EPA Method 23-Determination of Polychlorinated Dibenzo-p-Dioxins and Polychlorinated Dibenzofurans From Stationary Sources
| Published date | 14 January 2020 |
| Record Number | 2019-27842 |
| Section | Proposed rules |
| Court | Environmental Protection Agency |
Federal Register, Volume 85 Issue 9 (Tuesday, January 14, 2020)
[Federal Register Volume 85, Number 9 (Tuesday, January 14, 2020)]
[Proposed Rules]
[Pages 2234-2277]
From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[FR Doc No: 2019-27842]
[[Page 2233]]
Vol. 85
Tuesday,
No. 9
January 14, 2020
Part IIEnvironmental Protection Agency-----------------------------------------------------------------------40 CFR Parts 60, 63, and 266EPA Method 23--Determination of Polychlorinated Dibenzo-p-Dioxins and
Polychlorinated Dibenzofurans From Stationary Sources; Proposed Rule
Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 /
Proposed Rules
[[Page 2234]]
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ENVIRONMENTAL PROTECTION AGENCY
40 CFR Parts 60, 63, and 266
[EPA-HQ-OAR-2016-0677; FRL-10003-67-OAR]
RIN 2060-AT09
EPA Method 23--Determination of Polychlorinated Dibenzo-p-Dioxins
and Polychlorinated Dibenzofurans From Stationary Sources
AGENCY: Environmental Protection Agency.
ACTION: Proposed rule.
-----------------------------------------------------------------------
SUMMARY: This action proposes editorial and technical revisions to the
Environmental Protection Agency's Method 23 (Determination of
Polychlorinated Dibenzo-p-Dioxins and Polychlorinated Dibenzofurans
from Stationary Sources). Proposed revisions include incorporating
isotope dilution for quantifying all target compounds 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 proposing revisions that will expand the list of
target compounds of Method 23 to include polycyclic aromatic
hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). The proposed
revisions will improve the accuracy of Method 23 and will provide
flexibility to stack testers and analytical laboratories who measure
semivolatile organic compounds (SVOC) from stationary sources while
ensuring that the stack testing community can consistently implement
the method across emissions sources and facilities.
DATES: Comments. Comments must be received on or before March 16, 2020.
ADDRESSES: Comments: Submit your comments, identified by Docket ID No.
EPA-HQ-OAR-2016-0677, at https://www.regulations.gov. Follow the online
instructions for submitting comments. Once submitted, comments cannot
be edited or removed from Regulations.gov. See SUPPLEMENTARY
INFORMATION section for details about how the Environmental Protection
Agency (EPA) treats submitted comments. Regulations.gov is our
preferred method of receiving comments. However, the following other
submission methods are also accepted:
Email: [email protected]. Include Docket ID No. EPA-
HQ-OAR-2016-0677 in the subject line of the message.
Fax: (202) 566-9744. Attention Docket ID No. EPA-HQ-OAR-
2016-0677.
Mail: To ship or send mail via the United States Postal
Service, use the following address: U.S. Environmental Protection
Agency, EPA Docket Center, Docket ID No. EPA-HQ-OAR-2016-0677, Mail
Code 28221T, 1200 Pennsylvania Avenue NW, Washington, DC 20460.
Hand/Courier Delivery: Use the following Docket Center
address if you are using express mail, commercial delivery, hand
delivery, or courier: EPA Docket Center, EPA WJC West Building, Room
3334, 1301 Constitution Avenue NW, Washington, DC 20004. Delivery
verification signatures will be available only during regular business
hours.
FOR FURTHER INFORMATION CONTACT: Dr. Raymond Merrill, Office of Air
Quality Planning and Standards, Air Quality Assessment Division (E143-
02), Environmental Protection Agency, Research Triangle Park, NC 27711;
telephone number: (919) 541-5225; fax number: (919) 541-0516; email
address: [email protected].
