Analysis. If the identity of the compounds of interest in the 
wastewater is not known, a representative sample of the wastewater 
shall be analyzed in order to identify all of the compounds of interest 
present. A gas chromatography/mass spectrometry screening method is 
recommended.
    11.1.1  After identifying the compounds of interest in the 
wastewater, develop and/or use one or more analytical techniques 
capable of measuring each of those compounds (more than one analytical 
technique may be required, depending on the characteristics of the 
wastewater). Test Method 18, found in appendix A of 40 CFR 60, may be 
used as a guideline in developing the analytical technique. Purge and 
trap techniques may be used for analysis providing the target 
components are sufficiently volatile to make this technique 
appropriate. The limit of quantitation for each compound shall be 
determined (see reference 1). If the effluent concentration of any 
target compound is below the limit of quantitation determined for that 
compound, the operation of the Method 304 unit may be altered to 
attempt to increase the effluent concentration above the limit of 
quantitation. Modifications to the method shall be approved prior to 
the test. The request should be addressed to Method 304 contact, 
Emissions Measurement Center, Mail Drop 19, U.S. Environmental 
Protection Agency, Research Triangle Park, NC 27711.

12.0  Data Analysis and Calculations

    12.1  Nomenclature. The following symbols are used in the 
calculations.

Ci = Average inlet feed concentration for a compound of 
interest, as analyzed (mg/L)
Co = Average outlet (effluent) concentration for a compound 
of interest, as analyzed (mg/L)
X = Biomass concentration, mixed liquor suspended solids (g/L)
t = Hydraulic residence time in the benchtop bioreactor (hours)
V = Volume of the benchtop bioreactor (L)
Q = Flow rate of wastewater into the benchtop bioreactor, average (L/
hour)

    12.2  Residence Time. The hydraulic residence time of the benchtop 
bioreactor is equal to the ratio of the volume of the benchtop 
bioreactor (L) to the flow rate (L/h):
[GRAPHIC] [TIFF OMITTED] TR17OC00.550

    12.3  Rate of Biodegradation. Calculate the rate of biodegradation 
for each component with the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.551

    12.4  First-Order Biorate Constant. Calculate the first-order 
biorate constant (K1) for each component with the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.552

    12.5  Relative Standard Deviation (RSD). Determine the standard 
deviation of both the influent and effluent sample concentrations (S) 
using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.553


[[Page 62231]]


    12.6  Determination of Percent Air Emissions and Percent 
Biodegraded. Use the results from this test method and follow the 
applicable procedures in appendix C of 40 CFR part 63, entitled, 
``Determination of the Fraction Biodegraded (Fbio) in a 
Biological Treatment Unit'' to determine Fbio.

13.0  Method Performance, [Reserved]

14.0  Pollution Prevention, [Reserved]

15.0  Waste Management, [Reserved]

16.0  References

    1. ``Guidelines for data acquisition and data quality evaluation 
in Environmental Chemistry,'' Daniel MacDoughal, Analytical 
Chemistry, Volume 52, p. 2242, 1980.
    2. Test Method 18, 40 CFR 60, appendix A.
    3. Standard Methods for the Examination of Water and Wastewater, 
16th Edition, Method 209C, Total Suspended Solids Dried at 103-105 
deg.C, APHA, 1985.
    4. Water7, Hazardous Waste Treatment, Storage, and Disposal 
Facilities (TSDF)--Air Emission Models, U.S. Environmental 
Protection Agency, EPA-450/3-87-026, Review Draft, November 1989.
    5. Chemdat7, Hazardous Waste Treatment, Storage, and Disposal 
Facilities (TSDF)--Air Emission Models, U.S. Environmental 
Protection Agency, EPA-450/3-87-026, Review Draft, November 1989.

[[Page 62232]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.554


[[Page 62233]]



Method 304B: Determination of Biodegradation Rates of Organic 
Compounds (Scrubber Option)

1.0  Scope and Application

    1.1  Applicability. This method is applicable for the determination 
of biodegradation rates of organic compounds in an activated sludge 
process. The test method is designed to evaluate the ability of an 
aerobic biological reaction system to degrade or destroy specific 
components in waste streams. The method may also be used to determine 
the effects of changes in wastewater composition on operation. The 
biodegradation rates determined by utilizing this method are not 
representative of a full-scale system. Full-scale systems embody 
biodegradation and air emissions in competing reactions. This method 
measures biodegradation in absence of air emissions. The rates measured 
by this method shall be used in conjunction with the procedures listed 
in appendix C of this part to calculate the fraction emitted to the air 
versus the fraction biodegraded.

2.0  Summary of Method

    2.1  A self-contained benchtop bioreactor system is assembled in 
the laboratory. A sample of mixed liquor is added and the waste stream 
is then fed continuously. The benchtop bioreactor is operated under 
conditions nearly identical to the target full-scale activated sludge 
process, except that air emissions are not a factor. The benchtop 
bioreactor temperature, dissolved oxygen concentration, average 
residence time in the reactor, waste composition, biomass 
concentration, and biomass composition of the target full-scale process 
are the parameters which are duplicated in the laboratory system. 
Biomass shall be removed from the target full-scale activated sludge 
unit and held for no more than 4 hours prior to use in the benchtop 
bioreactor. If antifoaming agents are used in the full-scale system, 
they shall also be used in the benchtop bioreactor. The feed flowing 
into and the effluent exiting the benchtop bioreactor are analyzed to 
determine the biodegradation rates of the target compounds. The choice 
of analytical methodology for measuring the compounds of interest at 
the inlet and outlet to the benchtop bioreactor are left to the 
discretion of the source, except where validated methods are available.

3.0  Definitions. [Reserved]

4.0  Interferences. [Reserved]

5.0  Safety

    5.1  If explosive gases are produced as a byproduct of 
biodegradation and could realistically pose a hazard, closely monitor 
headspace concentration of these gases to ensure laboratory safety. 
Placement of the benchtop bioreactor system inside a laboratory hood is 
recommended regardless of byproducts produced.

6.0  Equipment and Supplies

    Note: Figure 304B-1 illustrates a typical laboratory apparatus 
used to measure biodegradation rates. While the following 
description refers to Figure 304B-1, the EPA recognizes that 
alternative reactor configurations, such as alternative reactor 
shapes and locations of probes and the feed inlet, will also meet 
the intent of this method. Ensure that the benchtop bioreactor 
system is self-contained and isolated from the atmosphere by leak-
checking fittings, tubing, etc.

    6.1  Benchtop Bioreactor. The biological reaction is conducted in a 
biological oxidation reactor of at least 6-liters capacity. The 
benchtop bioreactor is sealed and equipped with internal probes for 
controlling and monitoring dissolved oxygen and internal temperature. 
The top of the benchtop bioreactor is equipped for aerators, gas flow 
ports, and instrumentation (while ensuring that no leaks to the 
atmosphere exist around the fittings).
    6.2  Aeration gas. Aeration gas is added to the benchtop bioreactor 
through three diffusers, which are glass tubes that extend to the 
bottom fifth of the reactor depth. A pure oxygen pressurized cylinder 
is recommended in order to maintain the specified oxygen concentration. 
Install a blower (e.g., Diaphragm Type, 15 SCFH capacity) to blow the 
aeration gas into the benchtop bioreactor diffusers. Measure the 
aeration gas flow rate with a rotameter (e.g., 0-15 SCFH recommended). 
The aeration gas will rise through the benchtop bioreactor, dissolving 
oxygen into the mixture in the process. The aeration gas must provide 
sufficient agitation to keep the solids in suspension. Provide an exit 
for the aeration gas from the top flange of the benchtop bioreactor 
through a water-cooled (e.g., Allihn-type) vertical condenser. Install 
the condenser through a gas-tight fitting in the benchtop bioreactor 
closure. Design the system so that at least 10 percent of the gas flows 
through an alkaline scrubber containing 175 mL of 45 percent by weight 
solution of potassium hydroxide (KOH) and 5 drops of 0.2 percent 
alizarin yellow dye. Route the balance of the gas through an adjustable 
scrubber bypass. Route all of the gas through a 1-L knock-out flask to 
remove entrained moisture and then to the intake of the blower. The 
blower recirculates the gas to the benchtop bioreactor.
    6.3  Wastewater Feed. Supply the wastewater feed to the benchtop 
bioreactor in a collapsible low-density polyethylene container or 
collapsible liner in a container (e.g., 20 L) equipped with a spigot 
cap (collapsible containers or liners of other material may be required 
due to the permeability of some volatile compounds through 
polyethylene). Obtain the wastewater feed by sampling the wastewater 
feed in the target process. A representative sample of wastewater shall 
be obtained from the piping leading to the aeration tank. This sample 
may be obtained from existing sampling valves at the discharge of the 
wastewater feed pump, or collected from a pipe discharging to the 
aeration tank, or by pumping from a well-mixed equalization tank 
upstream from the aeration tank. Alternatively, wastewater can be 
pumped continuously to the laboratory apparatus from a bleed stream 
taken from the equalization tank of the full-scale treatment system.
    6.3.1  Refrigeration System. Keep the wastewater feed cool by ice 
or by refrigeration to 4 deg.C. If using a bleed stream from the 
equalization tank, refrigeration is not required if the residence time 
in the bleed stream is less than five minutes.
    6.3.2  Wastewater Feed Pump. The wastewater is pumped from the 
refrigerated container using a variable-speed peristaltic pump drive 
equipped with a peristaltic pump head. Add the feed solution to the 
benchtop bioreactor through a fitting on the top flange. Determine the 
rate of feed addition to provide a retention time in the benchtop 
bioreactor that is numerically equivalent to the retention time in the 
target full-scale system. The wastewater shall be fed at a rate 
sufficient to achieve 90 to 100 percent of the target full-scale system 
residence time.
    6.3.3  Treated wastewater feed. The benchtop bioreactor effluent 
exits at the bottom of the reactor through a tube and proceeds to the 
clarifier.
    6.4  Clarifier. The effluent flows to a separate closed clarifier 
that allows separation of biomass and effluent (e.g., 2-liter pear-
shaped glass separatory funnel, modified by removing the stopcock and 
adding a 25-mm OD glass tube at the bottom). Benchtop bioreactor 
effluent enters the clarifier through a tube inserted to a depth of 
0.08 m (3 in.)

[[Page 62234]]

through a stopper at the top of the clarifier. System effluent flows 
from a tube inserted through the stopper at the top of the clarifier to 
a drain (or sample bottle when sampling). The underflow from the 
clarifier leaves from the glass tube at the bottom of the clarifier. 
Flexible tubing connects this fitting to the sludge recycle pump. This 
pump is coupled to a variable speed pump drive. The discharge from this 
pump is returned through a tube inserted in a port on the side of the 
benchtop bioreactor. An additional port is provided near the bottom of 
the benchtop bioreactor for sampling the reactor contents. The mixed 
liquor from the benchtop bioreactor flows into the center of the 
clarifier. The clarified system effluent separates from the biomass and 
flows through an exit near the top of the clarifier. There shall be no 
headspace in the clarifier.
    6.5  Temperature Control Apparatus. Capable of maintaining the 
system at a temperature equal to the temperature of the full-scale 
system. The average temperature should be maintained within 
2  deg.C of the set point.
    6.5.1  Temperature Monitoring Device. A resistance type temperature 
probe or a thermocouple connected to a temperature readout with a 
resolution of 0.1 deg.C or better.
    6.5.2  Benchtop Bioreactor Heater. The heater is connected to the 
temperature control device.
    6.6  Oxygen Control System. Maintain the dissolved oxygen 
concentration at the levels present in the full-scale system. Target 
full-scale activated sludge systems with dissolved oxygen concentration 
below 2 mg/L are required to maintain the dissolved oxygen 
concentration in the benchtop bioreactor within 0.5 mg/L of the target 
dissolved oxygen level. Target full-scale activated sludge systems with 
dissolved oxygen concentration above 2 mg/L are required to maintain 
the dissolved oxygen concentration in the benchtop bioreactor within 
1.5 mg/L of the target dissolved oxygen concentration; however, for 
target full-scale activated sludge systems with dissolved oxygen 
concentrations above 2 mg/L, the dissolved oxygen concentration in the 
benchtop bioreactor may not drop below 1.5 mg/L. If the benchtop 
bioreactor is outside the control range, the dissolved oxygen is noted 
and the reactor operation is adjusted.
    6.6.1  Dissolved Oxygen Monitor. Dissolved oxygen is monitored with 
a polarographic probe (gas permeable membrane) connected to a dissolved 
oxygen meter (e.g., 0 to 15 mg/L, 0 to 50 deg.C).
    6.6.2  Benchtop Bioreactor Pressure Monitor. The benchtop 
bioreactor pressure is monitored through a port in the top flange of 
the reactor. This is connected to a gauge control with a span of 13-cm 
water vacuum to 13-cm water pressure or better. A relay is activated 
when the vacuum exceeds an adjustable setpoint which opens a solenoid 
valve (normally closed), admitting oxygen to the system. The vacuum 
setpoint controlling oxygen addition to the system shall be set at 
approximately 2.5  0.5 cm water and maintained at this 
setting except during brief periods when the dissolved oxygen 
concentration is adjusted.
    6.7  Connecting Tubing. All connecting tubing shall be Teflon or 
equivalent in impermeability. The only exception to this specification 
is the tubing directly inside the pump head of the wastewater feed 
pump, which may be Viton, Silicone or another type of flexible tubing.

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

7.0.  Reagents and Standards

    7.1  Wastewater. Obtain a representative sample of wastewater at 
the inlet to the full-scale treatment plant if there is an existing 
full-scale treatment plant (See Section 6.3). If there is no existing 
full-scale treatment plant, obtain the wastewater sample as close to 
the point of determination as possible. Collect the sample by pumping 
the wastewater into the 20-L collapsible container. The loss of 
volatiles shall be minimized from the wastewater by collapsing the 
container before filling, by minimizing the time of filling, and by 
avoiding a headspace in the container after filling. If the wastewater 
requires the addition of nutrients to support the biomass growth and 
maintain biomass characteristics, those nutrients are added and mixed 
with the container contents after the container is filled.
    7.2  Biomass. Obtain the biomass or activated sludge used for rate 
constant determination in the bench-scale process from the existing 
full-scale process or from a representative biomass culture (e.g., 
biomass that has been developed for a future full-scale process). This 
biomass is preferentially obtained from a thickened acclimated mixed 
liquor sample. Collect the sample either by bailing from the mixed 
liquor in the aeration tank with a weighted container, or by collecting 
aeration tank effluent at the effluent overflow weir. Transport the 
sample to the laboratory within no more than 4 hours of collection. 
Maintain the biomass concentration in the benchtop bioreactor at the 
level of the target full-scale system +10 percent throughout the 
sampling period of the test method.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Benchtop Bioreactor Operation. Charge the mixed liquor to the 
benchtop bioreactor, minimizing headspace over the liquid surface to 
minimize entrainment of mixed liquor in the circulating gas. Fasten the 
benchtop bioreactor headplate to the reactor over the liquid surface. 
Maintain the temperature of the contents of the benchtop bioreactor 
system at the temperature of the target full-scale system, 
2  deg.C, throughout the testing period. Monitor and record 
the temperature of the reactor contents at least to the nearest 
0.1 deg.C.
    8.1.1  Wastewater Storage. Collect the wastewater sample in the 20-
L collapsible container. Store the container at 4  deg.C throughout the 
testing period. Connect the container to the benchtop bioreactor feed 
pump.
    8.1.2  Wastewater Flow Rate.
    8.1.2.1  The hydraulic residence time of the aeration tank is 
calculated as the ratio of the volume of the tank (L) to the flow rate 
(L/min). At the beginning of a test, the container shall be connected 
to the feed pump and solution shall be pumped to the benchtop 
bioreactor at the required flow rate to achieve the calculated 
hydraulic residence time of wastewater in the aeration tank.
[GRAPHIC] [TIFF OMITTED] TR17OC00.555

Where:

Qtest = wastewater flow rate (L/min)
Qfs = average flow rate of full-scale process (L/min)
Vfs = volume of full-scale aeration tank (L)


[[Page 62235]]


    8.1.2.2  The target flow rate in the test apparatus is the same as 
the flow rate in the target full-scale process multiplied by the ratio 
of benchtop bioreactor volume (e.g., 6 L) to the volume of the full-
scale aeration tank. The hydraulic residence time shall be maintained 
at 90 to 100 percent of the residence time maintained in the target 
full-scale unit. A nominal flow rate is set on the pump based on a pump 
calibration. Changes in the elasticity of the tubing in the pump head 
and the accumulation of material in the tubing affect this calibration. 
The nominal pumping rate shall be changed as necessary based on 
volumetric flow measurements. Discharge the benchtop bioreactor 
effluent to a wastewater storage, treatment, or disposal facility, 
except during sampling or flow measurement periods.
    8.1.3  Sludge Recycle Rate. Set the sludge recycle rate at a rate 
sufficient to prevent accumulation in the bottom of the clarifier. Set 
the air circulation rate sufficient to maintain the biomass in 
suspension.
    8.1.4  Benchtop Bioreactor Operation and Maintenance. Temperature, 
dissolved oxygen concentration, flow rate, and air circulation rate 
shall be measured and recorded three times throughout each day of 
testing. If other parameters (such as pH) are measured and maintained 
in the target full-scale unit, these parameters shall, where 
appropriate, be monitored and maintained to full-scale specifications 
in the benchtop bioreactor. At the beginning of each sampling period 
(section 8.2), sample the benchtop bioreactor contents for suspended 
solids analysis. Take this sample by loosening a clamp on a length of 
tubing attached to the lower side port. Determine the suspended solids 
gravimetrically by the Gooch crucible/glass fiber filter method for 
total suspended solids, in accordance with Standard Methods3 
or equivalent. When necessary, sludge shall be wasted from the lower 
side port of the benchtop bioreactor, and the volume that is wasted 
shall be replaced with an equal volume of the benchtop bioreactor 
effluent. Add thickened activated sludge mixed liquor as necessary to 
the benchtop bioreactor to increase the suspended solids concentration 
to the desired level. Pump this mixed liquor to the benchtop bioreactor 
through the upper side port (Item 24 in Figure 304B-1). Change the 
membrane on the dissolved oxygen probe before starting the test. 
Calibrate the oxygen probe immediately before the start of the test and 
each time the membrane is changed. The scrubber solution shall be 
replaced each weekday with 175 mL 45 percent W/W KOH solution to which 
five drops of 0.2 percent alizarin yellow indicator in water have been 
added. The potassium hydroxide solution in the alkaline scrubber shall 
be changed if the alizarin yellow dye color changes.
    8.1.5  Inspection and Correction Procedures. If the feed line 
tubing becomes clogged, replace with new tubing. If the feed flow rate 
is not within 5 percent of target flow any time the flow rate is 
measured, reset pump or check the flow measuring device and measure 
flow rate again until target flow rate is achieved.
    8.2  Test Sampling. At least two and one half hydraulic residence 
times after the system has reached the targeted specifications shall be 
permitted to elapse before the first sample is taken. Effluent samples 
of the clarifier discharge (Item 20 in Figure 304B-1) and the influent 
wastewater feed are collected in 40-mL septum vials to which two drops 
of 1:10 hydrochloric acid (HCl) in water have been added. Sample the 
clarifier discharge directly from the drain line. These samples will be 
composed of the entire flow from the system for a period of several 
minutes. Feed samples shall be taken from the feed pump suction line 
after temporarily stopping the benchtop bioreactor feed, removing a 
connector, and squeezing the collapsible feed container. Store both 
influent and effluent samples at 4 deg.C immediately after collection 
and analyze within 8 hours of collection.
    8.2.1  Frequency of Sampling. During the test, sample and analyze 
the wastewater feed and the clarifier effluent at least six times. The 
sampling intervals shall be separated by at least 8 hours. During any 
individual sampling interval, sample the wastewater feed simultaneously 
with or immediately after the effluent sample. Calculate the RSD of the 
amount removed (i.e., effluent concentration--wastewater feed 
concentration). The RSD values shall be 15 percent. If an RSD value is 
>15 percent, continue sampling and analyzing influent and effluent sets 
of samples until the RSD values are within specifications.
    8.2.2  Sampling After Exposure of System to Atmosphere. If, after 
starting sampling procedures, the benchtop bioreactor system is exposed 
to the atmosphere (due to leaks, maintenance, etc.), allow at least one 
hydraulic residence time to elapse before resuming sampling.

9.0  Quality Control

    9.1  Dissolved Oxygen. Fluctuation in dissolved oxygen 
concentration may occur for numerous reasons, including undetected gas 
leaks, increases and decreases in mixed liquor suspended solids 
resulting from cell growth and solids loss in the effluent stream, 
changes in diffuser performance, cycling of effluent flow rate, and 
overcorrection due to faulty or sluggish dissolved oxygen probe 
response. Control the dissolved oxygen concentration in the benchtop 
bioreactor by changing the proportion of oxygen in the circulating 
aeration gas. Should the dissolved oxygen concentration drift below the 
designated experimental condition, bleed a small amount of aeration gas 
from the system on the pressure side (i.e., immediately upstream of one 
of the diffusers). This will create a vacuum in the system, triggering 
the pressure sensitive relay to open the solenoid valve and admit 
oxygen to the system. Should the dissolved oxygen concentration drift 
above the designated experimental condition, slow or stop the oxygen 
input to the system until the dissolved oxygen concentration approaches 
the correct level.
    9.2  Sludge Wasting.
    9.2.1  Determine the suspended solids concentration (section 8.1.4) 
at the beginning of a test, and once per day thereafter during the 
test. If the test is completed within a two day period, determine the 
suspended solids concentration after the final sample set is taken. If 
the suspended solids concentration exceeds the specified concentration, 
remove a fraction of the sludge from the benchtop bioreactor. The 
required volume of mixed liquor to remove is determined as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.556


[[Page 62236]]


Where:

Vw is the wasted volume (Liters),
Vr is the volume of the benchtop bioreactor (Liters),
Sm is the measured solids (g/L), and
Ss is the specified solids (g/L).

