Document ID: EPA-HQ-OAR-2016-0677-0042
Agency: epa
Document Type: Rule
Title: Method 23-Determination of Polychlorinated Dibenzo-p-Dioxins and Polychlorinated Dibenzofurans from Stationary Sources
Posted Date: 2023-03-20T04:00Z

[Federal Register Volume 88, Number 53 (Monday, March 20, 2023)]
[Rules and Regulations]
[Pages 16732-16774]
From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[FR Doc No: 2023-04958]

[[Page 16731]]

Vol. 88

Monday,

No. 53

March 20, 2023

Part II

Environmental Protection Agency

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40 CFR Parts 60, 63, and 266

EPA Method 23--Determination of Polychlorinated Dibenzo-p-Dioxins and 
Polychlorinated Dibenzofurans From Stationary Sources; Final Rule

  Federal Register / Vol. 88, No. 53 / Monday, March 20, 2023 / Rules 
and Regulations  

[[Page 16732]]

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ENVIRONMENTAL PROTECTION AGENCY

40 CFR Parts 60, 63, and 266

[EPA-HQ-OAR-2016-0677; FRL-5937-02-OAR]
RIN 2060-AT09

EPA Method 23--Determination of Polychlorinated Dibenzo-p-Dioxins 
and Polychlorinated Dibenzofurans From Stationary Sources

AGENCY: Environmental Protection Agency (EPA).

ACTION: Final rule.

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SUMMARY: This action finalizes editorial and technical revisions to the 
Environmental Protection Agency's (EPA's) Method 23 (Determination of 
Polychlorinated Dibenzo-p-Dioxins, Polychlorinated Dibenzofurans, and 
Polycyclic Aromatic Hydrocarbons from Stationary Sources). Final 
revisions include incorporating true, comprehensive, and stable isotope 
dilution for quantifying target compounds using corresponding carbon-13 
labeled compounds for each target compound including most of the 
polycyclic aromatic hydrocarbons (PAH) and changing the method quality 
control from the current prescriptive format to a more flexible 
performance-based approach with specified performance criteria. We are 
also finalizing revisions that expand the list of target compounds of 
Method 23 to include PAH and polychlorinated biphenyls (PCB). The final 
revisions allow facilities and their test teams flexibility when 
sampling and measuring polychlorinated dibenzo-p-dioxins and 
polychlorinated dibenzofurans (PCDD/PCDF), PAH, and PCB from stationary 
sources with a comprehensive isotope dilution method while ensuring 
that the stack testing community can consistently implement the method 
across emissions sources and facilities.

DATES: This final rule is effective on March 20, 2023. The 
incorporation by reference (IBR) of certain publications listed in the 
rule is approved by the Director of the Federal Register as of March 
20, 2023.

ADDRESSES: The U.S. Environmental Protection Agency (EPA) has 
established a docket for this action under Docket ID No. EPA-HQ-OAR-
2016-0677. All documents in the docket are listed on the https://www.regulations.gov website. Although listed, some information is not 
publicly available, e.g., Confidential Business Information or other 
information whose disclosure is restricted by statute. Certain other 
material, such as copyrighted material, is not placed on the internet 
and will be publicly available only in hard copy form. Publicly 
available docket materials are available either electronically through 
https://www.regulations.gov or in hard copy at the EPA Docket Center, 
WJC West Building, Room 3334, 1301 Constitution Avenue NW, Washington, 
DC 20004. Out of an abundance of caution for members of the public and 
our staff, the EPA Docket Center and Reading Room are closed to the 
public, with limited exceptions, to reduce the risk of transmitting 
Coronavirus 2019 (COVID-19). Our Docket Center staff will continue to 
provide remote customer service via email, phone, and webform.

FOR FURTHER INFORMATION CONTACT: For further questions about this final 
action, contact Dr. Raymond Merrill, Office of Air Quality Planning and 
Standards (OAQPS), Air Quality Assessment Division (AQAD), 
Environmental Protection Agency, Research Triangle Park, NC 27711; mail 
drop E143-02; telephone number: (919) 541-5225; fax number: (919) 541-
0516; email address: [email protected].

SUPPLEMENTARY INFORMATION: 
    Preamble acronyms and abbreviations. We use multiple acronyms in 
this preamble. While this list may not be exhaustive, to ease the 
reading of this preamble and for reference purposes, the EPA defines 
the following terms and acronyms here:

AQAD Air Quality Assessment Division
ASTM American Society for Testing and Materials International
CAA Clean Air Act
CARB California Environmental Protection Agency Air Resources Board
CCV continuing calibration verification
CFR Code of Federal Regulations
EDL estimated detection limit
EPA U.S. Environmental Protection Agency
FR Federal Register
GC gas chromatograph
HRGC high-resolution gas chromatography
HRMS high-resolution mass spectrometry
IBR incorporation by reference
IDC initial demonstration of capability
MDL method detection limit
MS mass spectrometer
NTTAA National Technology Transfer and Advancement Act
OAQPS Office of Air Quality Planning and Standards
OLEM Office of Land and Emergency Management
OMB Office of Management and Budget
OW Office of Water
PAH polycyclic aromatic hydrocarbons
PCB polychlorinated biphenyls
PCDD polychlorinated dibenzo-p-dioxins
PCDPE polychlorinated diphenyl ethers
PCDPF polychlorinated dibenzofurans
PRA Paperwork Reduction Act
QCS Quality Control Sample
RFA Regulatory Flexibility Act
RRF relative response factor
SVOC semivolatile organic compounds
SW solid waste
TTN Technology Transfer Network
UMRA Unfunded Mandates Reform Act

    Organization of this document. The information in this preamble is 
organized as follows:

I. General Information
    A. Does this final action apply to me?
    B. Where can I get a copy of this document and other related 
information?
    C. Judicial Review
II. Background
III. Incorporation by Reference
IV. Summary of Revisions to Method 23
    A. Section 1.0 Scope and Application
    B. Section 2.0 Summary of Method
    C. Section 3.0 Definitions
    D. Section 4.0 Interferences
    E. Section 5.0 Safety
    F. Section 6.0 Equipment and Supplies
    G. Section 7.0 Reagents, Media, and Standards
    H. Section 8.0 Sample Collection, Preservation, and Storage
    I. Section 9.0 Quality Control
    J. Section 10.0 Calibration and Standardization
    K. Section 11.0 Analysis Procedure
    L. Section 12.0 Data Analysis and Calculations
    M. Section 13.0 Method Performance
    N. Section 14.0 Pollution Prevention
    O. Section 15.0 Waste Management
    P. Section 16.0 Bibliography
    Q. Section 17.0 Tables, Diagrams, Flow Charts, and Validation 
Data
V. Summary of Final Revisions Related to 40 CFR Parts 60, 63, and 
266
    A. 40 CFR Part 60--Standards of Performance for New Stationary 
Sources
    B. 40 CFR Part 63--National Emission Standards for Hazardous Air 
Pollutants for Source Categories
    C. 40 CFR Part 266--Standards for the Management of Specific 
Hazardous Wastes and Specific Types of Hazardous Waste Management 
Facilities
VI. Statutory and Executive Order Reviews
    A. Executive Order 12866: Regulatory Planning and Review and 
Executive Order 13563: Improving Regulation and Regulatory Review
    B. Paperwork Reduction Act (PRA)
    C. Regulatory Flexibility Act (RFA)
    D. Unfunded Mandates Reform Act (UMRA)
    E. Executive Order 13132: Federalism
    F. Executive Order 13175: Consultation and Coordination With 
Indian Tribal Governments
    G. Executive Order 13045: Protection of Children From 
Environmental Health Risks and Safety Risks
    H. Executive Order 13211: Actions That Significantly Affect 
Energy Supply, Distribution, or Use
    I. National Technology Transfer and Advancement Act (NTTAA)
    J. Executive Order 12898: Federal Actions To Address 
Environmental Justice in Minority Populations and Low-Income 
Populations

[[Page 16733]]

    K. Congressional Review Act (CRA)
    L. Determination Under Clean Air Act Section 307(d)

I. General Information

A. Does this final action apply to me?

    The final amendments to Method 23 apply to stationary sources that 
are subject to certain provisions of 40 CFR parts 60, 62, 63, 79, and 
266. The source categories and entities potentially affected are listed 
in Table 1 of this preamble. This table is not intended to be 
exhaustive, but rather provides a guide for readers regarding entities 
likely to be affected by this action. This table lists the types of 
entities that EPA is now aware could potentially be affected by this 
action. Other types of entities not listed in the table could also be 
affected.

             Table 1--Potentially Affected Source Categories
------------------------------------------------------------------------
                                                  Examples of regulated
            Category                NAICS \a\            entities
------------------------------------------------------------------------
Industry.......................          332410  Fossil fuel steam
                                                  generators.
                                         332410  Industrial, commercial,
                                                  institutional steam
                                                  generating units.
                                         562213  Municipal Waste
                                                  Combustors.
                                         322110  Hazardous Waste
                                                  Combustors.
                                         325211  Polyvinyl Chloride
                                                  Resins Manufacturing.
                                         327310  Portland cement plants.
                                         324122  Asphalt Shingle and
                                                  Coating Materials
                                                  Manufacturing.
                                         331314  Secondary aluminum
                                                  plants.
                                         327120  Clay Building Material
                                                  and Refractories
                                                  Manufacturing.
                                         331410  Nonferrous Metal
                                                  (except Aluminum)
                                                  Smelting and Refining.
------------------------------------------------------------------------
\a\ North American Industry Classification System.

    If you have any questions regarding the applicability of the final 
changes to Method 23, contact the person listed in the preceding FOR 
FURTHER INFORMATION CONTACT section.

B. Where can I get a copy of this document and other related 
information?

    The docket number for this action is Docket ID No. EPA-HQ-OAR-2016-
0677. In addition to being available in the docket, an electronic copy 
of the final method revisions is available on the Technology Transfer 
Network (TTN) website at https://www.epa.gov/ttn/emc/methods/. The TTN 
provides information and technology exchange in various areas of air 
pollution control.

C. Judicial Review

    Under Clean Air Act (CAA) section 307(b)(1), judicial review of 
this final rule is available only by filing a petition for review in 
the U.S. Court of Appeals for the District of Columbia Circuit by May 
19, 2023. Moreover, under section 307(b)(2) of the CAA, the 
requirements established by this final rule may not be challenged 
separately in any civil or criminal proceedings brought by the EPA to 
enforce these requirements. Section 307(d)(7)(B) of the CAA further 
provides that ``[o]nly an objection to a rule or procedure which was 
raised with reasonable specificity during the period for public comment 
(including any public hearing) may be raised during judicial review.'' 
This section also provides a mechanism for the EPA to convene a 
proceeding for reconsideration, ``[i]f the person raising an objection 
can demonstrate to the EPA that it was impracticable to raise such 
objection within [the period for public comment] or if the grounds for 
such objection arose after the period for public comment, (but within 
the time specified for judicial review) and if such objection is of 
central relevance to the outcome of the rule.'' Any person seeking to 
make such a demonstration should submit a Petition for Reconsideration 
to the Office of the Administrator, U.S. EPA, Room 3000, WJC South 
Building, 1200 Pennsylvania Ave. NW, Washington, DC 20460, with a copy 
to both the person listed in the preceding FOR FURTHER INFORMATION 
CONTACT section, and the Associate General Counsel for the Air and 
Radiation Law Office, Office of General Counsel (Mail Code 2344A), U.S. 
EPA, 1200 Pennsylvania Ave. NW, Washington, DC 20460.

II. Background

    The EPA's Method 23 (Determination of Polychlorinated Dibenzo-p-
Dioxins and Polychlorinated Dibenzofurans from Stationary Sources) is 
EPA's current reference test method used to determine the amount of 
polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated 
dibenzofurans (PCDF) emitted from stationary sources.
    The EPA promulgated Method 23 (Appendix A of 40 Code of Federal 
Regulations (CFR) Part 60, Test Methods) on February 13, 1991 (56 FR 
5758). Since promulgation, the ability to measure PCDD and PCDF has 
evolved as analytical laboratories, EPA, and state entities have 
developed new standard operating procedures and methods to reflect 
improvements in sampling and analytical techniques. Examples of newer 
PCDD/PCDF methods include:
     Office of Land and Emergency Management (OLEM) Solid Waste 
(SW) SW-846 EPA Method 8290A, Polychlorinated Dibenzo-p-Dioxins and 
Polychlorinated Dibenzofurans (PCDF) by High-Resolution Gas 
Chromatography/High-Resolution Mass Spectrometry (HRGC/HRMS).
     Office of Water (OW) EPA Method 1613, Tetra- through Octa-
Chlorinated Dioxins and Furans by Isotope Dilution HRGC/HRMS.
     California Environmental Protection Agency Air Resources 
Board (CARB) Method 428, Determination of Polychlorinated Dibenzo-p-
Dioxin (PCDD), Polychlorinated Dibenzofuran (PCDF), and Polychlorinated 
Biphenyls Emissions from Stationary Sources.
    Beginning in 2016, the EPA held a series of informal discussions 
with stakeholders to identify technical issues related to the sampling 
and analysis of PCDD and PCDF and potential revisions to Method 23. The 
stakeholders consisted of a cross section of interested parties 
including representatives from state regulatory entities, various EPA 
offices, analytical laboratories, regulated sources, emission testing 
firms, analytical standards vendors, instrument vendors, and others 
with experience in sampling and analysis of PCDD and PCDF and with the 
equipment, materials, and performance of Method 23 and other PCDD/PCDF 
methods. In the discussions, EPA also sought stakeholder input 
regarding their experience combining procedures for sampling and 
analysis of PCDD and PCDF with procedures for sampling and analysis of 
PAH and PCB emitted from

[[Page 16734]]

stationary sources. The docket contains summaries of the stakeholder 
discussions. EPA proposed editorial and technical revisions to Method 
23 on January 14, 2020 (85 FR 2234). EPA received comments on the 
proposed revisions to the method and has addressed these in a separate 
response to comments document, the Summary of Public Comments and 
Responses for the Proposed EPA Method 23--Determination of 
Polychlorinated Dibenzo-p-Dioxins and Polychlorinated Dibenzofurans 
from Stationary Sources. This final action summarizes the changes made 
in response to comments.

III. Incorporation by Reference

    The EPA is incorporating by reference American Society for Testing 
and Materials (ASTM) D6911-15 and ASTM D4840-99(2018)e1 in Method 23. 
ASTM D6911-15 includes a guide for packaging and shipping environmental 
samples for laboratory analysis and ASTM D4840-99(2018)e1 includes a 
standard guide for sample chain-of-custody procedures. These standards 
were developed and adopted by ASTM International and may be obtained 
from https://www.astm.org or from the American Society for Testing and 
Materials 100 Barr Harbor Drive, P.O. Box C700, West Conshohocken, PA 
19428-2959.

IV. Summary of Revisions to Method 23

    In this action, we are finalizing technical revisions and editorial 
changes to clarify and update the requirements and procedures specified 
in Method 23 and reformatting the method to conform with the current 
EPA method format (see https://www.epa.gov/measurements-modeling/method-development#format). We are also expanding the applicability of 
Method 23 to include procedures for sampling and analyzing PAH and PCB. 
In addition, we are finalizing revisions to various sections of the CFR 
that either require Method 23 or require the analysis of PCDD/PCDF, 
PAH, or PCB.
    Our intent for the final revisions is to ensure that Method 23 is 
implemented consistently. EPA has updated the method procedures to 
include many current best practices. We have added flexibility to the 
method based on meeting quality control requirements.
    The primary focus of the final revisions to Method 23 is to change 
the method from a prescriptive method to a method which allows users to 
have flexibility in implementing the method (e.g., choice of gas 
chromatograph (GC) column, the procedures used for sample cleanup) 
while still meeting performance criteria that the EPA believes are 
necessary for demonstrating and documenting the quality of the 
measurements for the target compounds. The final revisions also address 
concerns over recovery of target compounds from particulate matter by 
requiring a pre-extraction filter recovery standard procedure and 
acceptance criteria for the pre-extraction filter recovery standard 
recovery as a tool to evaluate filter extraction. These new 
requirements resolve the concerns that led to the criteria in 40 CFR 
63.1208 that required Administrator approval prior to use of Method 23 
for measurement of PCDD/PCDF.
    The EPA's second focus for the final revisions is to modify the 
method to allow isotope dilution with isotopically labeled compounds 
for each target compound. Quantitation is based on isotope dilution, 
moving from nine to 17 labeled compounds for 17 target toxic 2,3,7,8-
substituted PCDD/PCDF. These revisions to the method are possible 
because additional isotopically labeled standards for the target 
compounds have become available from vendors since the original 
promulgation of Method 23. The final revisions eliminate biases with 
recovery correction based on individual corresponding labeled 
compounds.
    The third major focus for the EPA's final revisions to Method 23 is 
to include options for combining sampling and analysis of PCDD/PCDF 
with sampling and analysis of PAH and PCB to allow the measurement of 
these toxic semivolatile organic compounds (SVOC). Therefore, PCB and 
PAH were added to the list of target compounds measured by Method 23.
    The EPA's final amendments to Method 23 in response to public 
comments are presented below for each section of Method 23. The 
proposed revisions to sections of Method 23 that EPA is not changing 
based on public comments are finalized as proposed. A summary of public 
comments and our responses are provided in a separate response to 
comments document in the docket for this action.

A. Section 1.0 Scope and Application

    In this action, EPA is renaming Section 1.0 from ``Applicability 
and Principle'' to ``Scope and Application,'' and revising the text to 
expand the target compounds for Method 23 to include PCB and PAH. We 
are also adding statements that emphasize the need for working 
knowledge of the EPA Methods 1 through 5 of Appendices A-1, A-2, and A-
3 to 40 CFR part 60, isotope dilution, and the use of high-resolution 
gas chromatography/high resolution mass spectrometry (HRGC/HRMS) when 
applying Method 23. We are also adding language to specify that Method 
23 is performance-based and allows users to modify parts of the method 
to overcome interferences or to substitute alternative materials and 
equipment provided that all performance criteria in the method are met.

B. Section 2.0 Summary of Method

    The EPA is renaming Section 2.0 from ``Apparatus'' to ``Summary of 
Method,'' and revising Section 2.0 to provide an overview of the 
method's sampling and analytical procedures. We are also moving the 
current language in Section 2.0, which describes the materials needed 
to conduct Method 23, to a new Section 6.0 (Equipment and Supplies).

C. Section 3.0 Definitions

    The current version of Method 23 does not include definitions of 
key terms and variables used in Method 23. In this action, we are 
adding a new Section 3.0 titled ``Definitions.'' We are defining 
acronyms and technical terms to improve the clarity of the method 
principles and procedures. We are also moving language from the current 
Section 3.0 to a new Section 7.0 (Reagents, Media, and Standards).

D. Section 4.0 Interferences

    The current version of Method 23 does not discuss the conditions 
that can potentially interfere with measurements obtained using the 
method. In this action, we are adding a new Section 4.0 titled 
``Interferences,'' that presents the potential causes and 
recommendations for avoiding or mitigating interferences or sample 
contamination. We are stating that enhanced selectivity, or confidence 
in the data, is based on the fractionation, GC separation, HRMS 
sensitivity, and monitoring for polychlorinated diphenyl ether (PCDPE) 
interferences. We are also moving language from the current Section 4.0 
to a new Section 8.0 (Sample Collection, Preservation, and Storage).

E. Section 5 Safety

    Currently, Method 23 does not provide procedures for safety. In 
this action, we are adding a new Section 5.0 titled ``Safety,'' that 
presents the health hazards and procedures for minimizing risks to 
field and laboratory personnel when conducting Method 23. We are also 
moving language from the current Section 5.0 to a new Section 11.0 
(Analysis Procedure).

F. Section 6.0 Equipment and Supplies

    In this action, we are renumbering and moving the current language 
in Section 2.0 (Apparatus) to a new

[[Page 16735]]

Section 6.0 titled ``Equipment and Supplies,'' and making clarifying 
edits and technical revisions to the specifications in Section 6.0. 
Table 2 of this preamble identifies the new numbering for the 
subsections currently in Section 2.0 and Table 3 of this preamble 
identifies new specifications (and the associated subsection) we are 
including in Section 6.0.

       Table 2--Crosswalk for Revisions to Current Method Sections
------------------------------------------------------------------------
            Description              Current section    Revised section
------------------------------------------------------------------------
Filter holder.....................              2.1.1              6.1.3
Condenser.........................              2.1.2              6.1.7
Water circulating bath............              2.1.3              6.1.8
Adsorbent module..................              2.1.4              6.1.9
Fitting caps......................              2.2.1              6.2.1
Wash bottles......................              2.2.2              6.2.2
Filter storage container..........              2.2.4              6.2.4
Field balance.....................              2.2.5              6.2.5
Aluminum foil.....................              2.2.6              6.2.6
Glass sample storage container....              2.2.9              6.2.8
Extraction thimble................              2.3.4            6.3.3.3
Pasteur pipettes..................              2.3.5              6.4.1
GC oven...........................           2.3.10.1            6.5.1.1
GC Temperature monitor............           2.3.10.2            6.5.1.2
GC Flow system....................           2.3.10.3            6.5.1.3
Capillary GC column...............           2.3.10.4              6.5.2
Mass spectrometer (MS)............             2.3.11              6.5.3
MS data system....................             2.3.12              6.5.4
------------------------------------------------------------------------

           Table 3--Additional Specifications for Section 6.0
------------------------------------------------------------------------
                     Description                        Revised section
------------------------------------------------------------------------
Probe liner..........................................              6.1.2
Filter heating system................................              6.1.4
Filter temperature sensor............................              6.1.5
Sample transfer line.................................              6.1.6
Impingers............................................             6.1.10
Soxhlet extraction apparatus.........................            6.3.3.1
Moisture trap of extraction apparatus................            6.3.3.2
Heating mantle.......................................            6.3.3.4
Kuderna-Danish concentrator..........................              6.3.4
Liquid chromatography columns........................              6.4.2
GC Injection port....................................            6.5.1.4
PCDD/PCDF GC column..................................            6.5.2.1
PAH GC column........................................            6.5.2.2
PCB GC column........................................            6.5.2.3
------------------------------------------------------------------------

    In Section 6, we are also finalizing changes to:
     Prohibit the use of brominated flame-retardant coated tape 
in assembling the sampling train and use of silicon tubing in direct 
contact with flue gases to avoid sample contamination.
     Revise the specification for a rotary evaporator with a 
note to use a Kuderna-Danish concentrator for PCB and PAH to avoid the 
loss of higher vapor pressure target compounds.
     Remove specifications for the graduated cylinder to 
improve the accuracy of moisture measurements and make Method 23 more 
consistent with other isokinetic sampling methods.
     Remove the volume requirement for wash bottles to allow 
greater flexibility in field sample recovery.
    We are also moving language from Method 23's current Section 6.0 to 
new Section 10.0 (Calibration and Standardization).

G. Section 7.0 Reagents, Media, and Standards

    In this action, the EPA is renumbering and moving the current 
language in Section 3.0 (Reagents) to a new Section 7.0 titled 
``Reagents, Media, and Standards,'' and making clarifying edits and 
technical revisions to the specifications. Table 4 of this preamble 
identifies the new numbering for the subsections currently in Section 
3.0 and Table 5 of this preamble identifies new specifications (and the 
associated subsection) we are including in Section 7.0.

       Table 4--Crosswalk for Revisions to Current Method Sections
------------------------------------------------------------------------
            Description              Current section    Revised section
------------------------------------------------------------------------
Filter............................              3.1.1                7.1
Adsorbent resin...................              3.1.2                7.2
Glass wool........................              3.1.3                7.3
Water.............................              3.1.4                7.4

[[Page 16736]]

 
Silica gel........................              3.1.5                7.5
Methylene chloride................              3.2.2                7.6
Sodium sulfate....................              3.3.2              7.8.2
Basic alumina.....................             3.3.13          7.8.9.1.2
Silica gel........................             3.3.14            7.8.9.3
Carbon/Celite[supreg].............             3.3.17            7.8.9.4
Nitrogen..........................             3.3.18             7.8.10
------------------------------------------------------------------------

           Table 5--Additional Specifications for Section 7.0
------------------------------------------------------------------------
                     Description                        Revised section
------------------------------------------------------------------------
High-boiling alkanes used as keeper solvents.........              7.8.8
Liquid column packing materials......................              7.8.9
Acidic alumina.......................................          7.8.9.1.1
Florisil[supreg].....................................            7.8.9.2
Helium...............................................              7.9.1
Spiking standards....................................              7.9.2
Pre-sampling adsorbent standard......................              7.9.3
Pre-extraction filter recovery standard..............              7.9.4
Pre-extraction standard..............................              7.9.5
Pre-analysis standard................................              7.9.6
------------------------------------------------------------------------

    We are replacing the filter precleaning procedures of the current 
method with specifications for conducting a filter quality control 
check. We are also deleting unnecessary specifications (presented in 
Table 6 of this preamble) to reflect modern methods. We are renaming 
the isotopic spiking standard mixtures to better relate the standards 
to their use in the final method. We are ensuring that the isotopically 
labeled spiking standards are named consistently throughout the final 
method.

 Table 6--Deletions of Material Specifications in the Current Method 23
------------------------------------------------------------------------
                       Material                         Current section
------------------------------------------------------------------------
Chromic acid cleaning solution.......................              3.1.6
Benzene..............................................              3.3.7
Ethyl acetate........................................              3.3.8
Cyclohexane..........................................             3.3.12
Hydrogen.............................................             3.3.19
Internal standard solution...........................             3.3.20
Surrogate standard solution..........................             3.3.21
Recovery standard solution...........................             3.3.22
------------------------------------------------------------------------

    We are also moving the current Section 7.0 to a new Section 9.0 
(Quality Control).

H. Section 8.0 Sample Collection, Preservation, and Storage

    In this action, the EPA is renumbering and moving the current 
language in Section 4.0 (Procedure) to a new Section 8.0 titled 
``Sample Collection, Preservation, and Storage,'' and making clarifying 
edits and technical revisions to the current procedures for sampling 
and field sample recovery. The new Section 8.0 also includes added 
requirements for sample storage conditions and holding times.
    Under the sampling procedures of Method 23, we are finalizing 
revisions to the current requirements in Section 4.1.1 for pretest 
preparations. Table 7 of this preamble identifies the new numbering to 
revise and replace the requirements in Section 4.1.

       Table 7--Crosswalk for Revisions to Current Method Sections
------------------------------------------------------------------------
            Description              Current section    Revised section
------------------------------------------------------------------------
Glassware cleaning................            4.1.1.1            8.1.1.1
Assembling the adsorbent module...            4.1.1.2            8.1.1.2
Maintaining the sampling train                4.1.1.3            8.1.1.3
 components.......................
Silica Gel........................            4.1.1.4            8.1.1.4
Checking and packing filters......            4.1.1.5            8.1.1.5
Field preparation of the sampling             4.1.3.1            8.1.3.1
 train............................
Impinger assembly.................            4.1.3.2            8.1.3.2
Sampling probe and nozzle                     4.1.3.4            8.1.3.4
 preparation......................
------------------------------------------------------------------------

[[Page 16737]]

    Table 8 of this preamble shows the specifications we are adding to 
the new Section 8.0. This action finalizes a minimum sample volume and 
sampling time requirements at each traverse point for continuous 
industrial processes that align Method 23 with other isokinetic 
stationary source methods, such as Method 5. The sampling time at each 
traverse point for batch industrial processes ensure measurements are 
made for the entire process cycle. The final filter check requirements 
add details that were absent from the original Method 23 and align the 
method with the requirements of other isokinetic stationary source 
methods, such as Methods 5, 26A, and 29, also in Appendix A of this 
Part. The final adsorbent module orientation requirements clarify the 
configuration of the adsorbent module to ensure that condensed moisture 
flows through the module into the water collection impinger. We are 
adding sampling filter temperature monitoring requirements to align 
Method 23 with other isokinetic stationary source methods. Also, we are 
adding adsorbent module temperature monitoring to confirm that the 
sorbent material was not exposed to elevated temperatures that could 
bias sample collection and results.

           Table 8--Additional Specifications for Section 8.1
------------------------------------------------------------------------
                     Description                        Revised section
------------------------------------------------------------------------
Minimum sample volume................................            8.1.2.1
Sampling time for continuous processes...............            8.1.2.2
Sampling time for batch processes....................            8.1.2.3
Filter assembly......................................            8.1.3.3
Orientation of the condenser and adsorbent module....            8.1.3.4
Monitoring the filter temperature....................            8.1.5.1
Monitoring the adsorbent module temperature..........            8.1.5.2
------------------------------------------------------------------------

    Under sample recovery procedures, we are finalizing technical 
revisions as shown in Table 9 of this preamble. In this action, we are 
also adding specifications as shown in Table 10 of this preamble.

       Table 9--Crosswalk for Revisions to Current Method Sections
------------------------------------------------------------------------
            Description              Current section    Revised section
------------------------------------------------------------------------
Adsorbent module sample                         4.2.2              8.2.5
 preparation......................
Preparation of Container No. 2....              4.2.3              8.2.6
Rinsing of the filter holder and                4.2.3              8.2.7
 condenser........................
Weighing impinger water...........              4.2.5              8.2.8
Preparation of Container No. 3....              4.2.4              8.2.9
Silica gel........................             4. 2.7             8.2.10
------------------------------------------------------------------------

           Table 10--Additional Specifications for Section 8.2
------------------------------------------------------------------------
                     Description                        Revised section
------------------------------------------------------------------------
Conducting a post-test leak check....................              8.2.1
Storage conditions for Container No. 1...............              8.2.4
Field sample handling, storage, and transport........             8.2.11
Sample chain of custody..............................             8.2.12
------------------------------------------------------------------------

    In the new Section 8.2.6, acetone and toluene rinses are collected 
in one bottle rather than separately. New Section 8.2.8 measures 
moisture by weight rather than by volume.

I. Section 9.0 Quality Control

    In this action, the EPA is moving and renumbering the current 
Section 7.0 (Quality Control) to a new Section 9.0 titled ``Quality 
Control,'' and making clarifying and technical revisions to the new 
Section 9.0. We are adding an introductory note that addresses 
maintaining, and documenting quality control compliance required in 
Method 23. We are adding a new subsection that clarifies the 
recordkeeping and reporting necessary to demonstrate compliance with 
quality control requirements of this method. We are also adding 
specifications for conducting pre-sampling, pre-extraction, and pre-
analysis standard recoveries of isotopically-labeled standards and 
adding specifications for:
     Initial demonstration of capability (IDC).
     Quality Control Sample (QCS).
     Method detection limits (MDL).
     Laboratory method blank (LMB).
     Estimated detection limits (EDL).
     Field train proof blank.
    It should be noted that the EDLs as proposed remain in the method 
and are sample specific. It should also be noted that the second source 
QCS also serves as an initial calibration verification. We are also 
moving language from the current Section 9.0 to new Section 12.0 (Data 
Analysis and Calculations).

J. Section 10.0 Calibration and Standardization

    In this action, the EPA is renumbering and moving the text in 
Section 6.0 (Calibration) of the current method to a new Section 10.0 
titled ``Calibration and Standardization,'' and making clarifying and 
technical revisions to the specifications for calibrating the sampling 
and the HRGC/HRMS systems. We are adding specifications for tuning the 
HRMS system, moving the specification for HRMS resolution (currently in 
Section 5) to this new section, and adding text on the procedures for 
assessing the relative standard deviation for the mean instrument 
response factors to bring Method 23 up to date with current laboratory 
practice. We are also

[[Page 16738]]

updating the requirements for ion abundance ratio limits, and 
resolution checks under the continuing calibration verification to 
serve as performance indicators for analysis quality. We are adding a 
specification to prepare the continuing calibration verification (CCV) 
standard at the same time as the batch of field samples using the same 
labeled standards. We are also moving language in the current Section 
10.0 to a new Section 16.0 (Bibliography).

K. Section 11.0 Analysis Procedure

    In this action, the EPA is renumbering and moving the text in 
Section 5.0 (Analysis) of the current method to a new Section 11.0 
titled ``Analysis Procedure,'' and making clarifying and technical 
revisions to the current specifications for sample extraction and 
sample cleanup and fractionation. We are also adding a new subsection 
describing how sample extract aliquots are prepared for cleanup and 
analysis.
    We are also adding the specifications and recommendations for 
analysis procedures shown in Table 11 of this preamble.

