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Rule2023-04958

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

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Published

March 20, 2023

Effective

March 20, 2023

Issuing agencies

Environmental Protection Agency

Abstract

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.

Full Text

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[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 [<a href="http://www.gpo.gov">www.gpo.gov</a>]
[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.

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

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 <a href="https://www.regulations.gov">https://www.regulations.gov</a> 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
<a href="https://www.regulations.gov">https://www.regulations.gov</a> 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: <a href="/cdn-cgi/l/email-protection#88e5edfafae1e4e4a6fae9f1e5e7e6ecc8edf8e9a6efe7fe"><span class="__cf_email__" data-cfemail="18757d6a6a717474366a79617577767c587d6879367f776e">[email&#160;protected]</span></a>.

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 <a href="https://www.epa.gov/ttn/emc/methods/">https://www.epa.gov/ttn/emc/methods/</a>. 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:
<bullet> 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).
<bullet> Office of Water (OW) EPA Method 1613, Tetra- through Octa-
Chlorinated Dioxins and Furans by Isotope Dilution HRGC/HRMS.
<bullet> 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 <a href="https://www.astm.org">https://www.astm.org</a> 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 <a href="https://www.epa.gov/measurements-modeling/method-development#format">https://www.epa.gov/measurements-modeling/method-development#format</a>). 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:
<bullet> 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.
<bullet> 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.
<bullet> Remove specifications for the graduated cylinder to
improve the accuracy of moisture measurements and make Method 23 more
consistent with other isokinetic sampling methods.
<bullet> 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:
<bullet> Initial demonstration of capability (IDC).
<bullet> Quality Control Sample (QCS).
<bullet> Method detection limits (MDL).
<bullet> Laboratory method blank (LMB).
<bullet> Estimated detection limits (EDL).
<bullet> 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:

<bullet> 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.
<bullet> 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.
<bullet> Stieglitz, L., Zwick, G., Roth, W. Investigation of
different treatment techniques for PCDD/PCDF in fly ash. Chemosphere
15: 1135-1140; 1986.
<bullet> 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.
<bullet> 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.
<bullet> U.S. Environmental Protection Agency. Method 1625C--
Semivolatile Organic Compounds by Isotope Dilution GCMS.
<bullet> U.S Environmental Protection Agency. Method 1613B--Tetra-
through Octa-Chlorinated Dioxins and Furans by Isotope Dilution
HRGC/HRMS.
<bullet> U.S. Environmental Protection Agency. Method 1668C--
Chlorinated Biphenyl Congeners in Water, Soil, Sediment, Biosolids,
and Tissue by HRGC/HRMS.
<bullet> 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.
<bullet> 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.
<bullet> 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.
<bullet> 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.
<bullet> 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.
<bullet> 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.
<bullet> 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 <a href="https://www.epa.gov/laws-regulations/laws-and-executive-orders">https://www.epa.gov/laws-regulations/laws-and-executive-orders</a>.

[[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 <a href="https://www.astm.org">https://www.astm.org</a> 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: <a href="https://www.epa.gov/sites/production/files/2015-09/documents/method_1668c_2010.pdf">https://www.epa.gov/sites/production/files/2015-09/documents/method_1668c_2010.pdf</a>) 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 (Cl<INF>2</INF>) or 2 Cl<INF>2</INF> during ionization
processes. With HRMS, GC separation, and fractionation, PCB should
not pose a problem for PCDD/PCDF identification and quantitation.
PCDPE, when losing Cl<INF>2,</INF> 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 <plus-minus>
14 [deg]C (248 <plus-minus> 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
<plus-minus> 14 [deg]C (248 <plus-minus> 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 <plus-minus>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
<plus-minus> 14 [deg]C (248 [deg]F <plus-minus> 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 <plus-minus>
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 <plus-minus> 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 TEQ<INF>PCB</INF> 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 <plus-minus> 14 [deg]C
(248 [deg]F <plus-minus> 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 <plus-minus>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\C<INF>12</INF>-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.

A1<INF>n</INF> = Integrated ion current of the primary m/z values
for the target native compound.
A1<INF>pe</INF> = 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).
A1<INF>pa</INF> = Integrated ion current of the primary m/z values
for the pre-analysis standard compound.
A2<INF>n</INF> = Integrated ion current of the secondary m/z values
for the target native compound. For PAH A2<INF>n</INF> = 0.
A2<INF>pe</INF> = Integrated ion current of the secondary m/z's for
the pre-extraction standard compound. For PAH A2<INF>l</INF> = 0.
A2<INF>pa</INF> = Integrated ion current of the secondary m/z values
for the pre-analysis standard compound.
C<INF>i</INF> = Mass of compound i in the sample, pg.
C<INF>idscm</INF> = Concentration of target native compound i in the
emission gas, pg/dscm.
C<INF>T</INF> = 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.
H<INF>ai</INF> = Summed heights of the noise for each quantitation
ion for native target compounds.
H<INF>ci</INF> = Summed heights of the noise at the primary and
secondary m/z's of the pre-extraction standard i.
L<INF>PIR</INF> = 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,
%.
Q<INF>n</INF> = Quantity of the target native compound, pg.
Q<INF>pe</INF> = Quantity of the pre-extraction standard, pg.
Q<INF>pa</INF> = Quantity of the pre-analysis standard, pg.
R = Recovery of pre-sampling adsorbent standard and pre-extraction
filter recovery standard, %.
R<INF>pe</INF> = Recovery of pre-extraction standard, %.
RRF<INF>i</INF> = Relative response factor of a native target
compound or pre-sampling adsorbent standard and pre-extraction
filter recovery standard at calibration level i.
RRF<INF>pe</INF> = Relative response factor of a pre-extraction
standard compound.
RRF<INF>ccv</INF> = 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.
SD<INF>RRF</INF> = Standard deviation of initial calibration RRFs.
U<INF>PIR</INF> = 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 Q<INF>pe</INF> and Q<INF>n</INF> in Eq. 23-1
and the units for Q<INF>pa</INF> and Q<INF>pe</INF> 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
C<INF>T</INF> from Eq. 23-12 for C<INF>i</INF> 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: R<INF>pe</INF> 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, R<INF>pe</INF>
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 TEQ<INF>PCB.</INF> 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: <a href="https://www.epa.gov/emc/emc-guideline-documents">https://www.epa.gov/emc/emc-guideline-documents</a>.
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
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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

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