    9.2.2  Remove the mixed liquor from the benchtop bioreactor by 
loosening a clamp on the mixed liquor sampling tube and allowing the 
required volume to drain to a graduated flask. Clamp the tube when the 
correct volume has been wasted. Replace the volume of the liquid wasted 
by pouring the same volume of effluent back into the benchtop 
bioreactor. Dispose of the waste sludge properly.
    9.3  Sludge Makeup. In the event that the suspended solids 
concentration is lower than the specifications, add makeup sludge back 
into the benchtop bioreactor. Determine the amount of sludge added by 
the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.557

Where:

Vw is the volume of sludge to add (Liters),
Vr is the volume of the benchtop bioreactor (Liters),
Sw is the solids in the makeup sludge (g/L),
Sm is the measured solids (g/L), and
Ss is the specified solids (g/L).

10.0  Calibration and Standardizations

    10.1  Wastewater Pump Calibration. Determine the wastewater flow 
rate by collecting the system effluent for a time period of at least 
one hour, and measuring the volume with a graduated cylinder. Record 
the collection time period and volume collected. Determine flow rate. 
Adjust the pump speed to deliver the specified flow rate.
    10.2  Calibration Standards. Prepare calibration standards from 
pure certified standards in an aqueous medium. Prepare and analyze 
three concentrations of calibration standards for each target component 
(or for a mixture of components) in triplicate daily throughout the 
analyses of the test samples. At each concentration level, a single 
calibration shall be within 5 percent of the average of the three 
calibration results. The low and medium calibration standards shall 
bracket the expected concentration of the effluent (treated) 
wastewater. The medium and high standards shall bracket the expected 
influent concentration.

11.0  Analytical Test Procedures

    11.1  Analysis. If the identity of the compounds of interest in the 
wastewater is not known, a representative sample of the wastewater 
shall be analyzed in order to identify all of the compounds of interest 
present. A gas chromatography/mass spectrometry screening method is 
recommended.
    11.1.1  After identifying the compounds of interest in the 
wastewater, develop and/or use one or more analytical technique capable 
of measuring each of those compounds (more than one analytical 
technique may be required, depending on the characteristics of the 
wastewater). Method 18, found in appendix A of 40 CFR 60, may be used 
as a guideline in developing the analytical technique. Purge and trap 
techniques may be used for analysis providing the target components are 
sufficiently volatile to make this technique appropriate. The limit of 
quantitation for each compound shall be determined.\1\ If the effluent 
concentration of any target compound is below the limit of quantitation 
determined for that compound, the operation of the Method 304 unit may 
be altered to attempt to increase the effluent concentration above the 
limit of quantitation. Modifications to the method shall be approved 
prior to the test. The request should be addressed to Method 304 
contact, Emissions Measurement Center, Mail Drop 19, U.S. Environmental 
Protection Agency, Research Triangle Park, NC 27711.

12.0  Data Analysis and Calculations

    12.1  Nomenclature. The following symbols are used in the 
calculations.

Ci = Average inlet feed concentration for a compound of 
interest, as analyzed (mg/L)
Co = Average outlet (effluent) concentration for a compound 
of interest, as analyzed (mg/L)
X = Biomass concentration, mixed liquor suspended solids (g/L)
t = Hydraulic residence time in the benchtop bioreactor (hours)
V = Volume of the benchtop bioreactor (L)
Q = Flow rate of wastewater into the benchtop bioreactor, average (L/
hour)

    12.2  Residence Time. The hydraulic residence time of the benchtop 
bioreactor is equal to the ratio of the volume of the benchtop 
bioreactor (L) to the flow rate (L/h)
[GRAPHIC] [TIFF OMITTED] TR17OC00.558

    12.3  Rate of Biodegradation. Calculate the rate of biodegradation 
for each component with the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.559

    12.4  First-Order Biorate Constant. Calculate the first-order 
biorate constant (K1) for each component with the following equation:

[[Page 62237]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.560

    12.5  Relative Standard Deviation (RSD). Determine the standard 
deviation of both the influent and effluent sample concentrations (S) 
using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.561

    12.6  Determination of Percent Air Emissions and Percent 
Biodegraded. Use the results from this test method and follow the 
applicable procedures in appendix C of 40 CFR Part 63, entitled, 
``Determination of the Fraction Biodegraded (Fbio) in a 
Biological Treatment Unit'' to determine Fbio.

13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References

    1. ``Guidelines for data acquisition and data quality evaluation 
in Environmental Chemistry'', Daniel MacDoughal, Analytical 
Chemistry, Volume 52, p. 2242, 1980.
    2. Test Method 18, 40 CFR 60, Appendix A.
    3. Standard Methods for the Examination of Water and Wastewater, 
16th Edition, Method 209C, Total Suspended Solids Dried at 103-
105 deg.C, APHA, 1985.
    4. Water--7, Hazardous Waste Treatment, Storage, and Disposal 
Facilities (TSDF)--Air Emission Models, U.S. Environmental 
Protection Agency, EPA-450/3-87-026, Review Draft, November 1989.
    5. Chemdat7, Hazardous Waste Treatment, Storage, and Disposal 
Facilities (TSDF)--Air Emission Models, U.S. Environmental 
Protection Agency, EPA-450/3-87-026, Review Draft, November 1989.
BILLING CODE 6560-50-P

[[Page 62238]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.562

BILLING CODE 6560-50-C

[[Page 62239]]

Method 305: Measurement of Emission Potential of Individual 
Volatile Organic Compounds in Waste

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in 40 CFR Part 60, 
Appendix A. Therefore, to obtain reliable results, persons using 
this method should have a thorough knowledge of at least Method 25D.

1.0  Scope and Application

    1.1  Analyte. Volatile Organics. No CAS No. assigned.
    1.2  Applicability. This procedure is used to determine the 
emission potential of individual volatile organics (VOs) in waste.
    1.3  Data Quality Objectives. Adherence to the requirements of this 
method will enhance the quality of the data obtained from air pollutant 
sampling methods.

2.0  Summary of Method

    2.1  The heated purge conditions established by Method 25D (40 CFR 
Part 60, Appendix A) are used to remove VOs from a 10 gram sample of 
waste suspended in a 50/50 solution of polyethylene glycol (PEG) and 
water. The purged VOs are quantified by using the sample collection and 
analytical techniques (e.g. gas chromatography) appropriate for the VOs 
present in the waste. The recovery efficiency of the sample collection 
and analytical technique is determined for each waste matrix. A 
correction factor is determined for each compound (if acceptable 
recovery criteria requirements are met of 70 to 130 percent recovery 
for every target compound), and the measured waste concentration is 
corrected with the correction factor for each compound. A minimum of 
three replicate waste samples shall be analyzed.

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety

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

6.0  Equipment and Supplies

    6.1  Method 25D Purge Apparatus.
    6.1.1  Purge Chamber. The purge chamber shall accommodate the 10 
gram sample of waste suspended in a matrix of 50 mL of PEG and 50 mL of 
deionized, hydrocarbon-free water. Three fittings are used on the glass 
chamber top. Two #7 Ace-threads are used for the purge gas inlet and 
outlet connections. A #50 Ace-thread is used to connect the top of the 
chamber to the base (see Figure 305-1). The base of the chamber has a 
side-arm equipped with a #22 Sovirel fitting to allow for easy sample 
introductions into the chamber. The dimensions of the chamber are shown 
in Figure 305-1.
    6.1.2  Flow Distribution Device (FDD). The FDD enhances the gas-to-
liquid contact for improved purging efficiency. The FDD is a 6 mm OD 
(0.2 in) by 30 cm (12 in) long glass tube equipped with four arm 
bubblers as shown in Figure 305-1. Each arm shall have an opening of 1 
mm (0.04 in) in diameter.
    6.1.3  Coalescing Filter. The coalescing filter serves to 
discourage aerosol formation of sample gas once it leaves the purge 
chamber. The glass filter has a fritted disc mounted 10 cm (3.9 in) 
from the bottom. Two #7 Ace-threads are used for the inlet and outlet 
connections. The dimensions of the chamber are shown in Figure 305-2.
    6.1.4  Oven. A forced convection airflow oven capable of 
maintaining the purge chamber and coalescing filter at 75  
2 deg.C (167  3.6 deg.F).
    6.1.5  Toggle Valve. An on/off valve constructed from brass or 
stainless steel rated to 100 psig. This valve is placed in line between 
the purge nitrogen source and the flow controller.
    6.1.6  Flow Controller. High-quality stainless steel flow 
controller capable of restricting a flow of nitrogen to 6  
0.06 L/min (0.2  0.002 ft3/min) at 40 psig.
    6.1.7  Polyethylene Glycol Cleaning System.
    6.1.7.1  Round-Bottom Flask. One liter, three-neck glass round-
bottom flask for cleaning PEG. Standard taper 24/40 joints are mounted 
on each neck.
    6.1.7.2  Heating Mantle. Capable of heating contents of the 1-L 
flask to 120  deg.C (248  deg.F).
    6.1.7.3  Nitrogen Bubbler. Teflon or glass tube, 0.25 in 
OD (6.35 mm).
    6.1.7.4  Temperature Sensor. Partial immersion glass thermometer.
    6.1.7.5  Hose Adapter. Glass with 24/40 standard tapered joint.
    6.2  Volatile Organic Recovery System.
    6.2.1  Splitter Valve (Optional). Stainless steel cross-pattern 
valve capable of splitting nominal flow rates from the purge flow of 6 
L/min (0.2 ft3/min). The valve shall be maintained at 75 + 
2 deg.C (167  3.6 deg.F) in the heated zone and shall be 
placed downstream of the coalescing filter. It is recommended that 
0.125 in OD (3.175 mm) tubing be used to direct the split vent flow 
from the heated zone. The back pressure caused by the 0.125 in OD 
(3.175 mm) tubing is critical for maintaining proper split valve 
operation.

    Note: The splitter valve design is optional; it may be used in 
cases where the concentration of a pollutant would saturate the 
adsorbents.

    6.2.2  Injection Port. Stainless steel 1/4 in OD (6.35 mm) 
compression fitting tee with a 6 mm (0.2 in) septum fixed on the top 
port. The injection port is the point of entry for the recovery study 
solution. If using a gaseous standard to determine recovery efficiency, 
connect the gaseous standard to the injection port of the tee.
    6.2.3  Knockout Trap (Optional but Recommended). A 25 mL capacity 
glass reservoir body with a full-stem impinger (to avoid leaks, a 
modified midget glass impinger with a screw cap and ball/socket clamps 
on the inlet and outlet is recommended). The empty impinger is placed 
in an ice water bath between the injection port and the sorbent 
cartridge. Its purpose is to reduce the water content of the purge gas 
(saturated at 75  deg.C (167  deg.F)) before the sorbent cartridge.
    6.2.4  Insulated Ice Bath. A 350 mL dewar or other type of 
insulated bath is used to maintain ice water around the knockout trap.
    6.2.5  Sorbent Cartridges. Commercially available glass or 
stainless steel cartridge packed with one or more appropriate sorbents. 
The amount of adsorbent packed in the cartridge depends on the 
breakthrough volume of the test compounds but is limited by back 
pressure caused by the packing (not to exceed 7 psig). More than one 
sorbent cartridge placed in series may be necessary depending upon the 
mixture of the measured components.
    6.2.6  Volumetric Glassware. Type A glass 10 mL volumetric flasks 
for measuring a final volume from the water catch in the knockout trap.
    6.2.7  Thermal Desorption Unit. A clam-shell type oven, used for 
the desorption of direct thermal desorption sorbent tubes. The oven 
shall be capable of increasing the temperature of the desorption tubes 
rapidly to recommended desorption temperature.
    6.2.8  Ultrasonic Bath. Small bath used to agitate sorbent material 
and desorption solvent. Ice water shall be used in the bath because of 
heat transfer caused by operation of the bath.

[[Page 62240]]

    6.2.9  Desorption Vials. Four-dram (15 mL) capacity borosilicate 
glass vials with Teflon-lined caps.
    6.3  Analytical System. A gas chromatograph (GC) is commonly used 
to separate and quantify compounds from the sample collection and 
recovery procedure. Method 18 (40 CFR Part 60, Appendix A) may be used 
as a guideline for determining the appropriate GC column and GC 
detector based on the test compounds to be determined. Other types of 
analytical instrumentation may be used (HPLC) in lieu of GC systems as 
long as the recovery efficiency criteria of this method are met.
    6.3.1  Gas Chromatograph (GC). The GC shall be equipped with a 
constant-temperature liquid injection port or a heated sampling loop/
valve system, as appropriate. The GC oven shall be temperature-
programmable over the useful range of the GC column. The choice of 
detectors is based on the test compounds to be determined.
    6.3.2  GC Column. Select the appropriate GC column based on (1) 
literature review or previous experience, (2) polarity of the analytes, 
(3) capacity of the column, or (4) resolving power (e.g., length, 
diameter, film thickness) required.
    6.3.3  Data System. A programmable electronic integrator for 
recording, analyzing, and storing the signal generated by the detector.

7.0  Reagents and Standards

    7.1  Method 25D Purge Apparatus.
    7.1.1  Polyethylene Glycol (PEG). Ninety-eight percent pure organic 
polymer with an average molecular weight of 400 g/mol. Volatile 
organics are removed from the PEG prior to use by heating to 120 
 5 deg.C (248  9 deg.F) and purging with pure 
nitrogen at 1 L/min (0.04 ft3/min) for 2 hours. After 
purging and heating, the PEG is maintained at room temperature under a 
nitrogen purge maintained at 1 L/min (0.04 ft3/min) until 
used. A typical apparatus used to clean the PEG is shown in Figure 305-
3.
    7.1.2  Water. Organic-free deionized water is required.
    7.1.3  Nitrogen. High-purity nitrogen (less than 0.5 ppm total 
hydrocarbons) is used to remove test compounds from the purge matrix. 
The source of nitrogen shall be regulated continuously to 40 psig 
before the on/off toggle valve.
    7.2  Volatile Organic Recovery System.
    7.2.1  Water. Organic-free deionized water is required.
    7.2.2  Desorption Solvent (when used). Appropriate high-purity 
(99.99 percent) solvent for desorption shall be used. Analysis shall be 
performed (utilizing the same analytical technique as that used in the 
analysis of the waste samples) on each lot to determine purity.
    7.3  Analytical System. The gases required for GC operation shall 
be of the highest obtainable purity (hydrocarbon free). Consult the 
operating manual for recommended settings.

8.0  Sample Collection, Preservation, Storage, and Transport

    8.1  Assemble the glassware and associated fittings (see Figures 
305-3 and 305-4, as appropriate) and leak-check the system 
(approximately 7 psig is the target pressure). After an initial leak 
check, mark the pressure gauge and use the initial checkpoint to 
monitor for leaks throughout subsequent analyses. If the pressure in 
the system drops below the target pressure at any time during analysis, 
that analysis shall be considered invalid.
    8.2  Recovery Efficiency Determination. Determine the individual 
recovery efficiency (RE) for each of the target compounds in duplicate 
before the waste samples are analyzed. To determine the RE, generate a 
water blank (Section 11.1) and use the injection port to introduce a 
known volume of spike solution (or certified gaseous standard) 
containing all of the target compounds at the levels expected in the 
waste sample. Introduce the spike solution immediately after the 
nitrogen purge has been started (Section 8.3.2). Follow the procedures 
outlined in Section 8.3.3. Analyze the recovery efficiency samples 
using the techniques described in Section 11.2. Determine the recovery 
efficiency (Equation 305-1, Section 12.2) by comparing the amount of 
compound recovered to the theoretical amount spiked. Determine the RE 
twice for each compound; the relative standard deviation, (RSD) shall 
be  10 percent for each compound. If the RSD for any 
compound is not  10 percent, modify the sampling/analytical 
procedure and complete an RE study in duplicate, or continue 
determining RE until the RSD meets the acceptable criteria. The average 
RE shall be 0.70  RE  1.30 for each compound. If 
the average RE does not meet these criteria, an alternative sample 
collection and/or analysis technique shall be developed and the 
recovery efficiency determination shall be repeated for that compound 
until the criteria are met for every target compound. Example 
modifications of the sampling/analytical system include changing the 
adsorbent material, changing the desorption solvent, utilizing direct 
thermal desorption of test compounds from the sorbent tubes, utilizing 
another analytical technique.
    8.3  Sample Collection and Recovery.
    8.3.1  The sample collection procedure in Method 25D shall be used 
to collect (into a preweighed vial) 10 g of waste into PEG, cool, and 
ship to the laboratory. Remove the sample container from the cooler and 
wipe the exterior to remove any ice or water. Weigh the container and 
sample to the nearest 0.01 g and record the weight. Pour the sample 
from the container into the purge flask. Rinse the sample container 
three times with approximately 6 mL of PEG (or the volume needed to 
total 50 mL of PEG in the purge flask), transferring the rinses to the 
purge flask. Add 50 mL of organic-free deionized water to the purge 
flask. Cap the purge flask tightly in between each rinse and after 
adding all the components into the flask.
    8.3.2  Allow the oven to equilibrate to 75  2  deg.C 
(167  3.6  deg.F). Begin the sample recovery process by 
turning the toggle valve on, thus allowing a 6 L/min flow of pure 
nitrogen through the purge chamber.
    8.3.3  Stop the purge after 30 min. Immediately remove the sorbent 
tube(s) from the apparatus and cap both ends. Remove the knockout trap 
and transfer the water catch to a 10 mL volumetric flask. Rinse the 
trap with organic-free deionized water and transfer the rinse to the 
volumetric flask. Dilute to the 10 mL mark with water. Transfer the 
water sample to a sample vial and store at 4  deg.C (39.2  deg.F) with 
zero headspace. The analysis of the contents of the water knockout trap 
is optional for this method. If the target compounds are water soluble, 
analysis of the water is recommended; meeting the recovery efficiency 
criteria in these cases would be difficult without adding the amount 
captured in the knockout trap.

9.0  Quality Control

    9.1  Miscellaneous Quality Control Measures.

[[Page 62241]]



------------------------------------------------------------------------
                                 Quality control
            Section                  measure               Effect
------------------------------------------------------------------------
8.1...........................  Sampling           Ensures accurate
                                 equipment leak-    measurement of
                                 check.             sample volume.
8.2...........................  Recovery           Ensures accurate
                                 efficiency (RE)    sample collection
                                 determination      and analysis.
                                 for each
                                 measured
                                 compound..
8.3...........................  Calibration of     Ensures linear
                                 analytical         measurement of
                                 instrument with    compounds over the
                                 at least 3         instrument span.
                                 calibration
                                 standards..
------------------------------------------------------------------------

10.0  Calibration and Standardization

    10.1  The analytical instrument shall be calibrated with a minimum 
of three levels of standards for each compound whose concentrations 
bracket the concentration of test compounds from the sorbent tubes. 
Liquid calibration standards shall be used for calibration in the 
analysis of the solvent extracts. The liquid calibration standards 
shall be prepared in the desorption solvent matrix. The calibration 
standards may be prepared and injected individually or as a mixture. If 
thermal desorption and focusing (onto another sorbent or cryogen 
focusing) are used, a certified gaseous mixture or a series of gaseous 
standards shall be used for calibration of the instrument. The gaseous 
standards shall be focused and analyzed in the same manner as the 
samples.
    10.2  The analytical system shall be certified free from 
contaminants before a calibration is performed (see Section 11.1). The 
calibration standards are used to determine the linearity of the 
analytical system. Perform an initial calibration and linearity check 
by analyzing the three calibration standards for each target compound 
in triplicate starting with the lowest level and continuing to the 
highest level. If the triplicate analyses do not agree within 5 percent 
of their average, additional analyses will be needed until the 5 
percent criteria is met. Calculate the response factor (Equation 305-3, 
Section 12.4) from the average area counts of the injections for each 
concentration level. Average the response factors of the standards for 
each compound. The linearity of the detector is acceptable if the 
response factor of each compound at a particular concentration is 
within 10 percent of the overall mean response factor for that 
compound. Analyze daily a mid-level calibration standard in duplicate 
and calculate a new response factor. Compare the daily response factor 
average to the average response factor calculated for the mid-level 
calibration during the initial linearity check; repeat the three-level 
calibration procedure if the daily average response factor differs from 
the initial linearity check mid-level response factor by more than 10 
percent. Otherwise, proceed with the sample analysis.