          Table 11--Additional Specifications for Section 11.0
------------------------------------------------------------------------
                Description                        Revised section
------------------------------------------------------------------------
Preparing and operating the extraction       11.1.7 through 11.1.9.
 apparatus.
Allow the extraction apparatus to cool.....  11.2.1.
Initial extract concentration..............  11.2.2.
Allow the sample extract to cool...........  11.2.3.
Recommended minimum volume for PCDD/PCDF     11.2.3.
 analysis.
Further concentration of sample (if needed)  11.2.4.
 for cleanup and analysis.
Sample cleanup and fractionation for PAH     11.3.1.
 and PCDPE.
Sample cleanup and fractionation for PCDD/   11.3.2.
 PCDF and PCB.
Addressing unresolved compounds............  11.4.1.2.1.
Relative retention time for PCB............  11.4.3.4.5.
Chlorodiphenyl ether interference..........  11.4.3.4.8.
MS lock-mass ions..........................  11.4.3.4.9.
Identification criteria for PAH............  11.4.3.4.10.
Calculations of target mass and mass per     11.4.3.5.1 and 11.4.3.5.2.
 dry standard cubic meter.
Quantifying native PCDD/PCDF...............  11.4.3.5.3.
Reporting options..........................  11.4.3.5.4 through
                                              11.4.3.5.6.
------------------------------------------------------------------------

L. Section 12.0 Data Analysis and Calculations

    In this action, the EPA is renumbering and moving the current 
language in Section 9.0 (Calculations) to a new Section 12.0 titled 
``Data Analysis and Calculations,'' and revising the equation variable 
list. We are revising the equations shown in Table 12 of this preamble.

              Table 12--Equation Revisions for Section 12.0
------------------------------------------------------------------------
       Current equation              Description        Revised section
------------------------------------------------------------------------
23-1..........................  Individual relative                 12.2
                                 response factor
                                 (RRF) for each
                                 compound.
23-2..........................  Amount of individual                12.7
                                 target compound i in
                                 the extract using
                                 the RRF of the CCV.
23-4..........................  Recovery of Labeled                 12.9
                                 Compound Standards.
23-7..........................  Estimated detection                12.10
                                 limit.
23-8..........................  Total concentration..              12.11
------------------------------------------------------------------------

    This section specifies that the CCV RRFs are used to quantify the 
target compounds rather than the initial calibration RRFs. We are also 
removing and replacing the current equations in Method 23 with the 
equations shown in Table 13 of this preamble to accommodate the final 
changes to the method procedures.

             Table 13--Additional Equations for Section 12.0
------------------------------------------------------------------------
         New equation                Description        Revised section
------------------------------------------------------------------------
23-1..........................  Individual compound                 12.2
                                 RRF for each
                                 calibration level.
23-2..........................  Individual compound                 12.2
                                 RRF for pre-
                                 extraction standard.
23-4..........................  Percent relative                    12.4
                                 standard deviation
                                 of the RRFs for a
                                 compound over the
                                 calibration levels.
23-5..........................  Standard deviation of               12.5
                                 the RRFs for a
                                 compound over the
                                 calibration levels.
23-6..........................  Percent difference of               12.6
                                 the RRF of the
                                 continuing
                                 calibration
                                 verification
                                 compared to the
                                 average RRF from the
                                 initial calibration
                                 for each target
                                 compound.
23-9..........................  Concentration of the                12.8
                                 Individual Target
                                 Compound or Group i
                                 in the Emission Gas.
23-13.........................  Half range for the                 12.12
                                 prediction interval
                                 of results.
23-14.........................  Upper limit for the                12.12
                                 prediction interval
                                 of results.
23-15.........................  Lower limit for the                12.12
                                 prediction interval
                                 of results.
------------------------------------------------------------------------

[[Page 16739]]

M. Section 13.0 Method Performance

    In this action, the EPA is adding a new Section 13.0 titled 
``Method Performance,'' that includes the specifications shown in Table 
14 of this preamble. The new Section 13 provides the basis for 
assessing accuracy with LMBs, increases labeled standards, and 
establishes performance criteria to monitor method performance.

      Table 14--Method Performance Specifications for Section 13.0
------------------------------------------------------------------------
                Description                        Revised section
------------------------------------------------------------------------
Background assessment of field train proof   13.1.
 blank, LMB, and Materials (filters,
 adsorbent resin, glass wool, etc.).
GC column systems used to measure PCDD/      13.2 through 13.5.
 PCDF, PAH, and PCB target compounds.
Detection limits (Method detection limits    13.6.
 and Estimated detection limits).
Tuning HRGC/HRMS system....................  13.7.
MS lock-mass ions..........................  13.8.
Initial calibration and continuing           13.9 and 13.10.
 calibration verification.
QCS analysis...............................  13.11.
Identification of target compounds.........  13.12 and 13.13.
Pre-sampling and pre-extraction standard     13.14 and 13.15.
 recovery requirements.
Pre-analysis standard sensitivity            13.16.
 requirements.
IDC-Lowest calibration concentration,        13.17.
 Demonstration of precision, Demonstration
 of accuracy.
Modifications of the method................  13.18 and 13.19.
------------------------------------------------------------------------

N. Section 14.0 Pollution Prevention

    In this action, the EPA is adding a new Section 14.0 titled 
``Pollution Prevention,'' that specifies the procedures for minimizing 
or preventing pollution associated with preparing and using Method 23 
standards.

O. Section 15.0 Waste Management

    In this action, the EPA is adding a new Section 15.0 titled ``Waste 
Management,'' that specifies the laboratory responsibilities for 
managing the waste streams associated with collecting and analyzing 
Method 23 samples.

P. Section 16.0 Bibliography

    In this action, the EPA is renumbering and moving the current 
language in Section 10.0 (Bibliography) to a new Section 16.0 titled 
``Bibliography.'' We are deleting previous reference number 3 which is 
no longer relevant and adding new citations for the following 
references:

 Fishman, V.N., Martin, G.D. and Lamparski, L.L. Comparison 
of a variety of gas chromatographic columns with different 
polarities for the separation of chlorinated dibenzo-p-dioxins and 
dibenzofurans by high-resolution mass spectrometry. Journal of 
Chromatography A 1139 (2007) 285-300.
 International Agency for Research on Cancer. Environmental 
Carcinogens Methods of Analysis and Exposure Measurement, Volume 
11--Polychlorinated Dioxins and Dibenzofurans. IARC Scientific 
Publications No. 108, 1991.
 Stieglitz, L., Zwick, G., Roth, W. Investigation of 
different treatment techniques for PCDD/PCDF in fly ash. Chemosphere 
15: 1135-1140; 1986.
 U.S. Environmental Protection Agency. Method 8290A--
Polychlorinated Dibenzo-p-dioxin (PCDDs) and Polychlorinated 
Dibenzofurans (PCDFs) by High-Resolution Gas Chromatography/High-
Resolution Mass Spectrometry (HRGC/HRMS), Revision 1. February 2007. 
In: Test Methods for Evaluating Solid Waste. Washington, DC. SW-846.
 U.S. Environmental Protection Agency. Office of Air 
Programs Publication No. APTD-0576: Maintenance, Calibration, and 
Operation of Isokinetic Source Sampling Equipment. Research Triangle 
Park, NC. March 1972.
 U.S. Environmental Protection Agency. Method 1625C--
Semivolatile Organic Compounds by Isotope Dilution GCMS.
 U.S Environmental Protection Agency. Method 1613B--Tetra- 
through Octa-Chlorinated Dioxins and Furans by Isotope Dilution 
HRGC/HRMS.
 U.S. Environmental Protection Agency. Method 1668C--
Chlorinated Biphenyl Congeners in Water, Soil, Sediment, Biosolids, 
and Tissue by HRGC/HRMS.
 Tondeur, Y., Nestrick, T., Silva, H[eacute]ctor A., Vining, 
B., Hart, J. Analytical procedures for the determination of 
polychlorinated-p-dioxins, polychlorinated dibenzofurans, and 
hexachlorobenzene in pentachlorophenol. Chemosphere Volume 80, Issue 
2, June 2010, pages 157-164.
 U.S. Environmental Protection Agency. Definition and 
Procedure for the Determination of the Method Detection Limit, 
Revision 2. EPA 821-R-16-006. December 2016.
 Tondeur Y, Niederhut WJ, Missler SR. A hybrid HRGC/MS/MS 
Method for the Characterization of Tetrachlorodibenzo-p-Dioxins in 
Environmental Samples; Bio. Med. and Environ. Mass Spectr. 14, pages 
449-456, 1987.
 Gianluca R., Mosca S., Guerriero E., Rotatori M. 
Development of a new automated clean-up system for the simultaneous 
analysis of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans 
(PCDFs) and `dioxin-like' polychlorinated biphenyls (dl-PCB) in flue 
gas emissions by GPC-SPE. J. Environ. Monit. 14, pages 1082-1090, 
2012.
 U.S. Environmental Protection Agency. The National Dioxin 
Air Monitoring Network (NDAMN) Report of the Results of Atmospheric 
Measurements of Polychlorinated Dibenzo-p-Dioxins (PCDDs), 
Polychlorinated Dibenzofurans (PCDFs), and Dioxin-like 
Polychlorinated Biphenyl (PCBs) in Rural and Remote Areas of the 
United States from June 1998 through November 2004. EPA/600/R-13/
183F. August 2013.
 Guo, Y., Kannan, K. Analytical Methods for the Measurement 
of Legacy and Emerging Persistent Organic Pollutants in Complex 
Sample Matrices. Comprehensive Analytical Chemistry. Vol. 67. 
January 2015.
 U.S. Environmental Protection Agency. USEPA Contract 
Laboratory Program (CLP) National Functional Guidelines for 
Chlorinated Dibenzo-p-Dioxins (CDDs) and Chlorinated Dibenzofurans 
(CDFs) Data Review. EPA-540-R-11-016. September 2011.

Q. Section 17.0 Tables, Diagrams, Flow Charts, and Validation Data

    In this action, the EPA is adding a new Section 17 titled ``Tables, 
Diagrams, Flow Charts, and Validation Data,'' that contains all tables, 
diagrams, flow charts, and validation data referenced in Method 23. We 
are revising Figures 23-1 and 23-2 and renaming and/or renumbering the 
current Method 23 tables as shown in Table 15 of this preamble.

[[Page 16740]]

                 Table 15--Revisions to Method 23 Tables
------------------------------------------------------------------------
             Current method                        Final method
------------------------------------------------------------------------
Table 1--Composition of the Sample       Table 23-7. Concentration of
 Fortification and Recovery Standards     the Sample Fortification for
 Solutions.                               PCDD and PCDF.
Table 2--Composition of the Initial      Table 23-11. Concentration of
 Calibration Solutions.                   the Initial Calibration
                                          Standard Solutions for PCDD
                                          and PCDF.
Table 3--Elemental Compositions and      Table 23-4. Elemental
 Exact Masses of the Ions Monitored by    Compositions and Exact Masses
 High Resolution Mass Spectrometry for    of the Ions Monitored by High-
 PCDD's and PCDF's.                       Resolution Mass Spectrometry
                                          for PCDD and PCDF.
Table 4--Acceptable Ranges for Ion-      Table 23-15. Recommended Ion
 Abundance Ratios of PCDD's and PCDF's.   Type and Acceptable Ion
                                          Abundance Ratios.
Table 5--Minimum Requirements for        Table 23-14. Minimum
 Initial and Daily Calibration Response   Requirements for Initial and
 Factors.                                 Continuing Calibration
                                          Response Factors for
                                          Isotopically Labeled and
                                          Native Compounds.
------------------------------------------------------------------------

    We are also adding Figure 23-3 (Soxhlet/Dean-Stark Extractor) and 
Figure 23-4 (Sample Preparation Flow Chart) and adding the tables 
listed in Table 16 of this preamble.

                Table 16--Additional Tables to Method 23
------------------------------------------------------------------------
           Revised table                         Description
------------------------------------------------------------------------
23-1..............................  Polychlorinated Dibenzo-p-dioxin and
                                     Polychlorinated Dibenzofuran Target
                                     Analytes.
23-2..............................  Polycyclic Aromatic Hydrocarbon
                                     Target Analytes.
23-3..............................  Polychlorinated Biphenyl Target
                                     Analytes.
23-5..............................  Elemental Compositions and Exact
                                     Masses of the Ions Monitored by
                                     High-Resolution Mass Spectrometry
                                     for PAH.
23-6..............................  Elemental Compositions and Exact
                                     Masses of the Ions Monitored by
                                     High-Resolution Mass Spectrometry
                                     for PCB.
23-8..............................  Concentration of the Sample
                                     Fortification for PAH.
23-9..............................  Concentration of the Sample
                                     Fortification for PCB.
23-10.............................  Sample Storage Conditions and
                                     Laboratory Hold Times.
23-12.............................  Concentration of the Initial
                                     Calibration Standard Solutions for
                                     PAH.
23-13.............................  Concentration of the Initial
                                     Calibration Standard Solutions for
                                     PCB.
23-16.............................  Typical DB5-MS Column Conditions.
23-17.............................  Assignment of Pre-extraction
                                     Standards for Quantitation of
                                     Target PCB.
23-18.............................  Initial Demonstration of Capability
                                     Quality Control (QC) Requirements.
------------------------------------------------------------------------

V. Summary of Final Revisions Related to 40 CFR Parts 60, 63, and 266

A. 40 CFR Part 60--Standards of Performance for New Stationary Sources

    In 40 CFR 60.17(h), we are incorporating by reference ASTM D4840-
99(2018)e1, Standard Guide for Sample Chain-of-Custody Procedures, and 
amending the reference to ASTM D6911-15, Guide for Packaging and 
Shipping Environmental Samples for Laboratory Analysis, to include for 
use in Method 23.
    In 40 CFR part 60, subpart CCCC, we are revising 40 CFR 
60.2125(g)(2) and (j)(2) to realign the requirement for quantifying 
isomers to the reorganized Section 11.4.2.4 in the revisions of Method 
23.
    In 40 CFR part 60, subpart DDDD, we are revising 40 CFR 
60.2690(g)(2) and (j)(2) to realign the requirement for identifying 
isomers to the reorganized Section 11.4.2.4 in the revisions of Method 
23.

B. 40 CFR Part 63--National Emission Standards for Hazardous Air 
Pollutants for Source Categories

    In 40 CFR 63.849(a)(13) and (a)(14), we are replacing CARB Method 
428 with EPA Method 23 for the measurement of PCB emissions from roof 
monitors not employing wet roof scrubbers.
    In 40 CFR 63.1208(b)(1), we are removing the requirement for 
administrator's approval to use Method 23 for measuring PCDD/PCDF 
emissions from hazardous waste combustors.
    In 40 CFR 63.1625(b)(10), we are replacing CARB Method 429 with EPA 
Method 23 for measuring the emissions of PAH from ferromanganese 
electric arc furnaces.
    In Table 3 to Subpart AAAAAAA, we are replacing the requirement for 
analysis of PAH by SW-846 Method 8270 with a requirement to use EPA 
Method 23. Specifically, we are deleting ``with analysis by SW-846 
Method 8270D'' in row 6 of Table 3 to Subpart AAAAAAA. Because 
revisions to Method 23 eliminate the use of methylene chloride in field 
sampling activities, we are also removing footnote ``b'' in Table 3 to 
Subpart AAAAAAA.

C. 40 CFR Part 266--Standards for the Management of Specific Hazardous 
Wastes and Specific Types of Hazardous Waste Management Facilities

    In 40 CFR 266.104, we are adding EPA Method 23 as an alternative to 
SW-846 Method 0023A. We proposed to make this change to 40 CFR 266.104. 
In addition to this specific change, we are making a conforming change 
in 40 CFR part 266 Appendix IX. EPA considers this conforming change a 
logical outgrowth of the proposed revisions to Method 23.

VI. Statutory and Executive Order Reviews

    Additional information about these statutes and Executive Orders 
can be found at https://www.epa.gov/laws-regulations/laws-and-executive-orders.

[[Page 16741]]

A. Executive Order 12866: Regulatory Planning and Review and Executive 
Order 13563: Improving Regulation and Regulatory Review

    This action is not a significant regulatory action and was, 
therefore, not submitted to the Office of Management and Budget (OMB) 
for review.

B. Paperwork Reduction Act (PRA)

    This action does not impose an information collection burden under 
the PRA. The revisions being promulgated in this action to Method 23 do 
not add information collection requirements, but make corrections, 
clarifications, and updates to existing testing methodology.

C. Regulatory Flexibility Act (RFA)

    I certify that this action does not have a significant economic 
impact on a substantial number of small entities under the RFA. This 
action does not impose any requirements on small entities. The final 
revisions to Method 23 do not impose any requirements on regulated 
entities. Rather, the final changes improve the quality of the results 
when required by other rules to use Method 23. Revisions to Method 23 
allow contemporary advances in analysis techniques to be used. Further, 
the final changes in Method 23 analysis procedures reduce the impact of 
this method by bringing it into alignment with other agency methods.

D. Unfunded Mandates Reform Act (UMRA)

    This action does not contain any unfunded mandate of $100 million 
or more as described in UMRA, 2 U.S.C. 1531-1538. The action imposes no 
enforceable duty on any State, local or tribal governments or the 
private sector.

E. Executive Order 13132: Federalism

    This action does not have federalism implications. It 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.

F. Executive Order 13175: Consultation and Coordination With Indian 
Tribal Governments

    This action does not have tribal implications, as specified in 
Executive Order 13175. It will not have substantial direct effects on 
the Indian Tribal Governments, on the relationship between the national 
government and the Indian Tribal Governments, or on the distribution of 
power and responsibilities among Indian Tribal Governments and the 
various levels of government. Thus, Executive Order 13175 does not 
apply to this action.

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

    The EPA interprets Executive Order 13045 as applying only to those 
regulatory actions that concern environmental health or safety risks 
that the EPA has reason to believe may disproportionately affect 
children, per the definition of ``covered regulatory action'' in 
Section 2-202 of the Executive Order. This action is not subject to 
Executive Order 13045 because it does not establish or revise a 
standard that provides protection to children against environmental 
health and safety risks.

H. Executive Order 13211: Actions That Significantly Affect Energy 
Supply, Distribution or Use

    This action is not subject to Executive Order 13211, because it is 
not a significant regulatory action under Executive Order 12866.

I. National Technology Transfer and Advancement Act (NTTAA)

    This action involves technical standards. The EPA will use ASTM 
D6911-15 (Guide for Packaging and Shipping Environmental Samples for 
Laboratory Analysis) and ASTM D4840-99(2018)e1 (Standard Guide for 
Sample Chain-of-Custody Procedures). These ASTM standards cover best 
practices that guide sample shipping and tracking from collection 
through analysis.
    These standards were developed and adopted by ASTM International. 
The standard may be obtained from https://www.astm.org or from the ASTM 
at 100 Barr Harbor Drive, P.O. Box C700, West Conshohocken, PA 19428-
2959.

J. Executive Order 12898: Federal Actions To Address Environmental 
Justice in Minority Populations and Low-Income Populations

    Executive Order 12898 (59 FR 7629, February 16, 1994) directs 
federal agencies, to the greatest extent practicable and permitted by 
law, to make environmental justice part of their mission by identifying 
and addressing, as appropriate, disproportionately high and adverse 
human health or environmental effects of their programs, policies, and 
activities on minority populations (people of color) and low-income 
populations.
    The EPA believes that this type of action does not concern human 
health or environmental conditions and, therefore, cannot be evaluated 
with respect to potentially disproportionate and adverse effects on 
people of color, low-income populations and/or Indigenous peoples. This 
action updates Method 23, which will improve the quality of the results 
when required by other rules to use Method 23.

K. Congressional Review Act (CRA)

    This action is subject to the CRA and the EPA will submit a rule 
report to each House of the Congress and to the Comptroller General of 
the United States. This action is not a ``major rule'' as defined by 5 
U.S.C. 804(2).

L. Determination Under Clean Air Act Section 307(d)

    This final rule is not subject to the provisions of CAA section 
307(d). This final rule does not promulgate any of the actions listed 
in CAA section 307(d)(1).

List of Subjects

40 CFR Part 60

    Environmental protection, Air pollution control, Hazardous air 
pollutants, Incorporation by reference, Method 23, Polychlorinated 
biphenyls, Polychlorinated dibenzofurans, Polychlorinated dibenzo-p-
dioxins, Polycyclic aromatic compounds, Test methods.

40 CFR Part 63

    Environmental protection, Air pollution control, Method 23, New 
source performance, Polychlorinated biphenyls, Polychlorinated 
dibenzofurans, Polychlorinated dibenzo-p-dioxins, Polycyclic aromatic 
hydrocarbons, Test methods.

40 CFR Part 266

    Environmental protection, Air pollution control, Hazardous air 
pollutants, Hazardous waste, Method 23, Polychlorinated biphenyls, 
Polychlorinated dibenzofurans, Polychlorinated dibenzo-p-dioxins, 
Polycyclic aromatic hydrocarbons, Test methods, Waste management.

Michael S. Regan,
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

0
1. The authority citation for part 60 continues to read as follows:

    Authority: 42 U.S.C. 7401 et seq.

[[Page 16742]]

Subpart A--General Provisions

0
2. In Sec.  60.17:
0
a. Redesignate paragraphs (h)(168) through (h)(213) as (h)(169) through 
(h)(214);
0
b. Add new paragraph (h)(168); and
0
c. Revise newly redesignated paragraph (h)(194).
    The addition and revision read as follows:

Sec.  60.17  Incorporations by reference.

* * * * *
    (h) * * *
    (168) ASTM D4840-99(2018)e1 Standard Guide for Sample Chain-of-
Custody Procedures, approved August 2018; IBR approved for Appendix A-
7: Method 23.
* * * * *
    (194) ASTM D6911-15 Standard Guide for Packaging and Shipping 
Environmental Samples for Laboratory Analysis, approved January 15, 
2015; IBR approved for Appendix A-7: Method 23; Appendix A-8: Method 
30B.
* * * * *

Subpart CCCC--Standards of Performance for Commercial and 
Industrial Solid Waste Incineration Units

0
3. In Sec.  60.2125, revise paragraphs (g)(2) and (j)(2) to read as 
follows:

Sec.  60.2125  How do I conduct the initial and annual performance 
test?

* * * * *
    (g) * * *
    (2) Quantify isomers meeting identification criteria in Section 
11.4.3.4 of Method 23, regardless of whether the isomers meet 
identification criteria in Section 11.4.3.4.1 of Method 23. You must 
quantify the isomers per Section 11.4.3.5 of Method 23. (Note: You may 
reanalyze the sample aliquot or split to reduce the number of isomers 
to meet the identification criteria in Section 11.4.3.4 of Method 23.)
* * * * *
    (j) * * *
    (2) Quantify isomers meeting identification criteria in Section 
11.4.3.4 of Method 23, regardless of whether the isomers meet 
identification Section 11.4.3.4.1 of Method 23. You must quantify the 
isomers per Section 11.4.3.5 of Method 23. (Note: You may reanalyze the 
sample aliquot or split to reduce the number of isomers to meet the 
identification criteria in Section 11.4.3.4 of Method 23.)
* * * * *

Subpart DDDD--Emissions Guidelines and Compliance Times for 
Commercial and Industrial Solid Waste Incineration Units

0
4. In Sec.  60.2690, revise paragraphs (g)(2) and (j)(2) to read as 
follows:

Sec.  60.2690  How do I conduct the initial and annual performance 
test?

* * * * *
    (g) * * *
    (2) Quantify isomers meeting identification criteria in Section 
11.4.3.4 of Method 23, regardless of whether the isomers meet 
identification Section 11.4.3.4.1 of Method 23. You must quantify the 
isomers per Section 11.4.3.5 of Method 23. (Note: You may reanalyze the 
sample aliquot or split to reduce the number of isomers to meet the 
identification criteria in Section 11.4.3.4 of Method 23.)
* * * * *
    (j) * * *
    (2) Quantify isomers meeting identification criteria in Section 
11.4.3.4 of Method 23, regardless of whether the isomers meet 
identification Section 11.4.3.4.1 of Method 23. You must quantify the 
isomers per Section 11.4.3.5 of Method 23. (Note: You may reanalyze the 
sample aliquot or split to reduce the number of isomers to meet the 
identification criteria in Section 11.4.3.4 of Method 23.); and
* * * * *

0
5. Revise Method 23 of Appendix A-7 to Part 60 to read as follows:

Appendix A-7 to Part 60--Test Methods 19 Through 25E

* * * * *

Method 23--Determination of Polychlorinated Dibenzo-p-Dioxins, 
Polychlorinated Dibenzofurans, Polychlorinated Biphenyls, and 
Polycyclic Aromatic Hydrocarbons From Stationary Sources

1.0 Scope and Application

    1.1 Applicability. This method applies to the measurement of 
polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans 
(PCDD/PCDF), polychlorinated biphenyls (PCB), and/or polycyclic 
aromatic hydrocarbons (PAH) in emissions from stationary sources. 
Using this method, you can measure these analyte groups individually 
or in any combination using a single sample acquisition unless 
otherwise specified in a rule, regulation, or permit. Tables 23-1 
through 23-3 of this method list the applicable target analytes for 
Method 23. If all 209 PCB are analyzed, the 17 toxic PCB congeners 
should be resolved and reported while the other PCB can be reported 
as totals by homolog, for example, total trichlorobiphenyl (TrCB).
    1.2 Scope. This method describes the sampling and analytical 
procedures used to measure selected PCDD and PCDF in stationary 
sources when required in an applicable subpart. This method also 
describes how the same sampling and analysis technology can be used 
to measure selected PCB and PAH from stationary source in 
combination or as each individual compound class when required in an 
applicable subpart. However, Method 23 incorporates by reference 
some of the specifications (e.g., equipment and supplies) and 
procedures (e.g., sampling and analytical) from other methods in 
this part that are essential to conducting Method 23. To obtain 
reliable samples, source sampling teams should be trained and 
experienced with the following additional EPA test methods: Method 
1, Method 2, Method 3, Method 4, and Method 5 of Appendices A-1, A-
2, and A-3 to 40 CFR part 60. Laboratory analysis teams should be 
trained and experienced with Method 1668C (found at: https://www.epa.gov/sites/production/files/2015-09/documents/method_1668c_2010.pdf) and Method 1613B of 40 CFR part 136 Appendix 
A and have a working knowledge of isotope dilution and the use of 
high-resolution gas chromatography/high-resolution mass spectrometry 
(HRGC/HRMS).
    1.3 The HRGC/HRMS portions of this method are for use by 
laboratory analysts experienced with HRGC/HRMS analysis of PCDD, 
PCDF, PCB, and PAH or under the close supervision of such qualified 
persons. Each source testing team, including the sampling and 
laboratory organization(s) that use this method, must demonstrate 
the ability to generate acceptable results that meet the performance 
criteria in Section 13 of this method.
    1.4 This method is ``performance-based'' and includes 
acceptability criteria for assessing sampling and analytical 
procedures. Users may modify the method to overcome interferences or 
to substitute superior materials and equipment, provided that they 
meet all performance criteria in this method. Section 13 of this 
method presents requirements for method performance.

2.0 Summary of Method

    This method identifies and determines the concentration of 
specific PCDD, PCDF, PCB, and PAH compounds. Gaseous and particulate 
bound target pollutants are withdrawn from the gas stream 
isokinetically and collected in the sample probe, on a glass fiber 
or quartz filter, and on a packed column of adsorbent material. This 
method is not intended to differentiate between target compounds in 
particulate or vapor fractions. The target compounds are extracted 
from the combined sample collection media. Portions of the extract 
are chromatographically fractionated to remove interferences, 
separated into individual compounds or simple mixtures by HRGC, and 
measured with HRMS. This method uses isotopically labeled standards 
to improve method accuracy and precision through isotope dilution 
quantitation.