SUPPLEMENTARY INFORMATION:
Public Participation
A. Written Comments
Submit your comments, identified by Docket ID No. EPA-HQ-OAR-2016-
0677, at https://www.regulations.gov (our preferred method), or the
other methods identified in the ADDRESSES section. Once submitted,
comments cannot be edited or removed from the docket. The EPA may
publish any comment received to its public docket. Do not submit
electronically any information you consider to be Confidential Business
Information (CBI) or other information whose disclosure is restricted
by statute. Multimedia submissions (audio, video, etc.) must be
accompanied by a written comment. The written comment is considered the
official comment and should include discussion of all points you wish
to make. The EPA will generally not consider comments or comment
contents located outside of the primary submission (i.e., on the Web,
cloud, or other file sharing system). For additional submission
methods, the full EPA public comment policy, information about CBI or
multimedia submissions, and general guidance on making effective
comments, please visit https://www.epa.gov/dockets/commenting-epa-dockets.
Submitting CBI: Clearly mark the part or all of the information
that you claim to be CBI. For CBI information in a disk or CD-ROM that
you mail to the EPA, mark the outside of the disk or CD-ROM as CBI and
then identify electronically within the disk or CD-ROM the specific
information that is claimed as CBI. In addition to one complete version
of the comment that includes information claimed as CBI, a copy of the
comment that does not contain the information claimed as CBI must be
submitted for inclusion in the public docket. Information marked as CBI
will not be disclosed except in accordance with procedures set forth in
Title 40 Code of Federal Regulations (CFR) part 2.
Do not submit information that you consider to be CBI or otherwise
protected through https://www.regulations.gov or email. Send or deliver
information identified as CBI to only the following address: OAQPS
Document Control Officer (Room C404-02), U.S. EPA, Research Triangle
Park, NC 27711, Attention Docket ID No. EPA-HQ-OAR-2016-0677.
If you have any questions about CBI or the procedures for claiming
CBI, please consult the person identified in the FOR FURTHER
INFORMATION CONTACT section.
Docket: All documents in the docket are listed in the https://www.regulations.gov index. Although listed in the index, some
information is not publicly available, e.g., CBI (Confidential Business
Information) or other information whose disclosure is restricted by
statute. Certain other material, such as copyrighted material, will be
publicly available only in hard copy. Publicly available docket
materials are available either electronically in https://www.regulations.gov or in hard copy at the EPA Docket Center, EPA/DC,
EPA WJC West Building, Room 3334, 1301 Constitution Ave. NW,
Washington, DC. This Docket Facility is open from 8:30 a.m. to 4:30
p.m., Monday through Friday, excluding legal holidays. The telephone
number for the Public Reading Room is (202) 566-1744, and the telephone
number for the Air Docket is (202) 566-1742.
B. Participation at Public Hearing
Public hearing. If a public hearing is requested by January 21,
2020, then we will hold a public hearing at the EPA William Jefferson
Clinton (WJC) East Building, 1201 Constitution Avenue NW, Washington,
DC 20004. If a public hearing is requested, additional details about
the public hearing will be provided in a separate Federal Register
notice and on our website at https://www3.epa.gov/ttn/emc/methods. To
request a hearing, to register to speak at a hearing, or to inquire if
a hearing will be held, please contact Raymond Merrill
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by email at [email protected] or phone at (919) 541-5225. The
last day to pre-register in advance to speak at the public hearing will
be January 27, 2020. If held, the public hearing will convene at 9:00
a.m. (local time) and will conclude at 4:00 p.m. (local time).
Because this hearing is being held at a U.S. government facility,
individuals planning to attend the hearing should be prepared to show
valid picture identification to the security staff in order to gain
access to the meeting room. Please note that the REAL ID Act, passed by
Congress in 2005, established new requirements for entering federal
facilities. For purposes of the REAL ID Act, EPA will accept
government-issued IDs, including drivers' licenses, from the District
of Columbia and all states and territories except from American Samoa.
If your identification is issued by American Samoa, you must present an
additional form of identification to enter the federal building where
the public hearing will be held. Acceptable alternative forms of
identification include: Federal employee badges, passports, enhanced
driver's licenses, and military identification cards. For additional
information for the status of your state regarding REAL ID, go to:
https://www.dhs.gov/real-id-enforcement-brieffrequently-asked-questions. Any objects brought into the building need to fit through
the security screening system, such as a purse, laptop bag, or small
backpack. Demonstrations will not be allowed on federal property for
security reasons.
Table of Contents
The following outline is provided to aid in locating information in
this preamble.
I. General Information
A. Does this action apply to me?
B. Where can I get a copy of this document and other related
information?