11.0  Analytical Procedure

    11.1  Water Blank Analysis. A water blank shall be analyzed daily 
to determine the cleanliness of the purge and recovery system. A water 
blank is generated by adding 60 mL of organic-free deionized water to 
50 mL of PEG in the purge chamber. Treat the blank as described in 
Sections 8.3.2 and 8.3.3. The purpose of the water blank is to insure 
that no contaminants exist in the sampling and analytical apparatus 
which would interfere with the quantitation of the target compounds. If 
contaminants are present, locate the source of contamination, remove 
it, and repeat the water blank analysis.
    11.2  Sample Analysis. Sample analysis in the context of this 
method refers to techniques to remove the target compounds from the 
sorbent tubes, separate them using a chromatography technique, and 
quantify them with an appropriate detector. Two types of sample 
extraction techniques typically used for sorbents include solvent 
desorption or direct thermal desorption of test compounds to a 
secondary focusing unit (either sorbent or cryogen based). The test 
compounds are then typically transferred to a GC system for analysis. 
Other analytical systems may be used (e.g., HPLC) in lieu of GC systems 
as long as the recovery efficiency criteria of this method are met.
    11.2.1  Recover the test compounds from the sorbent tubes that 
require solvent desorption by transferring the adsorbent material to a 
sample vial containing the desorption solvent. The desorption solvent 
shall be the same as the solvent used to prepare calibration standards. 
The volume of solvent depends on the amount of adsorbed material to be 
desorbed (1.0 mL per 100 mg of adsorbent material) and also on the 
amount of test compounds present. Final volume adjustment and or 
dilution can be made so that the concentration of test compounds in the 
desorption solvent is bracketed by the concentration of the calibration 
solutions. Ultrasonicate the desorption solvent for 15 min in an ice 
bath. Allow the sample to sit for a period of time so that the 
adsorbent material can settle to the bottom of the vial. Transfer the 
solvent with a pasteur pipet (minimizing the amount of adsorbent 
material taken) to another vial and store at 4  deg.C (39.2  deg.F).
    11.2.2  Analyze the desorption solvent or direct thermal desorption 
tubes from each sample using the same analytical parameters used for 
the calibration standard. Calculate the total weight detected for each 
compound (Equation 305-4, Section 12.5). The slope (area/amount) and y-
intercept are calculated from the line bracketed between the two 
closest calibration points. Correct the concentration of each waste 
sample with the appropriate recovery efficiency factor and the split 
flow ratio (if used). The final concentration of each individual test 
compound is calculated by dividing the corrected measured weight for 
that compound by the weight of the original sample determined in 
Section 8.3.1 (Equation 305-5, Section 12.6).
    11.2.3  Repeat the analysis for the three samples collected in 
Section 8.3. Report the corrected concentration of each of the waste 
samples, average waste concentration, and relative standard deviation 
(Equation 305-6, Section 12.7).

12.0  Data Analysis and Calculations.

    12.1  Nomenclature.

AS = Mean area counts of test compound in standard.
AU = Mean area counts of test compound in sample desorption 
solvent.
b = Y-intercept of the line formed between the two closest calibration 
standards that bracket the concentration of the sample.
CT = Amount of test compound (g) in calibration 
standard.
CF = Correction for adjusting final amount of sample 
detected for losses during individual sample runs.
FP = Nitrogen flow through the purge chamber (6 L/min).
FS = Nitrogen split flow directed to the sample recovery 
system (use 6 L/min if split flow design was not used).
PPM = Final concentration of test compound in waste sample [g/
g (which is equivalent to parts per million by weight (ppmw))].
RE = Recovery efficiency for adjusting final amount of sample detected 
for losses due to inefficient trapping and desorption techniques.

[[Page 62242]]

R.F. = Response factor for test compound, calculated from a calibration 
standard.
S = Slope of the line (area counts/CT) formed between two 
closest calibration points that bracket the concentration of the 
sample.
WC = Weight of test compound expected to be recovered in 
spike solution based on theoretical amount (g).
WE = Weight of vial and PEG (g).
WF = Weight of vial, PEG and waste sample (g).
WS = Weight of original waste sample (g).
WT = Corrected weight of test compound measured (g) 
in sample.
WX = Weight of test compound measured during analysis of 
recovery efficiency spike samples (g).

    12.2  Recovery efficiency for determining trapping/desorption 
efficiency of individual test compounds in the spike solution, decimal 
value.
[GRAPHIC] [TIFF OMITTED] TR17OC00.563

    12.3  Weight of waste sample (g).
    [GRAPHIC] [TIFF OMITTED] TR17OC00.564
    
    12.4  Response factor for individual test compounds.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.565
    
    12.5  Corrected weight of a test compound in the sample, in 
g.
[GRAPHIC] [TIFF OMITTED] TR17OC00.566

    12.6  Final concentration of a test compound in the sample in ppmw.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.567
    
    12.7  Relative standard deviation (RSD) calculation.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.568
    
13.0  Method Performance. [Reserved]

14.0  Pollution Prevention. [Reserved]

15.0  Waste Management. [Reserved]

16.0  References. [Reserved]

[[Page 62243]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.569


[[Page 62244]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.570


[[Page 62245]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.571


[[Page 62246]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.572

BILLING CODE 6560-50-C

Method 306--Determination of Chromium Emissions From Decorative and 
Hard Chromium Electroplating and Chromium Anodizing Operations--
Isokinetic Method

    Note: This method does not include all of the specifications (e.g., 
equipment and supplies) and procedures (e.g., sampling and analytical) 
essential to its performance. Some material is incorporated by 
reference from other methods in 40 CFR Part 60, Appendix A. Therefore, 
to obtain reliable results, persons using this method should have a 
thorough knowledge of at least Method 5.

1.0  Scope and Application

    1.1  Analytes.

------------------------------------------------------------------------
            Analyte                  CAS No.            Sensitivity
------------------------------------------------------------------------
Chromium......................  7440-47-3........  See Sec. 13.2.
------------------------------------------------------------------------

    1.2  Applicability. This method applies to the determination of 
chromium (Cr) in emissions from decorative and hard chrome 
electroplating facilities, chromium anodizing operations, and 
continuous chromium plating operations at iron and steel facilities.
    1.3  Data Quality Objectives. [Reserved]

2.0  Summary of Method

    2.1  Sampling. An emission sample is extracted isokinetically from 
the source using an unheated Method 5 sampling train (40 CFR Part 60, 
Appendix A), with a glass nozzle and probe liner, but with the filter 
omitted. The sample time shall be at least two hours. The Cr emissions 
are collected in an alkaline solution containing 0.1 N sodium hydroxide 
(NaOH) or 0.1 N sodium bicarbonate (NaHCO3). The collected 
samples are recovered using an alkaline solution and are then

[[Page 62247]]

transported to the laboratory for analysis.
    2.2  Analysis.
    2.2.1  Total chromium samples with high chromium concentrations 
(35 g/L) may be analyzed using inductively coupled 
plasma emission spectrometry (ICP) at 267.72 nm.

    Note: The ICP analysis is applicable for this method only when 
the solution analyzed has a Cr concentration greater than or equal 
to 35 g/L or five times the method detection limit as 
determined according to Appendix B in 40 CFR Part 136.

    2.2.2  Alternatively, when lower total chromium concentrations (35 
g/L) are encountered, a portion of the alkaline sample 
solution may be digested with nitric acid and analyzed by graphite 
furnace atomic absorption spectroscopy (GFAAS) at 357.9 nm.
    2.2.3  If it is desirable to determine hexavalent chromium 
(Cr+6) emissions, the samples may be analyzed using an ion 
chromatograph equipped with a post-column reactor (IC/PCR) and a 
visible wavelength detector. To increase sensitivity for trace levels 
of Cr+6, a preconcentration system may be used in 
conjunction with the IC/PCR.

3.0  Definitions

    3.1  Total Chromium--measured chromium content that includes both 
major chromium oxidation states (Cr+3, Cr+3).
    3.2  May--Implies an optional operation.
    3.3  Digestion--The analytical operation involving the complete (or 
nearly complete) dissolution of the sample in order to ensure the 
complete solubilization of the element (analyte) to be measured.
    3.4  Interferences--Physical, chemical, or spectral phenomena that 
may produce a high or low bias in the analytical result.
    3.5  Analytical System--All components of the analytical process 
including the sample digestion and measurement apparatus.
    3.6  Sample Recovery--The quantitative transfer of sample from the 
collection apparatus to the sample preparation (digestion, etc.) 
apparatus. This term should not be confused with analytical recovery.
    3.7  Matrix Modifier--A chemical modification to the sample during 
GFAAS determinations to ensure that the analyte is not lost during the 
measurement process (prior to the atomization stage)
    3.8  Calibration Reference Standards--Quality control standards 
used to check the accuracy of the instrument calibration curve prior to 
sample analysis.
    3.9  Continuing Check Standard--Quality control standards used to 
verify that unacceptable drift in the measurement system has not 
occurred.
    3.10  Calibration Blank--A blank used to verify that there has been 
no unacceptable shift in the baseline either immediately following 
calibration or during the course of the analytical measurement.
    3.11  Interference Check--An analytical/measurement operation that 
ascertains whether a measurable interference in the sample exists.
    3.12  Interelement Correction Factors--Factors used to correct for 
interfering elements that produce a false signal (high bias).
    3.13  Duplicate Sample Analysis--Either the repeat measurement of a 
single solution or the measurement of duplicate preparations of the 
same sample. It is important to be aware of which approach is required 
for a particular type of measurement. For example, no digestion is 
required for the ICP determination and the duplicate instrument 
measurement is therefore adequate whereas duplicate digestion/
instrument measurements are required for GFAAS.
    3.14  Matrix Spiking--Analytical spikes that have been added to the 
actual sample matrix either before (Section 9.2.5.2) or after (Section 
9.1.6). Spikes added to the sample prior to a preparation technique 
(e.g., digestion) allow for the assessment of an overall method 
accuracy while those added after only provide for the measurement 
accuracy determination.

4.0  Interferences

    4.1  ICP Interferences.
    4.1.1  ICP Spectral Interferences. Spectral interferences are 
caused by: overlap of a spectral line from another element; unresolved 
overlap of molecular band spectra; background contribution from 
continuous or recombination phenomena; and, stray light from the line 
emission of high-concentrated elements. Spectral overlap may be 
compensated for by correcting the raw data with a computer and 
measuring the interfering element. At the 267.72 nm Cr analytical 
wavelength, iron, manganese, and uranium are potential interfering 
elements. Background and stray light interferences can usually be 
compensated for by a background correction adjacent to the analytical 
line. Unresolved overlap requires the selection of an alternative 
chromium wavelength. Consult the instrument manufacturer's operation 
manual for interference correction procedures.
    4.1.2  ICP Physical Interferences. High levels of dissolved solids 
in the samples may cause significant inaccuracies due to salt buildup 
at the nebulizer and torch tips. This problem can be controlled by 
diluting the sample or by extending the rinse times between sample 
analyses. Standards shall be prepared in the same solution matrix as 
the samples (i.e., 0.1 N NaOH or 0.1 N NaHCO3).
    4.1.3  ICP Chemical Interferences. These include molecular compound 
formation, ionization effects and solute vaporization effects, and are 
usually not significant in the ICP procedure, especially if the 
standards and samples are matrix matched.
    4.2  GFAAS Interferences.
    4.2.1  GFAAS Chemical Interferences. Low concentrations of calcium 
and/or phosphate may cause interferences; at concentrations above 200 
g/L, calcium's effect is constant and eliminates the effect of 
phosphate. Calcium nitrate is therefore added to the concentrated 
analyte to ensure a known constant effect. Other matrix modifiers 
recommended by the instrument manufacturer may also be considered.
    4.2.2  GFAAS Cyanide Band Interferences. Nitrogen should not be 
used as the purge gas due to cyanide band interference.
    4.2.3  GFAAS Spectral Interferences. Background correction may be 
required because of possible significant levels of nonspecific 
absorption and scattering at the 357.9 nm analytical wavelength.
    4.2.4  GFAAS Background Interferences. Zeeman or Smith-Hieftje 
background correction is recommended for interferences resulting from 
high levels of dissolved solids in the alkaline impinger solutions.
    4.3  IC/PCR Interferences.
    4.3.1  IC/PCR Chemical Interferences. Components in the sample 
matrix may cause Cr+6 to convert to trivalent chromium 
(Cr+3) or cause Cr+3 to convert to 
Cr+6. The chromatographic separation of Cr+6 
using ion chromatography reduces the potential for other metals to 
interfere with the post column reaction. For the IC/PCR analysis, only 
compounds that coelute with Cr+6 and affect the 
diphenylcarbazide reaction will cause interference.
    4.3.2  IC/PCR Background Interferences. Periodic analyses of 
reagent water blanks are used to demonstrate that the analytical system 
is essentially free of contamination. Sample cross-contamination can 
occur when high-level and low-level samples or standards are analyzed 
alternately and can be eliminated by thorough purging of the sample 
loop. Purging of

[[Page 62248]]

the sample can easily be achieved by increasing the injection volume to 
ten times the size of the sample loop.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method may not address all of the 
safety problems associated with its use. It is the responsibility of 
the user to establish appropriate safety and health practices and to 
determine the applicability of regulatory limitations prior to 
performing this test method.
    5.2  Hexavalent chromium compounds have been listed as carcinogens 
although chromium (III) compounds show little or no toxicity. Chromium 
can be a skin and respiratory irritant.

6.0  Equipment and Supplies

    6.1  Sampling Train.
    6.1.1  A schematic of the sampling train used in this method is 
shown in Figure 306-1. The train is the same as shown in Method 5, 
Section 6.0 (40 CFR Part 60, Appendix A) except that the probe liner is 
unheated, the particulate filter is omitted, and quartz or borosilicate 
glass must be used for the probe nozzle and liner in place of stainless 
steel.
    6.1.2  Probe fittings of plastic such as Teflon, polypropylene, 
etc. are recommended over metal fittings to prevent contamination. If 
desired, a single combined probe nozzle and liner may be used, but such 
a single glass assembly is not a requirement of this methodology.
    6.1.3  Use 0.1 N NaOH or 0.1 N NaHCO3 in the impingers 
in place of water.
    6.1.4  Operating and maintenance procedures for the sampling train 
are described in APTD-0576 of Method 5. Users should read the APTD-0576 
document and adopt the outlined procedures.
    6.1.5  Similar collection systems which have been approved by the 
Administrator may be used.
    6.2  Sample Recovery. Same as Method 5, [40 CFR Part 60, Appendix 
A], with the following exceptions:
    6.2.1  Probe-Liner and Probe-Nozzle Brushes. Brushes are not 
necessary for sample recovery. If a probe brush is used, it must be 
non-metallic.
    6.2.2  Sample Recovery Solution. Use 0.1 N NaOH or 0.1 N 
NaHCO3, whichever is used as the impinger absorbing 
solution, in place of acetone to recover the sample.
    6.2.3  Sample Storage Containers. Polyethylene, with leak-free 
screw cap, 250 mL, 500 mL or 1,000 mL.
    6.3  Analysis.
    6.3.1  General. For analysis, the following equipment is needed.
    6.3.1.1  Phillips Beakers. (Phillips beakers are preferred, but 
regular beakers may also be used.)
    6.3.1.2  Hot Plate.
    6.3.1.3  Volumetric Flasks. Class A, various sizes as appropriate.
    6.3.1.4  Assorted Pipettes.
    6.3.2  Analysis by ICP.
    6.3.2.1  ICP Spectrometer. Computer-controlled emission 
spectrometer with background correction and radio frequency generator.
    6.3.2.2  Argon Gas Supply. Welding grade or better.
    6.3.3  Analysis by GFAAS.
    6.3.3.1  Chromium Hollow Cathode Lamp or Electrodeless Discharge 
Lamp.
    6.3.3.2  Graphite Furnace Atomic Absorption Spectrophotometer.
    6.3.3.3  Furnace Autosampler.
    6.3.4  Analysis by IC/PCR.
    6.3.4.1  IC/PCR System. High performance liquid chromatograph pump, 
sample injection valve, post-column reagent delivery and mixing system, 
and a visible detector, capable of operating at 520 nm-540 nm, all with 
a non-metallic (or inert) flow path. An electronic peak area mode is 
recommended, but other recording devices and integration techniques are 
acceptable provided the repeatability criteria and the linearity 
criteria for the calibration curve described in Section 10.4 can be 
satisfied. A sample loading system is required if preconcentration is 
employed.
    6.3.4.2  Analytical Column. A high performance ion chromatograph 
(HPIC) non-metallic column with anion separation characteristics and a 
high loading capacity designed for separation of metal chelating 
compounds to prevent metal interference. Resolution described in 
Section 11.6 must be obtained. A non-metallic guard column with the 
same ion-exchange material is recommended.
    6.3.4.3  Preconcentration Column (for older instruments). An HPIC 
non-metallic column with acceptable anion retention characteristics and 
sample loading rates must be used as described in Section 11.6.
    6.3.4.4  Filtration Apparatus for IC/PCR.
    6.3.4.4.1  Teflon, or equivalent, filter holder to accommodate 
0.45-m acetate, or equivalent, filter, if needed to remove 
insoluble particulate matter.
    6.3.4.4.2  0.45-m Filter Cartridge. For the removal of 
insoluble material. To be used just prior to sample injection/analysis.

7.0  Reagents and Standards

    Note: Unless otherwise indicated, all reagents should conform to 
the specifications established by the Committee on Analytical 
Reagents of the American Chemical Society (ACS reagent grade). Where 
such specifications are not available, use the best available grade. 
Reagents should be checked by the appropriate analysis prior to 
field use to assure that contamination is below the analytical 
detection limit for the ICP or GFAAS total chromium analysis; and 
that contamination is below the analytical detection limit for 
Cr+6 using IC/PCR for direct injection or, if selected, 
preconcentration.

    7.1  Sampling.
    7.1.1  Water. Reagent water that conforms to ASTM Specification 
D1193-77 or 91 Type II (incorporated by reference see Sec. 63.14). All 
references to water in the method refer to reagent water unless 
otherwise specified. It is recommended that water blanks be checked 
prior to preparing the sampling reagents to ensure that the Cr content 
is less than three (3) times the anticipated detection limit of the 
analytical method.
    7.1.2  Sodium Hydroxide (NaOH) Absorbing Solution, 0.1 N. Dissolve 
4.0 g of sodium hydroxide in 1 liter of water to obtain a pH of 
approximately 8.5.
    7.1.3  Sodium Bicarbonate (NaHCO3) Absorbing Solution, 
0.1 N. Dissolve approximately 8.5 g of sodium bicarbonate in 1 liter of 
water to obtain a pH of approximately 8.3.
    7.1.4  Chromium Contamination.
    7.1.4.1  The absorbing solution shall not exceed the QC criteria 
noted in Section 7.1.1 ( 3 times the instrument detection 
limit).
    7.1.4.2  When the Cr+6 content in the field samples 
exceeds the blank concentration by at least a factor of ten (10), 
Cr+6 blank concentrations  10 times the detection 
limit will be allowed.

    Note: At sources with high concentrations of acids and/or 
SO2, the concentration of NaOH or NaHCO3 
should be  0.5 N to insure that the pH of the solution 
remains at or above 8.5 for NaOH and 8.0 for NaHCO3 
during and after sampling.

    7.1.5  Silica Gel. Same as in Method 5.
    7.2  Sample Recovery.
    7.2.1  0.1 N NaOH or 0.1 N NaHCO3. Use the same solution 
for the sample recovery that is used for the impinger absorbing 
solution.
    7.2.2  pH Indicator Strip, for IC/PCR. pH indicator capable of 
determining the pH of solutions between the pH range of 7 and 12, at 
0.5 pH increments.
    7.3  Sample Preparation and Analysis.
    7.3.1  Nitric Acid (HNO3), Concentrated, for GFAAS. 
Trace metals

[[Page 62249]]

grade or better HNO3 must be used for reagent preparation. 
The ACS reagent grade HNO3 is acceptable for cleaning 
glassware.
    7.3.2  HNO3, 1.0% (v/v), for GFAAS. Prepare, by slowly 
stirring, 10 mL of concentrated HNO3) into 800 mL of reagent 
water. Dilute to 1,000 mL with reagent water. The solution shall 
contain less than 0.001 mg Cr/L.
    7.3.3  Calcium Nitrate Ca(NO3)2 Solution (10 
g Ca/mL) for GFAAS analysis. Prepare the solution by weighing 
40.9 mg of Ca(NO3)2 into a 1 liter volumetric 
flask. Dilute with reagent water to 1 liter.
    7.3.4  Matrix Modifier, for GFAAS. See instrument manufacturer's 
manual for suggested matrix modifier.
    7.3.5  Chromatographic Eluent, for IC/PCR. The eluent used in the 
analytical system is ammonium sulfate based.
    7.3.5.1  Prepare by adding 6.5 mL of 29 percent ammonium hydroxide 
(NH4OH) and 33 g of ammonium sulfate 
((NH4)2SO4) to 500 mL of reagent 
water. Dilute to 1 liter with reagent water and mix well.
    7.3.5.2  Other combinations of eluents and/or columns may be 
employed provided peak resolution, repeatability, linearity, and 
analytical sensitivity as described in Sections 9.3 and 11.6 are 
acceptable.
    7.3.6  Post-Column Reagent, for IC/PCR. An effective post-column 
reagent for use with the chromatographic eluent described in Section 
7.3.5 is a diphenylcarbazide (DPC)-based system. Dissolve 0.5 g of 1,5-
diphenylcarbazide in 100 mL of ACS grade methanol. Add 500 mL of 
reagent water containing 50 mL of 96 percent spectrophotometric grade 
sulfuric acid. Dilute to 1 liter with reagent water.
    7.3.7  Chromium Standard Stock Solution (1000 mg/L). Procure a 
certified aqueous standard or dissolve 2.829 g of potassium dichromate 
(K2Cr2O7), in reagent water and dilute 
to 1 liter.
    7.3.8  Calibration Standards for ICP or IC/PCR. Prepare calibration 
standards for ICP or IC/PCR by diluting the Cr standard stock solution 
(Section 7.3.7) with 0.1 N NaOH or 0.1 N NaHCO3, whichever 
is used as the impinger absorbing solution, to achieve a matrix similar 
to the actual field samples. Suggested levels are 0, 50, 100, and 200 
g Cr/L for ICP, and 0, 1, 5, and 10 g 
Cr+6/L for IC/PCR.
    7.3.9  Calibration Standards for GFAAS. Chromium solutions for 
GFAAS calibration shall contain 1.0 percent (v/v) HNO3. The 
zero standard shall be 1.0 percent (v/v) HNO3. Calibration 
standards should be prepared daily by diluting the Cr standard stock 
solution (Section 7.3.7) with 1.0 percent HNO3. Use at least 
four standards to make the calibration curve. Suggested levels are 0, 
10, 50, and 100 g Cr/L.
    7.4  Glassware Cleaning Reagents.
    7.4.1  HNO3, Concentrated. ACS reagent grade or 
equivalent.
    7.4.2  Water. Reagent water that conforms to ASTM Specification 
D1193-77 or 91 Type II.
    7.4.3  HNO3, 10 percent (v/v). Add by stirring 500 mL of 
concentrated HNO3 into a flask containing approximately 
4,000 mL of reagent water. Dilute to 5,000 mL with reagent water. Mix 
well. The reagent shall contain less than 2 g Cr/L.
    7.5  Quality Assurance Audit Samples.
    7.5.1  When making compliance determinations, and upon 
availability, audit samples shall be obtained from the appropriate EPA 
regional Office or from the responsible enforcement authority and 
analyzed in conjunction with the field samples.
    7.5.2  If EPA or National Institute of Standards and Technology 
(NIST) reference audit sample are not available, a mid-range standard, 
prepared from an independent commercial source, may be used.