3.0 Definitions

    3.1 Alternate Recovery Standards. A group of isotopically 
labeled compounds that is not otherwise designated in this method

[[Page 16743]]

for quality control (QC) purposes. Alternate recovery standards can 
be used to assess the recovery of a compound class relative to any 
step in the sampling and analysis procedure that is not already 
assessed as a mandatory part of this method, such as the cleanup 
step.
    3.2 Benzo[a]pyrene Toxic Equivalency Quotient (B[a]P-TEQ). One 
of several schemes that express the toxicity for PAH compounds in 
terms of the most toxic form of PAH, benzo[a]pyrene, as specified in 
applicable regulations, permits, or other requirements.
    3.3 Continuing Calibration Verification (CCV) Standard. A 
standard prepared at the mid-point concentration of the calibration 
used to verify the initial calibration. Prepare the CCV standard at 
the same time as the batch of field samples using the same labeled 
standards.
    3.4 Congener. An individual compound with a common structure 
(dioxin, furan, or biphenyl), only differing by the number of 
chlorine or other substituent attached to the structure.
    3.5 Estimated Detection Limit (EDL). The minimum qualitatively 
recognizable signal above background for a target compound. The EDL 
is a detection limit specific to each sample analysis based on the 
noise signal measured near the retention time of a target compound 
or target isomer group. Being sample specific, the EDL is affected 
by sample size, dilution, recoveries of pre-extraction standard, 
chemical noise from sample extract, electronic noise from 
instrument, extract aliquot, relative response of instrument, etc.
    3.6 Estimated Maximum Possible Concentration (EMPC). An EMPC is 
a worst-case estimate of the target compound concentration. Report 
the results as EMPC when the ion abundance ratio for a target 
analyte is outside the performance criteria. Calculate the EMPC 
using both quantitation ions.
    3.7 Field Train Proof Blank. A field train proof blank train is 
a QC sample to evaluate equipment preparation and potential 
contamination during sample recovery and consists of a fully 
assembled train at the sampling site, without actual sampling. The 
field train proof blank train uses glassware from the same 
preparation batch as the field samples.
    3.8 Homolog. A compound belonging to a series of compounds with 
the same general molecular formula, differing from each other by the 
number of repeating units of chlorine.
    3.9 Isomer. An individual compound with a common structure 
(dioxin, furan, or biphenyl), only differing by the position of 
chlorine atoms attached to the structure.
    3.10 Isotope Dilution. A means of determining a naturally 
occurring (native) compound by reference to the same compound in 
which one or more atoms has been isotopically enriched.
    3.11 Laboratory Method Blank (LMB). A quality control sample to 
assess background contamination or interference from media, 
reagents, equipment, etc. An LMB is prepared in the laboratory, 
composed of clean sampling media (filter and XAD-2), using same 
labeled standards, media, reagents, and materials (sodium sulfate, 
glass wool, etc.) and processed (extraction, fractionations, 
cleanup) and analyzed using the same procedures as a field sample.
    3.12 Polychlorinated Biphenyl (PCB) congeners. Any or all 209 
chlorinated biphenyl congeners. Table 23-3 of this method lists the 
primary target compounds and Appendix A to this method provides the 
full list of 209 PCB congeners and isomers.
    3.12.1 Monochlorobiphenyl (MoCB). Any or all three 
monochlorinated biphenyl isomers.
    3.12.2 Dichlorobiphenyl (DiCB). Any or all 12 dichlorinated 
biphenyl isomers.
    3.12.3 Trichlorobiphenyl (TrCB). Any or all 24 trichlorinated 
biphenyl isomers.
    3.12.4 Tetrachlorobiphenyl (TeCB). Any or all 42 
tetrachlorinated biphenyl isomers.
    3.12.5 Pentachlorobiphenyl (PeCB). Any or all 46 
pentachlorinated biphenyl isomers.
    3.12.6 Hexachlorobiphenyl (HxCB). Any or all 42 hexachlorinated 
biphenyl isomers.
    3.12.7 Heptachlorobiphenyl (HpCB). Any or all 24 
heptachlorinated biphenyl isomers.
    3.12.8 Octachlorobiphenyl (OcCB). Any or all 12 octachlorinated 
biphenyl isomers.
    3.12.9 Nonachlorobiphenyl (NoCB). Any or all three 
nonachlorinated biphenyl isomers.
    3.12.10 Decachlorobiphenyl (DeCB). Biphenyl fully chlorinated 
with 10 chlorine atom substituents replacing hydrogen in the parent 
compound.
    3.13 Polychlorinated dibenzo-p-dioxin (PCDD) congeners. Any or 
all 75 chlorinated dibenzo-p-dioxin congeners. There are seven 
2,3,7,8 substituted PCDD congeners and four PCDD homolog groups 
listed in Table 23-1 of this method. This method does not measure 
mono- through tri-PCDD and includes non-2,3,7,8 substituted 
congeners in the total homolog categories.
    3.13.1 Tetrachlorodibenzo-p-dioxin (TeCDD). Any or all 22 
tetrachlorinated dibenzo-p-dioxin isomers.
    3.13.2 Pentachlorodibenzo-p-dioxin (PeCDD). Any or all 14 
pentachlorinated dibenzo-p-dioxin isomers.
    3.13.3 Hexachlorodibenzo-p-dioxin (HxCDD). Any or all 10 
hexachlorinated dibenzo-p-dioxin isomers.
    3.13.4 Heptachlorodibenzo-p-dioxin (HpCDD). Any or all two 
heptachlorinated dibenzo-p-dioxin isomers.
    3.13.5 Octachlorodibenzo-p-dioxin (OCDD). Dibenzodioxin fully 
chlorinated with eight chlorine atom substituents replacing hydrogen 
in the parent compound.
    3.14 Polychlorinated dibenzofuran (PCDF) congeners. Any or all 
chlorinated dibenzofuran congeners. There are ten 2,3,7,8 
substituted PCDF congeners and four PCDF homolog groups listed in 
Table 23-1 of this method. This method does not measure mono- 
through tri-PCDF and includes non-2,3,7,8 substituted congeners in 
the total homolog categories.
    3.14.1 Tetrachlorodibenzofuran (TeCDF). Any or all 38 
tetrachlorinated dibenzofuran isomers.
    3.14.2 Pentachlorodibenzofuran (PeCDF). Any or all 28 
pentachlorinated dibenzofuran isomers.
    3.14.3 Hexachlorodibenzofuran (HxCDF). Any or all 16 
hexachlorinated dibenzofuran isomers.
    3.14.4 Heptachlordibenzofuran (HpCDF). Any or all four 
heptachlorinated dibenzofuran isomers.
    3.14.5 Octachlorodibenzofuran (OCDF). Dibenzofuran fully 
chlorinated with eight chlorine atom substituents replacing hydrogen 
in the parent compound.
    3.15 Polychlorinated diphenyl ethers (PCDPE). Any or all 
chlorinated substituted diphenyl ethers.
    3.15.1 Hexachlorodiphenyl ether (HxCDPE). Any or all 42 
hexachlorinated diphenyl ether isomers.
    3.15.2 Heptachlorodiphenyl ether (HpCDPE). Any or all 24 
heptachlorinated diphenyl ether isomers.
    3.15.3 Octachlorodiphenyl ether (OCDPE). Any or all 12 
octachlorinated diphenyl ether isomers.
    3.15.4 Nonachlorodiphenyl ether (NCDPE). Any or all three 
nonachlorinated diphenyl ether isomers.
    3.15.5 Decachlorodiphenyl ether (DCDPE).
    3.16 Polycyclic Aromatic Hydrocarbons (PAH). Any or all aromatic 
compounds with two or more fused six-member rings. Table 23-2 of 
this method lists the target PAH compounds for this method. You may 
add and analyze additional PAH compounds by adding the appropriate 
\13\C isotopically labeled compound to the pre-extraction standard 
mixture and by following the other requirements for target PAH 
compounds in this method.
    3.17 Pre-analysis Standard. A group of isotopically labeled 
compounds added at a known amount immediately prior to analysis and 
used to monitor instrument response, injection errors, instrument 
drift and to determine the recovery of the pre-extraction standard 
compounds. Add pre-analysis standard to every sample (including 
blank, QC samples, and calibration solutions) at a known amount.
    3.18 Pre-extraction Filter Recovery Standard. A group of 
isotopically labeled compounds added at a known amount to the filter 
used to indicate the extraction efficiency of the filter media. Add 
pre-extraction filter recovery standard to the filter samples just 
prior extraction. The pre-extraction filter recovery standard is not 
used for quantitating or recovery correction.
    3.19 Pre-extraction Standard. A group of isotopically labeled 
compounds added in a known amount to the XAD-2 adsorbent resin of 
each sample immediately before extraction and used for quantitation 
of target and other labeled compounds to correct for extraction, 
cleanup, and concentration recovery. These isotopically labeled 
compounds constitute a matrix spike of the resin. Add pre-extraction 
standard to every sample at the same level (including blank, QC 
samples, and calibration solutions).
    3.20 Pre-sampling Adsorbent Standard. A group of isotopically 
labeled compounds added in a known amount to the XAD-2 adsorbent 
prior to sampling used to monitor sampling aspects of the method.
    3.21 Pre-transport Standard. Spiking compound from the list of 
alternative recovery standards that can be added by the laboratory 
to the sample shipping containers used to transport field equipment 
rinse and

[[Page 16744]]

recovery samples prior to sampling. The measured concentration of 
the pre-transport recovery standard provides a quality check on 
potential probe rinse sample spillage or mishandling after sample 
collection and during shipping.
    3.22 Quality Control Sample (QCS). A mid-level standard prepared 
from a second source standard or prepared from a source of standards 
different from the source of calibration standards. The purpose of 
the QCS is to verify the integrity of the primary calibration 
standards. A QCS is analyzed during the initial demonstration of 
capability (IDC) and following each initial calibration (at a 
minimum quarterly) thereafter.
    3.23 Relative Response Factor (RRF). The response of the mass 
spectrometer (MS) to a known amount of an analyte relative to a 
known amount of an isotopically labeled standard.
    3.24 2,3,7,8-Tetrachlorodibenzo-p-dioxin Toxic Equivalency 
Quotient (2,3,7,8-TeCDD TEQ). A procedure that expresses the 
toxicity of PCDD, PCDF, and PCB in terms of the most toxic dioxin, 
as specified in applicable regulations, permits, or other 
requirements.

4.0 Interferences

    Despite interferences, confidence of the data is based on the 
enhanced selectivity of fractionation, gas chromatograph (GC) 
separation and detector resolving power, the QC check ions, and 
monitoring PCDPE.
    4.1 PCB and PCDPE have similar molecular weight and 
chromatographic properties to PCDD and PCDF. PCB may produce 
fragment ions at interfering mass-to-charge ratios (m/z) when losing 
chlorine (Cl2) or 2 Cl2 during ionization 
processes. With HRMS, GC separation, and fractionation, PCB should 
not pose a problem for PCDD/PCDF identification and quantitation. 
PCDPE, when losing Cl2, also produce interfering m/z 
values in the PCDF homolog group with two fewer chlorine atoms 
(i.e., an octachlorinated PCDPE can interfere with a hexachlorinated 
PCDF). The latter interferences are potentially detected by 
monitoring an m/z corresponding to the potentially interfering 
PCDPE; however, the fragmentation patterns of all PCDPE may not be 
known, complicating any attempt to quantify the extent of ether 
interference.
    Note: Consider monitoring 328 m/z if high levels of PCB are 
expected.
    4.2 Very high amounts of other organic compounds in the matrix 
may interfere with the analysis. This method provides examples of 
column-chromatographic cleanup as procedures to reduce, but not 
necessarily eliminate, matrix effects due to high concentrations of 
organic compounds (International Agency for Research on Cancer 
1991).
    4.3 Target compound contaminants or related organics in 
solvents, reagents, glassware, isotopically labeled spiking 
standards, and other sample processing hardware are potential method 
interferences. Routinely evaluate all these materials to demonstrate 
that they are either free from interferences under the conditions of 
the analysis, or that the interference does not compromise the 
quality of the analysis results. Evaluate chemical interference 
through the preparation and analysis of an LMB. Use high purity 
reagents, solvents, and standards to minimize interferences in 
sample analysis.
    4.4 PAH are subject to degradation when exposed to ultraviolet 
light. Take precautions to shield samples from sunlight or 
fluorescent light sources during sample collection, recovery, 
extraction, cleanup, and concentration.

5.0 Safety

    Note: Develop a strict laboratory safety program for the 
handling of PCDD, PCDF, PCB, and/or PAH.
    5.1 Compounds in the PCDD and PCDF classes such as 2,3,7,8-TeCDD 
are aneugenic, carcinogenic, and teratogenic in laboratory animal 
studies. Other PCDD and PCDF containing chlorine atoms in positions 
2,3,7,8 have toxicities comparable to that of 2,3,7,8-TeCDD.
    5.2 PCB and benzo[a]pyrene are classified as known or suspected 
human or mammalian carcinogens. Be aware of the potential for 
inhalation and ingestion exposure to laboratory analysts.
    5.3 This method recommends that the laboratory purchase dilute 
standard solutions of the analytes required for this method. 
However, if preparing primary solutions, use a hood or glove box. 
Laboratory personnel handling primary solutions should wear personal 
protective equipment including a toxic gas respirator mask fitted 
with charcoal filters approved by the National Institute for 
Occupational Safety and Health (NIOSH)/Mine Safety Health 
Administration (MSHA) to prevent the inhalation of airborne 
particulates if not working in an approved hood or glove box.
    5.4 The toxicity or carcinogenicity of other reagents or 
chemicals used in this method is not precisely defined. However, 
treat each chemical as a potential health hazard and minimize 
exposure to these chemicals. The laboratory is responsible for 
maintaining a current awareness file of Occupational Safety and 
Health Administration (OSHA) regulations regarding the safe handling 
of the chemicals specified in this method. Ensure that a reference 
file or list of internet sites that contain safety data sheets (SDS) 
is available to all personnel involved in the sampling and chemical 
analysis of samples known or suspected to contain PCDD, PCDF, PCB, 
and PAH.

6.0 Equipment and Supplies

    Note: Brand names, suppliers, and part numbers are for 
illustration purposes only and no endorsement is implied. Apparatus 
and materials other than those specified in this method may achieve 
equivalent performance. Meeting the performance requirements of this 
method is the responsibility of the source testing team and 
laboratory team.
    6.1 Sampling Apparatus. Figure 23-1 of this method shows a 
schematic of the Method 23 sampling train. Do not use sealing 
greases or brominated flame retardant-coated tape in assembling the 
train. Do not use silicon tubing in direct contact with flue gases. 
The train is identical to that described in Section 6.1.1 of Method 
5 of Appendix A-3 to 40 CFR part 60 with the following additions:
    6.1.1 Nozzle. The nozzle must be made of quartz, borosilicate 
glass, or titanium. Stainless steel nozzles should not be used.
    6.1.2 Probe Liner. Use either polytetrafluoroethylene (PTFE), 
borosilicate, or quartz glass probe liners with a heating system 
capable of maintaining a probe gas temperature 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 as approved by the Administrator. Use a PTFE ferrule or 
single-use PTFE coated O-ring to achieve the seal at the nozzle end 
of the probe for stack temperatures up to about 300 [deg]C (572 
[deg]F). Use a quartz glass liner and integrated quartz nozzle for 
stack temperatures between 300 and 1,200 [deg]C (572 and 2,192 
[deg]F).
    6.1.3 Filter Holder. Use a filter holder of borosilicate glass 
with a PTFE frit or PTFE-coated wire filter support. The holder 
design should provide a positive seal against leakage from the 
outside or around the filter. The holder should be durable, easy to 
load, leak-free in normal applications, and positioned immediately 
following the probe and cyclone bypass (or cyclone, if used) with 
the active side of the filter perpendicular to the source of the 
flow.
    6.1.4 Filter Heating System. Use any heating system capable of 
monitoring and maintaining the temperature around the filter to 
ensure that the sample gas temperature exiting the filter is 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.
    6.1.5 Filter Temperature Sensor. Install a temperature sensor 
capable of measuring temperature to within 3 [deg]C (5.4 
[deg]F) so that the sensing tip protrudes at least 1.3 centimeters 
(cm) (1-2 in.) into the sample gas exiting the filter. Encase the 
sensing tip of the sensor in glass or PTFE, if needed.
    6.1.6 Sample Transfer Line. The sample transfer line transports 
gaseous emissions from the heated filter holder to the condenser and 
must be heat traced and constructed of glass or PTFE with connecting 
fittings that form leak-free, vacuum-tight connections without using 
sealing greases or tapes. Keep the sample transfer lines as short as 
possible and maintain the lines at a temperature of 120 [deg]C 
 14 [deg]C (248 [deg]F  25 [deg]F) using 
active heating when necessary. Orient the sample transfer lines with 
the downstream end lower than the upstream end so that any 
condensate will flow away from the filter and into the condenser.
    6.1.7 Condenser. Glass, water-jacketed, coil-type with 
compatible fittings. Orient the condenser to cause moisture to flow 
down to the adsorbent module to facilitate condensate drainage. 
Figure 23-2 of this method shows a schematic diagram of the 
condenser.
    6.1.8 Water Circulating Bath. Use a bath pump circulating system 
capable of providing chilled water flow to the condenser and 
adsorbent module water jackets. Typically, a submersible pump is 
placed in the impinger ice water bath to circulate the ice water 
contained in the bath. Verify the function of this system by

[[Page 16745]]

measuring the gas temperature at the entrance to the adsorbent 
module. Maintain this temperature at <20 [deg]C (68 [deg]F).
    6.1.9 Adsorbent Module. Use a water-jacketed glass container to 
hold up to 40 grams (g) of the solid adsorbent. Figure 23-2 of this 
method shows a schematic diagram of the adsorbent module. Other 
physical configurations of the adsorbent resin module/condenser 
assembly are acceptable if the configuration contains the requisite 
amount of solid adsorbent and maintains the minimum length-to-width 
adsorbent bed ratio of two-to-one. Orient the adsorbent module 
vertically to facilitate condensate drainage. The connecting 
fittings must form leak-free, vacuum-tight seals. Include a coarse 
glass frit in the adsorbent module to retain the adsorbent.
    6.1.10 Impingers. Use five impingers connected in series with 
leak-free ground glass fittings or any similar leak-free 
noncontaminating fittings. The first impinger must be a short-stem 
(water-dropout) design or equivalent. The second, fourth, and fifth 
impingers must be of the Greenburg-Smith design, modified by 
replacing the tip with a 1.3 cm (\1/2\ in.) inside diameter (ID) 
glass tube extending to approximately 1.3 cm (\1/2\ in.) from the 
bottom of the flask. The third impinger must be of the Greenburg-
Smith design with the standard tip. The second and third impingers 
must contain known quantities of water, and the fifth impinger must 
contain a known weight of silica gel or equivalent desiccant. 
Alternatively, you may omit the first impinger if you do not expect 
excess moisture in the sample gas.
    6.2 Sample Recovery Equipment.
    6.2.1 Fitting Caps. Use leak-free ground glass fittings or any 
similar leak-free non-contaminating fitting to cap the sections of 
the sampling train exposed to the sample gas. Alternatively, use 
PTFE tape or contaminant-free aluminum foil for this purpose (see 
Section 6.2.6 of this method).
    6.2.2 Wash Bottles. Use PTFE bottles.
    6.2.3 Probe-Liner, Probe-Nozzle, and Filter-Holder Brushes. Use 
inert bristle brushes with precleaned stainless steel or PTFE 
handles. Extensions of the probe brush must be made of stainless 
steel or PTFE and be at least as long as the probe. Use brushes that 
are properly sized and shaped to remove accumulated material from 
the nozzle and probe liner if used.
    6.2.4 Filter Storage Container. Use a sealed filter holder, 
wide-mouth amber glass jar with PTFE-lined cap, or glass petri dish 
sealed with PTFE tape. Purchase precleaned amber glass jars and 
petri dishes, or clean according to the glassware cleaning 
procedures listed in Section 8.1.1.1 of this method.
    6.2.5 Field Balance. Use a weighing device capable of 
measurements to an accuracy of 0.5 g.
    6.2.6 Aluminum Foil. Use heavy duty aluminum foil cleaned by 
rinsing three times with hexane or toluene and stored in a pre-
cleaned glass petri dish or glass jar. Do not use aluminum foil to 
wrap or contact filter samples due to the possibility of reaction 
between the sample and the aluminum.
    6.2.7 Silica Adsorbent Storage Container. Use an air-tight 
container to store silica gel.
    6.2.8 Glass Sample Storage Container. Recover samples in amber 
glass bottles, 500- or 1000-milliliters (mL) with leak-free PTFE-
lined caps. Either purchase precleaned bottles or clean containers 
according to glassware cleaning procedures listed in Section 8.1.1.1 
of this method.
    6.3 Sample Extraction Equipment.
    6.3.1 Sample Container. Use 125- and 250-mL amber glass bottles 
with PTFE-lined caps.
    6.3.2 Test Tubes. Use glass test tubes or small (e.g., 5 to 10 
mL) amber vials.
    6.3.3 Soxhlet/Dean-Stark Extraction Apparatus.
    6.3.3.1 Soxhlet Apparatus. Use 200-mL capacity thimble holder 
capable of holding 43 x 123-millimeter (mm) extraction thimbles, 
with receiving flask (typically round-bottom).
    6.3.3.2 Moisture Trap. Use Dean-Stark or Barret with 
fluoropolymer stopcock trap to fit between the Soxhlet extractor 
body and the condenser as shown in Figure 23-3 of this method.
    Note: Dean-Stark or Barret traps are used to remove water with 
extraction solvents that are less dense and insoluble in water.
    6.3.3.3 Extraction Thimble. Use quartz, glass, or glass fiber 
thimble, typically 43 x 123 mm to fit Soxhlet apparatus. The use of 
cellulose thimbles for sample extraction in this method is 
prohibited.
    6.3.3.4 Heating Mantle. Use a hemispherical shaped heating 
mantle to fit round-bottom flask.
    6.3.4 Kuderna-Danish (KD) Concentrator. Use an apparatus 
consisting of a three-ball Snyder column, a flask with leak-free 
joint to accept the three-ball Snyder column at the top, a leak-free 
joint to receive a graduated concentration tube at the bottom and a 
heating mantle.
    Note: Rotary evaporation has only been demonstrated when 
analyzing PCDD/PCDF. The KD with Snyder column is recommended when 
analyzing for PAH and/or PCB to avoid evaporation loss resulting in 
failed performance criteria for pre-extraction spike recovery.
    6.3.5 Nitrogen Evaporative Concentrator. Use a nitrogen 
evaporative concentrator equipped with a water bath with the 
temperature controlled in the range of 30 to 60 [deg]C (86 to 140 
[deg]F) (N-Evap Organomation Associates, Inc., South Berlin, MA, or 
equivalent).
    6.3.6 Separatory Funnels. Use glass or PTFE 2-liter separatory 
funnels.
    6.4 Glass Liquid Chromatography Columns.
    6.4.1 Pasteur Pipettes. Use disposable pipettes, or glass 
serological pipettes typically 150 mm long x 6 mm ID.
    6.4.2 Liquid Chromatography Columns. 200 to 300 mm long x 20 mm 
ID with 250-mL reservoir.
    6.5 Analytical Equipment.
    6.5.1 Gas Chromatograph. Use a gas chromatograph consisting of 
the following components:
    6.5.1.1 GC Oven. Use an oven capable of maintaining the 
separation column at the proper operating temperature  
1.0 [deg]C (1.8 [deg]F) and performing programmed increases in 
temperature at rates of at least 40 [deg]C/min with isothermal hold.
    6.5.1.2 GC Temperature Monitor. Use a temperature monitor to 
measure column oven temperature to  1.0 [deg]C (1.8 
[deg]F).
    6.5.1.3 GC Flow System. Use an electronic pressure control or 
equivalent gas metering system to control carrier gas flow or 
pressure.
    6.5.1.4 GC Injection Port. Use a split/splitless injection port 
in the splitless mode or on-column injection port for the capillary 
column.
    6.5.2 Capillary GC Column. Use different columns for the 
analysis of the different target compound classes in this method, if 
needed. Perform the resolution checks in Sections 10.2.3.5 and 
10.2.3.6 of this method to document the required resolution. 
Compound separation must meet the resolution specifications in 
Section 10.2.3.5 of this method and the identification 
specifications found in Section 11.4.3.4 of this method.
    6.5.2.1 PCDD/PCDF Column. Gas chromatographic columns used to 
measure PCDD/PCDF should be capable of achieving separation of the 
17 PCDD/PCDF target compounds from the nearest eluting target 
compound(s). The valley height resolution between 2,3,7,8-
substituted TeCDD and TeCDF and the nearest eluting isomers must not 
exceed 25% of the taller of the two peaks. The valley height 
resolution between all other target PCDD/PCDF compounds and the 
nearest eluting targets (or interference) must not exceed 40% of the 
taller of the two peaks.
    Note: Fishman, et al. (see Section 16.3 of this method) 
demonstrated that all TEF isomers can be fully differentiated from 
closely eluting isomers using either of two sets of non-polar and 
polar stationary phase combinations. One set consisted of 5% phenyl 
methylpolysiloxane (DB-5, HP-5MS, Rtx-5MS, Equity-5) and 50% 
cyanopropylmethyl, 50% phenylmethylsiloxane (DB-225, SP 2331) GC 
columns and the other set consisted of 5% phenyl, 94% methyl, 1% 
vinyl silicone bonded-phase (DB-5MS, ZB-5MS, VF-5MS, CP-Sil 8 CB 
LowBleed/MS) with 50% cyanopropylmethyl, 50% phenylmethylsiloxane 
(SP-2331).
    6.5.2.2 PAH Column. Use column systems for measuring PAH that 
can achieve separation of anthracene and phenanthrene at m/z 178 
such that the valley between the peaks does not exceed 50% of the 
taller of the two peaks, and benzo[b]fluoranthene and 
benzo[k]fluoranthene such that the valley between the peaks is less 
than 60% of the height of the taller peak. These requirements are 
achievable using a 30-m narrow bore (0.25 mm ID) 5% phenyl 
polysilphenylene-siloxane (BPX5 or equivalent) bonded-phase, fused-
silica capillary column.
    6.5.2.3 PCB Column. Use column systems for measuring PCB that 
can achieve unique resolution and identification of the toxics for 
determination of a TEQPCB using toxic equivalency factors 
(TEF). Resolution is shown by a valley between the peaks not 
exceeding 40% of the taller of the two peaks. Isomers may be 
unresolved if they have the same TEF and RRF and if these unresolved 
isomers are uniquely resolved from all other congeners. These 
requirements are achievable using several 30-meter (m) narrow

[[Page 16746]]

bore (0.25 mm ID) columns including 8% phenyl polycarborane-siloxane 
(HT8), DB-XLB, and poly (50% n-octyl/50% methyl siloxane) (SPB-
Octyl). Quantification of unresolved isomers should use the nearest 
eluting target PCB pre-extraction standard in Appendix A of this 
method, unless otherwise specified in applicable rule, regulation, 
or permit.
    Note: If all 209 PCB are analyzed the 17 toxic PCB congeners 
should be resolved and reported while the other PCB can be reported 
as totals by homolog, for example, total TrCB.
    6.5.3 Mass Spectrometer. Instrument employing 28 to 70 electron 
volt ionization. The instrument and data system must be capable of 
repetitive monitoring of at least 12 exact m/z values with a mass 
resolution defined in Section 10.2.1 within the measurement mass 
range. The recommended lock-mass ions to be used for mass drift 
correction are presented in Tables 23-4, 23-5, and 23-6 of this 
method for PCDD/PCDF, PAH, and PCB, respectively, as applicable to 
target analytes. Mass drifts of 5 parts per million (ppm) or more 
can have serious effects on instrument performance.
    6.5.4 Mass Spectrometer Data System. Use a data system 
compatible with the mass spectrometer and capable of sequencing and 
monitoring multiple groups of selected ions.
    6.5.5 Analytical Balance. Use an analytical balance to measure 
within 0.1 milligram (mg).

7.0 Reagents, Media, and Standards

    7.1 Filter. Glass fiber filters, without organic binder, 
exhibiting at least 99.95% efficiency (<0.05% penetration) on 0.3-
micron dioctyl phthalate smoke particles.
    7.1.1 Conduct a QC check on the filter lot prior to the field 
test to demonstrate that filters are free from contamination or 
interference by extracting and analyzing a minimum of three filters 
from each lot as follows. Spike with pre-extraction and pre-
extraction filter recovery standards for target compounds to be 
measured and extract each filter separately with toluene as 
described in Section 11 of this method. After extraction, remove the 
filters and the solvent from the filters under clean conditions 
(e.g., a clean nitrogen stream). Analyze the extracts according to 
the procedures in Section 11 of this method, including adding pre-
analysis standard. This filter check analysis must meet the 
performance requirements in Section 13.1 of this method. Ongoing 
analysis of LMB can be used to fulfill this check. If criteria are 
not met for target compounds, repeat with additional filters from 
the lot or evaluate another lot.
    7.2 Adsorbent Resin. Amberlite[supreg] XAD-2 resin. All 
adsorbent resin must meet the cleanliness criteria described for LMB 
in Section 13.1 of this method following the same extraction, 
concentration, cleanup, and analysis steps as field samples. This 
method recommends using the procedures provided in Appendix B to 
this method to clean the resin before use, if needed. However, this 
method allows alternative cleanup procedures that use automated 
extraction equipment if the adsorbent meets the required performance 
criteria described for LMB in Section 13.1 of this method.
    7.2.1 Conduct a QC check on the cleaned adsorbent lot or batch 
following the extraction and analyses procedures in Section 11 of 
this method, including adding applicable labeled standards. The 
cleaned adsorbent must meet the criteria described for LMB in 
Section 13.1 of this method. An LMB conducted with an adsorbent lot 
or batch can serve this purpose.
    7.2.2 Storage. Store adsorbent in a solvent-rinsed nonporous 
clean container and secure lid.
    7.3 Glass Wool. Clean the glass wool to meet the specifications 
in Section 13.1 of this method. Glass wool is dried of the solvent 
and stored in a clean glass container with a PTFE-lined screw cap.
    7.4 Water. Use deionized or distilled water meeting requirements 
in Section 13.1 of this method and store in its original container 
or in a clean glass container with a PTFE-lined screw cap.
    7.5 Silica Gel. Indicating type for sampling, 6-16 mesh. If 
previously used, dry at 175 [deg]C (347 [deg]F) for two hours. Use 
new silica gel as received. As an alternative, use other types of 
desiccants (equivalent or better), subject to the approval of the 
Administrator.
    7.6 Methylene Chloride. Pesticide grade or better.
    7.7 Sample Recovery Reagents.
    7.7.1 Acetone. Pesticide grade or better.
    7.7.2 Toluene. Pesticide grade or better.
    7.8 Sample Extraction and Cleanup.
    7.8.1 Potassium Hydroxide. American Chemical Society (ACS) 
grade, 2% (weight/volume) in water.
    7.8.2 Sodium Sulfate. Granulated or powdered, reagent grade. 
Evaluate for cleanliness prior to use with an LMB. The LMB must meet 
the requirements in Section 13.1 of this method for target 
compounds. Store in a clean glass container with a PTFE-lined screw 
cap.
    7.8.3 Sulfuric Acid. Reagent grade.
    7.8.4 Sodium Hydroxide. 1.0 N. Weigh 40 g of sodium hydroxide 
into a 1-liter volumetric flask. Dilute to 1 liter with water.
    7.8.5 Hexane. Pesticide grade or better.
    7.8.6 Methanol. Pesticide grade or better.
    7.8.7 Toluene. Pesticide grade or better.
    7.8.8 High-Boiling Alkanes Used as Keeper Solvents (e.g., 
tetradecane, nonane, decane). Pesticide grade. Note: Lower 
homologous series alkanes (nonane or decane) are necessary for 
higher volatility targets such as MoCB and naphthalene to maintain 
retention during concentration procedures. However, do not take 
samples to dryness when using these lower alkane homologs.
    7.8.9 Liquid Column Chromatography Packing Materials. Use the 
following column chromatography packing materials, as needed, to 
prepare sample extracts by fractionation and removal of 
interferences. Commercially prepacked cleaning columns may be 
available for this purpose. The liquid column chromatography packing 
materials must be adequate to clean the samples to be fit for 
purpose and meet the performance criteria of this method. All 
procedures for preparing column chromatography packing materials are 
recommendations shown to meet the performance specifications 
required for the recovery of labeled compounds described in Section 
13 of this method.
    7.8.9.1 Alumina. Use either acidic or basic alumina in the 
cleanup of sample extracts. Use the same type of alumina for all 
samples in an analytical sequence, including those used to 
demonstrate LMB performance.
    7.8.9.1.1 Acidic Alumina (Sigma-Aldrich[supreg] 199966 or 
equivalent). Brockmann activity grade 1, 100-200 mesh. Prior to use, 
activate the alumina by heating for 12 hours at 130 [deg]C (266 
[deg]F). Store in a desiccator. You may use pre-activated alumina 
purchased from a supplier as received.
    7.8.9.1.2 Basic Alumina (Sigma-Aldrich[supreg] 19943 or 
equivalent). Brockmann activity grade 1. Activate by heating to 600 
[deg]C (1,112 [deg]F) for a minimum of 24 hours. Do not heat to over 
700 [deg]C (1,292 [deg]F) because this can lead to reduced capacity 
for retaining the target compounds. Store at 130 [deg]C (266 [deg]F) 
in a covered flask. Recommended storage time for acidic alumina is 
up to five days from baking. Use prepacked alumina columns 
immediately after opening the vacuum-sealed pouch or container.
    7.8.9.2 Florisil[supreg]. Activated, 60-100 mesh recommended. 
Heat previously activated Florisil[supreg] in a glass container 
loosely covered with aluminum foil in an oven at 130 to 150 [deg]C 
(266 to 302 [deg]F) for a minimum of 24 hours. Allow to cool and 
store activated Florisil[supreg] silica in a desiccator.
    7.8.9.3 Silica Gel. Use either activated, acid- or base-coated 
silica gel in the cleanup of sample extracts. Use the same type of 
silica gel for all samples in an analytical sequence, including 
those used to demonstrate LMB performance.
    7.8.9.3.1 Activated Silica Gel. Supelco[supreg] 1-3651, Bio-
Sil[supreg] A, 100-200 mesh (or equivalent). Prior to use, silica 
gel should be activated by solvent rinsing and heat activation. It 
is recommended to rinse with methylene chloride and activate the 
silica gel by heating for at least 1 hour at 180 [deg]C (356 
[deg]F). After allowing to cool, rinse the silica gel sequentially 
with methanol and toluene. Heat the rinsed silica gel at 50 [deg]C 
(122 [deg]F) for 10 minutes, then increase the temperature gradually 
to 180 [deg]C (356 [deg]F) over 25 minutes and maintain the gel at 
this temperature for 90 minutes. Allow to cool in a desiccator to 
room temperature and store in a glass container with a PTFE-lined 
screw cap. Alternative conditioning procedure may be used if the 
performance criteria in Section 13.1 are met for target compounds.
    7.8.9.3.2 Acidic Silica Gel (30% weight/weight). Combine 100 g 
of activated silica gel with 44 g of concentrated sulfuric acid in a 
clean screw-capped glass container and agitate thoroughly. Disperse 
the solids with a stirring rod until obtaining a uniform mixture of 
acid-coated silica gel. Store the mixture in a glass container with 
a PTFE-lined screw cap.
    7.8.9.3.3 Basic Silica Gel. Combine 30 g of 1 N sodium hydroxide 
with 100 g of activated silica gel in a clean screw-capped glass 
container and agitate thoroughly. Disperse solids with a stirring 
rod until obtaining a uniform mixture of base-coated silica gel. 
Store the mixture in glass container with a PTFE-lined screw cap.
    7.8.9.4 Carbon/Celite[supreg] 545 (or equivalent solid support). 
Use of a carbon-based column

[[Page 16747]]

cleanup material (e.g., one of the many including for example 
Carbopack[supreg] B or C) to further remove non-planar impurities 
from the samples prior to analysis may be necessary. You must 
evaluate alternative carbon-based sorbents for this purpose prior to 
their use. An 18% weight/weight mixture of Carbopack[supreg] C and 
Celite[supreg] 545 has been used for this purpose and should be 
activated at 130 [deg]C (266 [deg]F) for a minimum of 6 hours. Allow 
to cool and store this mixture in a desiccator.
    7.8.10 Nitrogen. 99.999% (ultra-high) purity.
    7.9 Sample Analysis.
    7.9.1 Helium. 99.999% (ultra-high) purity.
    7.9.2 Spiking Standards. Prepare spiking standards 
quantitatively at a convenient concentration (e.g., 10 nanograms 
(ng)/mL) or use commercial standards if available, to enable 
accurate spiking of a labeled standard at various stages of the 
sample and extract preparation. You may adjust the sample 
fortification concentrations from those recommended in Tables 23-7, 
23-8, and 23-9 of this method to accommodate the concentration of 
target compounds anticipated in samples if the performance criteria 
in Section 13 of this method are met.
    Note: When adjusting the fortification concentrations in the 
final sample extract, consider variables such as the aliquot of 
extract used and injection volume of samples and calibration.
    7.9.3 Pre-Sampling Adsorbent Standard. Prepare stock standard 
solutions in nonane to enable spiking so that the isotopically 
labeled compounds in the final sample extract are at the 
concentration shown under the heading ``Pre-sampling Adsorbent 
Standard'' in Tables 23-7, 23-8, and 23-9 of this method, for 
applicable target compound classes.
    7.9.4 Pre-extraction Filter Recovery Standard. Prepare stock 
standard solutions in nonane to enable spiking so that the 
isotopically labeled compounds in the final sample extract are at 
the concentration shown under the heading ``Pre-extraction Filter 
Recovery Standard'' in Tables 23-7, 23-8, and 23-9 of this method, 
for applicable target compound classes.
    7.9.5 Pre-extraction Standard. Prepare stock standard solutions 
in nonane to enable spiking so that the isotopically labeled 
compounds in the final sample extract are at the concentration shown 
under the heading ``Pre-extraction Standard'' in Tables 23-7, 23-8, 
and 23-9 of this method, for applicable target compound classes.
    7.9.6 Pre-analysis Standard. Prepare stock standard solutions in 
nonane to enable spiking so that the isotopically labeled compounds 
in the final sample extract are at the concentration shown under the 
heading ``Pre-analysis Standard'' in Tables 23-7, 23-8, and 23-9 of 
this method, for applicable target compound classes.