II. Background
III. Incorporation by Reference
IV. Summary of Proposed Revisions to Method 23
A. Section 1.0
B. Section 2.0
C. Section 3.0
D. Section 4.0
E. Section 5.0
F. Section 6.0
G. Section 7.0
H. Section 8.0
I. Section 9.0
J. Section 10.0
K. Section 11.0
L. Section 12.0
M. Section 13.0
N. Section 14.0
O. Section 15.0
P. Section 16.0
Q. Section 17.0
V. Summary of Proposed 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. Executive Order 13771: Reducing Regulations and Controlling
Regulatory Costs
C. Paperwork Reduction Act (PRA)
D. Regulatory Flexibility Act (RFA)
E. Unfunded Mandates Reform Act (UMRA)
F. Executive Order 13132: Federalism
G. Executive Order 13175: Consultation and Coordination With Indian
Tribal Governments
H. Executive Order 13045: Protection of Children From Environmental
Health Risks and Safety Risks
I. Executive Order 13211: Actions that Significantly Affect Energy
Supply, Distribution, or Use
J. National Technology Transfer and Advancement Act (NTTAA)
K. Executive Order 12898: Federal Actions To Address Environmental
Justice in Minority Populations and Low-Income Populations
I. General Information
A. Does this action apply to me?
The proposed amendments to Method 23 apply to industries that are
subject to certain provisions of parts 60, 62, 63, 79, and 266. The
source categories and entities potentially affected are listed in Table
1. This table is not intended to be exhaustive, but rather provides a
guide for readers regarding entities likely to be regulated 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 regulated.
Table 1--Potentially Affected Source Categories
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Examples of regulated
Category NAICSY \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
proposed 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 proposed method revisions is available on the Technology
Transfer Network (TTN) website at https://www3.epa.gov/ttn/emc/methods/. The TTN provides information and technology exchange in
various areas of air pollution control.
II. Background
The EPA's Method 23 (Determination of Polychlorinated Dibenzo-p-
Dioxins and Polychlorinated Dibenzofurans from Stationary Sources) is
our current reference test method for determination
[[Page 2236]]
of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated
dibenzofurans (PCDFs) emitted from stationary sources.
The EPA promulgated Method 23 (Appendix A of 40 CFR part 60, Test
Methods) on February 13, 1991 (56 FR 5758). Since promulgation, the
measurement of PCDDs and PCDFs has evolved as analytical laboratories,
EPA, and state entities have developed new standard operating
procedures and methods to reflect improvements in sampling and
analytical techniques. Examples of newer PCDD/PCDF methods include:
Office of Land and Emergency Management (OLEM) Solid Waste
(SW) SW-846 EPA Method 8290A, Polychlorinated Dibenzo-p-Dioxins and
Polychlorinated Dibenzofurans (PCDFs) by High-Resolution Gas
Chromatography/High-Resolution Mass Spectrometry (HRGC/HRMS);
Office of Water (OW) EPA Method 1613, Tetra- through Octa-
Chlorinated Dioxins and Furans by Isotope Dilution HRGC/HRMS; and
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 in the measurement community 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,
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 PAHs and PCBs emitted from stationary sources. The docket
contains summaries of the stakeholder discussions.
III. Incorporation by Reference
The EPA proposes to incorporate by reference ASTM D6911-15 and ASTM
D4840-99(2018)e1 in Method 23. The 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
the American society for Testing and Materials and may be obtained from
https://www.astm.org or from the ASTM at 100 Barr Harbor Drive, P.O.
Box C700, West Conshohocken, PA 19428-2959.
IV. Summary of Proposed Revisions to Method 23
In this action, we are proposing technical revisions and editorial
changes to clarify and update the requirements and procedures specified
in Method 23. We are also proposing to reformat the method to conform
with EPA's current method format (see https://www.epa.gov/measurements-modeling/method-development#format). We are proposing to expand the
applicability of Method 23 to include procedures for sampling and
analyzing PAHs and PCBs. In addition, we are proposing revisions to
various sections of the CFR that either require Method 23 or require
the analysis of PCDDs/PCDFs, PAHs, or PCBs.
Our intent for the proposed revisions is to ensure that Method 23
is implemented consistently and to update the method procedures to
include performance-based quality requirements that add flexibility
rather than the prescriptive requirements currently described in the
method.