    Note: To order audit samples, contact the responsible 
enforcement authority at least 30 days prior to the test date to 
allow sufficient time for the audit sample to be delivered.

8.0  Sample Collection, Preservation, Holding Times, Storage, and 
Transport

    Note: Prior to sample collection, consideration should be given 
to the type of analysis (Cr+\6\ or total Cr) that will be 
performed. Which analysis option(s) will be performed will determine 
which sample recovery and storage procedures will be required to 
process the sample (See Figures 306-3 and 306-4).

    8.1  Sample Collection. Same as Method 5 (40 CFR Part 60, Appendix 
A), with the following exceptions.
    8.1.1  Omit the particulate filter and filter holder from the 
sampling train. Use a glass nozzle and probe liner instead of stainless 
steel. Do not heat the probe. Place 100 mL of 0.1 N NaOH or 0.1 N 
NaHCO3 in each of the first two impingers, and record the 
data for each run on a data sheet such as shown in Figure 306-2.
    8.1.2  Clean all glassware prior to sampling in hot soapy water 
designed for laboratory cleaning of glassware. Next, rinse the 
glassware three times with tap water, followed by three additional 
rinses with reagent water. Then soak the glassware in 10% (v/v) 
HNO3 solution for a minimum of 4 hours, rinse three times 
with reagent water, and allow to air dry. Cover all glassware openings 
where contamination can occur with Parafilm, or equivalent, until the 
sampling train is assembled for sampling.
    8.1.3  Train Operation. Follow the basic procedures outlined in 
Method 5 in conjunction with the following instructions. Train sampling 
rate shall not exceed 0.030 m\3\/min (1.0 cfm) during a run.
    8.2  Sample Recovery. Follow the basic procedures of Method 5, with 
the exceptions noted.
    8.2.1  A particulate filter is not recovered from this train.
    8.2.2  Tester shall select either the total Cr or Cr+\6\ 
sample recovery option.
    8.2.3  Samples to be analyzed for both total Cr and 
Cr+\6\, shall be recovered using the Cr+\6\ 
sample option (Section 8.2.6).
    8.2.4  A field reagent blank shall be collected for either of the 
Cr or the Cr+\6\ analysis. If both analyses (Cr and 
Cr+\6\) are to be conducted on the samples, collect separate 
reagent blanks for each analysis.

    Note: Since particulate matter is not usually present at 
chromium electroplating and/or chromium anodizing operations, it is 
not necessary to filter the Cr+\6\ samples unless there 
is observed sediment in the collected solutions. If it is necessary 
to filter the Cr+\6\ solutions, please refer to Method 
0061, Determination of Hexavalent Chromium Emissions From Stationary 
Sources, Section 7.4, Sample Preparation in SW-846 (see Reference 
1).

    8.2.5  Total Cr Sample Option.
    8.2.5.1  Container No. 1. Measure the volume of the liquid in the 
first, second, and third impingers and quantitatively transfer into a 
labeled sample container.
    8.2.5.2  Use approximately 200 to 300 mL of the 0.1 N NaOH or 0.1 N 
NaHCO3 absorbing solution to rinse the probe nozzle, probe 
liner, three impingers, and connecting glassware; add this rinse to 
Container No. 1.
    8.2.6  Cr+\6\ Sample Option.
    8.2.6.1  Container No. 1. Measure and record the pH of the 
absorbing solution contained in the first impinger at the end of the 
sampling run using a pH indicator strip. The pH of the solution must be 
8.5 for NaOH and 8.0 for NaHCO3. If it 
is not, discard the collected sample, increase the normality of the 
NaOH or NaHCO3 impinger absorbing solution to 0.5 N or to a 
solution normality approved by the Administrator and collect another 
air emission sample.
    8.2.6.2  After determining the pH of the first impinger solution, 
combine and measure the volume of the liquid in the first, second, and 
third impingers and

[[Page 62250]]

quantitatively transfer into the labeled sample container. Use 
approximately 200 to 300 mL of the 0.1 N NaOH or 0.1 N 
NaHCO3 absorbing solution to rinse the probe nozzle, probe 
liner, three impingers, and connecting glassware; add this rinse to 
Container No. 1.
    8.2.7  Field Reagent Blank.
    8.2.7.1  Container No. 2.
    8.2.7.2  Place approximately 500 mL of the 0.1 N NaOH or 0.1 N 
NaHCO3 absorbing solution into a labeled sample container.
    8.3  Sample Preservation, Storage, and Transport.
    8.3.1  Total Cr Sample Option. Samples to be analyzed for total Cr 
need not be refrigerated.
    8.3.2  Cr+\6\ Sample Option. Samples to be analyzed for 
Cr+\6\ must be shipped and stored at 4 deg.C. Allow 
Cr+\6\ samples to return to ambient temperature prior to 
analysis.
    8.4  Sample Holding Times.
    8.4.1  Total Cr Sample Option. Samples to be analyzed for total Cr 
shall be analyzed within 60 days of collection.
    8.4.2  Cr+\6\ Sample Option. Samples to be analyzed for 
Cr+\6\ shall be analyzed within 14 days of collection.

9.0  Quality Control

    9.1  ICP Quality Control.
    9.1.1  ICP Calibration Reference Standards. Prepare a calibration 
reference standard using the same alkaline matrix as the calibration 
standards; it should be at least 10 times the instrumental detection 
limit.
    9.1.1.1  This reference standard must be prepared from a different 
Cr stock solution source than that used for preparation of the 
calibration curve standards.
    9.1.1.2  Prior to sample analysis, analyze at least one reference 
standard.
    9.1.1.3  The calibration reference standard must be measured within 
10 percent of it's true value for the curve to be considered valid.
    9.1.1.4  The curve must be validated before sample analyses are 
performed.
    9.1.2  ICP Continuing Check Standard.
    9.1.2.1  Perform analysis of the check standard with the field 
samples as described in Section 11.2 (at least after every 10 samples, 
and at the end of the analytical run).
    9.1.2.2  The check standard can either be the mid-range calibration 
standard or the reference standard. The results of the check standard 
shall agree within 10 percent of the expected value; if not, terminate 
the analyses, correct the problem, recalibrate the instrument, and 
rerun all samples analyzed subsequent to the last acceptable check 
standard analysis.
    9.1.3  ICP Calibration Blank.
    9.1.3.1  Perform analysis of the calibration blank with the field 
samples as described in Section 11.2 (at least after every 10 samples, 
and at the end of the analytical run).
    9.1.3.2  The results of the calibration blank shall agree within 
three standard deviations of the mean blank value. If not, analyze the 
calibration blank two more times and average the results. If the 
average is not within three standard deviations of the background mean, 
terminate the analyses, correct the problem, recalibrate, and reanalyze 
all samples analyzed subsequent to the last acceptable calibration 
blank analysis.
    9.1.4  ICP Interference Check. Prepare an interference check 
solution that contains known concentrations of interfering elements 
that will provide an adequate test of the correction factors in the 
event of potential spectral interferences.
    9.1.4.1  Two potential interferences, iron and manganese, may be 
prepared as 1000 g/mL and 200 g/mL solutions, 
respectively. The solutions should be prepared in dilute 
HNO3 (1-5 percent). Particular care must be used to ensure 
that the solutions and/or salts used to prepare the solutions are of 
ICP grade purity (i.e., that no measurable Cr contamination exists in 
the salts/solutions). Commercially prepared interfering element check 
standards are available.
    9.1.4.2  Verify the interelement correction factors every three 
months by analyzing the interference check solution. The correction 
factors are calculated according to the instrument manufacturer's 
directions. If the interelement correction factors are used properly, 
no false Cr should be detected.
    9.1.4.3  Negative results with an absolute value greater than three 
(3) times the detection limit are usually the results of the background 
correction position being set incorrectly. Scan the spectral region to 
ensure that the correction position has not been placed on an 
interfering peak.
    9.1.5  ICP Duplicate Sample Analysis. Perform one duplicate sample 
analysis for each compliance sample batch (3 runs).
    9.1.5.1  As there is no sample preparation required for the ICP 
analysis, a duplicate analysis is defined as a repeat analysis of one 
of the field samples. The selected sample shall be analyzed using the 
same procedures that were used to analyze the original sample.
    9.1.5.2  Duplicate sample analyses shall agree within 10 percent of 
the original measurement value.
    9.1.5.3  Report the original analysis value for the sample and 
report the duplicate analysis value as the QC check value. If agreement 
is not achieved, perform the duplicate analysis again. If agreement is 
not achieved the second time, perform corrective action to identify and 
correct the problem before analyzing the sample for a third time.
    9.1.6  ICP Matrix Spiking. Spiked samples shall be prepared and 
analyzed daily to ensure that there are no matrix effects, that samples 
and standards have been matrix-matched, and that the laboratory 
equipment is operating properly.
    9.1.6.1  Spiked sample recovery analyses should indicate a recovery 
for the Cr spike of between 75 and 125 percent.
    9.1.6.2  Cr levels in the spiked sample should provide final 
solution concentrations that are within the linear portion of the 
calibration curve, as well as, at a concentration level at least: equal 
to that of the original sample; and, ten (10) times the detection 
limit.
    9.1.6.3  If the spiked sample concentration meets the stated 
criteria but exceeds the linear calibration range, the spiked sample 
must be diluted with the field absorbing solution.
    9.1.6.4  If the recoveries for the Cr spiked samples do not meet 
the specified criteria, perform corrective action to identify and 
correct the problem prior to reanalyzing the samples.
    9.1.7  ICP Field Reagent Blank.
    9.1.7.1  Analyze a minimum of one matrix-matched field reagent 
blank (Section 8.2.4) per sample batch to determine if contamination or 
memory effects are occurring.
    9.1.7.2  If contamination or memory effects are observed, perform 
corrective action to identify and correct the problem before 
reanalyzing the samples.
    9.1.8  Audit Sample Analysis.
    9.1.8.1  When the method is used to analyze samples to demonstrate 
compliance with a source emission regulation, an audit sample must be 
analyzed, subject to availability.
    9.1.8.2  Concurrently analyze the audit sample and the compliance 
samples in the same manner to evaluate the technique of the analyst and 
the standards preparation.
    9.1.8.3  The same analyst, analytical reagents, and analytical 
system shall be used for the compliance samples and the audit sample. 
If this condition is met, duplicate auditing of subsequent compliance 
analyses for the same enforcement agency within a 30-day period is 
waived. An audit sample set may not be used to validate different

[[Page 62251]]

sets of compliance samples under the jurisdiction of separate 
enforcement agencies, unless prior arrangements have been made with 
both enforcement agencies.
    9.1.9  Audit Sample Results.
    9.1.9.1  Calculate the audit sample concentrations and submit 
results using the instructions provided with the audit samples.
    9.1.9.2  Report the results of the audit samples and the compliance 
determination samples along with their identification numbers, and the 
analyst's name to the responsible enforcement authority. Include this 
information with reports of any subsequent compliance analyses for the 
same enforcement authority during the 30-day period.
    9.1.9.3  The concentrations of the audit samples obtained by the 
analyst shall agree within the values specified by the compliance 
auditor. If the specified range is not met, reanalyze the compliance 
and audit samples, and include initial and reanalysis values in the 
test report.
    9.1.9.4  Failure to meet the specified range may require retests 
unless the audit problems are resolved. However, if the audit results 
do not affect the compliance or noncompliance status of the affected 
facility, the Administrator may waive the reanalysis requirement, 
further audits, or retests and accept the results of the compliance 
test. While steps are being taken to resolve audit analysis problems, 
the Administrator may also choose to use the data to determine the 
compliance or noncompliance status of the affected facility.
    9.2  GFAAS Quality Control.
    9.2.1  GFAAS Calibration Reference Standards. The calibration curve 
must be verified by using at least one calibration reference standard 
(made from a reference material or other independent standard material) 
at or near the mid-range of the calibration curve.
    9.2.1.1  The calibration curve must be validated before sample 
analyses are performed.
    9.2.1.2  The calibration reference standard must be measured within 
10 percent of its true value for the curve to be considered valid.
    9.2.2  GFAAS Continuing Check Standard.
    9.2.2.1  Perform analysis of the check standard with the field 
samples as described in Section 11.4 (at least after every 10 samples, 
and at the end of the analytical run).
    9.2.2.2  These standards are analyzed, in part, to monitor the life 
and performance of the graphite tube. Lack of reproducibility or a 
significant change in the signal for the check standard may indicate 
that the graphite tube should be replaced.
    9.2.2.3  The check standard may be either the mid-range calibration 
standard or the reference standard.
    9.2.2.4  The results of the check standard shall agree within 10 
percent of the expected value.
    9.2.2.5  If not, terminate the analyses, correct the problem, 
recalibrate the instrument, and reanalyze all samples analyzed 
subsequent to the last acceptable check standard analysis.
    9.2.3  GFAAS Calibration Blank.
    9.2.3.1  Perform analysis of the calibration blank with the field 
samples as described in Section 11.4 (at least after every 10 samples, 
and at the end of the analytical run).
    9.2.3.2  The calibration blank is analyzed to monitor the life and 
performance of the graphite tube as well as the existence of any memory 
effects. Lack of reproducibility or a significant change in the signal, 
may indicate that the graphite tube should be replaced.
    9.2.3.3  The results of the calibration blank shall agree within 
three standard deviations of the mean blank value.
    9.2.3.4  If not, analyze the calibration blank two more times and 
average the results. If the average is not within three standard 
deviations of the background mean, terminate the analyses, correct the 
problem, recalibrate, and reanalyze all samples analyzed subsequent to 
the last acceptable calibration blank analysis.
    9.2.4  GFAAS Duplicate Sample Analysis. Perform one duplicate 
sample analysis for each compliance sample batch (3 runs).
    9.2.4.1  A digested aliquot of the selected sample is processed and 
analyzed using the identical procedures that were used for the whole 
sample preparation and analytical efforts.
    9.2.4.2  Duplicate sample analyses results incorporating duplicate 
digestions shall agree within 20 percent for sample results exceeding 
ten (10) times the detection limit.
    9.2.4.3  Report the original analysis value for the sample and 
report the duplicate analysis value as the QC check value.
    9.2.4.4  If agreement is not achieved, perform the duplicate 
analysis again. If agreement is not achieved the second time, perform 
corrective action to identify and correct the problem before analyzing 
the sample for a third time.
    9.2.5  GFAAS Matrix Spiking.
    9.2.5.1  Spiked samples shall be prepared and analyzed daily to 
ensure that (1) correct procedures are being followed, (2) there are no 
matrix effects and (3) all equipment is operating properly.
    9.2.5.2  Cr spikes are added prior to any sample preparation.
    9.2.5.3  Cr levels in the spiked sample should provide final 
solution concentrations that are within the linear portion of the 
calibration curve, as well as, at a concentration level at least: equal 
to that of the original sample; and, ten (10) times the detection 
limit.
    9.2.5.4  Spiked sample recovery analyses should indicate a recovery 
for the Cr spike of between 75 and 125 percent.
    9.2.5.5  If the recoveries for the Cr spiked samples do not meet 
the specified criteria, perform corrective action to identify and 
correct the problem prior to reanalyzing the samples.
    9.2.6  GFAAS Method of Standard Additions.
    9.2.6.1  Method of Standard Additions. Perform procedures in 
Section 5.4 of Method 12 (40 CFR Part 60, Appendix A)
    9.2.6.2  Whenever sample matrix problems are suspected and 
standard/sample matrix matching is not possible or whenever a new 
sample matrix is being analyzed, perform referenced procedures to 
determine if the method of standard additions is necessary.
    9.2.7  GFAAS Field Reagent Blank.
    9.2.7.1  Analyze a minimum of one matrix-matched field reagent 
blank (Section 8.2.4) per sample batch to determine if contamination or 
memory effects are occurring.
    9.2.7.2 If contamination or memory effects are observed, perform 
corrective action to identify and correct the problem before 
reanalyzing the samples.
    9.2.8  Audit Sample Analysis.
    9.2.8.1  When the method is used to analyze samples to demonstrate 
compliance with a source emission regulation, an audit sample must be 
analyzed, subject to availability.
    9.2.8.2  Concurrently analyze the audit sample and the compliance 
samples in the same manner to evaluate the technique of the analyst and 
the standards preparation.
    9.2.8.3  The same analyst, analytical reagents, and analytical 
system shall be used for the compliance samples and the audit sample. 
If this condition is met, duplicate auditing of subsequent compliance 
analyses for the same enforcement agency within a 30-day period is 
waived. An audit sample set may not be used to validate different sets 
of compliance samples under the jurisdiction of separate enforcement 
agencies, unless prior arrangements have been made with both 
enforcement agencies.

[[Page 62252]]

    9.2.9  Audit Sample Results.
    9.2.9.1  Calculate the audit sample concentrations and submit 
results using the instructions provided with the audit samples.
    9.2.9.2  Report the results of the audit samples and the compliance 
determination samples along with their identification numbers, and the 
analyst's name to the responsible enforcement authority. Include this 
information with reports of any subsequent compliance analyses for the 
same enforcement authority during the 30-day period.
    9.2.9.3  The concentrations of the audit samples obtained by the 
analyst shall agree within the values specified by the compliance 
auditor. If the specified range is not met, reanalyze the compliance 
and audit samples, and include initial and reanalysis values in the 
test report.
    9.2.9.4  Failure to meet the specified range may require retests 
unless the audit problems are resolved. However, if the audit results 
do not affect the compliance or noncompliance status of the affected 
facility, the Administrator may waive the reanalysis requirement, 
further audits, or retests and accept the results of the compliance 
test. While steps are being taken to resolve audit analysis problems, 
the Administrator may also choose to use the data to determine the 
compliance or noncompliance status of the affected facility.
    9.3  IC/PCR Quality Control.
    9.3.1  IC/PCR Calibration Reference Standards.
    9.3.1.1  Prepare a calibration reference standard at a 
concentration that is at or near the mid-point of the calibration curve 
using the same alkaline matrix as the calibration standards. This 
reference standard should be prepared from a different Cr stock 
solution than that used to prepare the calibration curve standards. The 
reference standard is used to verify the accuracy of the calibration 
curve.
    9.3.1.2  The curve must be validated before sample analyses are 
performed. Prior to sample analysis, analyze at least one reference 
standard with an expected value within the calibration range.
    9.3.1.3  The results of this reference standard analysis must be 
within 10 percent of the true value of the reference standard for the 
calibration curve to be considered valid.
    9.3.2  IC/PCR Continuing Check Standard and Calibration Blank.
    9.3.2.1  Perform analysis of the check standard and the calibration 
blank with the field samples as described in Section 11.6 (at least 
after every 10 samples, and at the end of the analytical run).
    9.3.2.2  The result from the check standard must be within 10 
percent of the expected value.
    9.3.2.3  If the 10 percent criteria is exceeded, excessive drift 
and/or instrument degradation may have occurred, and must be corrected 
before further analyses can be performed.
    9.3.2.4  The results of the calibration blank analyses must agree 
within three standard deviations of the mean blank value.
    9.3.2.5  If not, analyze the calibration blank two more times and 
average the results.
    9.3.2.6  If the average is not within three standard deviations of 
the background mean, terminate the analyses, correct the problem, 
recalibrate, and reanalyze all samples analyzed subsequent to the last 
acceptable calibration blank analysis.
    9.3.3  IC/PCR Duplicate Sample Analysis.
    9.3.3.1  Perform one duplicate sample analysis for each compliance 
sample batch (3 runs).
    9.3.3.2  An aliquot of the selected sample is prepared and analyzed 
using procedures identical to those used for the emission samples (for 
example, filtration and/or, if necessary, preconcentration).
    9.3.3.3  Duplicate sample injection results shall agree within 10 
percent for sample results exceeding ten (10) times the detection 
limit.
    9.3.3.4  Report the original analysis value for the sample and 
report the duplicate analysis value as the QC check value.
    9.3.3.5  If agreement is not achieved, perform the duplicate 
analysis again.
    9.3.3.6  If agreement is not achieved the second time, perform 
corrective action to identify and correct the problem prior to 
analyzing the sample for a third time.
    9.3.4  ICP/PCR Matrix Spiking. Spiked samples shall be prepared and 
analyzed with each sample set to ensure that there are no matrix 
effects, that samples and standards have been matrix-matched, and that 
the equipment is operating properly.
    9.3.4.1  Spiked sample recovery analysis should indicate a recovery 
of the Cr+\6\ spike between 75 and 125 percent.
    9.3.4.2  The spiked sample concentration should be within the 
linear portion of the calibration curve and should be equal to or 
greater than the concentration of the original sample. In addition, the 
spiked sample concentration should be at least ten (10) times the 
detection limit.
    9.3.4.3  If the recoveries for the Cr+\6\ spiked samples 
do not meet the specified criteria, perform corrective action to 
identify and correct the problem prior to reanalyzing the samples.
    9.3.5  IC/PCR Field Reagent Blank.
    9.3.5.1  Analyze a minimum of one matrix-matched field reagent 
blank (Section 8.2.4) per sample batch to determine if contamination or 
memory effects are occurring.
    9.3.5.2  If contamination or memory effects are observed, perform 
corrective action to identify and correct the problem before 
reanalyzing the samples.
    9.3.6  Audit Sample Analysis.
    9.3.6.1  When the method is used to analyze samples to demonstrate 
compliance with source emission regulation, an audit sample must be 
analyzed, subject to availability.
    9.3.6.2  Concurrently analyze the audit sample and the compliance 
samples in the same manner to evaluate the technique of the analyst and 
the standards preparation.
    9.3.6.3  The same analyst, analytical reagents, and analytical 
system shall be used for the compliance samples and the audit sample. 
If this condition is met, duplicate auditing of subsequent compliance 
analyses for the same enforcement agency within a 30-day period is 
waived. An audit sample set may not be used to validate different sets 
of compliance samples under the jurisdiction of separate enforcement 
agencies, unless prior arrangements have been made with both 
enforcement agencies.
    9.3.7  Audit Sample Results.
    9.3.7.1  Calculate the audit sample concentrations and submit 
results using the instructions provided with the audit samples.
    9.3.7.2  Report the results of the audit samples and the compliance 
determination samples along with their identification numbers, and the 
analyst's name to the responsible enforcement authority. Include this 
information with reports of any subsequent compliance analyses for the 
same enforcement authority during the 30-day period.
    9.3.7.3  The concentrations of the audit samples obtained by the 
analyst shall agree within the values specified by the compliance 
auditor. If the specified range is not met, reanalyze the compliance 
and audit samples, and include initial and reanalysis values in the 
test report.
    9.3.7.4  Failure to meet the specified range may require retests 
unless the audit problems are resolved. However, if the audit results 
do not affect the compliance or noncompliance status of

[[Page 62253]]

the affected facility, the Administrator may waive the reanalysis 
requirement, further audits, or retests and accept the results of the 
compliance test. While steps are being taken to resolve audit analysis 
problems, the Administrator may also choose to use the data to 
determine the compliance or noncompliance status of the affected 
facility.