8.0 Sample Collection, Preservation, and Storage

    8.1 Sampling. This method involves collection and recovery of 
trace concentrations of target semivolatile organic compounds. 
Therefore, field sampling and recovery staff should be trained and 
experienced in the best practices for handling and using organic 
solvents in field environments to recover and protect samples from 
contamination.
    8.1.1 Pretest Preparation.
    8.1.1.1 Cleaning Glassware. Clean glassware thoroughly before 
using. This section provides a recommended procedure, but any 
protocol that consistently results in contamination-free glassware 
meeting the LMB criteria in Section 13.1 of this method is 
acceptable.
    8.1.1.1.1 Soak all glassware in hot soapy water (Alconox[supreg] 
or equivalent).
    8.1.1.1.2 Rinse with hot tap water.
    8.1.1.1.3 Rinse with deionized/distilled water.
    8.1.1.1.4 Rinse with methanol.
    8.1.1.1.5 Rinse with toluene.
    8.1.1.1.6 Baking glassware up to 400 [deg]C (752 [deg]F) for a 
minimum of 2 hours may be necessary to remove contaminants or 
interferents from particularly dirty samples. Allow glassware to 
cool after baking.
    Note: Repeated baking of glassware may cause active sites on the 
glass surface that may irreversibly adsorb target compounds.
    8.1.1.1.7 Cover glassware openings with clean glass fitting caps 
or cleaned aluminum foil (see Section 6.2.6 of this method).
    8.1.1.1.8 Rinse glassware immediately before use with acetone 
and toluene.
    Note: To prepare heavily soiled glassware, remove surface 
residuals from the glassware by soaking in hot soapy water, rinsing 
with hot water, then soaking with a non-chromic acid oxidizing 
cleaning reagent in a strong acid (e.g., NOCHROMIX[supreg] prepared 
according to manufacturer's directions). After the acid soak, rinse 
with hot water and repeat the cleaning procedures in Section 8.1.1.1 
of this method.
    8.1.1.2 Adsorbent Module. Load the modules in a clean area to 
avoid contamination. Fill a module with 20 to 40 g of XAD-2. Spike 
modules before the sampling event, but do not spike the modules in 
the field. Add the pre-sampling adsorbent standard to the top 
quarter of the adsorbent bed rather than onto the top or bottom of 
the adsorbent bed. Add sufficient spike (picograms (pg)/module) to 
result in the final sample theoretical concentrations specified in 
Tables 23-7, 23-8, and 23-9 of this method for PCDD/PCDF, PAH, and 
PCB, respectively, and to be above the lowest calibration 
concentration to ensure the standard recovery is quantitative. For 
samples with known or anticipated target compound concentration 
significantly higher or lower than the specified concentration in 
these tables, adjust the pre-sampling adsorbent standard 
concentration to the expected native compound concentration, but no 
less than 10 times the method detection limit (MDL). Follow the XAD-
2 with cleaned glass wool and tightly cap both ends of the module. 
For analysis that includes PAH, use spiked modules within 14 days of 
preparation. See Table 23-10 of this method for storage conditions.
    8.1.1.3 Sampling Train. Figure 23-1 of this method shows the 
complete sampling train. Follow the best practices by maintaining 
all sampling train components according to the procedure described 
in APTD-0576 Maintenance, Calibration, and Operation of Isokinetic 
Source-sampling Equipment (U.S. EPA 1972).
    8.1.1.4 Silica Gel. Weigh several 200 to 300 g portions of 
silica gel in an air-tight container to the nearest 0.5 g. Record 
the total weight of the silica gel plus container, on the outside of 
each container. As an alternative, directly weigh the silica gel in 
its impinger or sampling holder just prior to sampling.
    8.1.1.5 Filter. Check each filter against light for 
irregularities and flaws or pinhole leaks. Pack the filters flat in 
a clean glass container. Do not mark filters with ink or any other 
contaminating substance.
    8.1.2 Preliminary Determinations. Use the procedures specified 
in Section 8.2 of Method 5 of Appendix A-3 to 40 CFR part 60.
    8.1.2.1 Sample Volume. Unless otherwise specified in an 
applicable rule, regulation, or permit, sample for a minimum of 2 
minutes at each traverse point. This method recommends sampling a 
minimum of 2.5 dry standard cubic meters (dscm).
    8.1.2.2 For continuously operating processes, use the same 
sampling time at each traverse point. To avoid timekeeping errors, 
use an integer, or an integer plus one-half minute, for each 
traverse point.
    8.1.2.3 For batch processes, determine the minimum operating 
cycle duration, dividing the sampling time evenly between the 
required numbers of traverse points. After sampling all traverse 
points once, sample each point again for the same duration of time 
per sampling point in reverse order until the operating cycle is 
completed. Sample all traverse points at least once during each test 
run.
    8.1.3 Preparation of Sampling Train.
    8.1.3.1 During field preparation and assembly of the sampling 
train, keep all train openings where contamination can enter sealed 
until just prior to assembly or until sampling is about to begin. To 
protect the adsorbent module from radiant heat and sunlight, you 
must wrap the module with aluminum foil or other suitable material 
capable of shielding the module from light. The XAD-2 adsorbent 
resin temperature must never exceed 50 [deg]C (122 [deg]F) because 
thermal decomposition will occur. Clean and prepare a complete set 
of sampling train components that will contact the sample for each 
sampling run, including one complete set to be used as a field train 
proof blank as a tool to evaluate equipment preparation and 
potential contamination during sample recovery as described in 
Section 9.6 of this method.
    8.1.3.2 Place approximately 100 mL of water in the second and 
third impingers but leave the first and fourth impingers empty. 
Transfer approximately 200 g or more of silica gel from its 
container to the fifth impinger. Weigh each impinger and the 
adsorbent module, including the fitting caps, to the nearest 0.5 g 
using the field balance and record the weight for moisture 
determination. Remove the aluminum foil from the adsorbent module 
before weighing. Keep the module out of direct sunlight and rewrap 
the module with foil immediately after recording the module weight.

[[Page 16748]]

    8.1.3.3 Using tweezers or clean disposable surgical gloves, 
place a filter in the filter holder. Be sure that the filter is 
properly centered, and the gasket properly placed, to prevent the 
sample gas stream from circumventing the filter. Check the filter 
for tears after completing the assembly.
    8.1.3.4 Prepare the inside of the sampling probe and nozzle by 
brushing each component while rinsing three times each with acetone 
and toluene. Install the selected nozzle, using the connecting 
systems described in Section 6.1.2 of this method. 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. 
Assemble the train as shown in Figure 23-1 of this method. Orient 
the adsorbent module vertically so condensed moisture drains into 
the first impinger. See APTD-0576 Maintenance, Calibration, and 
Operation of Isokinetic Source-sampling Equipment (U.S. EPA 1972) 
for details.
    8.1.3.5 Turn on the recirculation pump to the adsorbent module 
and condenser coil and begin monitoring the temperature of the gas 
entering the adsorbent module. Ensure proper temperature of the gas 
entering the adsorbent module before proceeding.
    8.1.4 Leak-Check Procedure. Same as Section 8.4 of Method 5 of 
Appendix A-3 to 40 CFR part 60.
    8.1.5 Sampling Train Operation. Same as Sections 8.5.1 through 
8.5.9 of Method 5 of Appendix A-3 to 40 CFR part 60.
    8.1.5.1 Monitor the filter temperature with a sensor and record 
the filter temperature during sampling to ensure a sample gas 
temperature exiting the filter of 120 [deg]C  14 [deg]C 
(248 [deg]F  25 [deg]F), or such other temperature as 
specified by an applicable subpart of the standards or approved by 
the Administrator for an application of this method.
    8.1.5.2 During testing, you must record the temperature of the 
gas entering the XAD-2 adsorbent module. The temperature of the gas 
must not exceed 20 [deg]C (68 [deg]F) for efficient capture of the 
target compounds.
    8.2 Sample Recovery. Begin the cleanup procedure as soon as the 
probe is removed from the stack at the end of the sampling period. 
Seal the nozzle end of the sampling probe with PTFE tape or clean 
(e.g., toluene rinsed) aluminum foil.
    8.2.1 When the probe can be safely handled, wipe off all 
external particulate matter near the tip of the probe. Conduct a 
post-test leak check. Remove the probe from the train and close off 
both ends with PTFE tape or clean aluminum foil. Seal off the inlet 
to the train with PTFE tape, a ground glass cap, or clean aluminum 
foil.
    8.2.2 Transfer the probe and impinger assembly to the cleanup 
area. This method recommends cleaning and enclosing this area to 
minimize the chances of losing or contaminating the sample. To avoid 
sample contamination and unnecessary exposure to toxic chemicals, 
smoking or eating in the sample recovery area shall not be allowed.
    8.2.3 Inspect the train prior to and during disassembly. Note 
and record any abnormal conditions (e.g., broken filters, colored 
impinger liquid). Recover and prepare samples for shipping as 
follows in Sections 8.2.4 through 8.2.12 of this method.
    8.2.4 Container No. 1. Either seal the filter holder or 
carefully remove the filter from the filter holder and place it in 
its identified container. If it is necessary to remove the filter, 
use a pair of cleaned tweezers to handle the filter. If necessary, 
fold the filter such that the particulate cake is inside the fold. 
Carefully transfer to the container any particulate matter and 
filter fibers that adhere to the filter holder gasket by using a dry 
inert bristle brush and a sharp-edged blade. Seal the container and 
store cool (<=20 [deg]C, 68 [deg]F) for transport to the laboratory.
    8.2.5 Adsorbent Module Sample. Remove the module from the train, 
tightly cover both ends with fitting caps and PTFE tape, remove the 
foil, drain the recirculating water from the module, weigh and 
record the module weight, and label the adsorbent module. Moisture 
measurement in the field using the Method 23 train requires weighing 
the adsorbent module before sampling and after sampling as part of 
the sample recovery.
    8.2.6 Container No. 2. Quantitatively recover material deposited 
in the nozzle, the front half of the filter holder, and the cyclone, 
if used, by brushing while rinsing three times with acetone followed 
by three rinses with toluene. Collect all the rinses in Container 
No. 2.
    8.2.7 Rinse the back half of the filter holder three times with 
acetone followed by three rinses with toluene. Rinse the sample 
transfer line between the filter and the condenser three times with 
acetone followed by three rinses with toluene. If using a separate 
condenser and adsorbent module, rinse the condenser three times with 
acetone followed by three rinses with toluene. Collect all the 
rinses in Container No. 2 and mark the level of the liquid on the 
container.
    8.2.8 Moisture Weight. Weigh the adsorbent module, impingers, 
and silica gel impinger to within 0.5 g using the field 
balance and record the weights. This information is required to 
calculate the moisture content of the effluent gas. For PCDD/PCDF-
only measurements, discard the liquid after measuring and recording 
the weight.
    8.2.9 Container No. 3. You must save and analyze impinger water 
samples if PAH and/or PCB are the target compounds. Quantitatively 
recover impinger water samples for analysis if PAH and/or PCB are 
the target compounds by rinsing three times with acetone followed by 
three rinses with toluene. Collect impinger water and rinses in 
Container No. 3 and mark the level of the liquid on the container.
    8.2.10 Silica Gel. Note the color of the indicating silica gel 
to determine if it has been completely spent and report its 
condition on the field data sheet.
    8.2.11 Field Sample Handling, Preservation, Storage, and 
Transport. Store all field samples temporarily in cool (<=20 [deg]C, 
68 [deg]F) and dark conditions prior to transport to the laboratory. 
Ship samples cool (<=20 [deg]C, 68 [deg]F), shielded from 
ultraviolet light. In addition, follow the procedures in American 
Society for Testing and Materials (ASTM) D6911-15 (Guide for 
Packaging and Shipping Environmental Samples for Laboratory 
Analysis) for all samples, where appropriate. To avoid contamination 
of the samples, pay special attention to cleanliness during 
transport, field handling, sampling, recovery, and laboratory 
analysis, as well as during preparation of the adsorbent cartridges.
    8.2.12 Sample Custody. Proper procedures and documentation for 
sample chain of custody are critical to ensuring data integrity. 
Follow the chain of custody procedures in ASTM D4840-99(2018)e1 
(Standard Guide for Sample Chain-of-Custody Procedures) for all 
samples (including field samples and blanks).
    8.3 Sample Storage Conditions and Laboratory Hold Times.
    8.3.1 Table 23-10 of this method summarizes the sample storage 
conditions and laboratory hold times.
    8.3.2 Store sampling train rinses and filter samples in the dark 
at the storage conditions in Table 23-10 from the time the 
laboratory receives the samples until analysis.
    8.3.3 You may store adsorbent samples for PCDD/PCDF or PCB 
analysis prior to extraction in the dark at 6 [deg]C (43 [deg]F) or 
less for up to one year from the time the laboratory receives the 
samples.
    Note: The hold times listed in this method for adsorbent samples 
for PCDD/PCDF and PCB are recommendations as these compounds are 
very stable under the conditions listed in this section.
    8.3.4 Protect adsorbent samples destined for PAH analysis from 
ultraviolet light. You may store adsorbent samples for PAH analysis 
in the dark at 6 [deg]C (43 [deg]F) or less for up to 30 days from 
the time the laboratory receives the samples.
    8.3.5 Analyze PAH extracts within 40 days of extraction.
    8.3.6 You may store sample aliquots including archived extracts 
of PCDD/PCDF, PAH and/or PCB samples in the dark at -10 [deg]C (14 
[deg]F) or less for up to one year. Sample extracts must not be 
stored with pierced septa.
    Note: The hold times listed in this method for sample aliquots 
for PCDD/PCDF and PCB are recommendations as these compounds are 
very stable under the conditions listed in this section.

9.0 Quality Control

    Note: In recognition of advances that are occurring in sampling 
and analytical technology, and to allow the test team to overcome 
analyte sensitivity and matrix interferences, this method allows 
certain options to increase sample collection volume and to improve 
separations and the quality of the analysis results for target 
analytes. It is the laboratory's responsibility to establish the 
conditions for optimum sample extraction, cleanup, and concentration 
to meet the performance criteria in this method. However, you may 
not change the fundamental sampling and analysis techniques, 
isokinetic sampling with an adsorbent collection media followed by 
sample extraction, and HRMS detection and isotopic dilution 
quantification procedures. Section 13 of this method specifies the 
performance criteria to ensure that options employed for a sample 
set and analytes of interest are equal to or better than the

[[Page 16749]]

specificity of the techniques in this method. The minimum 
requirements of this method consist of the initial demonstration of 
capability (IDC) and ongoing QC requirements. The analysis team 
shall perform an IDC to demonstrate acceptable accuracy and 
precision with this method as described in Section 9.3. The ongoing 
QC includes performing CCVs and LMBs to evaluate an individual 
laboratory's performance against the criteria in this method. The 
method includes analysis of samples spiked with labeled compounds to 
evaluate and document data quality. Laboratory performance is 
compared to established performance criteria to determine if the 
results of analyses meet the performance characteristics and 
requirements of the method.
    9.1 Record and report data and information that will allow an 
independent reviewer to validate the determination of each target 
compound concentration. Record and report the data as described in 
Sections 9.1.1 through 9.1.7 of this method and performance criteria 
results required in Section 13 of this method.
    9.1.1 Sample numbers and other sample identifiers. Each sample 
must have a unique identifier.
    9.1.2 Field sample volume.
    9.1.3 Field sampling date.
    9.1.4 Extraction dates.
    9.1.5 Analysis dates and times.
    9.1.6 Analysis sequence/run chronology.
    9.1.7 Quantitation Reports.
    9.1.7.1 This method does not consider EMPC-flagged data to be 
zero concentrations. Calculate and report the EMPC concentrations.
    9.1.7.2 In determining compliance with any PCDD and PCDF 
standard developed using zero for values that are below the EDL of 
the method, including federal emission standards using Method 23 
promulgated under 40 CFR parts 60 and 63 prior to March 20, 2023, 
use zero for the determination of total and weighted concentrations 
when the target compound is not detected. For all other 
circumstances, unless otherwise specified in applicable regulations, 
permits, or other requirements, when a target compound is measured 
at or below EDL, use EDL as the concentration for calculating 
compliance.
    9.1.7.3 For each sample you must report EDLs, MDLs, LMBs and 
Field Train Proof Blank results and target compound analysis 
results.
    9.2 Isotopically Labeled Standard Recovery.
    9.2.1 Pre-sampling Adsorbent Standard and Pre-extraction Filter 
Recovery Standard Recoveries. Pre-sampling adsorbent standard and 
pre-extraction filter recovery standard recoveries must demonstrate 
on a per sample basis that recovery of the labeled standard achieved 
the requirements in Section 13 of this method. Recoveries below the 
acceptable range for the pre-sampling adsorbent standard may be an 
indication of breakthrough in the sampling train.
    9.2.1.1 If the pre-sampling adsorbent standard average percent 
recovery is below 70%, the sampling run is not valid, and the stack 
test must be repeated. As an alternative, you do not have to repeat 
the stack test for invalid analyses if the pre-sampling adsorbent 
standard average percent recovery is 25% or more and you divide the 
final results by the fraction of the pre-sampling adsorbent standard 
average percent recovery.
    9.2.1.2 If the percent recovery of all the pre-extraction filter 
recovery standard compounds is below 70%, you may reanalyze the 
sample. If the recovery is still below the limit, the filter 
sampling extraction is not valid, and you must repeat the stack or 
vent sampling and subsequent analysis.
    9.2.2 Pre-extraction Standard Recoveries. Pre-extraction 
standard recoveries must demonstrate on a per sample basis that 
recovery of the labeled standard achieved the requirements in 
Section 13.15 of this method. If the recovery criteria are not met, 
you may reanalyze the sample. If the recovery criteria are still not 
met, the sampling run is not valid, and the stack test must be 
repeated. Recoveries outside the acceptable range for pre-extraction 
standard are an indication that sample preparation procedures did 
not adequately address sample and or sample matrix processing to 
recover native target compounds.
    9.2.3 Pre-analysis Standard Response. Pre-analysis standard 
recoveries must demonstrate on a per sample basis that adequate 
labeled standard signal meets the requirements in Section 13.16 of 
this method. Add pre-analysis standard to every sample (including 
blanks, QC samples, and calibration solutions) in a known 
concentration. If the prepared samples do not meet the pre-analysis 
standard response criteria, you may reanalyze and/or prepare and 
analyze archive samples to attempt meeting requirements for the 
compounds that do not meet the pre-analysis standard response 
criteria. Poor sensitivity compared to initial calibration response 
may indicate injection errors or instrument drift.
    9.3 Initial Demonstration of Capability (IDC). The IDC must be 
successfully performed prior to analyzing field samples by meeting 
the QC requirements in Table 23-18. The IDC must be repeated if 
changes are made to analytical parameters not previously validated 
during the IDC. This may include, for example, changing the sample 
volume, selecting alternate quantitation ions, extending the 
calibration range, adding additional pre-analysis standard, or 
adding additional pre-extraction standard. The same calibration 
range used during the IDC must be used for the analysis of field 
samples.
    9.3.1 Perform initial calibration following the procedures in 
Section 10. The lowest calibration standard used to establish the 
initial calibration must not be less than three times the MDL. The 
initial calibration must meet performance criteria in Section 13.9.
    9.3.2 Lowest Calibration Concentration Confirmation. Establish a 
target concentration for the lowest calibration standard based on 
the intended use of the method. The lowest calibration concentration 
may be established by a laboratory or programmatic lowest 
quantitative reporting requirement. The laboratory calibration curve 
must be set at or below this level. Perform seven replicate analyses 
of a calibration sample prepared at proposed lowest calibration 
concentration. The replicate analyses of the lowest calibration 
concentrations standards must meet the criteria in Sections 13.9 and 
13.17.1.
    Note: Consider that establishing the lowest calibration 
concentration too low may cause repeated failure of ongoing QC 
requirements.
    9.3.3 Calculate Lowest Calibration Statistics. Calculate the 
mean and standard deviation for each analyte in these replicates 
(those used in Section 9.3.2). Determine the Half Range for the 
Prediction Interval of Results (HRPIR) using Equation 23-13. 
Calculate the Upper and Lower Limits for the Prediction Interval of 
Results (PIR) with Equations 23-14 and 23-15.
    9.3.4 Lowest Calibration Point Acceptance Criteria. The 
laboratory's ability to measure analyte concentrations down to the 
lowest calibration point is confirmed if the criteria presented in 
Section 13.17.1 are met. If these criteria are not met, the lowest 
calibration point as been set too low and must be confirmed at a 
higher concentration.
    9.3.5 Demonstration of Low System Background. Analyze an LMB 
after the highest standard in the calibration range. If an automated 
extraction system is used, an LMB must be extracted on each port. 
Performance criteria are presented in Section 13.1. Note: When using 
automated systems, the same systems must be used for samples and QC 
samples, such as blanks and resin checks.
    9.3.6 Initial Calibration Verification. A QCS must be analyzed 
during the IDC, and then following each initial calibration 
thereafter (at a minimum quarterly). A QCS is a mid-level standard 
prepared from a second source standard or prepared from a source of 
standards different from the source of calibration standards. The 
purpose of the QCS is to verify the integrity of the primary 
calibration standards. The acceptance criterion is presented in 
Section 13.11.
    9.3.7 MDL. Perform an MDL determination using a minimum of seven 
spiked combined filter/sorbent media samples, spiked within 2 to 10 
times of the expected MDL, and seven LMBs (combined filter/sorbent 
media) through all the steps of the method following the 
requirements in 40 CFR part 136 Appendix B. Confirm target compounds 
meet the qualitative identification criteria in Sections 13.12 and 
13.13. The criteria for the MDL determination are presented in 
Section 13.6.1 of this method.
    9.3.8 MDL Confirmation. Confirm newly determined MDLs by 
preparing a low-level spiked combined filter/sorbent media sample by 
spiking the sorbent with native target compounds at 1 to 5 times the 
MDL and pre-extraction standard at the concentration used to analyze 
field samples and analyze. The criterion for the MDL confirmation is 
presented in Section 13.6.1 of this method.
    9.3.9 Demonstration of Precision. Prepare, extract, and analyze 
seven replicate spiked samples in a valid Extraction Batch. Fortify 
the spiked samples near the midpoint of the initial calibration 
curve. The criterion is presented in Section 13.17.2 and Table 23-
18. Demonstration is repeated for failed compounds only.
    9.3.10 Demonstration of Accuracy. Using the same set of 
replicate data generated for

[[Page 16750]]

Section 9.3.9 of this method, calculate the average % recovery. The 
criterion is presented in Section 13.17.3 and Table 23-18. 
Demonstration is repeated for failed compounds only.
    9.4 LMBs. Evaluate background contamination from glassware, 
equipment, solvents, standards, and media used for sample batches 
using an LMB prepared and analyzed identically to the field samples, 
including the same labeled standards, media, sodium sulfate, glass 
wool, glassware, solvents, etc. An LMB must be extracted with every 
batch of samples. Analyze an LMB at least once during each 
analytical sequence or every 12 hours, whichever period is shorter. 
If multiple LMB are required for an analytical sequence, report the 
initial LMB associated with each 12 hour analysis period.
    9.5 EDL. Calculate the EDL using Equation 23-11 of this method.
    Note: If the applicable compliance limit is total dioxin or 
total furan, report the sum of the EDLs for all the target 
compounds. If the applicable rule limit is a TEQ value, report the 
sum of the EDLs for all target compounds multiplied by their 
corresponding compound specific TEF.
    9.6 Field Train Proof Blank Assessment. Conduct at least one 
field train proof blank for each test series at a single facility. A 
field train proof blank is used to evaluate equipment preparation 
and potential contamination during sample recovery and consists of a 
fully assembled train at the sampling site. Prepare and assemble the 
field train proof blank train in a manner identical to that 
described in Sections 8.1.3 and 8.1.4 of this method using glassware 
from the same preparation batch as the field samples. The field 
train proof blank train must remain assembled for the same average 
amount of time samples are collected. Recover the field train proof 
blank train as described in Section 8.2 of this method. Follow all 
subsequent steps for field train proof blank train sample 
preparation and analysis used for field samples including data 
reporting. Section 13.1 of this method describes the criteria for 
the field train proof blank.

10.0 Calibration and Standardization

    10.1 Sampling System. Same as Sections 6.1 and 10.1 through 10.7 
of Method 5 of Appendix A-3 to 40 CFR part 60.
    10.2 HRGC/HRMS System.
    10.2.1 Mass Resolution. Tune the HRMS instrument to a resolving 
power of at least 10,000 at 10% percent of the peak height or 25,000 
at 50% percent of the peak height. The resolving power for PAH and 
PCB analysis may be 8,000 at 10% of the peak height or 15,000 at 50% 
of the peak height. Assess the resolution at three exact m/z's 
representing the low-, mid-, and high-m/z range of the masses used 
to measure the target compound class. You may use peak matching and 
the chosen perfluoro-kerosene (PFK) or perfluorotributylamine (FC43) 
reference peak to verify that the exact mass is within 5 ppm of the 
required value.
    10.2.2 Initial Calibration. Calibrate the HRGC/HRMS system using 
a minimum of five concentrations over a range that brackets expected 
field sample concentrations and the concentration of isotopically 
labeled standards in spiked samples. Tables 23-11, 23-12, and/or 23-
13 of this method show the calibration concentrations recommended by 
this method, as applicable to the target compound classes. Determine 
the initial relative response factors for the target compounds and 
isotopically labeled standards using the initial calibration. 
Criteria for the initial calibration is in Section 13.9 of this 
method.
    10.2.2.1 Lock-Mass Ions. Tables 23-4, 23-5, and 23-6 of this 
method present the recommended mass spectrometer lock-mass ions for 
PCDD/PCDF, PAH, and PCB, respectively. The reference compounds PFK 
or FC43 have ions that may be selected as your lock-mass and QC 
check ions. Monitor the QC check ions specified in these tables to 
verify instrument stability during the analysis (see Section 13.8 
for performance criteria). Additional cleanup of the sample extract 
(or archive extract) and reanalysis is necessary for failure to 
maintain the lock-mass during analysis.
    10.2.2.2 The relative standard deviation (RSD) for the mean 
calibration relative response factor from each of the unlabeled 
analytes and isotopically labeled compounds used in an analysis must 
be less than or equal to the values in Table 23-14 of this method.
    10.2.2.3 The signal-to-noise (S/N) ratio for the GC/MS signal 
present in every selected ion current profile must be greater than 
or equal to 10 in all concentrations of calibration standards for 
unlabeled targets and isotopically labeled standards. The ion 
abundance ratios must be within the control limits in Table 23-15 of 
this method.
    Note: An interference with PFK m/z 223.9872 may preclude meeting 
10:1 S/N for the DiCB congeners at the optional Cal 1 level (Table 
23-11). If this interference occurs, 10:1 S/N must be met at the Cal 
2 level.
    10.2.3 Continuing Calibration Verification.
    10.2.3.1 Prepare the CCV standard at the same time as the batch 
of field samples using the same labeled standards. Prepare CCV 
standards at mid-level of the calibration (C3 level from Tables 23-
11, 23-12, or 23-13 of this method). Inject a CCV standard, for the 
target compound class, at least once every 12 hours during an 
analysis sequence. Calculate the RRF for each compound and compare 
each RRF to the corresponding mean RRF obtained during the initial 
calibration. The RRF for each native compound measured in a CCV must 
not deviate from the initial calibration RRF by more than the limits 
shown in Table 23-14.
    10.2.3.2 The ion abundance ratios must be within the allowable 
control limits shown in Table 23-15 of this method.
    10.2.3.3 The S/N ratio for the GC/MS signal present in every 
selected ion current profile must be greater than or equal to 10.
    10.2.3.4 Repeat the initial calibration when there is a failure 
to meet the requirements for acceptable CCV standard analysis.
    10.2.3.5 Column Separation Check. Use the results from a CCV to 
verify and document the resolution required in Section 13.2, 13.3, 
or 13.4 of this method for the target compound classes analyzed with 
this method. If target compounds are not sufficiently resolved to 
meet the requirement, an analysis on a confirmation column is 
recommended (see Section 13.5 of this method).
    10.2.3.6 If you use a confirmation column, perform the 
resolution check in Section 10.2.3.5 of this method to document the 
required resolution on the confirmation column. See Section 13.5 of 
this method on confirmation columns, if needed.

11.0 Analysis Procedure

    11.1 Sample Extraction and Concentration. The sample extraction 
procedures in this method are the same for PCDD, PCDF, PCB and PAH 
targets. Figure 23-4 provides a flow chart showing sample container 
combination and extraction steps. Do not allow samples and extracts 
destined for PAH or PCB analysis to concentrate to dryness because 
the lower molecular weight PAH and the mono- through tri-
chlorobiphenyls may be totally or partially lost. Note: Rotary 
evaporation is applicable when analyzing for PCDD/PCDF only. Snyder 
column apparatus is recommended when analyzing for PAH and PCB.
    11.1.1 Optional Soxhlet Precleaning. Place an extraction thimble 
(see Section 6.3.3.3 of this method) and a plug of glass wool into 
the Soxhlet apparatus equipped with a Dean-Stark trap, charge the 
apparatus with toluene, and reflux for a minimum of 3 hours. Remove 
the toluene and discard it. Remove the extraction thimble from the 
extraction system and place it in a glass beaker to catch the 
solvent rinses from sample transfer to the extraction thimble. 
Retain the clean glass wool plug. Alternatively, confirm that the 
LMB for associated reagents, materials, and media meets the 
performance requirements in Section 13.1 of this method.
    11.1.2 Container No. 1 (Filter) Preparation. Spike the filter 
with the appropriate pre-extraction filter recovery standard to 
result in the final sample extract concentrations shown in Tables 
23-7, 23-8, and 23-9 of this method taking care that all spike 
liquid is distributed on the filter. Allow the filter to dry enough 
to prevent overspill, then transfer the filter and the contents of 
Container No. 1 directly to the glass extraction thimble in the 
glass solvent rinse catch beaker so that the filter will be 
completely immersed in the solvent during extraction.
    11.1.3 Adsorbent Module. Spike the adsorbent with the 
appropriate pre-extraction standard to result in the final sample 
extract concentrations shown in Tables 23-7, 23-8, and 23-9 of this 
method, as applicable, spiked into the adsorbent, not on top of the 
adsorbent. Transfer the adsorbent material to the glass extraction 
thimble in the glass solvent rinse catch beaker. Rinse the module 
into the thimble in the beaker with the contents of Container No. 1. 
Alternatively, suspend the adsorbent module directly over the 
extraction thimble in a beaker, then, using a wash bottle containing 
methanol, flush the XAD-2 into the thimble onto the filter. 
Thoroughly rinse the interior of the glass module that contained the 
XAD-2 with toluene.