The primary focus of the proposed revisions to Method 23 is to
change the method from a prescriptive method to a performance-based
method, which will allow 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 proposed
revisions also address concerns over recovery of target compounds from
particulate matter by requiring a pre-extraction filter spike recovery
procedure and acceptance criteria for the filter spike recovery. 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 PCDDs/PCDFs.
The EPA's second focus for the proposed revisions is to convert the
method entirely to quantitation based on isotope dilution. 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 third major focus for the EPA's proposed revision to Method 23
is to include options for combining sampling and analysis of PCDDs/
PCDFs with PAHs and PCBs to allow the measurement of toxic SVOC. In
addition, adding PCBs and PAHs to the list of target compounds measured
by Method 23 is responsive to multiple requests for alternative method
approval from facilities and source test teams that are responding to
EPA information collection requests (ICRs).
The EPA's proposed amendments to Method 23 are presented below for
each section of Method 23.
A. Section 1.0
In this action, EPA is proposing to rename section 1.0 from
``Applicability and Principle'' to ``Scope and Application,'' and
revise the text to expand the target compounds for Method 23 to include
PCBs and PAHs. We are also proposing to add 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, and the use of high-
resolution gas chromatography/high-resolution mass spectrometry (HRGC/
HRMS) when applying Method 23. We are also proposing language to
specify that Method 23 is performance-based and to allow 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
The EPA is proposing to rename section 2.0 from ``Apparatus'' to
``Summary of Method,'' and revise section 2.0 with language to provide
an overview of the method's sampling and analytical procedures. We are
also proposing to move the current language in section 2.0, which
describes the materials needed to conduct Method 23, to a proposed new
section 6.0.
C. Section 3.0
The current version of Method 23 does not include definitions of
key terms and variables used in Method 23. In this action, we are
proposing to add a new section 3.0 titled ``Definitions,'' absent in
the current promulgated version of Method 23. We are providing
definitions to acronyms and technical terms to improve the clarity of
the method principles and procedures. We also propose to move language
from the
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current section 3.0 to a proposed new section 7.0.
D. Section 4.0
The current version of Method 23 does not discuss the conditions
that can potentially interfere with measurements obtained when using
the method. In this action, we are proposing to add a new section 4.0
titled ``Interferences,'' that would present the potential causes and
recommendations for avoiding or mitigating interferences or sample
contamination. We also propose to move language from the current
section 4.0 to a proposed new section 8.0.
E. Section 5.0
Currently, Method 23 does not provide procedures for safety. In
this action, we are proposing to add a new section 5.0 titled
``Safety,'' that would present the health hazards and procedures for
minimizing risks to field and laboratory personnel when conducting
Method 23. We also propose to move language from the current section
5.0 to a proposed new section 11.0.
F. Section 6.0
In this action, we are proposing to renumber and move the text in
section 2.0 (Apparatus) of the current method to section 6.0 titled
``Equipment and Supplies,'' and to make clarifying edits and technical
revisions to the specifications in this section. Table 2 of this
preamble identifies the proposed 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 proposing to
include in section 6.0.
Table 2--Crosswalk for Proposed Revisions to Current Method Sections
------------------------------------------------------------------------
Description Current section Proposed 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
Absorbent module.................. 2.1.4 6.1.9
Fitting cap....................... 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 containers... 2.2.9 6.2.8
Extraction thimble................ 2.3.4 6.3.3.3
Pasteur pipette................... 2.3.5 6.4.1
GC oven........................... 2.3.10.1 6.5.1.1
Temperature monitor for GC oven... 2.3.10.2 6.5.1.2
GC Flow system.................... 2.3.10.3 6.5.1.3
Capillary column.................. 2.3.10.4 6.5.2
Mass spectrometer................. 2.3.11 6.5.3
Mass spectrometer data system..... 2.3.12 6.5.4
------------------------------------------------------------------------
Table 3--Proposed Additional Specifications for Section 6.0
------------------------------------------------------------------------
Description Proposed 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
Kuderna-Danish concentrator.......................... 6.3.4
Heating mantle....................................... 6.3.3.4
Chromatography column................................ 6.4.2
Injection port....................................... 6.5.1.4
PCDD/PCDF column system.............................. 6.5.2.1
PAH column system.................................... 6.5.2.2
PCB column system.................................... 6.5.2.3
------------------------------------------------------------------------
In this section, we are also proposing to:
Prohibit the use of brominated flame-retardant coated tape
in assembling the sampling train to avoid sample contamination;
Revise the specification for a rotary evaporator with
specifications for a Kuderna-Danish concentrator to avoid the loss of
higher vapor pressure target compounds;
Remove specifications for the graduated cylinder to
improve the accuracy of moisture measurements and to make Method 23
more consistent with other isokinetic sampling methods; and
Remove the volume requirement for wash bottles to allow
greater flexibility in field sample recovery.