10.0  Calibration and Standardization

    10.1  Sampling Train Calibration. Perform calibrations described in 
Method 5, (40 CFR Part 60, Appendix A). The alternate calibration 
procedures described in Method 5, may also be used.
    10.2  ICP Calibration.
    10.2.1  Calibrate the instrument according to the instrument 
manufacturer's recommended procedures, using a calibration blank and 
three standards for the initial calibration.
    10.2.2  Calibration standards should be prepared fresh daily, as 
described in Section 7.3.8. Be sure that samples and calibration 
standards are matrix matched. Flush the system with the calibration 
blank between each standard.
    10.2.3  Use the average intensity of multiple exposures (3 or more) 
for both standardization and sample analysis to reduce random error.
    10.2.4  Employing linear regression, calculate the correlation 
coefficient .
    10.2.5  The correlation coefficient must equal or exceed 0.995.
    10.2.6  If linearity is not acceptable, prepare and rerun another 
set of calibration standards or reduce the range of the calibration 
standards, as necessary.
    10.3  GFAAS Calibration.
    10.3.1  For instruments that measure directly in concentration, set 
the instrument software to display the correct concentration, if 
applicable.
    10.3.2  Curve must be linear in order to correctly perform the 
method of standard additions which is customarily performed 
automatically with most instrument computer-based data systems.
    10.3.3  The calibration curve (direct calibration or standard 
additions) must be prepared daily with a minimum of a calibration blank 
and three standards that are prepared fresh daily.
    10.3.4  The calibration curve acceptance criteria must equal or 
exceed 0.995.
    10.3.5  If linearity is not acceptable, prepare and rerun another 
set of calibration standards or reduce the range of calibration 
standards, as necessary.
    10.4  IC/PCR Calibration.
    10.4.1  Prepare a calibration curve using the calibration blank and 
three calibration standards prepared fresh daily as described in 
Section 7.3.8.
    10.4.2  The calibration curve acceptance criteria must equal or 
exceed 0.995.
    10.4.3  If linearity is not acceptable, remake and/or rerun the 
calibration standards. If the calibration curve is still unacceptable, 
reduce the range of the curve.
    10.4.4  Analyze the standards with the field samples as described 
in Section 11.6.

11.0  Analytical Procedures

    Note: The method determines the chromium concentration in 
g Cr/mL. It is important that the analyst measure the field 
sample volume prior to analyzing the sample. This will allow for 
conversion of g Cr/mL to g Cr/sample.


    11.1  ICP Sample Preparation.
    11.1.1  The ICP analysis is performed directly on the alkaline 
impinger solution; acid digestion is not necessary, provided the 
samples and standards are matrix matched.
    11.1.2  The ICP analysis should only be employed when the solution 
analyzed has a Cr concentration greater than 35 g/L or five 
times the method detection limit as determined according to Appendix B 
in 40 CFR Part 136 or by other commonly accepted analytical procedures.
    11.2  ICP Sample Analysis.
    11.2.1  The ICP analysis is applicable for the determination of 
total chromium only.
    11.2.2  ICP Blanks. Two types of blanks are required for the ICP 
analysis.
    11.2.2.1  Calibration Blank. The calibration blank is used in 
establishing the calibration curve. For the calibration blank, use 
either 0.1 N NaOH or 0.1 N NaHCO3, whichever is used for the 
impinger absorbing solution. The calibration blank can be prepared 
fresh in the laboratory; it does not have to be prepared from the same 
batch of solution that was used in the field. A sufficient quantity 
should be prepared to flush the system between standards and samples.
    11.2.2.2  Field Reagent Blank. The field reagent blank is collected 
in the field during the testing program. The field reagent blank 
(Section 8.2.4) is an aliquot of the absorbing solution prepared in 
Section 7.1.2. The reagent blank is used to assess possible 
contamination resulting from sample processing.
    11.2.3  ICP Instrument Adjustment.
    11.2.3.1  Adjust the ICP instrument for proper operating parameters 
including wavelength, background correction settings (if necessary), 
and interfering element correction settings (if necessary).
    11.2.3.2  The instrument must be allowed to become thermally stable 
before beginning measurements (usually requiring at least 30 min of 
operation prior to calibration). During this warmup period, the optical 
calibration and torch position optimization may be performed (consult 
the operator's manual).
    11.2.4  ICP Instrument Calibration.
    11.2.4.1  Calibrate the instrument according to the instrument 
manufacturer's recommended procedures, and the procedures specified in 
Section 10.2.
    11.2.4.2  Prior to analyzing the field samples, reanalyze the 
highest calibration standard as if it were a sample.
    11.2.4.3  Concentration values obtained should not deviate from the 
actual values or from the established control limits by more than 5 
percent, whichever is lower (see Sections 9.1 and 10.2).
    11.2.4.4  If they do, follow the recommendations of the instrument 
manufacturer to correct the problem.
    11.2.5  ICP Operational Quality Control Procedures.
    11.2.5.1  Flush the system with the calibration blank solution for 
at least 1 min before the analysis of each sample or standard.
    11.2.5.2  Analyze the continuing check standard and the calibration 
blank after each batch of 10 samples.
    11.2.5.3  Use the average intensity of multiple exposures for both 
standardization and sample analysis to reduce random error.
    11.2.6  ICP Sample Dilution.
    11.2.6.1  Dilute and reanalyze samples that are more concentrated 
than the linear calibration limit or use an alternate, less sensitive 
Cr wavelength for which quality control data have already been 
established.
    11.2.6.2  When dilutions are performed, the appropriate factors 
must be applied to sample measurement results.
    11.2.7  Reporting Analytical Results. All analytical results should 
be reported in g Cr/mL using three significant figures. Field 
sample volumes (mL) must be reported also.
    11.3  GFAAS Sample Preparation.
    11.3.1  GFAAS Acid Digestion. An acid digestion of the alkaline 
impinger solution is required for the GFAAS analysis.
    11.3.1.1  In a beaker, add 10 mL of concentrated HNO3 to 
a 100 mL sample aliquot that has been well mixed. Cover

[[Page 62254]]

the beaker with a watch glass. Place the beaker on a hot plate and 
reflux the sample to near dryness. Add another 5 mL of concentrated 
HNO3 to complete the digestion. Again, carefully reflux the 
sample volume to near dryness. Rinse the beaker walls and watch glass 
with reagent water.
    11.3.1.2  The final concentration of HNO3 in the 
solution should be 1 percent (v/v).
    11.3.1.3  Transfer the digested sample to a 50-mL volumetric flask. 
Add 0.5 mL of concentrated HNO3 and 1 mL of the 10 
g/mL of Ca(NO3)2. Dilute to 50 mL with 
reagent water.
    11.3.2  HNO3 Concentration. A different final volume may 
be used based on the expected Cr concentration, but the HNO3 
concentration must be maintained at 1 percent (v/v).
    11.4  GFAAS Sample Analysis.
    11.4.1  The GFAAS analysis is applicable for the determination of 
total chromium only.
    11.4.2  GFAAS Blanks. Two types of blanks are required for the 
GFAAS analysis.
    11.4.2.1  Calibration Blank. The 1.0 percent HNO3 is the 
calibration blank which is used in establishing the calibration curve.
    11.4.2.2  Field Reagent Blank. An aliquot of the 0.1 N NaOH 
solution or the 0.1 N NaHCO3 prepared in Section 7.1.2 is 
collected for the field reagent blank. The field reagent blank is used 
to assess possible contamination resulting from processing the sample.
    11.4.2.2.1  The reagent blank must be subjected to the entire 
series of sample preparation and analytical procedures, including the 
acid digestion.
    11.4.2.2.2  The reagent blank's final solution must contain the 
same acid concentration as the sample solutions.
    11.4.3  GFAAS Instrument Adjustment.
    11.4.3.1  The 357.9 nm wavelength line shall be used.
    11.4.3.2  Follow the manufacturer's instructions for all other 
spectrophotometer operating parameters.
    11.4.4  Furnace Operational Parameters. Parameters suggested by the 
manufacturer should be employed as guidelines.
    11.4.4.1  Temperature-sensing mechanisms and temperature 
controllers can vary between instruments and/or with time; the validity 
of the furnace operating parameters must be periodically confirmed by 
systematically altering the furnace parameters while analyzing a 
standard. In this manner, losses of analyte due to higher-than-
necessary temperature settings or losses in sensitivity due to less 
than optimum settings can be minimized.
    11.4.4.2  Similar verification of furnace operating parameters may 
be required for complex sample matrices (consult instrument manual for 
additional information). Calibrate the GFAAS system following the 
procedures specified in Section 10.3.
    11.4.5  GFAAS Operational Quality Control Procedures.
    11.4.5.1  Introduce a measured aliquot of digested sample into the 
furnace and atomize.
    11.4.5.2  If the measured concentration exceeds the calibration 
range, the sample should be diluted with the calibration blank solution 
(1.0 percent HNO3) and reanalyzed.
    11.4.5.3  Consult the operator's manual for suggested injection 
volumes. The use of multiple injections can improve accuracy and assist 
in detecting furnace pipetting errors.
    11.4.5.4  Analyze a minimum of one matrix-matched reagent blank per 
sample batch to determine if contamination or any memory effects are 
occurring.
    11.4.5.5  Analyze a calibration blank and a continuing check 
standard after approximately every batch of 10 sample injections.
    11.4.6  GFAAS Sample Dilution.
    11.4.6.1  Dilute and reanalyze samples that are more concentrated 
than the instrument calibration range.
    11.4.6.2  If dilutions are performed, the appropriate factors must 
be applied to sample measurement results.
    11.4.7  Reporting Analytical Results.
    11.4.7.1  Calculate the Cr concentrations by the method of standard 
additions (see operator's manual) or, from direct calibration. All 
dilution and/or concentration factors must be used when calculating the 
results.
    11.4.7.2  Analytical results should be reported in g Cr/mL 
using three significant figures. Field sample volumes (mL) must be 
reported also.
    11.5  IC/PCR Sample Preparation.
    11.5.1  Sample pH. Measure and record the sample pH prior to 
analysis.
    11.5.2  Sample Filtration. Prior to preconcentration and/or 
analysis, filter all field samples through a 0.45-m filter. 
The filtration step should be conducted just prior to sample injection/
analysis.
    11.5.2.1  Use a portion of the sample to rinse the syringe 
filtration unit and acetate filter and then collect the required volume 
of filtrate.
    11.5.2.2  Retain the filter if total Cr is to be determined also.
    11.5.3  Sample Preconcentration (older instruments).
    11.5.3.1  For older instruments, a preconcentration system may be 
used in conjunction with the IC/PCR to increase sensitivity for trace 
levels of Cr+6.
    11.5.3.2  The preconcentration is accomplished by selectively 
retaining the analyte on a solid absorbent, followed by removal of the 
analyte from the absorbent (consult instrument manual).
    11.5.3.3  For a manual system, position the injection valve so that 
the eluent displaces the concentrated Cr+\6\ sample, 
transferring it from the preconcentration column and onto the IC anion 
separation column.
    11.6  IC/PCR Sample Analyses.
    11.6.1  The IC/PCR analysis is applicable for hexavalent chromium 
measurements only.
    11.6.2  IC/PCR Blanks. Two types of blanks are required for the IC/
PCR analysis.
    11.6.2.1  Calibration Blank. The calibration blank is used in 
establishing the analytical curve. For the calibration blank, use 
either 0.1 N NaOH or 0.1 N NaHCO3, whichever is used for the 
impinger solution. The calibration blank can be prepared fresh in the 
laboratory; it does not have to be prepared from the same batch of 
absorbing solution that is used in the field.
    11.6.2.2  Field Reagent Blank. An aliquot of the 0.1 N NaOH 
solution or the 0.1 N NaHCO3 solution prepared in Section 
7.1.2 is collected for the field reagent blank. The field reagent blank 
is used to assess possible contamination resulting from processing the 
sample.
    11.6.3  Stabilized Baseline. Prior to sample analysis, establish a 
stable baseline with the detector set at the required attenuation by 
setting the eluent and post-column reagent flow rates according to the 
manufacturers recommendations.

    Note: As long as the ratio of eluent flow rate to PCR flow rate 
remains constant, the standard curve should remain linear. Inject a 
sample of reagent water to ensure that no Cr+6 appears in 
the water blank.

    11.6.4  Sample Injection Loop. Size of injection loop is based on 
standard/sample concentrations and the selected attenuator setting.
    11.6.4.1  A 50-L loop is normally sufficient for most 
higher concentrations.
    11.6.4.2  The sample volume used to load the injection loop should 
be at least 10 times the loop size so that all tubing in contact with 
the sample is thoroughly flushed with the new sample to prevent cross 
contamination.
    11.6.5  IC/PCR Instrument Calibration.
    11.6.5.1  First, inject the calibration standards prepared, as 
described in

[[Page 62255]]

Section 7.3.8 to correspond to the appropriate concentration range, 
starting with the lowest standard first.
    11.6.5.2  Check the performance of the instrument and verify the 
calibration using data gathered from analyses of laboratory blanks, 
calibration standards, and a quality control sample.
    11.6.5.3  Verify the calibration by analyzing a calibration 
reference standard. If the measured concentration exceeds the 
established value by more than 10 percent, perform a second analysis. 
If the measured concentration still exceeds the established value by 
more than 10 percent, terminate the analysis until the problem can be 
identified and corrected.
    11.6.6  IC/PCR Instrument Operation.
    11.6.6.1  Inject the calibration reference standard (as described 
in Section 9.3.1), followed by the field reagent blank (Section 8.2.4), 
and the field samples.
    11.6.6.1.1  Standards (and QC standards) and samples are injected 
into the sample loop of the desired size (use a larger size loop for 
greater sensitivity). The Cr+6 is collected on the resin bed 
of the column.
    11.6.6.1.2  After separation from other sample components, the 
Cr+6 forms a specific complex in the post-column reactor 
with the DPC reaction solution, and the complex is detected by visible 
absorbance at a maximum wavelength of 540 nm.
    11.6.6.1.3  The amount of absorbance measured is proportional to 
the concentration of the Cr+6 complex formed.
    11.6.6.1.4  The IC retention time and the absorbance of the 
Cr+6 complex with known Cr+6 standards analyzed 
under identical conditions must be compared to provide both qualitative 
and quantitative analyses.
    11.6.6.1.5  If a sample peak appears near the expected retention 
time of the Cr+6 ion, spike the sample according to Section 
9.3.4 to verify peak identity.
    11.6.7  IC/PCR Operational Quality Control Procedures.
    11.6.7.1  Samples should be at a pH 8.5 for NaOH and 
8.0 if using NaHCO3; document any discrepancies.
    11.6.7.2  Refrigerated samples should be allowed to equilibrate to 
ambient temperature prior to preparation and analysis.
    11.6.7.3  Repeat the injection of the calibration standards at the 
end of the analytical run to assess instrument drift. Measure areas or 
heights of the Cr+6/DPC complex chromatogram peaks.
    11.6.7.4  To ensure the precision of the sample injection (manual 
or autosampler), the response for the second set of injected standards 
must be within 10 percent of the average response.
    11.6.7.5  If the 10 percent criteria duplicate injection cannot be 
achieved, identify the source of the problem and rerun the calibration 
standards.
    11.6.7.6  Use peak areas or peak heights from the injections of 
calibration standards to generate a linear calibration curve. From the 
calibration curve, determine the concentrations of the field samples.
    11.6.8  IC/PCR Sample Dilution.
    11.6.8.1  Samples having concentrations higher than the established 
calibration range must be diluted into the calibration range and re-
analyzed.
    11.6.8.2  If dilutions are performed, the appropriate factors must 
be applied to sample measurement results.
    11.6.9  Reporting Analytical Results. Results should be reported in 
g Cr+6/mL using three significant figures. Field 
sample volumes (mL) must be reported also.

12.0  Data Analysis and Calculations

    12.1  Pretest Calculations.
    12.1.1  Pretest Protocol (Site Test Plan).
    12.1.1.1  The pretest protocol should define and address the test 
data quality objectives (DQOs), with all assumptions, that will be 
required by the end user (enforcement authority); what data are needed? 
why are the data needed? how will the data be used? what are method 
detection limits? and what are estimated target analyte levels for the 
following test parameters.
    12.1.1.1.1  Estimated source concentration for total chromium and/
or Cr+6.
    12.1.1.1.2  Estimated minimum sampling time and/or volume required 
to meet method detection limit requirements (Appendix B 40 CFR Part 
136) for measurement of total chromium and/or Cr+6.
    12.1.1.1.3  Demonstrate that planned sampling parameters will meet 
DQOs. The protocol must demonstrate that the planned sampling 
parameters calculated by the tester will meet the needs of the source 
and the enforcement authority.
    12.1.1.2  The pre-test protocol should include information on 
equipment, logistics, personnel, process operation, and other resources 
necessary for an efficient and coordinated test.
    12.1.1.3  At a minimum, the pre-test protocol should identify and 
be approved by the source, the tester, the analytical laboratory, and 
the regulatory enforcement authority. The tester should not proceed 
with the compliance testing before obtaining approval from the 
enforcement authority.
    12.1.2  Post Test Calculations.
    12.1.2.1  Perform the calculations, retaining one extra decimal 
figure beyond that of the acquired data. Round off figures after final 
calculations.
    12.1.2.2  Nomenclature.

CS = Concentration of Cr in sample solution, g Cr/
mL.
Ccr = Concentration of Cr in stack gas, dry basis, corrected 
to standard conditions, mg/dscm.
D = Digestion factor, dimension less.
F = Dilution factor, dimension less.
MCr = Total Cr in each sample, g.
Vad = Volume of sample aliquot after digestion, mL.
Vaf = Volume of sample aliquot after dilution, mL.
Vbd = Volume of sample aliquot submitted to digestion, mL.
Vbf = Volume of sample aliquot before dilution, mL.
VmL = Volume of impinger contents plus rinses, mL.
Vm(std) = Volume of gas sample measured by the dry gas 
meter, corrected to standard conditions, dscm.

    12.1.2.3  Dilution Factor. The dilution factor is the ratio of the 
volume of sample aliquot after dilution to the volume before dilution. 
This ratio is given by the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.573

    12.1.2.4  Digestion Factor. The digestion factor is the ratio of 
the volume of sample aliquot after digestion to the volume before 
digestion. This ratio is given by Equation 306-2.