[[Page 16751]]

    11.1.4 Container No. 2 (Acetone and Toluene Rinses). Concentrate 
the sample to a volume of no less than 5 mL. Concentrate samples 
containing toluene using a heating mantle and three-ball Snyder 
column or a rotary evaporator. Rinse sample Container No. 2 three 
times with small portions of toluene and add these to the 
concentrated solution and concentrate further to no less than 5 mL. 
This residue contains particulate matter removed in the rinse of the 
train probe and nozzle. Rinse the concentrated material from 
Container No. 2 into the glass extraction thimble containing the 
filter and the XAD-2 resin.
    11.1.5 Transfer the solvent contained in the glass solvent rinse 
catch beaker to the extraction apparatus solvent reservoir. Rinse 
the beaker into the Soxhlet extraction apparatus solvent reservoir 
three times with small portions of toluene.
    11.1.6 Container No. 3 (Impinger Water and Rinses). For PAH and 
PCB analysis, transfer the contents of Container No. 3 to a 
separatory funnel. Adjust to pH 2 with 6 N sulfuric acid, if 
necessary. Rinse the sample container with three successive 10-mL 
aliquots of the toluene and add these rinses to the separatory 
funnel. Extract the sample by vigorously shaking the separatory 
funnel for 5 minutes. After complete separation of the phases, 
remove the solvent and filter it through a bed of precleaned, dry 
sodium sulfate into the Soxhlet extraction apparatus solvent 
reservoir. Repeat the extraction step two additional times. Adjust 
the pH to 11 with 6 N sodium hydroxide, re-extract the impinger 
water and rinses, and filter it through a bed of precleaned, dry 
sodium sulfate into the Soxhlet extraction apparatus solvent 
reservoir. Rinse the sodium sulfate into the extraction apparatus 
solvent reservoir with fresh solvent and discard the sodium sulfate.
    11.1.7 Add the appropriate pre-extraction standard for the 
target compound classes (to result in the final sample extract 
concentrations shown in Tables 23-7, 23-8, and 23-9 of this method) 
to the extraction thimble containing the combined filter and 
adsorbent sample fractions. Cover the contents of the extraction 
thimble with the cleaned glass wool plug to prevent the XAD-2 resin 
from splashing into the solvent reservoir of the extractor. Place 
the extraction thimble into the Soxhlet extraction apparatus.
    11.1.8 Pour additional toluene to fill the solvent reservoir to 
approximately two-thirds capacity. Add PTFE boiling chips and 
assemble the apparatus.
    11.1.9 Adjust the heat source to cause the extractor to cycle 
approximately three times per hour. Extract the sample for 
sufficient time to meet the pre-extraction standard recovery 
performance criteria in Section 13.15 of this method. The solvent 
should cycle completely through the system a minimum of 48 times.
    11.2 Sample Aliquots for Cleanup and Analysis.
    11.2.1 After extraction, allow the Soxhlet apparatus to cool.
    11.2.2 Initial Extract Concentration. You may perform an initial 
concentration of the sample extract using the techniques (e.g., 
Kuderna Danish, rotary evaporation, nitrogen blowdown) found to 
recover the pre-extraction standard sufficient to meet the 
performance criteria in Section 13.15 of this method. Concentrate 
initial extracts in toluene using a heating mantle and three-ball 
Snyder column or a rotary evaporator. Concentrate the field train 
proof blank and LMB samples in the same manner as samples.
    Note: To meet isotopically labeled standard recoveries for low 
molecular weight PCB and PAH, do not evaporate samples to dryness 
and do not use a rotary evaporator to concentrate extracts.
    11.2.3 Allow the sample extract to cool. You should use a 
minimum of one half of the sample extract for PCDD/PCDF analysis. 
You may archive the remaining sample extract or further split the 
sample extract for PCB and/or PAH analysis and archive.
    Note: If using amount other than half the sample extract, adjust 
the spiking amount of the labeled standards accordingly.
    11.2.4 If necessary, further concentrate the sample extract for 
cleanup and analysis using concentration techniques (e.g., Kuderna 
Danish, rotary evaporation, nitrogen blowdown) found to recover the 
pre-extraction standard sufficient to meet the performance criteria 
in Section 13 of this method.
    11.3 Sample Cleanup and Fractionation. You may process a 
separate aliquot/split of the sample extract for each of the 
compound classes analyzed by this method. Sample cleanup for each 
compound class may include techniques in addition to column 
chromatography such as acid/base back-extraction, Gel Permeation 
Chromatography, or high-performance liquid chromatography (HPLC) to 
isolate target compounds from interferences. This section includes a 
description of column chromatography shown to meet the performance 
criteria in Sections 9.2 and 13 of this method. The following sample 
cleanup and fractionation procedures are recommended but not 
required. You may modify cleanup column dimensions to meet manual or 
automated cleanup procedures as technology changes and improves. You 
must evaluate the cleanup and fractionation procedures used to 
confirm acceptable recovery of isotopically labeled standards. The 
alternative procedures must provide sufficient cleanup to meet 
method identification criteria (Section 11.4.3.4 of this method) and 
recovery criteria (Section 9.2 of this method). Section 13 of this 
method summarizes the method performance requirements.
    Note: Recommendations in this section provide a cleanup approach 
that may allow multiple compound class measurement from a single 
aliquot of the original sample extract. Typically, Florisil[supreg] 
and alumina are used to separate PAH and PCDPE from PCDD and PCDF 
target compounds. Use acid, neutral, and basic silica gel and 
cleanup procedures to remove nonpolar and polar interferences from 
samples destined for PCB and PCDD/PCDF analysis. Use 
Carbopack[supreg]/Celite[supreg] (or other equivalent carbon-based 
column material) to remove other nonpolar interferences.
    11.3.1 PAH and PCDPE Fractionation and Cleanup. You may use a 
Florisil[supreg] column to remove PAH and PCDPE from the sample 
extract. You may also fractionate sample extracts using 
Florisil[supreg] as the first cleanup step to separate PAH for 
analysis.
    Note: High concentrations of PAH may interfere, leading to 
failure of performance criteria for PCDD/PCDF or PCB analysis.
    11.3.1.1 Pack a 6-mm ID chromatographic column or equivalent 
diameter glass pipet with a glass wool plug followed by 
approximately 1.5 g (approximately 2 mL) of activated 
Florisil[supreg]. Add approximately 1 cm (approximately 1 mL) of 
anhydrous sodium sulfate followed by a glass wool plug to the head 
of the column. Pre-elute the column with 10 mL of methylene chloride 
followed by 10 mL of hexane and discard the eluate.
    11.3.1.2 When the solvent is within 1 mm of the packing, 
transfer the concentrated extract (up to 5 mL) to the top of the 
Florisil[supreg] column, rinse the sample container twice with 1 to 
2 mL of hexane, adding each rinse to the column, and elute the 
column with 35 mL of 5% dichloromethane in hexane. This fraction 
(Fraction 1) should contain target PCB, and selected hydrocarbons 
and chlorinated monoaromatic compounds.
    11.3.1.3 Elute the column with 35 mL of 15% of dichloromethane 
in hexane and collect the eluate. This fraction (Fraction 2) should 
contain target PCDD/PCDF compounds.
    11.3.1.4 Elute the column with 50 mL of 50% dichloromethane in 
hexane. The fraction (Fraction 3) should contain target PAH.
    11.3.1.5 If necessary to remove any remaining polar organic 
compounds, elute the column with 70 mL of 15% acetone in hexane.
    11.3.2 PCDD/PCDF and PCB Fractionation and Cleanup. You may 
remove PAH from the original aliquot of sample extract used for 
PCDD/PCDF analysis as described in Section 11.3.1 of this method. 
Design the column cleanup chromatography for PCDD/PCDF and PCB such 
that two consecutive fractions are collected (one with PCDD/PCDF and 
one with PCB) without impacting the detection limits. Depending on 
the source and sample matrix of the original sample, one or more of 
the following column cleanup approaches may be necessary to further 
remove polyhalogenated diphenyl ethers. You may use any number of 
permutations found in the referenced literature for this cleanup if 
the pre-extraction standard recoveries from field and LMB samples 
meet the associated performance criteria in Section 13 of this 
method. Alternatively, you may use an automated cleanup approach 
that meets the labeled spike recovery requirements in Section 13 of 
this method.
    11.3.2.1 Silica Gel Column Chromatography. Pack one end of a 
glass column, approximately 20 mm ID x 230 mm long, with glass wool. 
Add in sequence to the glass column, 1 g of silica gel, 2 g of 
sodium hydroxide impregnated silica gel, 1 g of silica gel, 4 g of 
acid-modified silica gel, 1 g of silica gel, and 1 cm layer of 
anhydrous sodium sulfate. Pre-elute the column with 30 to 50 mL of 
hexane leaving a small quantity of hexane above the sodium sulfate 
layer. Discard the pre-elution hexane. Add the

[[Page 16752]]

sample extract, dissolved in 5 mL of hexane to the head of the 
column. Allow the sample to flow into the column leaving a small 
quantity of hexane above the sodium sulfate layer. Rinse the extract 
container with two additional 5-mL rinses of hexane and apply each 
rinse to the column separately as the previous addition elutes. 
Elute the column with an additional 90 mL of hexane and retain the 
entire eluate. Concentrate this solution to a volume of about 1 mL 
using the nitrogen evaporative concentrator (see Section 6.3.5 of 
this method).
    11.3.2.2 Silver Nitrate Silica Gel Column Chromatography. Pack a 
column (6 mm ID, 150 mm in length) sequentially with 1 g of silica 
gel and 1 g of 10% silver nitrate silica gel followed by a layer of 
about 10 mm of sodium sulfate (anhydrous). Wash the column 
sufficiently with hexane, elute until the liquid level reaches to 
the upper end of the column, and then transfer the concentrated 
sample (about 5 mL). Rinse the container several times with a small 
amount of hexane, elute with 200 mL of hexane at a flow rate about 
2.5 mL/min (approximately one drop per second) to elute PCDD/PCDF.
    11.3.2.3 Multi-layer Silica Gel Column Chromatography. You may 
use a multi-layer silica gel column in place of separate silica 
columns. Pack a column of 20 mm ID and 300 mm in length sequentially 
by the dry pack method with 0.9 g of silica gel, 3.0 g of 2% 
potassium hydroxide silica gel, 0.9 g of silica gel, 4.5 g of 44% 
sulfuric acid silica gel, 6.0 g of 22% sulfuric acid silica gel, 0.9 
g of silica gel, 3.0 g of 10% silver nitrate silica gel, 2.0 g of 
silica gel and 6.0 g of sodium sulfate (anhydrous). Wash the column 
sufficiently with hexane, elute until the liquid level reaches to 
the upper end of the column, and then load the sample solution. 
Rinse the container several times with a small amount of hexane, 
elute with 150-200 mL of hexane at a flow rate about 2.5 mL/min 
(approximately one drop per second) to elute PCDD/PCDF.
    11.3.2.4 Basic Alumina Column Chromatography. Pack a column (20 
mm ID, 300 mm in length) with approximately 6 to 12 g of basic 
alumina. Pre-elute the column with 50 to 100 mL of hexane. Transfer 
the concentrated extract from the previous column cleanup to the top 
of the basic alumina column. Allow the sample to flow into the 
column leaving a small quantity of solvent above the top of the bed. 
Rinse the extract container with two additional 1-mL rinses of 
hexane and apply each rinse to the column separately as the previous 
addition elutes. Elute the column with 100 mL hexane to remove the 
interferences. Elute the PCDD/PCDF from the column with 20 to 40 mL 
of 50% methylene chloride in hexane. The ratio of methylene chloride 
to hexane may vary depending on the activity of the alumina used in 
the column preparation. Do not let the head of the column go without 
solvent. The first 100 mL hexane eluate is not used for subsequent 
PCDD/PCDF analysis. The eluate is concentrated to approximately 0.5 
mL using the nitrogen evaporative concentrator.
    11.3.2.5 Carbopack[supreg] C/Celite[supreg] 545 Column or 
Equivalent. Cut both ends from a 10 mL disposable Pasteur pipette 
(see Section 6.4.1 of this method) to produce a 10 cm column. Fire-
polish both ends and flare both ends if desired. Insert a glass wool 
plug at one end and pack the column with 0.55 g of 
Carbopack[supreg]/Celite[supreg] (see Section 7.8.9.4 of this 
method) to form an adsorbent bed approximately 2 cm long. Insert a 
glass wool plug on top of the bed to hold the adsorbent in place. 
Pre-elute the column with 5 mL of toluene followed by 2 mL of 
methylene chloride:methanol:toluene (15:4:1 volume/volume (v/v)), 1 
mL of methylene chloride:cyclohexane (1:1 v/v), and 5 mL of hexane. 
If the flow rate of eluate exceeds 0.5 mL/minute, discard the 
column. Do not let the head of the column go without solvent. Add 
the sample extract to the column. Rinse the sample container twice 
with 1 mL portions of hexane and apply separately to the column. 
Apply 2 mL of hexane to the head of the column to complete the 
transfer. Elute the interfering compounds with two 3 mL portions of 
hexane, 2 mL of methylene chloride:cyclohexane (1:1 v/v), and 2 mL 
of methylene chloride:methanol:toluene (15:4:1 v/v). Discard the 
eluate. Invert the column and elute the PCDD/PCDF with 20 mL of 
toluene. If carbon particles are present in the eluate, filter 
through glass-fiber filter paper. Concentrate the eluate to 
approximately 0.5 mL using the nitrogen evaporative concentrator for 
further cleanup or analysis by HRGC/HRMS.
    11.4 PCDD, PCDF, PCB and PAH Analysis.
    11.4.1 Analyze the sample extract with an HRGC/HRMS using the 
instrumental parameters in Sections 11.4.2 and 11.4.3 of this 
method.
    11.4.1.1 Immediately prior to analysis, add an aliquot 
(typically 20 microliters ([micro]l)) of the pre-analysis standard 
to result in the final sample extract concentrations in Tables 23-7, 
23-8, and 23-9 of this method to each sample as appropriate for the 
compounds you are measuring by this method.
    11.4.1.2 Inject an aliquot of the sample extract into the GC, 
typically 1 [micro]l. You may perform separate analyses using 
different GC columns for each of the target compound classes. 
Perform calibration and sample analysis for each target compound 
class using the same instrument operating conditions including 
injection volume.
    11.4.1.2.1 If target compounds are not resolved sufficiently 
from other target compounds or interferences in the sample to meet 
the requirements in Section 10.2.3.5 or 10.2.3.6 of this method, as 
applicable to the compound class being analyzed, or as otherwise 
specified in an applicable regulation, permit, or other requirement, 
analyze sample (or another aliquot of the sample) using an 
alternative column that provides elution order to uniquely quantify 
the target compounds subject to interference on the first GC column.
    11.4.1.2.2 You may use column systems other than those 
recommended in this method provided the analyst is able to 
demonstrate, using calibration and CCVs, that the alternative column 
system is able to meet the applicable specifications of Section 
10.2.3.5 or 10.2.3.6 of this method.
    11.4.2 Example Gas Chromatograph Operating Conditions.
    11.4.2.1 Injector. Configured for capillary column, splitless, 
250 [deg]C (482 [deg]F).
    11.4.2.2 Carrier Gas. Helium, 1 to 2 mL/min.
    11.4.2.3 Oven. Optimize the GC temperature program to achieve 
the required separation and target compound recovery for the GC 
column in use. Table 23-16 of this method presents the typical 
conditions for a DB5-MS column.
    11.4.3 High-Resolution Mass Spectrometer.
    11.4.3.1 Ionization Mode. Electron ionization.
    11.4.3.2 Source Temperature. Maintain the source temperature in 
the range of 250 to 300 [deg]C (482 to 572 [deg]F).
    11.4.3.3 Ion Monitoring Mode. Tables 23-4, 23-5, and 23-6 of 
this method summarize the various ions to be monitored for PCDD/
PCDF, PAH, and PCB, respectively.
    11.4.3.4 Identification Criteria for Target Compounds. Use the 
following identification criteria for the characterization of target 
compounds in this method. The available native and isotopically 
labeled standards allow the unique identification of all PCDD/PCDF, 
PAH, and selected PCB congeners analyzed in this method. Also see 
Sections 13.12 and 13.13 of this method for identification criteria 
for PCDD/PCDF/PCB and PAH target compounds, respectively.
    11.4.3.4.1 For PCDD/PCDF and PCB, Table 23-15 of this method 
provides acceptance limits for the integrated ion abundance ratio of 
primary and secondary target compound ions. When the ion abundance 
ratio for a target analyte is outside the performance criteria, you 
may reanalyze samples on an alternative GC column to resolve 
chemical interferences, tune the mass spectrometer to operate at a 
higher mass resolution to discriminate against the interference(s), 
and/or further cleanup an archived sample to remove the 
interference(s). Report analysis results as an EMPC when a response 
meets identification criteria except the ion abundance ratio 
criteria or when a peak representing a PCDPE has been detected at 
the retention time. This method does not consider EMPC-flagged data 
to be zero concentrations.
    Note: Some EMPCs may be caused by poor ion statistics when the 
concentration of the target compound is at or near the DL.
    11.4.3.4.2 The retention time for the analytes must be within 3 
seconds of the corresponding labeled pre-extraction standard.
    11.4.3.4.3 The signals for the two exact masses in Tables 23-4 
and 23-6 of this method for PCDD/PCDF and PCB, respectively, must be 
present and must reach their maximum response within two seconds of 
each other.
    11.4.3.4.4 Identify and quantify specific target compounds or 
isomers that do not have corresponding pre-extraction standard 
compounds by comparing to the pre-extraction standard of the same 
compound class with the nearest retention time to target compound.
    11.4.3.4.5 For the identification of specific PCB congeners, the 
retention time of the native congener must be within 0.006 relative 
retention time (RRT) units of the pre-extraction standard.

[[Page 16753]]

    11.4.3.4.6 For qualitative identification, the S/N ratio for the 
GC signal present in every selected ion current profile for native 
compound response must be greater than or equal to 2.5.
    11.4.3.4.7 The separation of target compounds, including 
2,3,7,8-TeCDD and 2,3,7,8-TeCDF, must satisfy the separation 
criteria in Section 10.2.3.5 of this method and all the 
identification criteria specified in Sections 11.4.3.4.1 through 
11.4.3.4.6 of this method. See Section 13.5 of this method on 
confirmation columns, if needed.
    11.4.3.4.8 Chlorodiphenyl Ether Interference. If chromatographic 
peaks are detected at the retention time of any PCDF in any of the 
m/z channels used to monitor PCDPE, there is evidence of a positive 
interference and you may opt to flag data noting the interference 
and keep the value to calculate PCDF concentration as EMPC or 
reanalyze to remove or shift the interference. This method 
recommends alumina (see Section 11.3.2.4 of this method) and 
Florisil[supreg] (see Section 11.3.1 of this method) liquid column 
chromatography packing materials for removal of PCDPE during sample 
cleanup.
    11.4.3.4.9 The recommended MS lock-mass ions are specified in 
Tables 23-4, 23-5, and 23-6 of this method for PCDD/PCDF, PAH, and 
PCB, respectively. Monitor the QC check ions to verify instrument 
stability during the analysis. If the QC check ion signal varies by 
more than 25% from the average response across the run, flag results 
for all isomers at corresponding retention time as the lock-mass 
ions or QC check ions. You have the option to reanalyze after 
additional cleanup on the sample (or an archived portion of the 
sample if the archive is available), or after dilution of the 
sample. Alternately, determine through additional quality review 
whether the target analyte and its corresponding isotopically 
labeled standard are equally affected by the change in lock-mass 
ions and/or QC check ions. When you reanalyze a sample, ensure all 
concentration calculations are reported from the reanalyzed sample.
    11.4.3.4.10 For the identification of PAH, the RRT of each 
native to its labeled compound must be within 0.006 RRT units 
compared to the corresponding RRTs in the continuing calibration. 
The signals for the characteristic ion listed in Table 23-5 of this 
method must be present.
    11.4.3.5 Quantitation. Measure the response of each native 
target compound and the corresponding pre-extraction standard. Using 
the CCV RRF, calculate the mass of each target compound, using 
equations in Section 12.7 of this method. Use the pre-extraction 
standard to correct the native target compounds result for 
variations in performance of the extraction, cleanup, and 
concentration steps of the analysis. Recovery of pre-extraction 
standard must meet the minimum specifications in Section 9.2. of 
this method to ensure that the method performance and reliability 
have not been compromised by unacceptable losses during sample 
processing. Table 23-17 of this method shows the assignments for 
pre-extraction standard compounds for use in calculating the 
response factor and the concentrations of PCB. Recoveries of all 
labeled standard compounds must meet the minimum recovery 
specifications in Section 13 of this method. Note: Unacceptably low 
recoveries can be an indication of a sample processing step that 
caused the low recoveries, such as spiking errors.
    11.4.3.5.1 Use Equation 23-7 to calculate the amount of each 
target compound or group in the sample.
    11.4.3.5.2 Use Equation 23-8 to calculate the concentration per 
dscm of each target compound or group in the gas.
    11.4.3.5.3 Quantify native PCDD and PCDF in its homologous 
series using the corresponding native and pre-extraction standard 
response in its homologous series. For example, use 
\13\C12-2,3,7,8-TeCDD to calculate the concentrations of 
all other tetra chlorinated isomers.
    11.4.3.5.4 As an option or as required or specified in 
applicable regulations, permits, or other requirements, you may 
quantify any or all other PCB congeners as resolved or coeluting 
combinations using the RRF of the nearest eluting native target PCB 
in the same homolog group and the pre-extraction standard assigned 
in Appendix A to this method.
    11.4.3.5.5 As an option or as required or specified in 
applicable regulations, permits, or other requirements, report the 
total concentration of congeners at a given level of chlorination 
(homolog; i.e., total TrCB, total PeCB, total HxCB, etc.) by summing 
the concentrations of all congeners identified in the retention time 
window for the homologs as assigned in Appendix A to this method.
    11.4.3.5.6 As an option or if required in an applicable 
regulation, permit or other requirement, total PCB may be reported 
by summing all congeners identified at all window-defining congeners 
(WDCs) as assigned in Appendix A to this method.

12.0 Data Analysis and Calculations

    Note: Same as Section 12 of Method 5 of Appendix A-3 to 40 CFR 
part 60, with the following additions.
    12.1 Nomenclature.

A1n = Integrated ion current of the primary m/z values 
for the target native compound.
A1pe = Integrated ion current of the primary m/z values 
for the pre-extraction standard compound (assigned in Tables 23-4, 
23-5, and 23-6 of this method).
A1pa = Integrated ion current of the primary m/z values 
for the pre-analysis standard compound.
A2n = Integrated ion current of the secondary m/z values 
for the target native compound. For PAH A2n = 0.
A2pe = Integrated ion current of the secondary m/z's for 
the pre-extraction standard compound. For PAH A2l = 0.
A2pa = Integrated ion current of the secondary m/z values 
for the pre-analysis standard compound.
Ci = Mass of compound i in the sample, pg.
Cidscm = Concentration of target native compound i in the 
emission gas, pg/dscm.
CT = Total mass of target compounds in the sample, pg/
sample.
dscm = Dry standard cubic meters of gas volume sample measured by 
the dry gas meter, corrected to standard conditions.
Hai = Summed heights of the noise for each quantitation 
ion for native target compounds.
Hci = Summed heights of the noise at the primary and 
secondary m/z's of the pre-extraction standard i.
LPIR = Lower limit for the prediction interval of 
results.
n = Number of values.
PD = Percent Difference in the RRF of the continuing calibration 
verification compared to the average RRF of the initial calibration, 
%.
Qn = Quantity of the target native compound, pg.
Qpe = Quantity of the pre-extraction standard, pg.
Qpa = Quantity of the pre-analysis standard, pg.
R = Recovery of pre-sampling adsorbent standard and pre-extraction 
filter recovery standard, %.
Rpe = Recovery of pre-extraction standard, %.
RRFi = Relative response factor of a native target 
compound or pre-sampling adsorbent standard and pre-extraction 
filter recovery standard at calibration level i.
RRFpe = Relative response factor of a pre-extraction 
standard compound.
RRFccv = Relative response factor of a native target 
compound or pre-sampling adsorbent standard and pre-extraction 
filter recovery standard in the continuing calibration verification.
RSD = Relative standard deviation, in this case, of RRFs over the 
calibration levels, %.
SD = Standard deviation.
SDRRF = Standard deviation of initial calibration RRFs.
UPIR = Upper limit for the prediction interval of 
results.
WDC = Window-defining congener representing an isotopically labeled 
compound that defines the beginning or end of a retention time 
window bracketing a target homolog.

    12.2 Individual Compound RRF for Each Calibration Level i. 
Equation 23-1 for the response factor of each target native compound 
relative to its labeled pre-extraction standard analog includes the 
integrated ion current of both the primary and secondary m/z values 
for each compound in the calibration standard, excluding PAH, which 
use only primary m/z values. Use Equation 23-2 to calculate the RRF 
for pre-extraction standard.

[[Page 16754]]

[GRAPHIC] [TIFF OMITTED] TR20MR23.006

    Note: the units for Qpe and Qn in Eq. 23-1 
and the units for Qpa and Qpe in Equation 23-2 
must be the same.
    12.3 Average RRF for Each Compound Over the Minimum of Five 
Calibration Levels.
[GRAPHIC] [TIFF OMITTED] TR20MR23.007

    12.4 Percent RSD of the RRFs for a Compound Over the Calibration 
Levels. The requirement for the initial calibration RSD is in 
Section 13.9 and Table 23-14 of this method.
[GRAPHIC] [TIFF OMITTED] TR20MR23.008

    12.5 Standard Deviation of the RRFs for a Compound Over the 
Calibration Levels.
[GRAPHIC] [TIFF OMITTED] TR20MR23.009

    12.6 Percent Difference of the RRF of the Continuing Calibration 
Verification Compared to the Average RRF from the Initial 
Calibration for Each Target Compound. Use Equation 23-1 to calculate 
the RRF for the continuing calibration verification for comparison 
to the average RRF from the initial calibration. The requirement for 
the continuing calibration verification % difference is in Section 
13.10 and Table 23-14 of this method.
[GRAPHIC] [TIFF OMITTED] TR20MR23.010

    12.7 Amount of Individual Target Compound i in the Sample by 
Isotope Dilution (pg). This equation corrects for the target native 
compound recovery based on its labeled pre-extraction standard 
analog. This equation is also used to calculate the amount of pre-
sampling adsorbent standard and pre-extraction filter recovery 
standard recovered.
[GRAPHIC] [TIFF OMITTED] TR20MR23.011

    Note: For the quantitation of the pre-sampling adsorbent 
standard and the pre-extraction filter recovery standard, use a 
corresponding pre-extraction isomer (or homolog) with the closest 
retention time.
    12.8 Concentration of the Individual Target Compound or Group i 
in the Emission Gas (pg/dscm). The total concentration of a target 
compound group in the sample can be calculated by substituting 
CT from Eq. 23-12 for Ci in Equation 23-8.
[GRAPHIC] [TIFF OMITTED] TR20MR23.012

    12.9 Recovery of Labeled Compound Standards. Use Equation 23-9 
to determine the recovery of pre-sampling adsorbent standard and the 
pre-extraction filter recovery standard. Use Equation 23-10 to 
determine the recovery of the pre-extraction standard. The recovery 
performance criteria for these standards are in Sections 13.14, 
13.15, and 13.16 of this method.

[[Page 16755]]

[GRAPHIC] [TIFF OMITTED] TR20MR23.013

[GRAPHIC] [TIFF OMITTED] TR20MR23.014

    Note: Recovery may be calculated based on mass instead of 
concentration, as needed.
    Note: Rpe must be corrected for the fraction of the 
original sample extract used for analysis. (e.g., if half of the 
extract is used for analysis of the target class, Rpe 
must be multiplied by a factor of 2).
    12.10 Estimated Detection Limit (EDL).
    [GRAPHIC] [TIFF OMITTED] TR20MR23.015
    
    12.11 Total Target Compound Mass.
    [GRAPHIC] [TIFF OMITTED] TR20MR23.016
    
    Note: Unless otherwise specified in applicable regulations, 
permits or other requirements, count any target compounds reported 
as non-detected as EDL when calculating the concentration of target 
compounds in the sample.
    12.12 Upper and Lower Limits for the Prediction Interval of 
Results (PIR)
    Half Range (HR) for the Predication Interval of Results
    [GRAPHIC] [TIFF OMITTED] TR20MR23.017
    
    Note: 3.963 is a constant value for seven replicates.
    Upper and Lower Limits for the Prediction Interval of Results
    [GRAPHIC] [TIFF OMITTED] TR20MR23.018
    
13.0 Method Performance

    Data generated with this method must be fit for purpose. 
Applicable results of method performance criteria in this section 
must be reported. Consequences of failed quality criteria are 
provided with the criteria in this section.
    13.1 Background Assessment--Field Train Proof Blank, LMB and 
Materials. Determine the contribution to target compound 
concentration from reagents, media and glassware used to make target 
compound measurements. Conduct at least one field train proof blank 
for each test series at a single facility. Analyze at least one LMB 
sample during an analytical sequence or every 12 hours, whichever is 
shorter. Native target compound concentrations in the field train 
proof blank, LMB and materials assessment must be less than or equal 
to three times the EDL of the method or 10 times lower than the 
quantitation limit required by the end use of the data (e.g., 
compliance limit or other limits set by consent decree or permit), 
whichever is higher. The field train proof blank, LMB and materials 
assessment must also meet the performance specifications in Tables 
23-7, 23-8, and 23-9, as applicable to the compound target list.
    13.2 GC column or column systems used to measure PCDD/PCDF must 
meet the column separation requirements in Section 6.5.2.1 of this 
method and the applicable requirements in Sections 10.2.3.5 and 
11.4.3.4 of this method using the continuing calibration 
verification. Failure to meet this chromatographic resolution 
criterion requires data from this analysis to be flagged explaining 
the potential bias of the results.
    13.3 GC column or column systems used to measure PAH must meet 
the column separation requirements in Section 6.5.2.2 of this method 
and the applicable requirements in Sections 10.2.3.5 and 11.4.3.4 of 
this method using the continuing calibration check. Failure to meet 
this chromatographic resolution criterion requires data from this 
analysis to be flagged explaining the potential bias of the results.
    13.4 GC column or column systems used to measure PCB must meet 
the column separation requirements in Section 6.5.2.3 of this method 
and the applicable requirements in Sections 10.2.3.5 and 11.4.3.4 of 
this method using the continuing calibration check and be able to 
achieve unique resolution and identification of the toxics for 
determination of a TEQPCB. The rule requiring the use of 
this method will establish which WHO TEF to use. Failure to meet 
this chromatographic resolution criterion requires data from this 
analysis to be flagged explaining the potential bias of the results.
    13.5 Confirmation Column. If target compounds are not 
sufficiently resolved from other target compounds or interferences 
in the sample to meet the requirements for target compounds in 
Sections 13.2, 13.3, and/or 13.4 of this method, analyze sample (or 
another aliquot of the sample) using an alternative column that 
provides elution order to uniquely quantify the target compounds 
subject to interference on the first GC column. When using a 
confirmation column, document the required resolution.
    13.6 Detection Limits.
    13.6.1 MDL. The MDLs are determined following the procedures in 
Section 9.3.7 of this method. MDLs are confirmed by