[[Page 62256]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.574

    12.1.2.5  Total Cr in Sample. Calculate MCr, the total g 
Cr in each sample, using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.575

    12.1.2.6  Average Dry Gas Meter Temperature and Average Orifice 
Pressure Drop. Same as Method 5.
    12.1.2.7  Dry Gas Volume, Volume of Water Vapor, Moisture Content. 
Same as Method 5.
    12.1.2.8  Cr Emission Concentration (CCr). Calculate 
CCr, the Cr concentration in the stack gas, in mg/dscm on a 
dry basis, corrected to standard conditions using the following 
equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.576

    12.1.2.9  Isokinetic Variation, Acceptable Results. Same as Method 
5.

13.0  Method Performance

    13.1  Range. The recommended working range for all of the three 
analytical techniques starts at five times the analytical detection 
limit (see also Section 13.2.2). The upper limit of all three 
techniques can be extended indefinitely by appropriate dilution.
    13.2  Sensitivity.
    13.2.1  Analytical Sensitivity. The estimated instrumental 
detection limits listed are provided as a guide for an instrumental 
limit. The actual method detection limits are sample and instrument 
dependent and may vary as the sample matrix varies.
    13.2.1.2  ICP Analytical Sensitivity. The minimum estimated 
detection limits for ICP, as reported in Method 6010A and the recently 
revised Method 6010B of SW-846 (Reference 1), are 7.0 g Cr/L 
and 4.7 g Cr/L, respectively.
    13.2.1.3  GFAAS Analytical Sensitivity. The minimum estimated 
detection limit for GFAAS, as reported in Methods 7000A and 7191 of SW-
846 (Reference 1), is 1 g Cr/L.
    13.2.1.4  IC/PCR Analytical Sensitivity. The minimum detection 
limit for IC/PCR with a preconcentrator, as reported in Methods 0061 
and 7199 of SW-846 (Reference 1), is 0.05 g Cr\+6\/L.
    1.3.2.1.5  Determination of Detection Limits. The laboratory 
performing the Cr\+6\ measurements must determine the method detection 
limit on a quarterly basis using a suitable procedure such as that 
found in 40 CFR, Part 136, Appendix B. The determination should be made 
on samples in the appropriate alkaline matrix. Normally this involves 
the preparation (if applicable) and consecutive measurement of seven 
(7) separate aliquots of a sample with a concentration 5 times the 
expected detection limit. The detection limit is 3.14 times the 
standard deviation of these results.
    13.2.2  In-stack Sensitivity. The in-stack sensitivity depends upon 
the analytical detection limit, the volume of stack gas sampled, the 
total volume of the impinger absorbing solution plus the rinses, and, 
in some cases, dilution or concentration factors from sample 
preparation. Using the analytical detection limits given in Sections 
13.2.1.1, 13.2.1.2, and 13.2.1.3; a stack gas sample volume of 1.7 
dscm; a total liquid sample volume of 500 mL; and the digestion 
concentration factor of 1/2 for the GFAAS analysis; the corresponding 
in-stack detection limits are 0.0014 mg Cr/dscm to 0.0021 mg Cr/dscm 
for ICP, 0.00015 mg Cr/dscm for GFAAS, and 0.000015 mg Cr\+6\/dscm for 
IC/PCR with preconcentration.


    Note: It is recommended that the concentration of Cr in the 
analytical solutions be at least five times the analytical detection 
limit to optimize sensitivity in the analyses. Using this guideline 
and the same assumptions for impinger sample volume, stack gas 
sample volume, and the digestion concentration factor for the GFAAS 
analysis (500 mL,1.7 dscm, and 1/2, respectively), the recommended 
minimum stack concentrations for optimum sensitivity are 0.0068 mg 
Cr/dscm to 0.0103 mg Cr/dscm for ICP, 0.00074 mg Cr/dscm for GFAAS, 
and 0.000074 mg Cr\+6\/dscm for IC/PCR with preconcentration. If 
required, the in-stack detection limits can be improved by either 
increasing the stack gas sample volume, further reducing the volume 
of the digested sample for GFAAS, improving the analytical detection 
limits, or any combination of the three.


    13.3  Precision.
    13.3.1  The following precision data have been reported for the 
three analytical methods. In each case, when the sampling precision is 
combined with the reported analytical precision, the resulting overall 
precision may decrease.
    13.3.2  Bias data is also reported for GFAAS.
    13.4  ICP Precision.
    13.4.1  As reported in Method 6010B of SW-846 (Reference 1), in an 
EPA round-robin Phase 1 study, seven laboratories applied the ICP 
technique to acid/distilled water matrices that had been spiked with 
various metal concentrates. For true values of 10, 50, and 150 
g Cr/L; the mean reported values were 10, 50, and 149 
g Cr/L; and the mean percent relative standard deviations were 
18, 3.3, and 3.8 percent, respectively.
    13.4.2  In another multi laboratory study cited in Method 6010B, a 
mean relative standard of 8.2 percent was reported for an aqueous 
sample concentration of approximately 3750 g Cr/L.
    13.5  GFAAS Precision. As reported in Method 7191 of SW-846 
(Reference 1), in a single laboratory (EMSL), using Cincinnati, Ohio 
tap water spiked at concentrations of 19, 48, and 77 g Cr/L, 
the standard deviations were 0.1, 0.2, and 
0.8, respectively. Recoveries at these levels were 97 
percent, 101 percent, and 102 percent, respectively.
    13.6  IC/PCR Precision. As reported in Methods 0061 and 7199 of SW-
846 (Reference 1), the precision of IC/PCR with sample preconcentration 
is 5 to 10 percent. The overall precision for

[[Page 62257]]

sewage sludge incinerators emitting 120 ng/dscm of Cr+\6\ 
and 3.5 g/dscm of total Cr was 25 percent and 9 percent, 
respectively; and for hazardous waste incinerators emitting 300 ng/dscm 
of C+\6\ the precision was 20 percent.

14.0  Pollution Prevention

    14.1  The only materials used in this method that could be 
considered pollutants are the chromium standards used for instrument 
calibration and acids used in the cleaning of the collection and 
measurement containers/labware, in the preparation of standards, and in 
the acid digestion of samples. Both reagents can be stored in the same 
waste container.
    14.2  Cleaning solutions containing acids should be prepared in 
volumes consistent with use to minimize the disposal of excessive 
volumes of acid.
    14.3  To the extent possible, the containers/vessels used to 
collect and prepare samples should be cleaned and reused to minimize 
the generation of solid waste.

15.0  Waste Management

    15.1  It is the responsibility of the laboratory and the sampling 
team to comply with all federal, state, and local regulations governing 
waste management, particularly the discharge regulations, hazardous 
waste identification rules, and land disposal restrictions; and to 
protect the air, water, and land by minimizing and controlling all 
releases from field operations.
    15.2  For further information on waste management, consult The 
Waste Management Manual for Laboratory Personnel and Less is Better--
Laboratory Chemical Management for Waste Reduction, available from the 
American Chemical Society's Department of Government Relations and 
Science Policy, 1155 16th Street NW, Washington, DC 20036.

16.0  References

    1. ``Test Methods for Evaluating Solid Waste, Physical/Chemical 
Methods, SW-846, Third Edition,'' as amended by Updates I, II, IIA, 
IIB, and III. Document No. 955-001-000001. Available from 
Superintendent of Documents, U.S. Government Printing Office, 
Washington, DC, November 1986.
    2. Cox, X.B., R.W. Linton, and F.E. Butler. Determination of 
Chromium Speciation in Environmental Particles--A Multi-technique 
Study of Ferrochrome Smelter Dust. Accepted for publication in 
Environmental Science and Technology.
    3. Same as Section 17.0 of Method 5, References 2, 3, 4, 5, and 
7.
    4. California Air Resources Board, ``Determination of Total 
Chromium and Hexavalent Chromium Emissions from Stationary 
Sources.'' Method 425, September 12, 1990.
    5. The Merck Index. Eleventh Edition. Merck & Co., Inc., 1989.
    6. Walpole, R.E., and R.H. Myers. ``Probability and Statistics 
for Scientists and Engineering.'' 3rd Edition. MacMillan Publishing 
Co., NewYork, N.Y., 1985.
BILLING CODE 6560-50-C

[[Page 62258]]

17.0  Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.577


[[Page 62259]]


[GRAPHIC] [TIFF OMITTED] TR17OC00.578

BILLING CODE 6560-50-C

[[Page 62260]]

Method 306A--Determination of Chromium Emissions From Decorative 
and Hard Chromium Electroplating and Chromium Anodizing Operations

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in 40 CFR Part 60, 
Appendix A and in this part. Therefore, to obtain reliable results, 
persons using this method should have a thorough knowledge of at 
least Methods 5 and 306.

1.0  Scope and Application

    1.1  Analyte. Chromium. CAS Number (7440-47-3).
    1.2  Applicability.
    1.2.1  This method applies to the determination of chromium (Cr) in 
emissions from decorative and hard chromium electroplating facilities, 
chromium anodizing operations, and continuous chromium plating at iron 
and steel facilities. The method is less expensive and less complex to 
conduct than Method 306. Correctly applied, the precision and bias of 
the sample results should be comparable to those obtained with the 
isokinetic Method 306. This method is applicable for the determination 
of air emissions under nominal ambient moisture, temperature, and 
pressure conditions.
    1.2.2  The method is also applicable to electroplating and 
anodizing sources controlled by wet scrubbers.
    1.3  Data Quality Objectives.
    1.3.1  Pretest Protocol.
    1.3.1.1  The pretest protocol should define and address the test 
data quality objectives (DQOs), with all assumptions, that will be 
required by the end user (enforcement authority); what data are needed? 
why are the data needed? how will data be used? what are method 
detection limits? and what are estimated target analyte levels for the 
following test parameters.
    1.3.1.1.1  Estimated source concentration for total chromium and/or 
Cr\+6\.
    1.3.1.1.2  Estimated minimum sampling time and/or volume required 
to meet method detection limit requirements (Appendix B 40 CFR Part 
136) for measurement of total chromium and/or Cr\+6\.
    1.3.1.1.3  Demonstrate that planned sampling parameters will meet 
DQOs. The protocol must demonstrate that the planned sampling 
parameters calculated by the tester will meet the needs of the source 
and the enforcement authority.
    1.3.1.2  The pre-test protocol should include information on 
equipment, logistics, personnel, process operation, and other resources 
necessary for an efficient and coordinated performance test.
    1.3.1.3  At a minimum, the pre-test protocol should identify and be 
approved by the source, the tester, the analytical laboratory, and the 
regulatory enforcement authority. The tester should not proceed with 
the compliance testing before obtaining approval from the enforcement 
authority.

2.0  Summary of Method

    2.1  Sampling.
    2.1.1  An emission sample is extracted from the source at a 
constant sampling rate determined by a critical orifice and collected 
in a sampling train composed of a probe and impingers. The proportional 
sampling time at the cross sectional traverse points is varied 
according to the stack gas velocity at each point. The total sample 
time must be at least two hours.
    2.1.2  The chromium emission concentration is determined by the 
same analytical procedures described in Method 306: inductively-coupled 
plasma emission spectrometry (ICP), graphite furnace atomic absorption 
spectrometry (GFAAS), or ion chromatography with a post-column reactor 
(IC/PCR).
    2.1.2.1  Total chromium samples with high chromium concentrations 
(35 g/L) may be analyzed using inductively coupled 
plasma emission spectrometry (ICP) at 267.72 nm.

    Note: The ICP analysis is applicable for this method only when 
the solution analyzed has a Cr concentration greater than or equal 
to 35 g/L or five times the method detection limit as 
determined according to Appendix B in 40 CFR Part 136.

    2.1.2.2  Alternatively, when lower total chromium concentrations 
(35 g/L) are encountered, a portion of the alkaline sample 
solution may be digested with nitric acid and analyzed by graphite 
furnace atomic absorption spectroscopy (GFAAS) at 357.9 nm.
    2.1.2.3  If it is desirable to determine hexavalent chromium 
(Cr\+6\) emissions, the samples may be analyzed using an ion 
chromatograph equipped with a post-column reactor (IC/PCR) and a 
visible wavelength detector. To increase sensitivity for trace levels 
of Cr\+6\, a preconcentration system may be used in conjunction with 
the IC/PCR.

3.0  Definitions

    3.1  Total Chromium--measured chromium content that includes both 
major chromium oxidation states (Cr+3, Cr+6).
    3.2  May--Implies an optional operation.
    3.3  Digestion--The analytical operation involving the complete (or 
nearly complete) dissolution of the sample in order to ensure the 
complete solubilization of the element (analyte) to be measured.
    3.4  Interferences--Physical, chemical, or spectral phenomena that 
may produce a high or low bias in the analytical result.
    3.5  Analytical System--All components of the analytical process 
including the sample digestion and measurement apparatus.
    3.6  Sample Recovery--The quantitative transfer of sample from the 
collection apparatus to the sample preparation (digestion, etc.) 
apparatus. This term should not be confused with analytical recovery.

4.0  Interferences

    4.1  Same as in Method 306, Section 4.0.

5.0  Safety

    5.1  Disclaimer. This method may involve hazardous materials, 
operations, and equipment. This test method does not purport to address 
all of the safety issues associated with its use. It is the 
responsibility of the user to establish appropriate safety and health 
practices and to determine the applicability of regulatory limitations 
prior to performing this test method.
    5.2  Chromium and some chromium compounds have been listed as 
carcinogens although Chromium (III) compounds show little or no 
toxicity. Chromium is a skin and respiratory irritant.

6.0  Equipment and Supplies

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

    6.1  Sampling Train. A schematic of the sampling train is shown in 
Figure 306A-1. The individual components of the train are available 
commercially, however, some fabrication and assembly are required.
    6.1.1  Probe Nozzle/Tubing and Sheath.
    6.1.1.1  Use approximately 6.4-mm (\1/4\-in.) inside diameter (ID) 
glass or rigid plastic tubing approximately 20 cm (8 in.) in length 
with a short 90 degree bend at one end to form the sampling nozzle. 
Grind a slight taper on the nozzle end before making the bend. Attach 
the nozzle to flexible tubing of sufficient length to enable collection 
of a sample from the stack.
    6.1.1.2  Use a straight piece of larger diameter rigid tubing (such 
as metal conduit or plastic water pipe) to form a sheath that begins 
about 2.5 cm (1 in.) from the 90 deg. bend on the nozzle and

[[Page 62261]]

encases and supports the flexible tubing.
    6.1.2 Type S Pitot Tube. Same as Method 2, Section 6.1 (40 CFR Part 
60, Appendix A).
    6.1.3  Temperature Sensor.
    6.1.3.1  A thermocouple, liquid-filled bulb thermometer, bimetallic 
thermometer, mercury-in-glass thermometer, or other sensor capable of 
measuring temperature to within 1.5 percent of the minimum absolute 
stack temperature.
    6.1.3.2  The temperature sensor shall either be positioned near the 
center of the stack, or be attached to the pitot tube as directed in 
Section 6.3 of Method 2.
    6.1.4  Sample Train Connectors.
    6.1.4.1  Use thick wall flexible plastic tubing (polyethylene, 
polypropylene, or polyvinyl chloride)  6.4-mm (\1/4\-in.) 
to 9.5-mm (\3/8\-in.) ID to connect the train components.
    6.1.4.2  A combination of rigid plastic tubing and thin wall 
flexible tubing may be used as long as tubing walls do not collapse 
when leak-checking the train. Metal tubing cannot be used.
    6.1.5  Impingers. Three, one-quart capacity, glass canning jars 
with vacuum seal lids, or three Greenburg-Smith (GS) design impingers 
connected in series, or equivalent, may be used.
    6.1.5.1  One-quart glass canning jar. Three separate jar containers 
are required: (1) the first jar contains the absorbing solution; (2) 
the second is empty and is used to collect any reagent carried over 
from the first container; and (3) the third contains the desiccant 
drying agent.
    6.1.5.2  Canning Jar Connectors. The jar containers are connected 
by leak-tight inlet and outlet tubes installed in the lids of each 
container for assembly with the train. The tubes may be made of 
 6.4 mm (\1/4\-in.) ID glass or rigid plastic tubing. For 
the inlet tube of the first impinger, heat the glass or plastic tubing 
and draw until the tubing separates. Fabricate the necked tip to form 
an orifice tip that is approximately 2.4 mm (\3/32\-in.) ID.
    6.1.5.2.1  When assembling the first container, place the orifice 
tip end of the tube approximately 4.8 mm (\3/16\-in.) above the inside 
bottom of the jar.
    6.1.5.2.2  For the second container, the inlet tube need not be 
drawn and sized, but the tip should be approximately 25 mm (1 in.) 
above the bottom of the jar.
    6.1.5.2.3  The inlet tube of the third container should extend to 
approximately 12.7 mm (\1/2\-in.) above the bottom of the jar.
    6.1.5.2.4  Extend the outlet tube for each container approximately 
50 mm (2 in.) above the jar lid and downward through the lid, 
approximately 12.7 mm (\1/2\-in.) beneath the bottom of the lid.
    6.1.5.3  Greenburg-Smith Impingers. Three separate impingers of the 
Greenburg-Smith (GS) design as described in Section 6.0 of Method 5 are 
required. The first GS impinger shall have a standard tip (orifice/
plate), and the second and third GS impingers shall be modified by 
replacing the orifice/plate tube with a 13 mm (\1/2\-in.) ID glass 
tube, having an unrestricted opening located 13 mm (\1/2\-in.) from the 
bottom of the outer flask.
    6.1.5.4  Greenburg-Smith Connectors. The GS impingers shall be 
connected by leak-free ground glass ``U'' tube connectors or by leak-
free non-contaminating flexible tubing. The first impinger shall 
contain the absorbing solution, the second is empty and the third 
contains the desiccant drying agent.
    6.1.6  Manometer. Inclined/vertical type, or equivalent device, as 
described in Section 6.2 of Method 2 (40 CFR Part 60, Appendix A).
    6.1.7  Critical Orifice. The critical orifice is a small 
restriction in the sample line that is located upstream of the vacuum 
pump. The orifice produces a constant sampling flow rate that is 
approximately 0.021 cubic meters per minute (m3/min) or 0.75 
cubic feet per minute (cfm).
    6.1.7.1  The critical orifice can be constructed by sealing a 2.4-
mm (\3/32\-in.) ID brass tube approximately 14.3 mm (\9/16\-in.) in 
length inside a second brass tube that is approximately 8 mm (\5/16\-
in.) ID and 14.3-mm (\9/16\-in.) in length .
    6.1.7.2  Materials other than brass can be used to construct the 
critical orifice as long as the flow through the sampling train can be 
maintained at approximately 0.021 cubic meter per minute (0.75) cfm.
    6.1.8  Connecting Hardware. Standard pipe and fittings, 9.5-mm (\3/
8\-in.), 6.4-mm (\1/4\-in.) or 3.2-mm (\1/8\-in.) ID, may be used to 
assemble the vacuum pump, dry gas meter and other sampling train 
components.
    6.1.9  Vacuum Gauge. Capable of measuring approximately 760 mm 
Hg (30 in. Hg) vacuum in 25.4 mm HG (1 
in. Hg) increments. Locate vacuum gauge between the critical 
orifice and the vacuum pump.
    6.1.10  Pump Oiler. A glass oil reservoir with a wick mounted at 
the vacuum pump inlet that lubricates the pump vanes. The oiler should 
be an in-line type and not vented to the atmosphere. See EMTIC 
Guideline Document No. GD-041.WPD for additional information.
    6.1.11  Vacuum Pump. Gast Model 0522-V103-G18DX, or equivalent, 
capable of delivering at least 1.5 cfm at 15 in. Hg vacuum.
    6.1.12  Oil Trap/Muffler. An empty glass oil reservoir without wick 
mounted at the pump outlet to control the pump noise and prevent oil 
from reaching the dry gas meter.
    6.1.13  By-pass Fine Adjust Valve (Optional). Needle valve assembly 
6.4-mm (\1/4\-in.), Whitey 1 RF 4-A, or equivalent, that allows for 
adjustment of the train vacuum.
    6.1.13.1  A fine-adjustment valve is positioned in the optional 
pump by-pass system that allows the gas flow to recirculate through the 
pump. This by-pass system allows the tester to control/reduce the 
maximum leak-check vacuum pressure produced by the pump.
    6.1.13.1.1  The tester must conduct the post test leak check at a 
vacuum equal to or greater than the maximum vacuum encountered during 
the sampling run.
    6.1.13.1.2  The pump by-pass assembly is not required, but is 
recommended if the tester intends to leak-check the 306A train at the 
vacuum experienced during a run.
    6.1.14  Dry Gas Meter. An Equimeter Model 110 test meter or, 
equivalent with temperature sensor(s) installed (inlet/outlet) to 
monitor the meter temperature. If only one temperature sensor is 
installed, locate the sensor at the outlet side of the meter. The dry 
gas meter must be capable of measuring the gaseous volume to within 
2% of the true volume.

    Note: The Method 306 sampling train is also commercially 
available and may be used to perform the Method 306A tests. The 
sampling train may be assembled as specified in Method 306A with the 
sampling rate being operated at the delta H@ specified 
for the calibrated orifice located in the meter box. The Method 306 
train is then operated as described in Method 306A.