[[Page 16756]]

preparing and analyzing a spiked sample (spiked at 1 to 5 times the 
determined MDL, see Section 9.3.8), then confirm that the target 
compounds meet the qualitative identification criteria in Section 
11.4.3.4 of this method. If the MDL confirmation criteria are not 
met, the MDL determination is repeated with a higher spike 
concentration until criteria are met.
    13.6.2 EDL. If the sample specific EDLs are less than 50% of the 
emission standard, the EDLs are acceptable.
    13.7 Tune. The groups of monitored ions are listed in Tables 23-
4, 23-5, and 23-6 of this method, as applicable for the target 
compound class. Tune the instrument to meet the required resolving 
power in Section 10.2.1 for the desired target compound class. 
Assess the resolution at three exact m/z's representing the low-, 
mid-, and high-m/z range of the masses used to measure the target 
compound class. You may use peak matching and the chosen PFK (or 
FC43) reference peak to verify that the exact mass is within 5 ppm 
of the required value.
    13.8 Lock-Mass Ions. The MS lock-mass and QC check ions in 
Tables 23-4, 23-5, and 23-6 of this method are recommended for PCDD/
PCDF, PCB, or PAH, respectively. The reference compounds PFK or FC43 
have ions that may be selected as your lock-mass and QC check ions. 
Monitor the QC check ions specified in these tables to verify 
instrument stability during the analysis; these must not vary >25% 
from the average response. Additional cleanup on sample extract (or 
archive extract) and reanalysis is necessary for failure to maintain 
lock-mass during analysis.
    13.9 Initial Calibration.
    13.9.1 The RSD for mean RRF from each of the target analytes and 
labeled standards in the calibration samples must not exceed the 
values in Table 23-14 of this method.
    13.9.2 The S/N in every selected ion current profile must be 
>=10 for all unlabeled targets and labeled standards in the 
calibration samples.
    13.9.3 The ion abundance ratios must be within the control 
limits in Table 23-15 of this method.
    13.10 Continuing Calibration Verification.
    13.10.1 The RRF for each unlabeled and labeled compound measured 
in a CCV must not deviate from the initial calibration RRF by more 
than the limits shown in Table 23-14 of this method.
    13.10.2 The ion abundance ratios must be within the control 
limits in Table 23-15 of this method.
    13.10.3 The S/N ratio for the GC/MS signal present in every 
selected ion current profile must be greater than or equal to 10.
    13.10.4 Repeat the initial calibration when there is a failure 
to meet the requirements for an acceptable CCV analysis.
    13.10.5 Column Separation Check. Use the results from a CCV to 
verify and document the resolution required in Sections 13.2, 13.3, 
or 13.4 of this method for the target compound classes analyzed with 
this method. The separation criteria are applicable to all the 
compounds in a target class whether analyzed by a single or multiple 
GC columns. If a confirmation column is used, document required 
resolution (see Section 13.5).
    13.11 QCS. A QCS must be analyzed during the IDC and after 
initial calibrations (at a minimum quarterly). The acceptance 
criterion for the QCS is 70-130% of the true value. If the accuracy 
for any analyte fails the recovery criterion, prepare a fresh 
standard dilution and repeat. If the freshly prepared QCS fails, 
determine the cause, recalibrate the instrument if necessary and 
reanalyze the QCS.
    13.12 Compound Identification for PCDD/PCDF and PCB.
    13.12.1 Target compounds must have ion abundance ratios within 
the control limits in Table 23-15 of this method. PAH target 
compounds have single ion identifiers with no ion abundance ratio 
requirement. Report analysis results as an EMPC when a response 
meets identification criteria but fails the ion abundance ratio 
criteria or when a peak representing a PCDPE has been detected at 
the target compound retention time.
    13.12.2 The retention time for the analytes must be within 3 
seconds of the corresponding pre-extraction standard.
    13.12.3 The monitored ions, shown in Table 23-4 of this method 
for a given PCDD/PCDF, must reach their maximum response within 2 
seconds of each other.
    13.12.4 The monitored ions, shown in Table 23-6 of this method 
for a given PCB, must reach their maximum response within 2 seconds 
of each other.
    13.12.5 For the identification of specific PCB, the RRT of the 
native congener must be within 0.006 RRT units of the pre-extraction 
standard RRT.
    13.12.6 The S/N ratio for the monitored ions for native 
compounds must be greater than or equal to 2.5.
    13.12.7 Identify and quantify isomers that do not have 
corresponding pre-extraction standard compounds by comparing to the 
pre-extraction standard of the same compound class with the nearest 
retention time to the target compound.
    13.12.8 If chromatographic peaks are detected at the retention 
time of any PCDD/PCDF in any of the m/z channels used to monitor 
PCDPE, there is evidence of interference and positive bias. Data 
must be flagged to indicate an interference. You may report the 
total with bias for the affected target. To reduce the bias, you may 
use a confirmatory column or perform additional clean up on an 
archived sample followed by reanalysis.
    13.13 Compound Identification for PAH.
    13.13.1 The signals for the characteristic ion listed in Table 
23-5 of this method must be present.
    13.13.2 The RRT between each native and labeled compound must be 
within 0.006 RRT units.
    13.14 Pre-sampling Adsorbent Standard and Pre-extraction Filter 
Recovery Standard Recovery. Recoveries of pre-sampling adsorbent 
standard added to the sample and pre-extraction filter recovery 
standard added to the filter must be between 70 and 130% (see Tables 
23-7, 23-8, and 23-9 of this method).
    13.14.1 If the recovery of all the pre-sampling adsorbent 
standard compounds is below 70%, the sampling runs are not valid, 
and you must repeat the stack or vent sampling. As an alternative, 
you do not have to repeat the test if the average pre-sampling 
adsorbent standard recovery is 25% or more and you divide the final 
results by the average fraction of pre-sampling adsorbent standard 
recovery.
    13.14.2 If the recovery of all the pre-extraction filter 
recovery standard compounds is below 70%, you may reanalyze the 
sample. If the recovery criteria are still not met, the sampling 
recovery is not valid, and you must repeat the stack or vent 
sampling.
    13.15 Pre-extraction Standard Recovery. Recoveries of all pre-
extraction standard compounds added to the sample must be between 20 
to 130% for PCDD/PCDF and PAH (see Tables 23-7 and 23-8 of this 
method) and between 20 to 145% for PCB (see Table 23-9 of this 
method). If the recovery criteria are not met, you may reanalyze the 
sample and/or prepare and analyze the archive sample. If the 
recovery criteria are still not met, the sampling run is not valid, 
and the stack test must be repeated.
    13.16 Pre-analysis Standard Response. Response of all pre-
analysis standard compounds must show a S/N for every selected ion 
current profile of >= 10. If the minimum response is not met, you 
must reanalyze the sample. Poor sensitivity compared to initial 
calibration response may indicate injection errors or instrument 
drift.
    13.17 IDC--Lowest calibration concentration, Demonstration of 
precision, Demonstration of accuracy.
    13.17.1 Lowest calibration concentration. The Upper PIR Limit 
must be less than, or equal, to 150%; and the Lower PIR Limit must 
be greater than, or equal to, 50%. If these criteria are not met, 
the lowest calibration point has been set too low and must be 
confirmed at a higher concentration.
    13.17.2 Demonstration of precision. The percent relative 
standard deviation (%RSD) of the concentrations from the replicate 
analyses must be less than 20% for all target analytes. 
Demonstration would be repeated for failed compounds only.
    13.17.3 Demonstration of accuracy. The average % recovery for 
each target analyte must be within 70 to 130%. Demonstration would 
be repeated for failed compounds only.
    13.18 Requirements for Equivalency. The Administrator considers 
any modification of this method, beyond those expressly permitted in 
this method as options, to be a major modification subject to 
application and approval of alternative test procedures following 
EPA Guidance Document 22 currently found at: https://www.epa.gov/emc/emc-guideline-documents.
    13.19 Records. As part of the laboratory's quality system, the 
laboratory must maintain records of modifications to this method.

14.0 Pollution Prevention

    The target compounds used as standards in this method are 
prepared in extremely small amounts and pose little threat to the 
environment when managed properly. Prepare standards in volumes 
consistent with laboratory use to minimize the disposal of excess 
volumes of expired standards.

[[Page 16757]]

15.0 Waste Management

    15.1 The laboratory is responsible for complying with all 
federal, state, and local regulations governing waste management, 
particularly the hazardous waste identification rules and land 
disposal restrictions, and for protecting the air, water, and land 
by minimizing and controlling all releases from fume hoods and bench 
operations. The laboratory must also comply with any sewage 
discharge permits and regulations. The EPA's Environmental 
Management Guide for Small Laboratories (EPA 233-B-98-001) provides 
an overview of requirements.
    15.2 Samples containing hydrogen chloride or sulfuric acid to pH 
<2 are hazardous and must be handled and disposed in accordance with 
federal, state, and local regulations.
    15.3 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 Bibliography

1. American Society of Mechanical Engineers. Analytical Procedures 
to Assay Stack Effluent Samples and Residual Combustion Products for 
Polychlorinated Dibenzo-p-Dioxins (PCDD) and Polychlorinated 
Dibenzofurans (PCDF). Prepared for the U.S. Department of Energy and 
U.S. Environmental Protection Agency. Washington, DC. December 1984. 
23 p.
2. American Society of Mechanical Engineers. Sampling for the 
Determination of Chlorinated Organic Compounds in Stack Emissions. 
Prepared for U.S. Department of Energy and U.S. Environmental 
Protection Agency. Washington DC. December 1984. 25 p.
3. Fishman, V.N., Martin, G.D. and Lamparski, L.L., Comparison of a 
variety of gas chromatographic columns with different polarities for 
the separation of chlorinated dibenzo-p-dioxins and dibenzofurans by 
high-resolution mass spectrometry, Journal of Chromatography A 1139 
(2007) 285-300.
4. International Agency for Research on Cancer. Environmental 
Carcinogens Methods of Analysis and Exposure Measurement, Volume 
11--Polychlorinated Dioxins and Dibenzofurans. IARC Scientific 
Publications No. 108, 1991.
5. Stieglitz, L., Zwick, G., Roth, W. Investigation of different 
treatment techniques for PCDD/PCDF in fly ash. Chemosphere 15: 1135-
1140; 1986.
6. Triangle Laboratories. Case Study: Analysis of Samples for the 
Presence of Tetra Through Octachloro-p-Dibenzodioxins and 
Dibenzofurans. Research Triangle Park, NC. 1988. 26 p.
7. U.S. Environmental Protection Agency. Method 8290A--
Polychlorinated Dibenzo-p-dioxins (PCDDs) and Polychlorinated 
Dibenzofurans (PCDFs) by High-Resolution Gas Chromatography/High-
Resolution Mass Spectrometry (HRGC/HRMS), Revision 1. February 2007. 
In: Test Methods for Evaluating Solid Waste, Physical/Chemical 
Methods, EPA publication SW-846. Washington, DC.
8. U.S. Environmental Protection Agency. Office of Air Programs 
Publication No. APTD-0576: Maintenance, Calibration, and Operation 
of Isokinetic Source Sampling Equipment. Research Triangle Park, NC. 
March 1972.
9. U.S. Environmental Protection Agency. Method 1625C-Semivolatile 
Organic Compounds by Isotope Dilution GCMS. June 1989.
10. U.S. Environmental Protection Agency. Method 1613B-Tetra- 
through Octa-Chlorinated Dioxins and Furans by Isotope Dilution 
HRGC/HRMS. October 1994.
11. U.S. Environmental Protection Agency. Method 1668C-Chlorinated 
Biphenyl Congeners in Water, Soil, Sediment, Biosolids, and Tissue 
by HRGC/HRMS. April 2010.
12. Tondeur, Y., Nestrick, T., Silva, H[eacute]ctor A., Vining, B., 
Hart, J. Analytical procedures for the determination of 
polychlorinated-p-dioxins, polychlorinated dibenzofurans, and 
hexachlorobenzene in pentachlorophenol, Chemosphere Volume 80, Issue 
2, June 2010 pages 157-164.
13. U.S. Environmental Protection Agency. Definition and Procedure 
for the Determination of the Method Detection Limit, Revision 2. EPA 
821-R-16-006. December 2016.
14. Tondeur Y, Niederhut WJ, Missler SR. A hybrid HRGC/MS/MS Method 
for the Characterization of Tetrachlorodibenzo-p-Dioxins in 
Environmental Samples; Bio. Med. and Environ. Mass Spectr. 14, pages 
449-456, 1987.
15. Gianluca R., Mosca S., Guerriero E., Rotatori M. Development of 
a new automated clean-up system for the simultaneous analysis of 
polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and 
`dioxin-like' polychlorinated biphenyls (dl-PCB) in flue gas 
emissions by GPC-SPE. J. Environ. Monit. 14, pages 1082-1090, 2012.
16. U.S. Environmental Protection Agency. The National Dioxin Air 
Monitoring Network (NDAMN) Report of the Results of Atmospheric 
Measurements of Polychlorinated Dibenzo-p-Dioxins (PCDDs), 
Polychlorinated Dibenzofurans (PCDFs), and Dioxin-like 
Polychlorinated Biphenyl (PCBs) in Rural and Remote Areas of the 
United States from June 1998 through November 2004. EPA/600/R-13/
183F. August 2013.
17. Guo, Y., Kannan, K. Analytical Methods for the Measurement of 
Legacy and Emerging Persistent Organic Pollutants in Complex Sample 
Matrices. Comprehensive Analytical Chemistry. Vol. 67. January 2015.
18. U.S. Environmental Protection Agency. USEPA Contract Laboratory 
Program (CLP) National Functional Guidelines for Chlorinated 
Dibenzo-p-Dioxins (CDDs) and Chlorinated Dibenzofurans (CDFs) Data 
Review. EPA-540-R-11-016. September 2011.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

          Table 23-1--Polychlorinated Dibenzo-p-dioxin and Polychlorinated Dibenzofuran Target Analytes
----------------------------------------------------------------------------------------------------------------
                                                    CAS \a\                                           CAS\a\
       Polychlorinated dibenzo-p-dioxins         Registry No.     Polychlorinated dibenzofurans    Registry No.
----------------------------------------------------------------------------------------------------------------
2,3,7,8-TeCDD.................................       1746-01-6  2,3,7,8-TeCDF...................      51207-31-9
1,2,3,7,8-PeCDD...............................      40321-76-4  1,2,3,7,8-PeCDF.................      57117-41-6
1,2,3,4,7,8-HxCDD.............................      39227-28-6  2,3,4,7,8-PeCDF.................      57117-31-4
1,2,3,6,7,8-HxCDD.............................      57653-85-7  1,2,3,4,7,8-HxCDF...............      70648-26-9
1,2,3,7,8,9-HxCDD.............................      19408-74-3  1,2,3,6,7,8-HxCDF...............      57117-44-9
1,2,3,4,6,7,8-HpCDD...........................      35822-46-9  1,2,3,7,8,9-HxCDF...............      72918-21-9
Total TeCDD...................................      41903-57-5  2,3,4,6,7,8-HxCDF...............      60851-34-5
Total PeCDD...................................      36088-22-9  1,2,3,4,6,7,8-HpCDF.............      67562-39-4
Total HxCDD...................................      34465-46-8  1,2,3,4,7,8,9-HpCDF.............      55673-89-7
Total HpCDD...................................      37871-00-4  Total TeCDF.....................      55722-27-5
OCDD..........................................       3268-87-9  Total PeCDF.....................      30402-15-4
                                                                Total HxCDF.....................      55684-94-1
                                                                Total HpCDF.....................      38998-75-3
                                                                OCDF............................      39001-02-0
----------------------------------------------------------------------------------------------------------------
\a\ Chemical Abstract Service.

[[Page 16758]]

                           Table 23-2--Polycyclic Aromatic Hydrocarbon Target Analytes
----------------------------------------------------------------------------------------------------------------
                                                    CAS \a\                                           CAS \a\
       Polycyclic aromatic hydrocarbons          Registry No.   Polycyclic aromatic hydrocarbons   Registry No.
----------------------------------------------------------------------------------------------------------------
Naphthalene...................................         91-20-3  Chrysene........................        218-01-9
2-Methylnaphthalene...........................         91-57-6  Benzo[b]fluoranthene............        205-99-2
Acenaphthylene................................        208-96-8  Benzo[k]fluoranthene............        207-08-9
Acenaphthene..................................         83-32-9  Perylene........................        198-55-8
Fluorene......................................         86-73-7  Benzo[a]pyrene..................         50-32-8
Anthracene....................................        120-12-7  Benzo[e]pyrene..................        192-97-2
Phenanthrene..................................         85-01-8  Benzo[g,h,i]perylene............        191-24-2
Fluoranthene..................................        206-44-0  Indeno[1,2,3-cd]pyrene..........        193-39-5
Pyrene........................................        129-00-0  Dibenz[a,h]anthracene...........         53-70-3
Benz[a]anthracene.............................         56-55-3
----------------------------------------------------------------------------------------------------------------
\a\ Chemical Abstract Service.

                              Table 23-3--Polychlorinated Biphenyl Target Analytes
----------------------------------------------------------------------------------------------------------------
                                                    CAS \b\                                           CAS \b\
         PCB congener              BZ No.\a\     Registry No.     PCB congener       BZ No.\a\     Registry No.
----------------------------------------------------------------------------------------------------------------
2,4'-DiCB.....................               8      34883-43-7  2,2',3,3',4,4'-              128      38380-07-3
                                                                 HxCB.
2,2',5-TrCB...................              18      37680-65-2  2,2',3,4,4',5'-              138      35065-28-2
                                                                 HxCB.
2,4,4'-TrCB...................              28       7012-37-5  2,2',4,4',5,5'-              153      35065-27-1
                                                                 HxCB.
2,2',3,5'-TeCB................              44      41464-39-5  2,3,3',4,4',5-               156      38380-08-4
                                                                 HxCB.
2,2',5,5'-TeCB................              52      35693-99-3  2,3,3',4,4',5'-              157      69782-90-7
                                                                 HxCB.
2,3',4,4'-TeCB................              66      32598-10-0  2,3',4,4',5,5'-              167      52663-72-6
                                                                 HxCB.
3,3',4,4'-TeCB................              77      32598-13-3  3,3',4,4',5,5'-              169      32774-16-6
                                                                 HxCB.
3,4,4',5-TeCB.................              81      70362-50-4  2,2',3,3',4,4',5-            170      35065-30-6
                                                                 HpCB.
2,2',4,5,5'-PeCB..............             101      37680-73-2  2,2',3,4,4',5,5'-            180      35065-29-3
                                                                 HpCB.
2,3,3',4,4'-PeCB..............             105      32598-14-4  2,2',3,4',5,5',6-            187      52663-68-0
                                                                 HpCB.
2,3,4,4',5-PeCB...............             114      74472-37-0  2,3,3',4,4',5,5'-            189      39635-31-9
                                                                 HpCB.
2,3',4,4',5-PeCB..............             118      31508-00-6  2,2',3,3',4,4',5             195      52663-78-2
                                                                 ,6-OcCB.
2',3,4,4',5-PeCB..............             123      65510-44-3  2,2',3,3',4,4',5             206      40186-72-9
                                                                 ,5',6-NoCB.
3,3',4,4',5-PeCB..............             126      57465-28-8  2,2',3,3',4,4',5             209       2051-24-3
                                                                 ,5',6,6'-DeCB.
----------------------------------------------------------------------------------------------------------------
\a\ BZ No.: Ballschmiter and Zell 1980, or International Union of Pure and Applied Chemistry (IUPAC) number.
\b\ Chemical Abstract Service.

            Table 23-4--Elemental Compositions and Exact Masses of the Ions Monitored by High-Resolution Mass Spectrometry for PCDD and PCDF
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                                Elemental                                                             Elemental
          Mass \a\             Ion type \b\    composition     Target analyte \b\      Mass \a\      Ion type \b\    composition     Target analyte \b\
--------------------------------------------------------------------------------------------------------------------------------------------------------
263.9871....................  LOCK.........  C5F10N.........  FC43................        383.8639  M............  \13\C12H2\35\Cl  HxCDF (S).
                                                                                                                    6O.
292.9825....................  LOCK.........  C7F11..........  PFK.................        385.8610  M+2..........  \13\C12H2\35\Cl  HxCDF (S).
                                                                                                                    5\37\ClO.
303.9016....................  M............  C12H4\35\Cl4O..  TeCDF...............        389.8157  M+2..........  C12H2\35\Cl5\37  HxCDD.
                                                                                                                    \ClO2.
305.8987....................  M+2..........  C12H4\35\Cl\37\  TeCDF...............        391.8127  M+4..........  C12H2\35\Cl4\37  HxCDD.
                                              ClO.                                                                  \Cl2O2.
313.9839....................  QC...........  C6F12N.........  FC43................        392.9760  LOCK.........  C9F15..........  PFK.
315.9419....................  M............  \13\C12H4\35\Cl  TeCDF (S)...........        401.8559  M+2..........  \13\C12H2\35\Cl  HxCDD (S).
                                              4O.                                                                   5\37\ClO2.
316.9745....................  M+2..........  \13\C12H4\35\Cl  TeCDF (S)...........        403.8529  M+4..........  \13\C12H2\35\Cl  HxCDD (S).
                                              3\37\ClO.                                                             4\37\Cl2O.
317.9389....................  M+2..........  \13\C12H4\35\Cl  TeCDF (S)...........        425.9775  QC...........  C9F16N.........  FC43.
                                              2\37\ClO.
319.8965....................  M............  C12H4\35\Cl4O2.  TeCDD...............        445.7555  M+4..........  C12H2\35\Cl6\37  OCDPE.
                                                                                                                    \Cl2O.
321.8936....................  M+2..........  C12H4\35\Cl3\37  TeCDD...............        407.7818  M+2..........  C12H\35\Cl6\37\  HpCDF.
                                              \ClO2.                                                                ClO.
325.9839....................  QC...........  C7F12N.........  FC43................        409.7789  M+4..........  C12H\35\Cl5\37\  HpCDF.
                                                                                                                    Cl2O.
330.9792....................  QC...........  C7F13..........  PFK.................        417.8253  M............  \13\C12H\35\Cl7  HpCDF (S).
                                                                                                                    O.
331.9368....................  M............  \13\C12H4\35\Cl  TeCDD (S)...........        419.8220  M+2..........  \13\C12H\35\Cl6  HpCDF (S).
                                              4O2.                                                                  \37\ClO.
333.9339....................  M+2..........  \13\C12H4\35\Cl  TeCDD (S)...........        423.7766  M+2..........  C12H\35\Cl6\37\  HpCDD.
                                              3\37\ClO2.                                                            ClO2.
339.8597....................  M+2..........  C12H3\35\Cl4\37  PeCDF...............        425.7737  M+4..........  C12H\35\Cl5\37\  HpCDD.
                                              \ClO.                                                                 Cl2O2.
341.8567....................  M+4..........  C12H3\35\Cl3\37  PeCDF...............        430.9729  QC...........  C9F17..........  PFK.
                                              \Cl2O.
354.9792....................  LOCK.........  C9F13..........  PFK.................        435.8169  M+2..........  \13\C12H\35\Cl6  HpCDD (S).
                                                                                                                    \37\ClO2.
351.9000....................  M+2..........  \13\C12H3\35\Cl  PeCDF (S)...........        437.8140  M+4..........  \13\C12H\35\Cl5  HpCDD (S).
                                              4\37\ClO.                                                             \37\Cl2O2.
353.8970....................  M+4..........  \13\C12H3\35\Cl  PeCDF (S)...........        442.9728  LOCK.........  C10F17.........  PFK.
                                              3\37\Cl2O.
355.8546....................  M+2..........  C12H3\35\Cl4\37  PeCDD...............        479.7165  M+4..........  C12H\35\Cl7\37\  NCPDE.
                                              \ClO2.                                                                Cl2O.
357.8516....................  M+4..........  C12H3\35\Cl3\37  PeCDD...............        430.9729  LOCK.........  C9F17..........  PFK.
                                              \Cl2O2.
367.8949....................  M+2..........  \13\C12H3\35\Cl  PeCDD (S)...........        441.7428  M+2..........  C12\35\Cl7\37\C  OCDF.
                                              4\37\ClO2.                                                            lO.
369.8919....................  M+4..........  \13\C12H3\35\Cl  PeCDD (S)...........        443.7399  M+4..........  C12\35\Cl6\37\C  OCDF.
                                              3\37\Cl2O2.                                                           l2O.
375.9807....................  QC...........  C8F14N.........  FC43................        457.7377  M+2..........  C12\35\Cl7\37\C  OCDD.
                                                                                                                    lO2.
375.8364....................  M+2..........  C12H4\35\Cl5\37  HxCDPE..............        459.7348  M+4..........  C12\35\Cl6\37\C  OCDD.
                                              \ClO.                                                                 l2O2.
409.7974....................  M+2..........  C12H3\35\Cl6\37  HpCPDE..............        463.9743  QC...........  C9F18N.........  FC43.
                                              \ClO.
373.8208....................  M+2..........  C12H235Cl5\37\C  HxCDF...............        469.7779  M+2..........  \13\C12\35\Cl7\  OCDD (S).
                                              lO.                                                                   37\ClO2.
375.8178....................  M+4..........  C12H2\35\Cl4\37  HxCDF...............        471.7750  M+4..........  \13\C12\35\Cl6\  OCDD (S).
                                              \Cl2O.                                                                37\Cl2O2.
375.9807....................  QC...........  C8F14N.........  FC43................        513.6775  M+4..........  C12\35\Cl8\37\C  DCDPE.
                                                                                                                    l2O2.
                                                                                          442.9728  QC...........  C10F17.........  PFK.
--------------------------------------------------------------------------------------------------------------------------------------------------------
\a\ The following nuclidic masses were used to calculate exact masses: H = 1.007825, C = 12.000000, \13\C = 13.003355, F = 18.9984, O = 15.994915, \35\C
  l= 34.968853, \37\Cl = 36.965903.
\b\ (S) = Labeled Standard. LOCK = Lock-Mass Ion PFK or FC43. QC = Quality Control Check Ion. Note: Consider monitoring 328 m/z if a high level of PCB
  is expected.

[[Page 16759]]

 Table 23-5--Elemental Compositions and Exact Masses of the Ions Monitored by High-Resolution Mass Spectrometry
                                                     for PAH
----------------------------------------------------------------------------------------------------------------
                                                                          Elemental
       Aromatic ring No.            Mass \a\        Ion type \b\         composition          Target analyte
----------------------------------------------------------------------------------------------------------------
2..............................        128.0624  M.................  C10H8.............  Naphthalene.
                                       130.9920  LOCK..............  ..................  PFK/FC43.
2..............................        134.0828  M.................  \13\C6\12\C4H8....  \13\C6-Naphthalene.
2..............................         142.078  M.................  C11H10............  2-Methylnaphthalene.
2..............................        148.0984  M.................  \13\C6\12\C5H10...  \13\C6-2-
                                                                                          Methylnaphthalene.
2..............................        152.0624  M.................  C12H8.............  Acenaphthylene.
2..............................        158.0828  M.................  \13\C6\12\C6H8....  \13\C6-Acenaphthylene.
2..............................         154.078  M.................  C12H10............  Acenaphthene.
2..............................         160.078  M.................  \13\C6\12\C6H10...  \13\C6-Acenaphthene.
2..............................         166.078  M.................  C13H10............  Fluorene.
                                        169.988  QC................  ..................  PFK/FC43.
2..............................        172.0984  M.................  \13\C6\12\C7H10...  \13\C6-Fluorene.
3..............................         178.078  M.................  C14H10............  Phenanthrene.
3..............................        184.0984  M.................  \13\C6 \12\C8H10..  \13\C6-Phenanthrene.
3..............................         178.078  M.................  C14H10............  Anthracene.
3..............................         184.078  M.................  \13\C6\12\C8H10...  \13\C6-Anthracene.
3..............................         202.078  M.................  C16H10............  Fluoranthene.
                                       204.9888  QC................  ..................  PFK.
3..............................        208.0984  M.................  \13\C6\12\C10H10..  \13\C6-Fluoranthene.
4..............................         202.078  M.................  C16H10............  Pyrene.
4..............................         205.078  M.................  \13\C3\12\C13H10..  \13\C3-Pyrene.
                                       213.9898  QC................  ..................  FC43.
                                       218.9856  LOCK..............  ..................  FC43.
4..............................        228.0936  M.................  C18H12............  Benz[a]anthracene.
                                       230.9856  LOCK..............  ..................  PFK.
4..............................         234.114  M.................  \13\C6C12H12......  \13\C6-
                                                                                          Benz[a]anthracene.
4..............................        228.0936  M.................  C18H12............  Chrysene.
4..............................         234.114  M.................  \13\C6\12\C12H12..  \13\C6-Chrysene.
4..............................        252.0936  M.................  C20H12............  Benzo[b]fluoranthene.
4..............................         258.114  M.................  \13\C6\12\C14H12..  \13\C6-
                                                                                          Benzo[b]fluoranthene.
4..............................          252.32  M.................  C20H12............  Benzo[k]fluoranthene.
4..............................         258.114  M.................  \13\C6\12\C14H12..  \13\C6-
                                                                                          Benzo[k]fluoranthene.
5..............................        252.0936  M.................  C20H12............  Benzo[e]pyrene.
5..............................        256.1072  M.................  \13\C4 \12\C16H12.  \13\C4-Benzo[e]pyrene.
5..............................        256.1072  M.................  \13\C4 \12\C16H12.  \13\C4-Benzo[a]pyrene.
5..............................        252.0936  M.................  C20H12............  Benzo[a]pyrene.
5..............................        252.0936  M.................  C20H12............  Perylene.
5..............................        264.1692  M.................  C20D12............  d12-Perylene.
                                       268.9824  QC................  ..................  PFK.
                                       263.9871  LOCK..............  ..................  FC43.
6..............................        276.0936  M.................  C22H12............  Indeno[1,2,3-cd]pyrene.
6..............................         282.114  M.................  \13\C6 \12\C16H12.  \13\C6-
                                                                                          Indeno[1,2,3,cd]pyrene
                                                                                          .
5..............................        278.1092  M.................  C22H14............  Dibenz[a,h]anthracene.
                                       280.9824  LOCK..............  ..................  PFK.
5..............................        284.1296  M.................  \13\C6 \12\C16H14.  \13\C6-
                                                                                          Dibenz[a,h]anthracene.
6..............................        276.0936  M.................  C22H12............  Benzo[g,h,i]perylene.
6..............................        288.1344  M.................  \13\C12 \12\C10H12  \13\C12-
                                                                                          Benzo[g,h,i]perylene.
                                       313.9839  QC................  ..................  FC43.
----------------------------------------------------------------------------------------------------------------
\a\ Isotopic masses used for accurate mass calculation: \1\H = 1.0078, \12\C = 12.0000, \13\C = 13.0034, \2\H =
  2.0141.
\b\ LOCK = Lock-Mass Ion PFK or FC43. QC = Quality Control Check Ion.

                                     Table 23-6--Elemental Compositions and Exact Masses of the Ions Monitored by High-Resolution Mass Spectrometry for PCB
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
    Chlorine                                                                                           Chlorine
  substitution     Mass \a\      Ion type \b\        Elemental composition       Target analyte      substitution    Mass \a\      Ion type \b\       Elemental composition      Target analyte
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Fn-1;...........    188.0393  M.................  \12\C12H9\35\Cl............  Cl-1 PCB..........  Fn-5;..........    323.8834  M................  \12\C12H5\35\Cl5..........  Cl-5 PCB.
Cl-1............                                                                                   Cl-5,6,7.......
                    190.0363  M+2...............  \12\C12H9\37\Cl............  Cl-1 PCB..........                     325.8804  M+2..............  \12\C12H5\35\Cl4\37\Cl....  Cl-5 PCB.
                    200.0795  M.................  \13\C12H9\35\Cl............  \13\C12 Cl-1 PCB..                     327.8775  M+4..............  \12\C12H5\35\Cl3\37\Cl2...  Cl-5 PCB.
                    202.0766  M+2...............  \12\C12H9\37\Cl............  \13\C12 Cl-1 PCB..                     337.9207  M+2..............  \13\C12H5\35\Cl4\37\Cl....  \13\C12 Cl-5 PCB.
                    218.9856  LOCK..............  C4F9.......................  PFK...............                     339.9178  M+4..............  \13\C12H5\35\Cl3\37\Cl2...  \13\C12 Cl-5 PCB.
Fn-2;...........    222.0003  M.................  \12\C12H8\35\Cl2...........  Cl-2 PCB..........                     354.9792  LOCK.............  C9F13.....................  PFK.
Cl-2,3..........
                    223.9974  M+2...............  \12\C12H8\35\Cl\37\Cl......  Cl-2 PCB..........                     359.8415  M+2..............  \12\C12H4\35\Cl5\37\Cl....  Cl-6 PCB.
                    225.9944  M+4...............  \12\C12H8\37\Cl2...........  Cl-2 PCB..........                     361.8385  M+4..............  \12\C12H4\35\Cl4\37\Cl2...  Cl-6 PCB.
                    234.0406  M.................  \13\C12H8\35\Cl2...........  \13\C12 Cl-2 PCB..                     363.8356  M+6..............  \12\C12H4\35\Cl3\37\Cl3...  Cl-6 PCB.
                    236.0376  M+2...............  \13\C12H8\35\Cl\37\Cl......  \13\C12 Cl-2 PCB..                     371.8817  M+2..............  \13\C12H4\35\Cl5\37\Cl....  \13\C12 Cl-6 PCB.
                    242.9856  LOCK..............  C4F9.......................  PFK...............                     373.8788  M+4..............  \13\C12H4\35\Cl4\37\Cl2...  \13\C12 Cl-6 PCB.
                    255.9613  M.................  \12\C12H7\35\Cl3...........  Cl-3 PCB..........                     393.8025  M+2..............  \12\C12H3\35\Cl6\37\Cl....  Cl-7 PCB.