    6.2  Barometer. Mercury aneroid barometer, or other barometer 
equivalent, capable of measuring atmospheric pressure to within 
2.5 mm Hg (0.1 in. Hg).
    6.2.1  A preliminary check of the barometer shall be made against a 
mercury-in-glass reference barometer or its equivalent.
    6.2.2  Tester may elect to obtain the absolute barometric pressure 
from a nearby National Weather Service station.
    6.2.2.1  The station value (which is the absolute barometric 
pressure) must be adjusted for elevation differences between the 
weather station and the sampling location. Either subtract 2.5

[[Page 62262]]

mm Hg (0.1 in. Hg) from the station value per 30 
m (100 ft) of elevation increase or add the same for an elevation 
decrease.
    6.2.2.2  If the field barometer cannot be adjusted to agree within 
0.1 in. Hg of the reference barometric, repair or discard 
the unit. The barometer pressure measurement shall be recorded on the 
sampling data sheet.
    6.3  Sample Recovery. Same as Method 5, Section 6.2 (40 CFR Part 
60, Appendix A), with the following exceptions:
    6.3.1  Probe-Liner and Probe-Nozzle Brushes. Brushes are not 
necessary for sample recovery. If a probe brush is used, it must be 
non-metallic.
    6.3.2  Wash Bottles. Polyethylene wash bottle, for sample recovery 
absorbing solution.
    6.3.3  Sample Recovery Solution. Use 0.1 N NaOH or 0.1 N 
NaHCO3, whichever is used as the impinger absorbing 
solution, to replace the acetone.
    6.3.4  Sample Storage Containers.
    6.3.4.1  Glass Canning Jar. The first canning jar container of the 
sampling train may serve as the sample shipping container. A new lid 
and sealing plastic wrap shall be substituted for the container lid 
assembly.
    6.3.4.2  Polyethylene or Glass Containers. Transfer the Greenburg-
Smith impinger contents to precleaned polyethylene or glass containers. 
The samples shall be stored and shipped in 250-mL, 500-mL or 1000-mL 
polyethylene or glass containers with leak-free, non metal screw caps.
    6.3.5  pH Indicator Strip, for Cr +6 Samples. pH 
indicator strips, or equivalent, capable of determining the pH of 
solutions between the range of 7 and 12, at 0.5 pH increments.
    6.3.6  Plastic Storage Containers. Air tight containers to store 
silica gel.
    6.4  Analysis. Same as Method 306, Section 6.3.

7.0  Reagents and Standards.

    Note: Unless otherwise indicated, all reagents shall conform to 
the specifications established by the Committee on Analytical 
Reagents of the American Chemical Society (ACS reagent grade). Where 
such specifications are not available, use the best available grade. 
It is recommended, but not required, that reagents be checked by the 
appropriate analysis prior to field use to assure that contamination 
is below the analytical detection limit for the ICP or GFAAS total 
chromium analysis; and that contamination is below the analytical 
detection limit for Cr+6 using IC/PCR for direct 
injection or, if selected, preconcentration.

    7.1  Sampling.
    7.1.1  Water. Reagent water that conforms to ASTM Specification 
D1193 Type II (incorporated by reference see Sec. 63.14). All 
references to water in the method refer to reagent water unless 
otherwise specified. It is recommended that water blanks be checked 
prior to preparing the sampling reagents to ensure that the Cr content 
is less than three (3) times the anticipated detection limit of the 
analytical method.
    7.1.2  Sodium Hydroxide (NaOH) Absorbing Solution, 0.1 N. Dissolve 
4.0 g of sodium hydroxide in 1 liter of water to obtain a pH of 
approximately 8.5.
    7.1.3  Sodium Bicarbonate (NaHCO3) Absorbing Solution, 
0.1 N. Dissolve approximately 8.5 g of sodium bicarbonate in 1 liter of 
water to obtain a pH of approximately 8.3.
    7.1.4  Chromium Contamination.
    7.1.4.1  The absorbing solution shall not exceed the QC criteria 
noted in Method 306, Section 7.1.1 (3 times the instrument 
detection limit).
    7.1.4.2  When the Cr+6 content in the field samples 
exceeds the blank concentration by at least a factor of ten (10), 
Cr+\6\ blank levels 10 times the detection limit 
will be allowed.


    Note: At sources with high concentrations of acids and/or 
SO2, the concentration of NaOH or NaHCO3 
should be 0.5 N to insure that the pH of the solution 
remains at or above 8.5 for NaOH and 8.0 for NaHCO3 
during and after sampling.


    7.1.3  Desiccant. Silica Gel, 6-16 mesh, indicating type. 
Alternatively, other types of desiccants may be used, subject to the 
approval of the Administrator.
    7.2  Sample Recovery. Same as Method 306, Section 7.2.
    7.3  Sample Preparation and Analysis. Same as Method 306, Section 
7.3.
    7.4  Glassware Cleaning Reagents. Same as Method 306, Section 7.4.
    7.5  Quality Assurance Audit Samples.
    7.5.1  It is recommended, but not required, that a performance 
audit sample be analyzed in conjunction with the field samples. The 
audit sample should be in a suitable sample matrix at a concentration 
similar to the actual field samples.
    7.5.2  When making compliance determinations, and upon 
availability, audit samples may be obtained from the appropriate EPA 
regional Office or from the responsible enforcement authority and 
analyzed in conjunction with the field samples.


    Note: The responsible enforcement authority should be notified 
at least 30 days prior to the test date to allow sufficient time for 
the audit sample to be delivered.

8.0  Sample Collection, Recovery, Preservation, Holding Times, Storage, 
and Transport

    Note: Prior to sample collection, consideration should be given 
as to the type of analysis (Cr+6 or total Cr) that will 
be performed. Deciding which analysis will be performed will enable 
the tester to determine which appropriate sample recovery and 
storage procedures will be required to process the sample.


    8.1  Sample Collection.
    8.1.1  Pretest Preparation.
    8.1.1.1  Selection of Measurement Site. Locate the sampling ports 
as specified in Section 11.0 of Method 1 (40 CFR Part 60, Appendix A).
    8.1.1.2  Location of Traverse Points.
    8.1.1.2.1  Locate the traverse points as specified in Section 11.0 
of Method 1 (40 CFR Part 60, Appendix A). Use a total of 24 sampling 
points for round ducts and 24 or 25 points for rectangular ducts. Mark 
the pitot and sampling probe to identify the sample traversing points.
    8.1.1.2.2  For round ducts less than 12 inches in diameter, use a 
total of 16 points.
    8.1.1.3  Velocity Pressure Traverse. Perform an initial velocity 
traverse before obtaining samples. The Figure 306A-2 data sheet may be 
used to record velocity traverse data.
    8.1.1.3.1  To demonstrate that the flow rate is constant over 
several days of testing, perform complete traverses at the beginning 
and end of each day's test effort, and calculate the deviation of the 
flow rate for each daily period. The beginning and end flow rates are 
considered constant if the deviation does not exceed 10 percent. If the 
flow rate exceeds the 10 percent criteria, either correct the 
inconsistent flow rate problem, or obtain the Administrator's approval 
for the test results.
    8.1.1.3.2  Perform traverses as specified in Section 8.0 of Method 
2, but record only the p (velocity pressure) values for each 
sampling point. If a mass emission rate is desired, stack velocity 
pressures shall be recorded before and after each test, and an average 
stack velocity pressure determined for the testing period.
    8.1.1.4  Verification of Absence of Cyclonic Flow. Check for 
cyclonic flow during the initial traverse to verify that it does not 
exist. Perform the cyclonic flow check as specified in Section 11.4 of 
Method 1 (40 CFR Part 60, Appendix A).
    8.1.1.4.1  If cyclonic flow is present, verify that the absolute 
average angle of the tangential flow does not exceed 20 degrees. If the 
average value exceeds 20 degrees at the sampling location, the flow 
condition in the stack is unacceptable for testing.
    8.1.1.4.2  Alternative procedures, subject to approval of the 
Administrator,

[[Page 62263]]

e.g., installing straightening vanes to eliminate the cyclonic flow, 
must be implemented prior to conducting the testing.
    8.1.1.5  Stack Gas Moisture Measurements. Not required. Measuring 
the moisture content is optional when a mass emission rate is to be 
calculated.
    8.1.1.5.1  The tester may elect to either measure the actual stack 
gas moisture during the sampling run or utilize a nominal moisture 
value of 2 percent.
    8.1.1.5.2  For additional information on determining sampling train 
moisture, please refer to Method 4 (40 CFR Part 60, Appendix A).
    8.1.1.6  Stack Temperature Measurements. If a mass emission rate is 
to be calculated, a temperature sensor must be placed either near the 
center of the stack, or attached to the pitot tube as described in 
Section 8.3 of Method 2. Stack temperature measurements, shall be 
recorded before and after each test, and an average stack temperature 
determined for the testing period.
    8.1.1.7  Point Sampling Times. Since the sampling rate of the train 
(0.75 cfm) is maintained constant by the critical orifice, it is 
necessary to calculate specific sampling times for each traverse point 
in order to obtain a proportional sample.
    8.1.1.7.1  If the sampling period (3 runs) is to be completed in a 
single day, the point sampling times shall be calculated only once.
    8.1.1.7.2  If the sampling period is to occur over several days, 
the sampling times must be calculated daily using the initial velocity 
pressure data recorded for that day. Determine the average of the 
p values obtained during the velocity traverse (Figure 306A-
2).
    8.1.1.7.3  If the stack diameter is less than 12 inches, use 7.5 
minutes in place of 5 minutes in the equation and 16 sampling points 
instead of 24 or 25 points. Calculate the sampling times for each 
traverse point using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.579

Where:
n = Sampling point number.
p = Average pressure differential across pitot tube, mm 
H2O (in. H2O).
Pavg = Average of p values, mm 
H2O (in. H2O).


    Note: Convert the decimal fractions for minutes to seconds.

    8.1.1.8  Pretest Preparation. It is recommended, but not required, 
that all items which will be in contact with the sample be cleaned 
prior to performing the testing to avoid possible sample contamination 
(positive chromium bias). These items include, but are not limited to: 
Sampling probe, connecting tubing, impingers, and jar containers.
    8.1.1.8.1  Sample train components should be: (1) Rinsed with hot 
tap water; (2) washed with hot soapy water; (3) rinsed with tap water; 
(4) rinsed with reagent water; (5) soaked in a 10 percent (v/v) nitric 
acid solution for at least four hours; and (6) rinsed throughly with 
reagent water before use.
    8.1.1.8.2  At a minimum, the tester should, rinse the probe, 
connecting tubing, and first and second impingers twice with either 0.1 
N sodium hydroxide (NaOH) or 0.1 N sodium bicarbonate 
(NaHCO3) and discard the rinse solution.
    8.1.1.8.3  If separate sample shipping containers are to be used, 
these also should be precleaned using the specified cleaning 
procedures.
    8.1.1.9  Preparation of Sampling Train. Assemble the sampling train 
as shown in Figure 306A-1. Secure the nozzle-liner assembly to the 
outer sheath to prevent movement when sampling.
    8.1.1.9.1  Place 250 mL of 0.1 N NaOH or 0.1 N NaHCO3 
absorbing solution into the first jar container or impinger. The second 
jar/impinger is to remain empty. Place 6 to 16 mesh indicating silica 
gel, or equivalent desiccant into the third jar/impinger until the 
container is half full ( 300 to 400 g).
    8.1.1.9.2  Place a small cotton ball in the outlet exit tube of the 
third jar to collect small silica gel particles that may dislodge and 
impair the pump and/or gas meter.
    8.1.1.10  Pretest Leak-Check. A pretest leak-check is recommended, 
but not required. If the tester opts to conduct the pretest leak-check, 
the following procedures shall be performed: (1) Place the jar/impinger 
containers into an ice bath and wait 10 minutes for the ice to cool the 
containers before performing the leak check and/or start sampling; (2) 
to perform the leak check, seal the nozzle using a piece of clear 
plastic wrap placed over the end of a finger and switch on the pump; 
and (3) the train system leak rate should not exceed 0.02 cfm at a 
vacuum of 380 mm Hg (15 in. Hg) or greater. If the leak rate does 
exceed the 0.02 cfm requirement, identify and repair the leak area and 
perform the leak check again.


    Note: Use caution when releasing the vacuum following the leak 
check. Always allow air to slowly flow through the nozzle end of the 
train system while the pump is still operating. Switching off the 
pump with vacuum on the system may result in the silica gel being 
pulled into the second jar container.

    8.1.1.11  Leak-Checks During Sample Run. If, during the sampling 
run, a component (e.g., jar container) exchange becomes necessary, a 
leak-check shall be conducted immediately before the component exchange 
is made. The leak-check shall be performed according to the procedure 
outlined in Section 8.1.1.10 of this method. If the leakage rate is 
found to be  0.02 cfm at the maximum operating vacuum, the 
results are acceptable. If, however, a higher leak rate is obtained, 
either record the leakage rate and correct the sample volume as shown 
in Section 12.3 of Method 5 or void the sample and initiate a 
replacement run. Following the component change, leak-checks are 
optional, but are recommended as are the pretest leak-checks.
    8.1.1.12  Post Test Leak Check. Remove the probe assembly and 
flexible tubing from the first jar/impinger container. Seal the inlet 
tube of the first container using clear plastic wrap and switch on the 
pump. The vacuum in the line between the pump and the critical orifice 
must be 15 in. Hg. Record the vacuum gauge measurement along 
with the leak rate observed on the train system.
    8.1.1.12.1  If the leak rate does not exceed 0.02 cfm, the results 
are acceptable and no sample volume correction is necessary.
    8.1.1.12.2  If, however, a higher leak rate is obtained (>0.02 
cfm), the tester shall either record the leakage rate and correct the 
sample volume as shown in Section 12.3 of Method 5, or void the 
sampling run and initiate a replacement run.  After completing the 
leak-check, slowly release the vacuum at the first

[[Page 62264]]

container while the pump is still operating. Afterwards, switch-off the 
pump.
    8.1.2  Sample Train Operation.
    8.1.2.1  Data Recording. Record all pertinent process and sampling 
data on the data sheet (see Figure 306A-3). Ensure that the process 
operation is suitable for sample collection.
    8.1.2.2  Starting the Test. Place the probe/nozzle into the duct at 
the first sampling point and switch on the pump. Start the sampling 
using the time interval calculated for the first point. When the first 
point sampling time has been completed, move to the second point and 
continue to sample for the time interval calculated for that point; 
sample each point on the traverse in this manner. Maintain ice around 
the sample containers during the run.
    8.1.2.3  Critical Flow. The sample line between the critical 
orifice and the pump must operate at a vacuum of  380 mm Hg 
(15 in. Hg) in order for critical flow to be maintained. 
This vacuum must be monitored and documented using the vacuum gauge 
located between the critical orifice and the pump.


    Note: Theoretically, critical flow for air occurs when the ratio 
of the orifice outlet absolute pressure to the orifice inlet 
absolute pressure is less than a factor of 0.53. This means that the 
system vacuum should be at least  356 mm Hg ( 
14 in. Hg) at sea level and  305 mm Hg ( 12 
in. Hg) at higher elevations.


    8.1.2.4  Completion of Test.
    8.1.2.4.1  Circular Stacks. Complete the first port traverse and 
switch off the pump. Testers may opt to perform a leak-check between 
the port changes to verify the leak rate however, this is not 
mandatory. Move the sampling train to the next sampling port and repeat 
the sequence. Be sure to record the final dry gas meter reading after 
completing the test run. After performing the post test leak check, 
disconnect the jar/impinger containers from the pump and meter assembly 
and transport the probe, connecting tubing, and containers to the 
sample recovery area.
    8.1.2.4.2  Rectangle Stacks. Complete each port traverse as per the 
instructions provided in 8.1.2.4.1.


    Note: If an approximate mass emission rate is to be calculated, 
measure and record the stack velocity pressure and temperature 
before and after the test run.


    8.2  Sample Recovery. After the train has been transferred to the 
sample recovery area, disconnect the tubing that connects the jar/
impingers. The tester shall select either the total Cr or 
Cr+\6\ sample recovery option. Samples to be analyzed for 
both total Cr and Cr+\6\ shall be recovered using the 
Cr+\6\ sample option (Section 8.2.2).


    Note: Collect a reagent blank sample for each of the total Cr or 
the Cr+\6\ analytical options. If both analyses (Cr and 
Cr+\6\) are to be conducted on the samples, collect 
separate reagent blanks for each analysis.


    8.2.1  Total Cr Sample Option.
    8.2.1.1  Shipping Container No. 1. The first jar container may 
either be used to store and transport the sample, or if GS impingers 
are used, samples may be stored and shipped in precleaned 250-mL, 500-
mL or 1000-mL polyethylene or glass bottles with leak-free, non-metal 
screw caps.
    8.2.1.1.1  Unscrew the lid from the first jar/impinger container.
    8.2.1.1.2  Lift the inner tube assembly almost out of the 
container, and using the wash bottle containing fresh absorbing 
solution, rinse the outside of the tube that was immersed in the 
container solution; rinse the inside of the tube as well, by rinsing 
twice from the top of the tube down through the inner tube into the 
container.
    8.2.1.2  Recover the contents of the second jar/impinger container 
by removing the lid and pouring any contents into the first shipping 
container.
    8.2.1.2.1  Rinse twice, using fresh absorbing solution, the inner 
walls of the second container including the inside and outside of the 
inner tube.
    8.2.1.2.2  Rinse the connecting tubing between the first and second 
sample containers with absorbing solution and place the rinses into the 
first container.
    8.2.1.3  Position the nozzle, probe and connecting plastic tubing 
in a vertical position so that the tubing forms a ``U''.
    8.2.1.3.1  Using the wash bottle, partially fill the tubing with 
fresh absorbing solution. Raise and lower the end of the plastic tubing 
several times to allow the solution to contact the internal surfaces. 
Do not allow the solution to overflow or part of the sample will be 
lost. Place the nozzle end of the probe over the mouth of the first 
container and elevate the plastic tubing so that the solution flows 
into the sample container.
    8.2.1.3.2  Repeat the probe/tubing sample recovery procedure but 
allow the solution to flow out the opposite end of the plastic tubing 
into the sample container. Repeat the entire sample recovery procedure 
once again.
    8.2.1.4  Use approximately 200 to 300 mL of the 0.1 N NaOH or 0.1 N 
NaHCO3 absorbing solution during the rinsing of the probe 
nozzle, probe liner, sample containers, and connecting tubing.
    8.2.1.5  Place a piece of clear plastic wrap over the mouth of the 
sample jar to seal the shipping container. Use a standard lid and band 
assembly to seal and secure the sample in the jar.
    8.2.1.5.1  Label the jar clearly to identify its contents, sample 
number and date.
    8.2.1.5.2  Mark the height of the liquid level on the container to 
identify any losses during shipping and handling.
    8.2.1.5.3  Prepare a chain-of-custody sheet to accompany the sample 
to the laboratory.
    8.2.2  Cr+\6\ Sample Option.
    8.2.2.1  Shipping Container No. 1. The first jar container may 
either be used to store and transport the sample, or if GS impingers 
are used, samples may be stored and shipped in precleaned 250-mL, 500-
mL or 1000-mL polyethylene or glass bottles with leak-free non-metal 
screw caps.
    8.2.2.1.1  Unscrew and remove the lid from the first jar container.
    8.2.2.1.2  Measure and record the pH of the solution in the first 
container by using a pH indicator strip. The pH of the solution must be 
8.5 for NaOH and 8.0 for NaHCO3. If 
not, discard the collected sample, increase the concentration of the 
NaOH or NaHCO3 absorbing solution to 0.5 M and collect another air 
emission sample.
    8.2.2.2 After measuring the pH of the first container, follow 
sample recovery procedures described in Sections 8.2.1.1 through 
8.2.1.5.


    Note: Since particulate matter is not usually present at 
chromium electroplating and/or chromium anodizing facilities, it is 
not necessary to filter the Cr+\6\ samples unless there 
is observed sediment in the collected solutions. If it is necessary 
to filter the Cr+\6\ solutions, please refer to the EPA 
Method 0061, Determination of Hexavalent Chromium Emissions from 
Stationary Sources, Section 7.4, Sample Preparation in SW-846 (see 
Reference 5) for procedure.


    8.2.3  Silica Gel Container. Observe the color of the indicating 
silica gel to determine if it has been completely spent and make a 
notation of its condition/color on the field data sheet. Do not use 
water or other liquids to remove and transfer the silica gel.
    8.2.4  Total Cr and/or Cr+\6\ Reagent Blank.
    8.2.4.1  Shipping Container No. 2. Place approximately 500 mL of 
the 0.1 N NaOH or 0.1 N NaHCO3 absorbing solution in a 
precleaned, labeled sample container and include with the field samples 
for analysis.
    8.3  Sample Preservation, Storage, and Transport.

[[Page 62265]]

    8.3.1  Total Cr Option. Samples that are to be analyzed for total 
Cr need not be refrigerated.
    8.3.2  Cr+\6\ Option. Samples that are to be analyzed 
for Cr+\6\ must be shipped and stored at 4 deg.C 
(40 deg.F).


    Note: Allow Cr+\6\ samples to return to ambient 
temperature prior to analysis.


    8.4  Sample Holding Times.
    8.4.1  Total Cr Option. Samples that are to be analyzed for total 
chromium must be analyzed within 60 days of collection.
    8.4.2  Cr+\6\ Option. Samples that are to be analyzed 
for Cr+\6\ must be analyzed within 14 days of collection.

9.0  Quality Control

    9.1  Same as Method 306, Section 9.0.

10.0  Calibration and Standardization

    Note: Tester shall maintain a performance log of all calibration 
results.