[[Page 16760]]

 
                    257.9584  M+2...............  \12\C12H7\35\Cl2\37\Cl.....  Cl-3 PCB..........                     395.7995  M+4..............  \12\C12H3\35\Cl5\37\Cl2...  Cl-7 PCB.
                    268.0016  M.................  \13\C12H7\35\Cl3...........  \13\C12 Cl-3 PCB..                     397.7966  M+6..............  \12\C12H3\35\Cl4\37\Cl3...  \37\Cl3 Cl-7 PCB.
                    269.9986  M+2...............  \13\C12H7\35\Cl2\37\Cl.....  \13\C12 Cl-3 PCB..                     405.8428  M+2..............  \13\C12H3\35\Cl6\37\Cl....  \13\C12 Cl-7 PCB.
Fn-3;...........    255.9613  M.................  \12\C12H7\35\Cl3...........  Cl-3 PCB..........                     407.8398  M+4..............  \13\C12H3\35\Cl5\37\Cl2...  \13\C12 Cl-7 PCB.
Cl-3,4,5........
                    257.9584  M+2...............  \12\C12 H7\35\Cl2\37\Cl....  Cl-3 PCB..........                     454.9728  QC...............  C11F17....................  PFK.
                    259.9554  M+4...............  \12\C12H7\35\Cl\37\Cl2.....  Cl-3 PCB..........  Fn-6;..........    393.8025  M+2..............  \12\C12H3\35\Cl6\37\Cl....  Cl-7 PCB.
                                                                                                   Cl-7,8,9,10....
                    268.0016  M.................  \13\C12H7\35\Cl3...........  \13\C12 Cl-3 PCB..                     395.7995  M+4..............  \12\C12H3\35\Cl5\37\Cl2...  Cl-7 PCB.
                    269.9986  M+2...............  \13\C12H7\35\Cl2\37\Cl.....  \13\C12 Cl-3 PCB..                     397.7966  M+6..............  \12\C12H3\35\Cl4\37\Cl3...  Cl-7 PCB.
                    280.9825  LOCK..............  C6F11......................  PFK...............                     405.8428  M+2..............  \13\C12H3\35\Cl6\37\Cl....  \13\C12 Cl-7 PCB.
                    289.9224  M.................  \12\C12H6\35\Cl4...........  Cl-4 PCB..........                     407.8398  M+4..............  \13\C12H3\35\Cl5\37\Cl2...  \13\C12 Cl-7 PCB.
                    291.9194  M+2...............  \12\C12H6\35\Cl3\37\Cl.....  Cl-4 PCB..........                     427.7635  M+2..............  \12\C12H2\35\Cl7\37\Cl....  Cl-8 PCB.
                    293.9165  M+4...............  \12\C12H6\35\Cl2\37\Cl2....  Cl-4 PCB..........                     429.7606  M+4..............  \12\C12H2\35\Cl6\37\Cl2...  Cl-8 PCB.
                    301.9626  M.................  \13\C12H6\35\Cl4...........  \13\C12 Cl-4 PCB..                     431.7576  M+6..............  \12\C12H2\35\Cl5\37\Cl3...  Cl-8 PCB.
                    303.9597  M+2...............  \13\C12H6\35\Cl3\37\Cl.....  \13\C12 Cl-4 PCB..                     439.8038  M+2..............  \13\C12H2\35\Cl7\37\Cl....  \13\C12 Cl-8 PCB.
                    323.8834  M.................  \12\C12H5\35\Cl5...........  Cl-5 PCB..........                     441.8008  M+4..............  \13\C12H2\35\Cl6\37\Cl2...  \13\C12 Cl-8 PCB.
                    325.8804  M+2...............  \12\C12H5\35\Cl4\37\Cl.....  Cl-5 PCB..........                     454.9728  QC...............  C11F17....................  PFK.
                    327.8775  M+4...............  \12\C12H5\35\Cl3\37\Cl2....  Cl-5 PCB..........                     427.7635  M+2..............  \12\C12H2\35\Cl7\37\Cl....  Cl-8 PCB.
                    337.9207  M+2...............  \13\C12H5\35\Cl4\37\Cl.....  \13\C12 Cl-5 PCB..                     429.7606  M+4..............  \12\C12H2\35\Cl6\37\Cl2...  Cl-8 PCB.
                    339.9178  M+4...............  \13\C12H5\35\Cl3\37\Cl2....  \13\C12 Cl-5 PCB..                     431.7576  M+6..............  \12\C12H2\35\Cl5\37\Cl3...  Cl-8 PCB.
Fn-4;...........    289.9224  M.................  \12\C12H6\35\Cl4...........  Cl-4 PCB..........                     439.8038  M+2..............  \13\C12H2\35\Cl7\37\Cl....  \13\C12 Cl-8 PCB.
Cl-4,5,6........
                    291.9194  M+2...............  \12\C12H6\35\Cl3\37\Cl.....  Cl-4 PCB..........                     441.8008  M+4..............  \13\C12H2\35\Cl6\37\Cl2...  \13\C12 Cl-8 PCB.
                    293.9165  M+4...............  \12\C12H6\35\Cl2\37\Cl2....  Cl-4 PCB..........                     442.9728  QC...............  C10F17....................  PFK.
                    301.9626  M+2...............  \13\C12H6\35\Cl3\37\Cl.....  \13\C12 Cl-4 PCB..                     454.9728  LOCK.............  C11F17....................  PFK.
                    303.9597  M+4...............  \13\C12H6\35\Cl2\37\Cl2....  \13\C12 Cl-4 PCB..                     461.7246  M+2..............  \12\C12H1\35\Cl8\37\Cl....  Cl-9 PCB.
                    323.8834  M.................  \12\C12H5\35\Cl5...........  Cl-5 PCB..........                     463.7216  M+4..............  \12\C12H1\35\Cl7\37\Cl2...  Cl-9 PCB.
                    325.8804  M+2...............  \12\C12H5\35\Cl4\37\Cl.....  Cl-5 PCB..........                     465.7187  M+6..............  \12\C12H1\35\Cl6\37\Cl3...  Cl-9 PCB.
                    327.8775  M+4...............  \12\C12H5\35\Cl3\37\Cl2....  Cl-5 PCB..........                     473.7648  M+2..............  \13\C12H1\35\Cl8\37\Cl....  \13\C12 Cl-9 PCB.
                    330.9792  LOCK..............  C7F15......................  PFK...............                     475.7619  M+4..............  \13\C12H1\35\Cl7\37\Cl2...  \13\C12 Cl-9 PCB.
                    337.9207  M+2...............  \13\C12H5\35\Cl4\37\Cl.....  \13\C12 Cl-5 PCB..                     495.6856  M+2..............  \13\C12H4 \5\Cl9\37\Cl....  Cl-10 PCB.
                    339.9178  M+4...............  \13\C12H5\35\Cl3\37\Cl2....  \13\C12Cl-5 PCB...                     499.6797  M+6..............  \12\C12H4\35\Cl8\37\Cl2...  Cl-10 PCB.
                    359.8415  M+2...............  \13\C12H4\35\Cl5\37\Cl.....  Cl-6 PCB..........                     501.6767  M+8..............  \12\C12H4\35\Cl7\37\Cl3...  Cl-10 PCB.
                    361.8385  M+4...............  \13\C12H4\35\Cl4\37\Cl2....  Cl-6 PCB..........                     507.7258  M+2..............  \13\C12H4\35\Cl9\37\Cl....  \13\C12 Cl-10
                                                                                                                                                                                PCB.
                    363.8356  M+6...............  \12\C12H4\35\Cl3\37\Cl3....  Cl-6 PCB..........                     509.7229  M+4..............  \13\C12H4\35\Cl8\37\Cl2...  \13\C12 Cl-10
                                                                                                                                                                                PCB.
                    371.8817  M+2...............  \13\C12H4\35\Cl5\37\Cl.....  \13\C12 Cl-6 PCB..                     511.7199  M+6..............  \13\C12H4\35\Cl7\37\Cl3...  \13\C12 Cl-10
                                                                                                                                                                                PCB.
                    373.8788  M+4...............  \13\C12H4\35\Cl4\37\Cl2....  \13\C12 Cl-6 PCB..
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
\a\ Isotopic masses used for accurate mass calculation: \1\H = 1.0078, \12\C = 12.0000, \13\C = 13.0034, \35\Cl = 34.9689, \37\Cl = 36.9659, \19\F = 18.9984. An interference with PFK m/z
  223.9872 may preclude meeting 10:1 S/N for the DiCB congeners at optional Cal 1 level (Table 23-11). If this interference occurs, 10:1 S/N must be met at the Cal 2 level.
\b\ LOCK = Lock-Mass Ion PFK or FC43. QC = Quality Control Check Ion.

 Table 23-7--Concentration of the Sample Fortification for PCDD and PCDF
                                   \a\
------------------------------------------------------------------------
                                         pg/[mu]L in
               Compound                 final extract    Spike recovery
                                             \b\
------------------------------------------------------------------------
                     Pre-sampling Adsorbent Standard
------------------------------------------------------------------------
\13\C12-1,2,3,4-TeCDD................              50            70-130%
\13\C12-1,2,3,4,7-PeCDD..............              50            70-130%
\13\C12-1,2,3,4,6-PeCDF..............              50            70-130%
\13\C12-1,2,3,4,6,9-HxCDF............              50            70-130%
\13\C12-1,2,3,4,6,8,9-HpCDF..........              50            70-130%
------------------------------------------------------------------------
                 Pre-extraction Filter Recovery Standard
------------------------------------------------------------------------
\13\C12-1,2,7,8-TeCDF................              50            70-130%
\13\C12-1,2,3,4,6,8-HxCDD............              50            70-130%
------------------------------------------------------------------------
                         Pre-extraction Standard
------------------------------------------------------------------------
\13\C12-2,3,7,8-TeCDD................              50            20-130%
\13\C12-2,3,7,8-TeCDF................              50            20-130%
\13\C12-1,2,3,7,8-PeCDD..............              50            20-130%
\13\C12-1,2,3,7,8-PeCDF..............              50            20-130%
\13\C12-2,3,4,7,8-PeCDF..............              50            20-130%
\13\C12-1,2,3,4,7,8-HxCDD............              50            20-130%
\13\C12-1,2,3,6,7,8-HxCDD............              50            20-130%
\13\C12-1,2,3,7,8,9-HxCDD............              50            20-130%
\13\C12-1,2,3,4,7,8-HxCDF............              50            20-130%

[[Page 16761]]

 
\13\C12-1,2,3,6,7,8-HxCDF............              50            20-130%
\13\C12-2,3,4,6,7,8-HxCDF............              50            20-130%
\13\C12-1,2,3,7,8,9-HxCDF............              50            20-130%
\13\C12-1,2,3,4,6,7,8-HpCDD..........              50            20-130%
\13\C12-1,2,3,4,6,7,8-HpCDF..........              50            20-130%
\13\C12-1,2,3,4,7,8,9-HpCDF..........              50            20-130%
\13\C12-OCDD.........................             100            20-130%
\13\C12-OCDF.........................             100            20-130%
------------------------------------------------------------------------
                          Pre-analysis Standard
------------------------------------------------------------------------
\13\C12-1,3,6,8-TeCDD................              50            S/N>=10
\13\C12-1,2,3,4-TeCDF................              50            S/N>=10
\13\C12-1,2,3,4,6,7-HxCDD............              50            S/N>=10
\13\C12-1,2,3,4,6,7,9-HpCDD..........              50            S/N>=10
------------------------------------------------------------------------
                       Alternate Recovery Standard
------------------------------------------------------------------------
\13\C12-1,3,7,8-TeCDD................              50            20-130%
\13\C12-1,2,4,7,8-PeCDD..............              50            20-130%
------------------------------------------------------------------------
\a\ Changes in the amounts of labeled standards added to the sample or
  its representative extract will necessitate an adjustment of the
  calibration solutions to prevent the introduction of inconsistencies.
  Spike concentration assumes 1 [micro]L sample injection volume for
  analysis or the injection volume for calibration standards and samples
  is the same.
\b\ Labeled standard concentrations are recommendations (equivalent mass
  per sample of 25 pg pre-extraction standard, as an example, based on a
  200 [micro]L extract volume split in half before cleanup with a 20
  [micro]L aliquot of a 500 pg/[micro]L spiking solution).
  Recommendations are based on assumption that half of the extract will
  be archived before cleanup. Spike levels may be adjusted for different
  split levels.
Note: all standards used should be reported.

    Table 23-8--Concentration of the Sample Fortification for PAH \a\
------------------------------------------------------------------------
                                       pg/[micro]L in
               Compound                 final extract    Spike recovery
                                             \b\
------------------------------------------------------------------------
                     Pre-sampling Adsorbent Standard
------------------------------------------------------------------------
\13\C6-Benzo[c]fluorene..............             100            70-130%
\13\C12-Benzo[j]fluoranthene.........             100            70-130%
------------------------------------------------------------------------
                 Pre-extraction Filter Recovery Standard
------------------------------------------------------------------------
d10-Anthracene.......................             100            70-130%
------------------------------------------------------------------------
                         Pre-extraction Standard
------------------------------------------------------------------------
\13\C6-Naphthalene...................             100            20-130%
\13\C6-2-Methylnaphthalene...........             100            20-130%
\13\C6-Acenaphthylene................             100            20-130%
\13\C6-Acenaphthene..................             100            20-130%
\13\C6-Fluorene......................             100            20-130%
\13\C6-Phenanthrene..................             100            20-130%
\13\C6-Anthracene....................             100            20-130%
\13\C6-Fluoranthene..................             100            20-130%
\13\C3-Pyrene........................             100            20-130%
\13\C6-Benz[a]anthracene.............             100            20-130%
\13\C6-Chrysene......................             100            20-130%
\13\C6-Benzo[b]fluoranthene..........             100            20-130%
\13\C6-Benzo[k]fluoranthene..........             100            20-130%
\13\C4-Benzo[e]pyrene................             100            20-130%
\13\C4-Benzo[a]pyrene................             100            20-130%
d12-Perylene.........................             100            20-130%
\13\C6-Indeno[1,2,3-cd]pyrene........             100            20-130%
\13\C6-Dibenz[a,h]anthracene.........             100            20-130%
\13\C12-Benzo[g,h,i]perylene.........             100            20-130%
------------------------------------------------------------------------
                          Pre-analysis Standard
------------------------------------------------------------------------
d10-Acenaphthene.....................             100            S/N>=10
d10-Pyrene...........................             100            S/N>=10
d12-Benzo[e]pyrene...................             100            S/N>=10
------------------------------------------------------------------------
\a\ Changes in the amounts of labeled standards added to the sample or
  its representative extract will necessitate an adjustment of the
  calibration solutions to prevent the introduction of inconsistencies.

[[Page 16762]]

 
\b\ Labeled standard concentrations are recommendations (equivalent mass
  per sample of 25 pg pre-extraction standard, as an example, based on a
  200 [micro]L extract volume split in half before cleanup with a 20
  [micro]L aliquot of a 1000 pg/[micro]L spiking solution).
  Recommendations are based on assumption that half of the extract will
  be archived before cleanup. Spike levels may be adjusted for different
  split levels.
Note: all standards used should be reported.

                        Table 23-9--Concentration of the Sample Fortification for PCB \a\
----------------------------------------------------------------------------------------------------------------
                                                                               pg/[micro]L in
                           Compound                               BZ No.\b\     final extract    Spike recovery
                                                                                     \c\
----------------------------------------------------------------------------------------------------------------
                                         Pre-sampling Adsorbent Standard
----------------------------------------------------------------------------------------------------------------
\13\C12-3,3'-DiCB............................................             11L             100            70-130%
\13\C12-2,4',5-TrCB..........................................             31L             100            70-130%
\13\C12-2,2',3,5',6-PeCB.....................................             95L             100            70-130%
\13\C12-2,2',4,4',5,5'-HxCB..................................            153L             100            70-130%
----------------------------------------------------------------------------------------------------------------
                                     Pre-extraction Filter Recovery Standard
----------------------------------------------------------------------------------------------------------------
\13\C12-2,3,3',4,5,5'-HxCB...................................            159L             100            70-130%
----------------------------------------------------------------------------------------------------------------
                                             Pre-extraction Standard
----------------------------------------------------------------------------------------------------------------
\13\C12-2-MoCB (WDC).........................................              1L             100            20-145%
\13\C12-4-MoCB (WDC).........................................              3L             100            20-145%
\13\C12-2,2'-DiCB (WDC)......................................              4L             100            20-145%
\13\C12-4,4'-DiCB (WDC)......................................             15L             100            20-145%
\13\C12-2,2',6-TrCB (WDC)....................................             19L             100            20-145%
\13\C12-3,4',4'-TrCB (WDC)...................................             37L             100            20-145%
\13\C12-2,2',6,6'-TeCB (WDC).................................             54L             100            20-145%
\13\C12-3,3',4,4'-TeCB (WDC) (WHOT) (NOAAT)..................             77L             100            20-145%
\13\C12-3,4,4',5-TeCB (WHOT).................................             81L             100            20-145%
\13\C12-2,2',4,6,6'-PeCB (WDC)...............................            104L             100            20-145%
\13\C12-2,3,3',4,4'-PeCB (WHOT)..............................            105L             100            20-145%
\13\C12-2,3,4,4',5-PeCB (WHO)................................            114L             100            20-145%
\13\C12-2,3',4,4',5-PeCB (WHOT)..............................            118L             100            20-145%
\13\C12-2',3,4,4',5-PeCB (WHOT)..............................            123L             100            20-145%
\13\C12-3,3',4,4',5-PeCB (WDC) (WHOT)........................            126L             100            20-145%
\13\C12-2,2',4,4',6,6'-HxCB (WDC)............................            155L             100            20-145%
\13\C12-2,3,3',4,4',5-HxCB (WHOT)............................            156L             100            20-145%
\13\C12-2,3,3',4,4',5'-HxCB (WHOT)...........................            157L             100            20-145%
\13\C12-2,3',4,4',5,5'-HxCB (WHOT)...........................            167L             100            20-145%
\13\C12-3,3',4,4',5,5'-HxCB (WDC) (WHOT) (NOAAT).............            169L             100            20-145%
\13\C12-2,2',3,3',4,4',5'-HpCB (NOAAT).......................            170L             100            20-145%
\13\C12-2,2',3,4,4',5,5'-HpCB (NOAAT)........................            180L             100            20-145%
\13\C12-2,2',3,4',5,6,6'-HpCB (WDC)..........................            188L             100            20-145%
\13\C12-2,3,3',4,4',5,5'-HpCB (WDC) (WHOT)...................            189L             100            20-145%
\13\C12-2,2',3',3',5,5',6,6'-OcCB (WDC)......................            202L             100            20-145%
\13\C12-2,3',3',4,4',5,5',6-OcCB (WDC).......................            205L             100            20-145%
\13\C12-2,2',3,3',4,4',5,5',6-NoCB (WDC).....................            206L             100            20-145%
\13\C12-2,2',3,3',4,5,5',6,6'-NoCB (WDC).....................            208L             100            20-145%
\13\C12-DeCB (WDC)...........................................            209L             100            20-145%
----------------------------------------------------------------------------------------------------------------
                                              Pre-analysis Standard
----------------------------------------------------------------------------------------------------------------
\13\C12-2,5-DiCB.............................................              9L             100            S/N>=10
\13\C12-2,2',5,5'-TeCB (NOAAT)...............................             52L             100            S/N>=10
\13\C12-2,2',4,5,5'-PeCB (NOAAT).............................            101L             100            S/N>=10
\13\C12-2,2',3,4,4',5'-HxCB (NOAAT)..........................            138L             100            S/N>=10
\13\C12-2,2',3,3',4,4',5,5'-OcCB.............................            194L             100            S/N>=10
----------------------------------------------------------------------------------------------------------------
                                            Optional Cleanup Standard
----------------------------------------------------------------------------------------------------------------
\13\C12-2-MoCB (NOAAT).......................................             28L             100            20-130%
\13\C12-2,2',4,5,5'-PeCB.....................................            111L             100            20-130%
\13\C12-2,2',3,3',5,5',6,6'-OcCB.............................            178L             100            20-130%
----------------------------------------------------------------------------------------------------------------
                                           Alternate Recovery Standard
----------------------------------------------------------------------------------------------------------------
\13\C12-2,3',4',5-TeCB.......................................             70L             100            20-130%
\13\C12-2,3,4,4'-TeCB........................................             60L             100            20-130%
\13\C12-3,3',4,5,5'-PeCB.....................................            127L             100            20-130%
----------------------------------------------------------------------------------------------------------------
\a\ Changes in the amounts of spike standards added to the sample or its representative extract will necessitate
  an adjustment of the calibration solutions to prevent the introduction of inconsistencies.
\b\ BZ No.: Ballschmiter and Zell 1980, or IUPAC number.

[[Page 16763]]

 
\c\ Labeled standard concentrations are recommendations (equivalent mass per sample of 25 pg pre-extraction
  standard, as an example, based on a 200 [micro]L extract volume split in half before cleanup with a 20
  [micro]L aliquot of a 1000 pg/[micro]L spiking solution). Recommendations are based on assumption that half of
  the extract will be archived before cleanup. Spike levels may be adjusted for different split levels.
NOAAT = PCB considered toxic by the National Oceanic and Atmospheric Administration.
WHOT = PCB considered toxic by the World Health Organization.
Note: all standards used should be reported.

                    Table 23-10--Sample Storage Conditions \a\ and Laboratory Hold Times \b\
----------------------------------------------------------------------------------------------------------------
              Sample type                      PCDD/PCDF                   PAH                      PCB
----------------------------------------------------------------------------------------------------------------
                                      Field Storage and Shipping Conditions
----------------------------------------------------------------------------------------------------------------
All Field Samples.....................  <=20 [deg]C, (68         <=20 [deg]C, (68         <=20 [deg]C, (68
                                         [deg]F).                 [deg]F).                 [deg]F).
----------------------------------------------------------------------------------------------------------------
                                          Laboratory Storage Conditions
----------------------------------------------------------------------------------------------------------------
Sampling Train Rinses and Filters.....  <=6 [deg]C (43 [deg]F).  <=6 [deg]C (43 [deg]F).  <=6 [deg]C (43
                                                                                           [deg]F).
Adsorbent.............................  <=6 [deg]C (43 [deg]F).  <=6 [deg]C (43 [deg]F).  <=6 [deg]C (43
                                                                                           [deg]F).
Extract and Archive...................  <26 [deg]C (79 [deg]F)   <-10 [deg]C (14 [deg]F)  <-10 [deg]C (14
                                         \c\.                                              [deg]F).
----------------------------------------------------------------------------------------------------------------
                                              Laboratory Hold Times
----------------------------------------------------------------------------------------------------------------
Extract and Archive...................  One year...............  45 Days................  One year.
----------------------------------------------------------------------------------------------------------------
\a\ Samples and extracts must be stored in the dark.
\b\ Hold times begin from the time the laboratory receives the sample.
\c\ Room temperature is acceptable if PCDD/PCDF are the only target compounds.
Note: Hold times for PCDD/PCDF and PCB are recommendations.

         Table 23-11--Concentration of the Initial Calibration Standard Solutions for PCDD and PCDF \a\
                                                   [pg/[mu]L]
----------------------------------------------------------------------------------------------------------------
                                      Cal 1                                                              Cal 7
        Standard compound          (optional)    Cal 2      Cal 3      Cal 4      Cal 5      Cal 6    (optional)
----------------------------------------------------------------------------------------------------------------
Target (Unlabeled) Analytes......        0.50        1.0        5.0       10.0         25         50         100
Pre-sampling Adsorbent Standard..          50         50         50         50         50         50          50
Pre-extraction Filter Recovery             50         50         50         50         50         50          50
 Standard........................
Pre-extraction Standard (\13\C12-          50         50         50         50         50         50          50
 OCDD, \13\C12-OCDF-100 pg/[mu]L)
Pre-analysis Standard............          50         50         50         50         50         50          50
Alternate Recovery Standard......          50         50         50         50         50         50          50
----------------------------------------------------------------------------------------------------------------
\a\ Assumes 1 [mu]L injection volume or the injection volume for standards and samples is the same.

              Table 23-12--Concentration of the Initial Calibration Standard Solutions for PAH \a\
                                                   [pg/[mu]L]
----------------------------------------------------------------------------------------------------------------
                                      Cal 1                                                              Cal 7
        Standard compound          (optional)    Cal 2      Cal 3      Cal 4      Cal 5      Cal 6    (optional)
----------------------------------------------------------------------------------------------------------------
Target (Unlabeled) Analytes......           1          2          4         20         80        400       1,000
Pre-sampling Adsorbent Standard..         100        100        100        100        100        100         100
Pre-extraction Filter Recovery            100        100        100        100        100        100         100
 Standard........................
Pre-extraction Standard..........         100        100        100        100        100        100         100
Pre-analysis Standard............         100        100        100        100        100        100         100
----------------------------------------------------------------------------------------------------------------
\a\ Assumes 1 [mu]L injection volume.

              Table 23-13--Concentration of the Initial Calibration Standard Solutions for PCB \a\
                                                   [pg/[mu]L]
----------------------------------------------------------------------------------------------------------------
                                      Cal 1                                                              Cal 7
        Standard compound          (optional)    Cal 2      Cal 3      Cal 4      Cal 5      Cal 6    (optional)
----------------------------------------------------------------------------------------------------------------
Target (Unlabeled) Analytes......        0.50          1          5         10         50        400       2,000
Pre-sampling Adsorbent Standard..         100        100        100        100        100        100         100
Pre-extraction Filter Recovery            100        100        100        100        100        100         100
 Standard........................
Pre-extraction Standard..........         100        100        100        100        100        100         100
Pre-analysis Standard............         100        100        100        100        100        100         100
Alternate Standard...............         100        100        100        100        100        100         100
----------------------------------------------------------------------------------------------------------------
\a\ Assumes 1 [mu]L injection volume.

[[Page 16764]]

Table 23-14--Minimum Requirements for Initial and Continuing Calibration
     Response Factors for Isotopically Labeled and Native Compounds
------------------------------------------------------------------------
                                                            Continuing
                                            Initial      calibration RRF
             Analyte group                calibration      compared to
                                            RRF RSD       ICAL RRF  (PD)
------------------------------------------------------------------------
Native (Unlabeled) Analytes...........               10               25
Pre-sampling Adsorbent Standard.......               20               25
Pre-extraction Filter Recovery                       20               25
 Standard.............................
Pre-extraction Standard...............               20               30
Alternative Recovery Standard.........               20               30
------------------------------------------------------------------------

                      Table 23-15--Recommended Ion Type and Acceptable Ion Abundance Ratios
----------------------------------------------------------------------------------------------------------------
                                                                    Theoretical    Lower control   Upper control
       Number of chlorine atoms                 Ion type               ratio           limit           limit
----------------------------------------------------------------------------------------------------------------
1.....................................  M/M+2...................            3.13            2.66            3.60
2.....................................  M/M+2...................            1.56            1.33            1.79
3.....................................  M/M+2...................            1.04            0.88            1.20
4.....................................  M/M+2...................            0.77            0.65            0.89
5.....................................  M+2/M+4.................            1.55            1.32            1.78
6.....................................  M+2/M+4.................            1.24            1.05            1.43
6 \a\.................................  M/M+2...................            0.51            0.43            0.59
7.....................................  M+2/M+4.................            1.05            0.89            1.21
7 \b\.................................  M/M+2...................            0.44            0.37            0.51
8.....................................  M+2/M+4.................            0.89            0.76            1.02
9.....................................  M+2/M+4.................            0.77            0.65            0.89
10....................................  M+4/M+6.................            1.16            0.99            1.33
----------------------------------------------------------------------------------------------------------------
\a\ Used only for \13\C-HxCDF.
\b\ Used only for \13\C-HpCDF.

                                  Table 23-16--Typical DB5-MS Column Conditions
----------------------------------------------------------------------------------------------------------------
           Column parameter                   PCDD/PCDF                   PAH                      PCB
----------------------------------------------------------------------------------------------------------------
Injector temperature.................  250 [deg]C.............  320 [deg]C.............  270 [deg]C.
Initial oven temperature.............  100 [deg]C.............  100 [deg]C.............  100 [deg]C.
Initial hold time (minutes)..........  2......................  2......................  2.
Temperature program..................  100 to 190 [deg]C at 40  100 to 300 [deg]C at     100 to 150 [deg]C at 15
                                        [deg]C/min, then 190     8[deg]C/min.             [deg]C/min, then 150
                                        to 300 [deg]C at                                  to 290 [deg]C at 2.5
                                        3[deg]C/min.                                      [deg]C/min.
----------------------------------------------------------------------------------------------------------------

             Table 23-17--Assignment of Pre-Extraction Standards for Quantitation of Target PCB \b\
----------------------------------------------------------------------------------------------------------------
                PCB Congener                    BZ No.\a\               Labeled analog                BZ No.
----------------------------------------------------------------------------------------------------------------
2,4'-DiCB (NOAAT)..........................               8  \13\C12-2,2'-DiCB..................              4L
2,2',5-TrCB (NOAAT)........................              18  \13\C12-2,2',6-TrCB................             19L
2,4,4'-TrCB (NOAAT)........................              28  \13\C12-2,2',6-TrCB................             19L
2,2',3,5'-TeCB (NOAAT).....................              52  \13\C12-2,2',6,6'-TeCB.............             54L
2,2',5,5'-TeCB (NOAAT).....................              52  \13\C12-2,2',6,6'-TeCB.............             54L
2,3',4,4'-TeCB (NOAAT).....................              66  \13\C12-2,2',6,6'-TeCB.............             54L
3,3',4,4'-TeCB (NOAAT) (WHOT)..............              77  \13\C12-3,3',4,4'-TeCB.............             77L
3,4,4',5-TeCB (WHOT).......................              81  \13\C12-3,4,4'',5-TeCB.............             81L
2,2',4,5,5'-PeCB (NOAAT)...................             101  \13\C12-2,2',4,5,5'-PeCB...........            104L
2,3,3',4,4'-PeCB (NOAAT) (WHOT)............             105  \13\C12-2,3,3',4,4'-PeCB...........            105L
2,3,4,4',5-PeCB (WHOT).....................             114  \13\C12-2,3,4,4',5-PeCB............            114L
2,3',4,4',5-PeCB (WHOT)....................             118  \13\C12-2,3',4,4',5-PeCB...........            118L
2',3,4,4',5-PeCB (WHOT)....................             123  \13\C12-2',3,4,4',5-PeCB...........            123L
3,3',4,4',5-PeCB (NOAAT) (WHOT)............             126  \13\C12-3,3',4,4',5-PeCB...........            126L
2,2',3,3',4,4'-HxCB (NOAAT)................             128  \13\C12-2,2',4,4',6,6'-HxCB........            155L
2,2',3,4,4',5'-HxCB (NOAAT)................             138  \13\C12-2,2',4,4',6,6'-HxCB........            155L
2,2',4,4',5,5'-HxCB (NOAAT)................             153  \13\C12-2,2',4,4',6,6'-HxCB........            155L
2,3,3',4,4',5-HxCB (WHOT)..................             156  \13\C12-2,3,3',4,4',5-HxCB.........            156L
2,3,3',4,4',5'-HxCB (WHOT).................             157  \13\C12-2,3,3',4,4',5'-HxCB........            157L
2,3',4,4',5,5'-HxCB (WHOT).................             167  \13\C12-2,3',4,4',5,5'-HxCB........            167L
3,3',4,4',5,5'-HxCB (NOAAT) (WHOT).........             169  \13\C12-3,3',4,4',5,5'-HxCB........            169L
2,2',3,3',4,4',5-HpCB (NOAAT)..............             170  \13\C12-2,2',3,3',4,4',5'-HpCB.....            170L
2,2',3,4,4',5,5'-HpCB (NOAAT)..............             180  \13\C12-2,2',3,4,4',5,5'-HpCB......            180L
2,2',3,4',5,5',6-HpCB (NOAAT)..............             187  \13\C12-2,2',3,4',5,6,6'-HpCB......            188L
2,3,3',4,4',5,5'-HpCB (WHOT)...............             189  \13\C12-2,3,3',4,4',5,5'-HpCB......            189L

[[Page 16765]]

 
2,2',3,3',4,4',5,6-OcCB (NOAAT)............             195  \13\C12-2,2' 3,3',5,5',6,6'-OcCB...            202L
2,2',3,3',4,4',5,5',6-NoCB (NOAAT).........             206  \13\C12-2,2',3,3',4,4',5,5',6-NoCB.            206L
2,2',3,3',4,4',5,5',6,6'-DeCB (NOAAT)......             209  \13\C12-DeCB.......................            209L
----------------------------------------------------------------------------------------------------------------
\a\ BZ No.: Ballschmiter and Zell 1980, or IUPAC number.
\b\ Assignments assume the use of the SPB-Octyl column. In the event you choose another column, you may select
  the labeled standard having the same number of chlorine substituents and the closest retention time to the
  target analyte in question as the labeled standard to use for quantitation.
NOAAT = PCB considered toxic by the National Oceanic and Atmospheric Administration.
WHOT = PCB considered toxic by the World Health Organization.

                        Table 23-18--Initial Demonstration of Capability QC Requirements
----------------------------------------------------------------------------------------------------------------
                                                                  Specification and
             Section                      Requirement                 frequency            Acceptance criteria
----------------------------------------------------------------------------------------------------------------
9.3.5............................  Demonstration of low       Analyze an LMB after the  Confirm that the LMB is
                                    system background.         highest calibration       free from contamination
                                                               standard.                 as defined in Section
                                                              Note: If an automated      13.1.
                                                               extraction system is
                                                               used, an LMB must be
                                                               extracted on each port.
9.3.7............................  Determination of MDL.....  Prepare, extract, and     See MDL confirmation.
                                                               analyze 7 replicate
                                                               spiked samples (spiked
                                                               within 2 to 10 times of
                                                               the expected MDL) and 7
                                                               LMBs.
                                                              See 40 CFR Part 136
                                                               Appendix B.
9.3.8............................  MDL confirmation.........  Prepare, extract, and     Confirm that the target
                                                               analyze a spiked sample   compounds meet the
                                                               (spiked at the MDL).      qualitative
                                                                                         identification criteria
                                                                                         in Section 11.4.3.4 of
                                                                                         this method.
9.3.9............................  Demonstration of           Prepare, extract, and     Percent relative
                                    precision.                 analyze 7 replicate       standard deviation must
                                                               spiked samples (spiked    be <=20%.
                                                               near mid-range).
9.3.10...........................  Demonstration of accuracy  Calculate mean recovery   Mean recovery within 70-
                                                               for replicate spiked      130% of true value.
                                                               samples in Section
                                                               9.3.9.
9.3.2............................  Lowest Calibration         Establish a target        Upper PIR <=150%.
                                    Concentration              concentration for the    Lower PIR >=50%.
                                    Confirmation.              lowest calibration
                                                               based on the intended
                                                               use of the method.
9.3.6............................  Calibration Verification.  Analyze a mid-level QCS.  Within limits in Section
                                                                                         13.11.
----------------------------------------------------------------------------------------------------------------

[[Page 16766]]

[GRAPHIC] [TIFF OMITTED] TR20MR23.019

Figure 23-1. Method 23 Sampling Train

[[Page 16767]]

[GRAPHIC] [TIFF OMITTED] TR20MR23.020

Figure 23-2. Condenser and Adsorbent Module

[[Page 16768]]

[GRAPHIC] [TIFF OMITTED] TR20MR23.021

Figure 23-3. Soxhlet/Dean-Stark Extractor

[[Page 16769]]

[GRAPHIC] [TIFF OMITTED] TR20MR23.022

Figure 23-4. Sample Preparation Flow Chart

[[Page 16770]]

Appendix A to Method 23

                   Complete List of 209 PCB Congeners and Their Isomers With Corresponding Isotope Dilution Quantitation Standards \a\
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                                   Unlabeled target                    Pre-extraction                    Unlabeled target
      Pre-extraction standard        BZ \b\ No.         analyte         BZ \b\ No.        standard         BZ \b\ No.         analyte         BZ \b\ No.
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                       MoCB                         DiCB
--------------------------------------------------------------------------------------------------------------------------------------------------------
\13\C12-2-MoCB....................           1L  2-MoCB..............            1  \13\C12-2,2'-DiCB...           4L  2,2'-DiCB...........            4
\13\C12-2-MoCB....................           1L  3-MoCB..............            2  \13\C12-2,2'-DiCB...           4L  2,3-DiCB............            5
\13\C12-4-MoCB....................           3L  4-MoCB..............            3  \13\C12-2,2'-DiCB...           4L  2,3'-DiCB...........            6
                                                                                    \13\C12-2,2'-DiCB...           4L  2,4-DiCB............            7
                                                                                    \13\C12-2,2'-DiCB...           4L  2,4'-DiCB...........            8
                                                                                    \13\C12-2,2'-DiCB...           4L  2,5-DiCB............            9
                                                                                    \13\C12-2,2'-DiCB...           4L  2,6-DiCB............           10
                                                                                    \13\C12-2,2'-DiCB...           4L  3,3'-DiCB...........           11
                                                                                    \13\C12-2,2'-DiCB...           4L  3,4-DiCB............           12
                                                                                    \13\C12-2,2'-DiCB...           4L  3,4'-DiCB...........           13
                                                                                    \13\C12-2,2'-DiCB...           4L  3,5-DiCB............           14
                                                                                    \13\C12-4,4'-DiCB...          15L  4,4'-DiCB...........           15
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                                                          TrCB
--------------------------------------------------------------------------------------------------------------------------------------------------------
\13\C12-2,2',6-TrCB...............          19L  2,2',3-TrCB.........           16  \13\C12-3,4,4'-TrCB.          19L  2,4,4'-TrCB.........           28
\13\C12-2,2',6-TrCB...............          19L  2,2',4-TrCB.........           17  \13\C12-3,4,4'-TrCB.          19L  2,4,5-TrCB..........           29
\13\C12-2,2',6-TrCB...............          19L  2,2',5-TrCB.........           18  \13\C12-3,4,4'-TrCB.          19L  2,4,6-TrCB..........           30
\13\C12-2,2',6-TrCB...............          19L  2,2',6-TrCB.........           19  \13\C12-3,4,4'-TrCB.          19L  2,4',5-TrCB.........           31
\13\C12-2,2',6-TrCB...............          19L  2,3,3'-TrCB.........           20  \13\C12-3,4,4'-TrCB.          19L  2,4',6-TrCB.........           32
\13\C12-2,2',6-TrCB...............          19L  2,3,4-TrCB..........           21  \13\C12-3,4,4'-TrCB.          19L  2',3,4-TrCB.........           33
\13\C12-2,2',6-TrCB...............          19L  2,3,4'-TrCB.........           22  \13\C12-3,4,4'-TrCB.          19L  2',3,5-TrCB.........           34
\13\C12-2,2',6-TrCB...............          19L  2,3,5- TrCB.........           23  \13\C12-3,4,4'-TrCB.          19L  3,3',4-TrCB.........           35
\13\C12-2,2',6-TrCB...............          19L  2,3,6- TrCB.........           23  \13\C12-3,4,4'-TrCB.          19L  3,3',5-TrCB.........           36
\13\C12-2,2',6-TrCB...............          19L  2,3',4-TrCB.........           25  \13\C12-3,4',4'-TrCB          37L  3,4,4'-TrCB.........           37
\13\C12-2,2',6-TrCB...............          19L  2,3',5-TrCB.........           26  \13\C12-3,4',4'-TrCB          37L  3,4,5-TrCB..........           38
\13\C12-2,2',6-TrCB...............          19L  2,3',6-TrCB.........           27  \13\C12-3,4',4'-TrCB          37L  3,4',5-TrCB.........           39
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                                                          TeCB
--------------------------------------------------------------------------------------------------------------------------------------------------------
\13\C12-2,2',6,6'-TeCB............          54L  2,2',3,3'-TeCB......           40  \13\C12-2,2',6,6'-            54L  2,3,4,5-TeCB........           61
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,2',3,4-TeCB.......           41  \13\C12-2,2',6,6'-            54L  2,3,4,6-TeCB........           62
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,2',3,4'-TeCB......           42  \13\C12-2,2',6,6'-            54L  2,3,4',5-TeCB.......           63
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,2',3,5-TeCB.......           43  \13\C12-2,2',6,6'-            54L  2,3,4',6-TeCB.......           64
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,2',3,5'-TeCB......           44  \13\C12-2,2',6,6'-            54L  2,3,5,6-TeCB........           65
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,2',3,6-TeCB.......           45  \13\C12-2,2',6,6'-            54L  2,3',4,4'-TeCB......           66
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,2',3,6'-TeCB......           46  \13\C12-2,2',6,6'-            54L  2,3',4,5-TeCB.......           67
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,2',4,4'-TeCB......           47  \13\C12-2,2',6,6'-            54L  2,3',4,5'-TeCB......           68
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,2',4,5-TeCB.......           48  \13\C12-2,2',6,6'-            54L  2,3',4,6-TeCB.......           69
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,2',4,5'-TeCB......           49  \13\C12-2,2',6,6'-            54L  2,3',4',5-TeCB......           70
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,2',4,6-TeCB.......           50  \13\C12-2,2',6,6'-            54L  2,3',4',6-TeCB......           71
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,2',4,6'-TeCB......           51  \13\C12-2,2',6,6'-            54L  2,3',5,5'-TeCB......           72
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,2',5,5'-TeCB......           52  \13\C12-2,2',6,6'-            54L  2,3',5',6-TeCB......           73
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,2',5,6'-TeCB......           53  \13\C12-2,2',6,6'-            54L  2,4,4',5-TeCB.......           74
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,2',6,6'-TeCB......           54  \13\C12-2,2',6,6'-            54L  2,4,4',6-TeCB.......           75
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,3,3',4'-TeCB......           55  \13\C12-2,2',6,6'-            54L  2',3,4,5-TeCB.......           76
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,3,3',4'-TeCB......           56  \13\C12-3,3',4,4'-            77L  3,3',4,4'-TeCB......           77
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,3,3',5-TeCB.......           57  \13\C12-3,3',4,4'-            77L  3,3',4,5-TeCB.......           78
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,3,3',5'-TeCB......           58  \13\C12-3,3',4,4'-            77L  3,3',4,5'-TeCB......           79
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,3,3',6-TeCB.......           59  \13\C12-3,3',4,4'-            77L  3,3',5,5'-TeCB......           80
                                                                                     TeCB.
\13\C12-2,2',6,6'-TeCB............          54L  2,3,4,4'-TeCB.......           60  \13\C12-3,4,4',5-             81L  3,4,4',5-TeCB.......           81
                                                                                     TeCB.
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                                                          PeCB
--------------------------------------------------------------------------------------------------------------------------------------------------------
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',3,3',4-PeCB....           82  \13\C12-2,3,3',4,4'-         105L  2,3,3',4,4'-PeCB....          105
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',3,3',5-PeCB....           83  \13\C12-2,3,3',4,4'-         105L  2,3,3',4,5-PeCB.....          106
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',3,3',6-PeCB....           84  \13\C12-2,3,3',4,4'-         105L  2,3,3',4',5-PeCB....          107
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',3,4,4'-PeCB....           85  \13\C12-2,3,3',4,4'-         105L  2,3,3',4,5'-PeCB....          108
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',3,4,5-PeCB.....           86  \13\C12-2,3,3',4,4'-         105L  2,3,3',4,6-PeCB.....          109
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',3,4,5'-PeCB....           87  \13\C12-2,3,3',4,4'-         105L  2,3,3',4',6-PeCB....          110
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',3,4,6-PeCB.....           88  \13\C12-2,3,3',4,4'-         105L  2,3,3',5,5'-PeCB....          111
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',3,4,6'-PeCB....           89  \13\C12-2,3,3',4,4'-         105L  2,3,3',5,6-PeCB.....          112
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',3,4',5-PeCB....           90  \13\C12-2,3,3',4,4'-         105L  2,3,3',5',6-PeCB....          113
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',3,4',6-PeCB....           91  \13\C12-2,3,4,4',5-          114L  2,3,4,4',5-PeCB.....          114
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',3,5,5'-PeCB....           92  \13\C12-2,3,4,4',5-          114L  2,3,4,4',6-PeCB.....          115
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',3,5,6-PeCB.....           93  \13\C12-2,3,4,4',5-          114L  2,3,4,5,6-PeCB......          116
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',3,5,6'-PeCB....           94  \13\C12-2,3,4,4',5-          114L  2,3,4',5,6-PeCB.....          117
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',3,5',6-PeCB....           95  \13\C12-2,3',4,4',5-         118L  2,3',4,4',5-PeCB....          118
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',3,6,6'-PeCB....           96  \13\C12-2,3',4,4',5-         118L  2,3',4,4',6-PeCB....          119
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',3',4,5-PeCB....           97  \13\C12-2,3',4,4',5-         118L  2,3',4,5,5'-PeCB....          120
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',3',4,6-PeCB....           98  \13\C12-2,3',4,4',5-         118L  2,3',4,5,'6-PeCB....          121
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',4,4',5-PeCB....           99  \13\C12-2,3',4,4',5-         118L  2',3,3',4,5-PeCB....          122
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',4,4',6-PeCB....          100  \13\C12-2',3,4,4',5-         123L  2',3,4,4',5-PeCB....          123
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',4,5,5'-PeCB....          101  \13\C12-2',3,4,4',5-         123L  2',3,4,5,5'-PeCB....          124
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',4,5,6'-PeCB....          102  \13\C12-2',3,4,4',5-         123L  2',3,4,5,6'-PeCB....          125
                                                                                     PeCB.
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',4,5,'6-PeCB....          103  \13\C12-3,3',4,4',5-         126L  3,3',4,4',5-PeCB....          126
                                                                                     PeCB.

[[Page 16771]]

 
\13\C12-2,2',4,6,6'-PeCB..........         104L  2,2',4,6,6'-PeCB....          104  \13\C12-3,3',4,4',5-         126L  3,3',4,5,5'-PeCB....          127
                                                                                     PeCB.
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                                                          HxCB
--------------------------------------------------------------------------------------------------------------------------------------------------------
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,3',4,4'-HxCB.          128  \13\C12-                     155L  2,2',3,4',5',6-HxCB.          149
                                                                                     2,2',4,4',6,6'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,3',4,5-HxCB..          129  \13\C12-                     155L  2,2',3,4',6,6'-HxCB.          150
                                                                                     2,2',4,4',6,6'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,3',4,5'-HxCB.          130  \13\C12-                     155L  2,2',3,5,5',6-HxCB..          151
                                                                                     2,2',4,4',6,6'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,3',4,6-HxCB..          131  \13\C12-                     155L  2,2',3,5,6,6'-HxCB..          152
                                                                                     2,2',4,4',6,6'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,3',4,6'-HxCB.          132  \13\C12-                     155L  2,2',4,4',5,5'-HxCB.          153
                                                                                     2,2',4,4',6,6'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,3',5,5'-HxCB.          133  \13\C12-                     155L  2,2',4,4',5',6-HxCB.          154
                                                                                     2,2',4,4',6,6'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,3',5,6-HxCB..          134  \13\C12-                     155L  2,2',4,4',6,6'-HxCB.          155
                                                                                     2,2',4,4',6,6'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,3',5,6'-HxCB.          135  \13\C12-                     156L  2,3,3',4,4',5-HxCB..          156
                                                                                     2,3,3',4,4',5- HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,3',6,6'-HxCB.          136  \13\C12-                     157L  2,3,3',4,4',5'-HxCB.          157
                                                                                     2,3,3',4,4',5'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,4,4',5-HxCB..          137  \13\C12-                     157L  2,3,3',4,4',6-HxCB..          158
                                                                                     2,3,3',4,4',5'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,4,4',5'-HxCB.          138  \13\C12-                     157L  2,3,3',4,5,5'-HxCB..          158
                                                                                     2,3,3',4,4',5'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,4,4',6-HxCB..          139  \13\C12-                     157L  2,3,3',4,5,6-HxCB...          160
                                                                                     2,3,3',4,4',5'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,4,4',6'-HxCB.          140  \13\C12-                     157L  2,3,3',4,5',6-HxCB..          161
                                                                                     2,3,3',4,4',5'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,4,5,5'-HxCB..          141  \13\C12-                     157L  2,3,3',4',5,5'-HxCB.          162
                                                                                     2,3,3',4,4',5'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,4,5,6-HxCB...          142  \13\C12-                     157L  2,3,3',4',5,6-HxCB..          163
                                                                                     2,3,3',4,4',5'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,4,5,6'-HxCB..          143  \13\C12-                     157L  2,3,3',4',5',6-HxCB.          164
                                                                                     2,3,3',4,4',5'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,4,5',6-HxCB..          144  \13\C12-                     157L  2,3,3',5,5',6-HxCB..          165
                                                                                     2,3,3',4,4',5'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,4,6,6'-HxCB..          145  \13\C12-                     157L  2,3,4,4',5,6-HxCB...          166
                                                                                     2,3,3',4,4',5'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,4',5,5'-HxCB.          146  \13\C12-                     167L  2,3',4,4',5,5'-HxCB.          167
                                                                                     2,3',4,4',5,5'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,4',5,6-HxCB..          147  \13\C12-                     167L  2,3',4,4',5',6-HxCB.          168
                                                                                     2,3',4,4',5,5'-HxCB.
\13\C12-2,2',4,4',6,6'-HxCB.......         155L  2,2',3,4',5,6'-HxCB.          148  \13\C12-                     169L  3,3',4,4',5,5'-HxCB.          169
                                                                                     3,3',4,4',5,5'-HxCB.
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                                                          HpCB
--------------------------------------------------------------------------------------------------------------------------------------------------------
\13\C12-2,2',3,4',5,6,6'-HpCB.....         188L  2,2',3,3',4,4',5-             170  \13\C12-                     188L  2,2',3,4,4',5,6'-             182
                                                  HpCB.                              2,2',3,4',5,6,6'-                  HpCB.
                                                                                     HpCB.
\13\C12-2,2',3,4',5,6,6'-HpCB.....         188L  2,2',3,3',4,4',6-             171  \13\C12-                     188L  2,2',3,4,4',5',6-             183
                                                  HpCB.                              2,2',3,4',5,6,6'-                  HpCB.
                                                                                     HpCB.
\13\C12-2,2',3,4',5,6,6'-HpCB.....         188L  2,2',3,3',4,5,5'-             172  \13\C12-                     188L  2,2',3,4,4',5',6-             184
                                                  HpCB.                              2,2',3,4',5,6,6'-                  HpCB.
                                                                                     HpCB.
\13\C12-2,2',3,4',5,6,6'-HpCB.....         188L  2,2',3,3',4,5,6-HpCB          173  \13\C12-                     188L  2,2',3,4,4',6,6'-             185
                                                                                     2,2',3,4',5,6,6'-                  HpCB.
                                                                                     HpCB.
\13\C12-2,2',3,4',5,6,6'-HpCB.....         188L  2,2',3,3',4,5,6'-             174  \13\C12-                     188L  2,2',3,4,5,5',6-HpCB          186
                                                  HpCB.                              2,2',3,4',5,6,6'-
                                                                                     HpCB.
\13\C12-2,2',3,4',5,6,6'-HpCB.....         188L  2,2',3,3',4,5',6-             175  \13\C12-                     188L  2,2',3,4',5,5',6-             187
                                                  HpCB.                              2,2',3,4',5,6,6'-                  HpCB.
                                                                                     HpCB.
\13\C12-2,2',3,4',5,6,6'-HpCB.....         188L  2,2',3,3',4,6,6'-             176  \13\C12-                     188L  2,2',3,4',5,6,6'-             188
                                                  HpCB.                              2,2',3,4',5,6,6'-                  HpCB.
                                                                                     HpCB.
\13\C12-2,2',3,4',5,6,6'-HpCB.....         188L  2,2',3,3',4',5,6-             177  \13\C12-                     189L  2,3,3',4,4',5,5'-             189
                                                  HpCB.                              2,3,3',4,4',5,5'-                  HpCB.
                                                                                     HpCB.
\13\C12-2,2',3,4',5,6,6'-HpCB.....         188L  2,2',3,3',5,5',6-             178  \13\C12-                     189L  2,3,3',4,4',5,6-HpCB          190
                                                  HpCB.                              2,3,3',4,4',5,5'-
                                                                                     HpCB.
\13\C12-2,2',3,4',5,6,6'-HpCB.....         188L  2,2',3,3',5,6,6'-             179  \13\C12-                     189L  2,3,3',4,4',5',6-             191
                                                  HpCB.                              2,3,3',4,4',5,5'-                  HpCB.
                                                                                     HpCB.
\13\C12-2,2',3,4',5,6,6'-HpCB.....         188L  2,2',3,4,4',5,5'-             180  \13\C12-                     189L  2,3,3',4,5,5',6-HpCB          192
                                                  HpCB.                              2,3,3',4,4',5,5'-
                                                                                     HpCB.
\13\C12-2,2',3,4',5,6,6'-HpCB.....         188L  2,2',3,4,4',5,6-HpCB          181  \13\C12-                     189L  2,3,3',4',5,5',6-             193
                                                                                     2,3,3',4,4',5,5'-                  HpCB.
                                                                                     HpCB.
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                       OcCB                         NoCB
--------------------------------------------------------------------------------------------------------------------------------------------------------
\13\C12-2,2',3,3',5,5',6,6'-OcCB..         202L  2,2',3,3',4,4',5,5'-          194  \13\C12-                     206L  2,2',3,3',4,4',5,5',          206
                                                  OcCB.                              2,2',3,3',4,4',5,5'                6-NoCB.
                                                                                     ,6-NoCB.

[[Page 16772]]

 
\13\C12-2,2',3,3',5,5',6,6'-OcCB..         202L  2,2',3,3',4,4',5,6-           195  \13\C12-                     206L  2,2',3,3',4,4',5,6,6          207
                                                  OcCB.                              2,2',3,3',4,4',5,5'                '-NoCB.
                                                                                     ,6-NoCB.
\13\C12-2,2',3,3',5,5',6,6'-OcCB..         202L  2,2',3,3',4,4',5,6'-          196  \13\C12-                     208L  2,2',3,3',4,5,5',6,6          208
                                                  OcCB.                              2,2',3,3',4,5,5',6,                '- NoCB.
                                                                                     6'-NoCB.
                                                                                   ---------------------------------------------------------------------
\13\C12-2,2',3,3',5,5',6,6'-OcCB..         202L  2,2',3,3',4,4',6,6'-          197                                  DeCB
                                                  OcCB.
                                                                                   ---------------------------------------------------------------------
\13\C12-2,2',3,3',5,5',6,6'-OcCB..         202L  2,2',3,3',4,5,5',6-           198  \13\C12-DeCB........         209L  2,2',3,3',4,4',5,5',          209
                                                  OcCB.                                                                 6,6'-DeCB.
\13\C12-2,2',3,3',5,5',6,6'-OcCB..         202L  2,2',3,3',4,5,5',6'-          199
                                                  OcCB.
\13\C12-2,2',3,3',5,5',6,6'-OcCB..         202L  2,2',3,3',4,5,6,6'-           200
                                                  OcCB.
\13\C12-2,2',3,3',5,5',6,6'-OcCB..         202L  2,2',3,3',4,5',6,6'-          201
                                                  OcCB.
\13\C12-2,2',3,3',5,5',6,6'-OcCB..         202L  2,2',3,3',5,5',6,6'-          202
                                                  OcCB.
\13\C12-2,3',3',4,4',5,5',6-OcCB..         205L  2,2',3,4,4',5,5',6-           203
                                                  OcCB.
\13\C12-2,3',3',4,4',5,5',6-OcCB..         205L  2,2',3,4,4',5,6,6'-           204
                                                  OcCB.
\13\C12-2,3',3',4,4',5,5',6-OcCB..         205L  2,3,3',4,4',5,5',6-           205
                                                  OcCB.
--------------------------------------------------------------------------------------------------------------------------------------------------------
\a\ Assignments assume the use of the SPB-Octyl column. In the event you choose another column, you may select the labeled standard having the same
  number of chlorine substituents and the closest retention time to the target analyte in question as the labeled standard to use for quantitation.
\b\ BZ No.: Ballschmiter and Zell 1980, also referred to as IUPAC number.

Appendix B to Method 23

Preparation of XAD-2 Adsorbent Resin

1.0 Scope and Application

    XAD-2[supreg] resin, as supplied by the original manufacturer, 
is impregnated with a bicarbonate solution to inhibit microbial 
growth during storage. Remove both the salt solution and any 
residual extractable chemicals used in the polymerization process 
before use. Prepare the resin by a series of water and organic 
extractions, followed by careful drying.

2.0 Extraction

    2.1 You may perform the extraction using a Soxhlet extractor or 
other apparatus that generates resin meeting the requirements in 
Section 13.1 of Method 23. Use an all-glass thimble containing an 
extra-coarse frit for extraction of the resin. The frit is recessed 
10-15 mm above a crenellated ring at the bottom of the thimble to 
facilitate drainage. Because the resin floats on methylene chloride, 
carefully retain the resin in the extractor cup with a glass wool 
plug and stainless-steel screen. This process involves sequential 
extraction with the following recommended solvents in the listed 
order.
     Water initial rinse: Place resin in a suitable 
container, soak for approximately 5 min with Type II water, remove 
fine floating resin particles and discard the water. Fill with Type 
II water a second time, let stand overnight, remove fine floating 
resin particles, and discard the water.
     Hot water: Extract with water for 8 hr.
     Methyl alcohol: Extract for 22 hr.
     Methylene chloride: Extract for 22 hr.
     Toluene: Extract for 22 hr.
     Methylene chloride: Extract for 22 hr.

    Note: You may store the resin in a sealed glass container filled 
with toluene prior to the final toluene extraction. It may be 
necessary to repeat the final methylene chloride extractions to meet 
the cleanliness requirements in Section 13.1 of Method 23.
    2.2 You may use alternative extraction procedures to clean large 
batches of resin. Any size extractor may be constructed; the choice 
depends on the needs of the sampling programs. The resin is held in 
a glass or stainless-steel cylinder between a pair of coarse and 
fine screens. Spacers placed under the bottom screen allow for even 
distribution of clean solvent. Clean solvent is circulated through 
the resin for extraction. A flow rate is maintained upward through 
the resin to allow maximum solvent contact and prevent channeling.
    2.2.1 Experience has shown that 1 mL/g of resin extracted is the 
minimum necessary to extract and clean the resin. The aqueous rinse 
is critical to the subsequent organic rinses and may be accomplished 
by simply flushing the canister with about 1 liter of distilled 
water for every 25 g of resin. A small pump may be useful for 
pumping the water through the canister. You should perform the water 
extraction at the rate of about 20 to 40 mL/min.
    2.2.2 All materials of construction are glass, PTFE, or 
stainless steel. Pumps, if used, should not contain extractable 
materials.

3.0 Drying

    3.1 Dry the adsorbent of extraction solvent before use. This 
section provides a recommended procedure to dry adsorbent that is 
wet with solvent. However, you may use other procedures if the 
cleanliness requirements in Section 13.1 of Method 23 are met.
    3.2 Drying Column. A simple column with suitable retainers will 
hold all the XAD-2 from the extractor or the Soxhlet extractor, as 
shown in Figure B-1, with sufficient space for drying the bed while 
generating a minimum backpressure in the column.
    3.3 Drying Procedure: Dry the adsorbent using clean inert gas. 
Liquid nitrogen from a standard commercial liquid nitrogen cylinder 
has proven to be a reliable source of large volumes of gas free from 
organic contaminants. You may use high-purity tank nitrogen to dry 
the resin. However, you should pass the high-purity nitrogen through 
a bed of activated charcoal approximately 150 mL in volume prior to 
entering the drying apparatus.
    3.3.1 Connect the gas vent of a liquid nitrogen cylinder or the 
exit of the activated carbon scrubber to the column by a length of 
precleaned copper tubing (e.g., 0.95 cm ID) coiled to pass through a 
heat source. A convenient heat source is a water bath heated from a 
steam line. The final nitrogen temperature should only be warm to 
the touch and not over 40 [deg]C.
    3.3.2 Allow the methylene chloride to drain from the resin prior 
to placing the resin in the drying apparatus.

[[Page 16773]]

    3.3.3 Flow nitrogen through the drying apparatus at a rate that 
does not fluidize or agitate the resin. Continue the nitrogen flow 
until the residual solvent is removed.
    Note: Experience has shown that about 500 g of resin may be 
dried overnight by consuming a full 160-L cylinder of liquid 
nitrogen.
[GRAPHIC] [TIFF OMITTED] TR20MR23.023

Figure B-1. XAD-2 fluidized-bed drying apparatus

PART 63--NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS 
FOR SOURCE CATEGORIES

0
6. The authority citation for part 63 continues to read as follows:

    Authority:  42 U.S.C. 7401 et seq.

Subpart LL--National Emission Standards for Hazardous Air 
Pollutants for Primary Aluminum Reduction Plants

0
7. In Sec.  63.849, revise paragraphs (a)(13) and (14) to read as 
follows:

Sec.  63.849  Test methods and procedures.

* * * * *
    (a) * * *
    (13) Method 23 of Appendix A-7 of 40 CFR part 60 for the 
measurement of Polychlorinated Biphenyls (PCBs) where stack or duct 
emissions are sampled; and
    (14) Method 23 of Appendix A-7 of 40 CFR part 60 and Method 14 or 
Method 14A in Appendix A to Part 60 of this chapter or an approved 
alternative method for the concentration of PCB where emissions are 
sampled from roof monitors not employing wet roof scrubbers.
* * * * *

Subpart EEE--National Emission Standards for Hazardous Air 
Pollutants from Hazardous Waste Combustors

0
8. In Sec.  63.1208, revise paragraph (b)(1) to read as follows:

Sec.  63.1208  What are the test methods?

* * * * *
    (b) * * *
    (1) Dioxins and furans. (i) To determine compliance with the 
emission standard for dioxins and furans, you must use:
    (A) Method 0023A, Sampling Method for Polychlorinated Dibenzo-p-
Dioxins and Polychlorinated Dibenzofurans emissions from Stationary 
Sources, EPA Publication SW-846 (incorporated by reference--see Sec.  
63.14); or
    (B) Method 23, provided in Appendix A, Part 60 of this chapter.
    (ii) You must sample for a minimum of three hours, and you must 
collect a minimum sample volume of 2.5 dscm.
    (iii) You may assume that nondetects are present at zero 
concentration.
* * * * *

Subpart XXX--National Emission Standards for Hazardous Air 
Pollutants for Ferroalloys Production: Ferromanganese and 
Silicomanganese

0
9. In Sec.  63.1625, revise paragraph (b)(10) to read as follows:

Sec.  63.1625  What are the performance test and compliance 
requirements for new, reconstructed, and existing facilities?

* * * * *
    (b) * * *
    (10) Method 23 of Appendix A-7 of 40 CFR part 60 to determine PAH.
* * * * *

Subpart AAAAAAA--National Emission Standards for Hazardous Air 
Pollutants for Area Sources: Asphalt Processing and Asphalt Roofing 
Manufacturing

0
10. In table 3 to Subpart AAAAAAA of Part 63 revise the entry ``6. 
Measuring the PAH emissions'' to read as follows:

[[Page 16774]]

           Table 3 to Subpart AAAAAAA of Part 63--Test Methods
------------------------------------------------------------------------
                 For * * *                       You must use * * *
------------------------------------------------------------------------
 
                                * * * * *
6. Measuring the PAH emissions............  EPA test method 23.
------------------------------------------------------------------------

* * * * *

PART 266--STANDARDS FOR THE MANAGEMENT OF SPECIFIC HAZARDOUS WASTES 
AND SPECIFIC TYPES OF HAZARDOUS WASTE MANAGEMENT FACILITIES

0
11. The authority citation for part 266 continues to read as follows:

    Authority: 42 U.S.C. 1006, 2002(a), 3001-3009, 3014, 3017, 6905, 
6906, 6912, 6921, 6922, 6924-6927, 6934, and 6937.

Subpart H--Hazardous Waste Burned in Boilers and Industrial 
Furnaces

0
12. In Sec.  266.104, revise paragraph (e)(1) to read as follows:

Sec.  266.104  Standards to control organic emissions.

* * * * *
    (e) * * *
    (1) During the trial burn (for new facilities or an interim status 
facility applying for a permit) or compliance test (for interim status 
facilities), determine emission rates of the tetra-octa congeners of 
chlorinated dibenzo-p-dioxins and dibenzofurans (CDDs/CDFs) using 
Method 0023A, Sampling Method for Polychlorinated Dibenzo-p-Dioxins and 
Polychlorinated Dibenzofurans Emissions from Stationary Sources, EPA 
Publication SW-846, as incorporated by reference in Sec.  260.11 of 
this chapter or Method 23, provided in Appendix A-7, Part 60 of this 
chapter.
* * * * *
[FR Doc. 2023-04958 Filed 3-17-23; 8:45 am]
BILLING CODE 6560-50-P