    10.1  Pitot Tube. The Type S pitot tube assembly shall be 
calibrated according to the procedures outlined in Section 10.1 of 
Method 2.
    10.2  Temperature Sensor. Use the procedure in Section 10.3 of 
Method 2 to calibrate the in-stack temperature sensor.
    10.3  Metering System.
    10.3.1  Sample Train Dry Gas Meter Calibration. Calibrations may be 
performed as described in Section 16.2 of Method 5 by either the 
manufacturer, a firm who provides calibration services, or the tester.
    10.3.2  Dry Gas Meter Calibration Coefficient (Ym). The 
meter calibration coefficient (Ym) must be determined prior 
to the initial use of the meter, and following each field test program. 
If the dry gas meter is new, the manufacturer will have specified the 
Ym value for the meter. This Ym value can be used 
as the pretest value for the first test. For subsequent tests, the 
tester must use the Ym value established during the pretest 
calibration.
    10.3.3  Calibration Orifice. The manufacturer may have included a 
calibration orifice and a summary spreadsheet with the meter that may 
be used for calibration purposes. The spreadsheet will provide data 
necessary to determine the calibration for the orifice and meter 
(standard cubic feet volume, sample time, etc.). These data were 
produced when the initial Ym value was determined for the 
meter.
    10.3.4  Ym Meter Value Verification or Meter 
Calibration.
    10.3.4.1  The Ym meter value may be determined by 
replacing the sampling train critical orifice with the calibration 
orifice. Replace the critical orifice assembly by installing the 
calibration orifice in the same location. The inlet side of the 
calibration orifice is to be left open to the atmosphere and is not to 
be reconnected to the sample train during the calibration procedure.
    10.3.4.2  If the vacuum pump is cold, switch on the pump and allow 
it to operate (become warm) for several minutes prior to starting the 
calibration. After stopping the pump, record the initial dry gas meter 
volume and meter temperature.
    10.3.4.3  Perform the calibration for the number of minutes 
specified by the manufacturer's data sheet (usually 5 minutes). Stop 
the pump and record the final dry gas meter volume and temperature. 
Subtract the start volume from the stop volume to obtain the 
Vm and average the meter temperatures (tm).
    10.3.5  Ym Value Calculation. Ym is the 
calculated value for the dry gas meter. Calculate Ym using 
the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.580

Where:

Pbar = Barometric pressure at meter, mm Hg, (in. Hg).
Pstd = Standard absolute pressure,
Metric = 760 mm Hg.
English = 29.92 in. Hg.
tm = Average dry gas meter temperature,  deg.C, ( deg.F).
Tm = Absolute average dry gas meter temperature,
Metric  deg.K = 273 + tm ( deg.C).
English  deg.R = 460 + tm( deg.F).
Tstd = Standard absolute temperature,
Metric = 293  deg.K.
English = 528  deg.R.
Vm = Volume of gas sample as measured (actual) by dry gas 
meter, dcm,(dcf).
Vm(std),mfg = Volume of gas sample measured by manufacture's 
calibrated orifice and dry gas meter, corrected to standard conditions 
(pressure/temperature) dscm (dscf).
Ym = Dry gas meter calibration factor, (dimensionless).

    10.3.6  Ym Comparison. Compare the Ym value 
provided by the manufacturer (Section 10.3.3) or the pretest 
Ym value to the post test Ym value using the 
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.581

    10.3.6.1  If this ratio is between 0.95 and 1.05, the designated 
Ym value for the meter is acceptable for use in later 
calculations.
    10.3.6.1.1  If the value is outside the specified range, the test 
series shall

[[Page 62266]]

either be: 1) voided and the samples discarded; or 2) calculations for 
the test series shall be conducted using whichever meter coefficient 
value (i.e., manufacturers's/pretest Ym value or post test 
Ym value) produces the lowest sample volume.
    10.3.6.1.2  If the post test dry gas meter Ym value 
differs by more than 5% as compared to the pretest value, either 
perform the calibration again to determine acceptability or return the 
meter to the manufacturer for recalibration.
    10.3.6.1.3  The calibration may also be conducted as specified in 
Section 10.3 or Section 16.0 of Method 5 (40 CFR Part 60, Appendix A), 
except that it is only necessary to check the calibration at one flow 
rate of  0.75 cfm.
    10.3.6.1.4  The calibration of the dry gas meter must be verified 
after each field test program using the same procedures.

    Note: The tester may elect to use the Ym post test 
value for the next pretest Ym value; e.g., Test 1 post 
test Ym value and Test 2 pretest Ym value 
would be the same.


    10.4  Barometer. Calibrate against a mercury barometer that has 
been corrected for temperature and elevation.
    10.5  ICP Spectrometer Calibration. Same as Method 306, Section 
10.2.
    10.6  GFAA Spectrometer Calibration. Same as Method 306, Section 
10.3.
    10.7  IC/PCR Calibration. Same as Method 306, Section 10.4.

11.0  Analytical Procedures

    Note: The method determines the chromium concentration in 
g Cr/mL. It is important that the analyst measure the 
volume of the field sample prior to analyzing the sample. This will 
allow for conversion of g Cr/mL to g Cr/sample.


    11.1  Analysis. Refer to Method 306 for sample preparation and 
analysis procedures.

12.0  Data Analysis and Calculations

    12.1  Calculations. Perform the calculations, retaining one extra 
decimal point beyond that of the acquired data. When reporting final 
results, round number of figures consistent with the original data.
    12.2  Nomenclature.

A = Cross-sectional area of stack, m2 (ft2).
Bws = Water vapor in gas stream, proportion by volume, 
dimensionless (assume 2 percent moisture = 0.02).
Cp = Pitot tube coefficient; ``S'' type pitot coefficient 
usually 0.840, dimensionless.
CS = Concentration of Cr in sample solution, g Cr/
mL.
CCr = Concentration of Cr in stack gas, dry basis, corrected 
to standard conditions g/dscm (gr/dscf).
d = Diameter of stack, m (ft).
D = Digestion factor, dimensionless.
ER = Approximate mass emission rate, mg/hr (lb/hr).
F = Dilution factor, dimensionless.
L = Length of a square or rectangular duct, m (ft).
MCr = Total Cr in each sample, g (gr).
Ms = Molecular weight of wet stack gas, wet basis, g/g-mole, 
(lb/lb-mole); in a nominal gas stream at 2% moisture the value is 
28.62.
Pbar = Barometric pressure at sampling site, mm Hg (in. Hg).
Ps = Absolute stack gas pressure; in this case, usually the 
same value as the barometric pressure, mm Hg (in. Hg).
Pstd = Standard absolute pressure:
    Metric = 760 mm Hg.
    English = 29.92 in. Hg.
Qstd = Average stack gas volumetric flow, dry, corrected to 
standard conditions, dscm/hr (dscf/hr).
tm = Average dry gas meter temperature,  deg.C ( deg.F).
Tm = Absolute average dry gas meter temperature:
    Metric  deg.K = 273 + tm ( deg.C).
    English  deg.R = 460 + tm( deg.F).
ts = Average stack temperature, deg.C ( deg.F).
Ts = Absolute average stack gas temperature: Metric  deg.K = 
273 + ts ( deg.C). English  deg.R = 460 + 
ts( deg.F).
Tstd = Standard absolute temperature: Metric = 293  deg.K. 
English = 528  deg.R.
Vad = Volume of sample aliquot after digestion (mL).
Vaf = Volume of sample aliquot after dilution (mL).
Vbd = Volume of sample aliquot submitted to digestion (mL).
Vbf = Volume of sample aliquot before dilution (mL).
Vm = Volume of gas sample as measured (actual, dry) by dry 
gas meter, dcm (dcf).
VmL = Volume of impinger contents plus rinses (mL).
Vm(std) = Volume of gas sample measured by the dry gas 
meter, corrected to standard conditions (temperature/pressure), dscm 
(dscf).
vs = Stack gas average velocity, calculated by Method 2, 
Equation 2-9, m/sec (ft/sec).
W = Width of a square or rectangular duct, m (ft).
Ym = Dry gas meter calibration factor, (dimensionless).
p = Velocity head measured by the Type S pitot tube, cm 
H2O (in. H2O).
pavg = Average of p values, mm 
H2O (in. H2O).

    12.3  Dilution Factor. The dilution factor is the ratio of the 
volume of sample aliquot after dilution to the volume before dilution. 
The dilution factor is usually calculated by the laboratory. This ratio 
is derived by the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.582

    12.4  Digestion Factor. The digestion factor is the ratio of the 
volume of sample aliquot after digestion to the volume before 
digestion. The digestion factor is usually calculated by the 
laboratory. This ratio is derived by the following equation.
[GRAPHIC] [TIFF OMITTED] TR17OC00.583


[[Page 62267]]


    12.5  Total Cr in Sample. Calculate MCr, the total 
g Cr in each sample, using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.584

    12.6  Dry Gas Volume. Correct the sample volume measured by the dry 
gas meter to standard conditions (20 deg.C, 760 mm Hg or 68'F, 29.92 
in. Hg) using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.585

Where:

K1 = Metric units--0.3855  deg.K/mm Hg.
English units--17.64  deg.R/in. Hg.

    12.7  Cr Emission Concentration (CCr). Calculate 
CCr, the Cr concentration in the stack gas, in g/
dscm (g/dscf) on a dry basis, corrected to standard 
conditions, using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.586

    Note: To convert g/dscm (g/dscf) to mg/dscm (mg/
dscf), divide by 1000.

    12.8  Stack Gas Velocity.
12.8.1  Kp = Velocity equation constant:
[GRAPHIC] [TIFF OMITTED] TR17OC00.587

[GRAPHIC] [TIFF OMITTED] TR17OC00.588

    12.8.2  Average Stack Gas Velocity.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.589
    
    12.9  Cross sectional area of stack.
    [GRAPHIC] [TIFF OMITTED] TR17OC00.591
    
    12.10  Average Stack Gas Dry Volumetric Flow Rate.
    Note: The emission rate may be based on a nominal stack moisture 
content of 2 percent (0.02). To calculate an emission rate, the tester 
may elect to use either the nominal stack gas moisture value or the 
actual stack gas moisture collected during the sampling run.
    Volumetric Flow Rate Equation:
    [GRAPHIC] [TIFF OMITTED] TR17OC00.592
    
Where:
3600 = Conversion factor, sec/hr.
[GRAPHIC] [TIFF OMITTED] TR17OC00.593

    Note: To convert Qstd from dscm/hr (dscf/hr) to dscm/
min (dscf/min), divide Qstd by 60.
    12.11  Mass emission rate, mg/hr (lb/hr):

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13.0  Method Performance

    13.1  Range. The recommended working range for all of the three 
analytical techniques starts at five times the analytical detection 
limit (see also Method 306, Section 13.2.2). The upper limit of all 
three techniques can be extended indefinitely by appropriate dilution.
    13.2  Sensitivity.
    13.2.1  Analytical Sensitivity. The estimated instrumental 
detection limits listed are provided as a guide for an instrumental 
limit. The actual method detection limits are sample and instrument 
dependent and may vary as the sample matrix varies.
    13.2.1.1  ICP Analytical Sensitivity. The minimum estimated 
detection limits for ICP, as reported in Method 6010A and the recently 
revised Method 6010B of SW-846 (Reference 1), are 7.0 g Cr/L 
and 4.7 g Cr/L, respectively.
    13.2.1.2  GFAAS Analytical Sensitivity. The minimum estimated 
detection limit for GFAAS, as reported in Methods 7000A and 7191 of SW-
846 (Reference 1), is 1.0 g Cr/L.
    13.2.1.3  IC/PCR Analytical Sensitivity. The minimum detection 
limit for IC/PCR with a preconcentrator, as reported in Methods 0061 
and 7199 of SW-846 (Reference 1), is 0.05 g Cr+6/L.
    13.2.2  In-stack Sensitivity. The in-stack sensitivity depends upon 
the analytical detection limit, the volume of stack gas sampled, and 
the total volume of the impinger absorbing solution plus the rinses. 
Using the analytical detection limits given in Sections 13.2.1.1, 
13.2.1.2, and 13.2.1.3; a stack gas sample volume of 1.7 dscm; and a 
total liquid sample volume of 500 mL; the corresponding in-stack 
detection limits are 0.0014 mg Cr/dscm to 0.0021 mg Cr/dscm for ICP, 
0.00029 mg Cr/dscm for GFAAS, and 0.000015 mg Cr+36/dscm for 
IC/PCR with preconcentration.

    Note: It is recommended that the concentration of Cr in the 
analytical solutions be at least five times the analytical detection 
limit to optimize sensitivity in the analyses. Using this guideline 
and the same assumptions for impinger sample volume and stack gas 
sample volume (500 mL and 1.7 dscm, respectively), the recommended 
minimum stack concentrations for optimum sensitivity are 0.0068 mg 
Cr/dscm to 0.0103 mg Cr/dscm for ICP, 0.0015 mg Cr/dscm for GFAAS, 
and 0.000074 mg Cr+6 dscm for IC/PCR with 
preconcentration. If required, the in-stack detection limits can be 
improved by either increasing the sampling time, the stack gas 
sample volume, reducing the volume of the digested sample for GFAAS, 
improving the analytical detection limits, or any combination of the 
three.


    13.3  Precision.
    13.3.1  The following precision data have been reported for the 
three analytical methods. In each case, when the sampling precision is 
combined with the reported analytical precision, the resulting overall 
precision may decrease.
    13.3.2  Bias data is also reported for GFAAS.
    13.4  ICP Precision.
    13.4.1  As reported in Method 6010B of SW-846 (Reference 1), in an 
EPA round-robin Phase 1 study, seven laboratories applied the ICP 
technique to acid/distilled water matrices that had been spiked with 
various metal concentrates. For true values of 10, 50, and 150 
g Cr/L; the mean reported values were 10, 50, and 149 
g Cr/L; and the mean percent relative standard deviations were 
18, 3.3, and 3.8 percent, respectively.
    13.4.2  In another multilaboratory study cited in Method 6010B, a 
mean relative standard of 8.2 percent was reported for an aqueous 
sample concentration of approximately 3750 g Cr/L.
    13.5  GFAAS Precision. As reported in Method 7191 of SW-846 
(Reference 1), in a single laboratory (EMSL), using Cincinnati, Ohio 
tap water spiked at concentrations of 19, 48, and 77 g Cr/L, 
the standard deviations were 0.1, 0.2, and 
0.8, respectively. Recoveries at these levels were 97 
percent, 101 percent, and 102 percent, respectively.
    13.6  IC/PCR Precision. As reported in Methods 0061 and 7199 of SW-
846 (Reference 1), the precision of IC/PCR with sample preconcentration 
is 5 to 10 percent; the overall precision for sewage sludge 
incinerators emitting 120 ng/dscm of Cr+6 and 3.5 
g/dscm of total Cr is 25 percent and 9 percent, respectively; 
and for hazardous waste incinerators emitting 300 ng/dscm of 
Cr+6 the precision is 20 percent.

14.0  Pollution Prevention

    14.1  The only materials used in this method that could be 
considered pollutants are the chromium standards used for instrument 
calibration and acids used in the cleaning of the collection and 
measurement containers/labware, in the preparation of standards, and in 
the acid digestion of samples. Both reagents can be stored in the same 
waste container.
    14.2  Cleaning solutions containing acids should be prepared in 
volumes consistent with use to minimize the disposal of excessive 
volumes of acid.
    14.3  To the extent possible, the containers/vessels used to 
collect and prepare samples should be cleaned and reused to minimize 
the generation of solid waste.

15.0  Waste Management

    15.1  It is the responsibility of the laboratory and the sampling 
team to comply with all federal, state, and local regulations governing 
waste management, particularly the discharge regulations, hazardous 
waste identification rules, and land disposal restrictions; and to 
protect the air, water, and land by minimizing and controlling all 
releases from field operations.
    15.2  For further information on waste management, consult The 
Waste Management Manual for Laboratory Personnel and Less is Better-
Laboratory Chemical Management for Waste Reduction, available from the 
American Chemical Society's Department of Government Relations and 
Science Policy, 1155 16th Street NW, Washington, DC 20036.

16.0  References

    1. F.R. Clay, Memo, Impinger Collection Efficiency--Mason Jars 
vs. Greenburg-Smith Impingers, Dec. 1989.
    2. Segall, R.R., W.G. DeWees, F.R. Clay, and J.W. Brown. 
Development of Screening Methods for Use in Chromium Emissions 
Measurement and Regulations Enforcement. In: Proceedings of the 1989 
EPA/A&WMA International Symposium-Measurement of Toxic and Related 
Air Pollutants, A&WMA Publication VIP-13, EPA Report No. 600/9-89-
060, p. 785.
    3. Clay, F.R., Chromium Sampling Method. In: Proceedings of the 
1990 EPA/A&WMA International Symposium-Measurement of Toxic and 
Related Air Pollutants, A&WMA Publication VIP-17, EPA Report No. 
600/9-90-026, p. 576.
    4. Clay, F.R., Proposed Sampling Method 306A for the 
Determination of Hexavalent Chromium Emissions from Electroplating 
and Anodizing Facilities. In: Proceedings of the 1992 EPA/A&WMA 
International Symposium-Measurement of Toxic and

[[Page 62269]]

Related Air Pollutants, A&WMA Publication VIP-25, EPA Report No. 
600/R-92/131, p. 209.
    5. Test Methods for Evaluating Solid Waste, Physical/Chemical 
Methods, SW-846, Third Edition as amended by Updates I, II, IIA, 
IIB, and III. Document No. 955-001-000001. Available from 
Superintendent of Documents, U.S. Government Printing Office, 
Washington, DC, November 1986.
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17.0  Tables, Diagrams, Flowcharts, and Validation Data
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Method 306B--Surface Tension Measurement for Tanks Used at 
Decorative Chromium Electroplating and Chromium Anodizing 
Facilities

    Note: This method does not include all of the specifications 
(e.g., equipment and supplies) and procedures (e.g., sampling and 
analytical) essential to its performance. Some material is 
incorporated by reference from other methods in 40 CFR Part 60, 
Appendix A and in this part. Therefore, to obtain reliable results, 
persons using this method should have a thorough knowledge of at 
least Methods 5 and 306.

1.0  Scope and Application

    1.1  Analyte. Not applicable.
    1.2  Applicability. This method is applicable to all decorative 
chromium plating and chromium anodizing operations, and continuous 
chromium plating at iron and steel facilities where a wetting agent is 
used in the tank as the primary mechanism for reducing emissions from 
the surface of the plating solution.

2.0  Summary of Method

    2.1  During an electroplating or anodizing operation, gas bubbles 
generated during the process rise to the surface of the liquid and 
burst. Upon bursting, tiny droplets of chromic acid become entrained in 
ambient air. The addition of a wetting agent to the tank bath reduces 
the surface tension of the liquid and diminishes the formation of these 
droplets.
    2.2  This method determines the surface tension of the bath using a 
stalagmometer or a tensiometer to confirm that there is sufficient 
wetting agent present.

3.0  Definitions [Reserved]

4.0  Interferences [Reserved]

5.0  Safety

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

6.0  Equipment and Supplies

    6.1  Stalagmometer. Any commercially available stalagmometer or 
equivalent surface tension measuring device may be used to measure the 
surface tension of the plating or anodizing tank liquid.
    6.2  Tensiometer. A tensiometer may be used to measure the surface 
tension of the tank liquid provided the procedures specified in ASTM 
Method D 1331-89, Standard Test Methods for Surface and Interfacial 
Tension of Solutions of Surface Active Agents (incorporated by 
reference--see Sec. 63.14) are followed.

7.0  Reagents and Standards [Reserved]

8.0  Sample Collection, Sample Recovery, Sample Preservation, Sample 
Holding Times, Storage, and Transport [Reserved]

9.0  Quality Control [Reserved]

10.0  Calibration and Standardization [Reserved]

11.0  Analytical Procedure

    11.1  Procedure. The surface tension of the tank bath may be 
measured by using a tensiometer, a stalagmometer or any other 
equivalent surface tension measuring device approved by the 
Administrator for measuring surface tension in dynes per centimeter. If 
the tensiometer is used, the procedures specified in ASTM Method D 
1331-89 must be followed. If a stalagmometer or other device is used to 
measure surface tension, the instructions provided with the measuring 
device must be followed.
    11.2  Frequency of Measurements.
    11.2.1  Measurements of the bath surface tension are performed 
using a progressive system which decreases the frequency of surface 
tension measurements required when the proper surface tension is 
maintained.
    11.2.1.1  Initially, following the compliance date, surface tension 
measurements must be conducted once every 4 hours of tank operation for 
the first 40 hours of tank operation.
    11.2.1.2  Once there are no exceedances during a period of 40 hours 
of tank operation, measurements may be conducted once every 8 hours of 
tank operation.
    11.2.1.3  Once there are no exceedances during a second period of 
40 consecutive hours of tank operation, measurements may be conducted 
once every 40 hours of tank operation on an on-going basis, until an 
exceedance occurs. The maximum time interval for measurements is once 
every 40 hours of tank operation.
    11.2.2  If a measurement of the surface tension of the solution is 
above the 45 dynes per centimeter limit, or above an alternate surface 
tension limit established during the performance test, the time 
interval shall revert back to the original monitoring schedule of once 
every 4 hours. A subsequent decrease in frequency would then be allowed 
according to Section 11.2.1.

12.0  Data Analysis and Calculations

    12.1  Log Book of Surface Tension Measurements and Fume Suppressant 
Additions.
    12.1.1  The surface tension of the plating or anodizing tank bath 
must be measured as specified in Section 11.2.
    12.1.2  The measurements must be recorded in the log book. In 
addition to the record of surface tension measurements, the frequency 
of fume suppressant maintenance additions and the amount of fume 
suppressant added during each maintenance addition must be recorded in 
the log book.
    12.1.3  The log book will be readily available for inspection by 
regulatory personnel.
    12.2  Instructions for Apparatus Used in Measuring Surface Tension.
    12.2.1  Included with the log book must be a copy of the 
instructions for the apparatus used for measuring the surface tension 
of the plating or anodizing bath.
    12.2.2  If a tensiometer is used, a copy of ASTM Method D 1331-89 
must be included with the log book.

13.0  Method Performance [Reserved]

14.0  Pollution Prevention [Reserved]

15.0  Waste Management [Reserved]

16.0  References [Reserved]

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

[FR Doc. 00-19099 Filed 10-16-00; 8:45 am]
BILLING CODE 6560-50-P