We are also proposing to move language from Method 23's current
section 6.0 to a proposed new section 10.0.
G. Section 7.0
In this action, the EPA is proposing to renumber and move the text
in section 3.0 (Reagents) of the current method to a new section 7.0
titled ``Reagents, Media and Standards,'' and to make clarifying edits
and technical revisions to the specifications in this section. Table 4
of this preamble identifies the
[[Page 2238]]
proposed 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 proposing to include in section 7.
Table 4--Crosswalk for Proposed Revisions to Current Method Sections
------------------------------------------------------------------------
Description Current section Proposed 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
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--Proposed Additional Specifications for Section 7.0
------------------------------------------------------------------------
Description Proposed 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 recovery standard solution.............. 7.9.3
Filter recovery spike standard solution.............. 7.9.4
Pre-extraction recovery standard solution............ 7.9.5
Pre-analysis recovery standard solution.............. 7.9.6
------------------------------------------------------------------------
We are proposing to replace the filter precleaning procedures of
the current method with specifications for conducting a filter quality
control check. We are proposing to delete unnecessary specifications
presented in Table 6 to reflect modern methods. We are also proposing
to rename the isotopic spiking standard mixtures to simple English
names that relate the standards to their use in the proposed method.
Table 6--Proposed 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
Nonane............................................... 3.3.11
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 proposing to move the current section 7.0 to a proposed
new section 9.0.
H. Section 8.0
In this action, the EPA is proposing to renumber and move the text
in section 4.0 (Procedure) of the current method to a new section 8.0
titled ``Sample Collection, Preservation and Storage,'' and to make
clarifying edits and technical revisions to the current procedures for
sampling and sample recovery. As proposed, the new section 8 also would
include added requirements for sample storage conditions and holding
times.
Under the sampling procedures of Method 23, we are proposing
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 Proposed Revisions to Current Method Sections
------------------------------------------------------------------------
Description Current section Proposed 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
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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......................
------------------------------------------------------------------------
Table 8 of this preamble shows the specifications we are proposing
to add to the new section 8.0. We are proposing a minimum sample volume
to assure that stack testers can attain the detection limits consistent
with current regulations. Sampling time requirements at each traverse
point for continuous industrial processes 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 proposed 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 proposed absorbent module
orientation requirements clarify the configuration of the absorbent
module to ensure that condensed moisture flows through the module into
the water collection impinger. We are proposing to add filter
monitoring requirements to align Method 23 with other isokinetic
stationary source methods. Also, we are proposing to add 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--Proposed Additional Specifications for Section 8.1
------------------------------------------------------------------------
Description Proposed 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 proposing technical
revisions as shown in Table 9 of this preamble. In this action, we are
also proposing to add a recommendation to use clean glassware and to
add specifications as shown in Table 10 of this preamble.
Table 9--Crosswalk for Proposed Revisions to Current Method Sections
------------------------------------------------------------------------
Description Current section Proposed section
------------------------------------------------------------------------
Adsorbent module sample 4.2.2 8.2.5
preparation......................
Preparation of Container No. 2.... 4.1.1.2 8.2.6
Rinsing of the filter holder and 4.1.1.3 8.2.7
condenser........................
Weighing impinger water........... 4.1.1.5 8.2.8
Preparation of Container No. 3.... 4.1.3.1 8.2.9
Silica gel........................ 4.1.3.2 8.2.10
------------------------------------------------------------------------
Table 10--Proposed Additional Specifications for Section 8.2
------------------------------------------------------------------------
Description Proposed 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 new section 8.2.8, we propose to measure moisture by weight
rather than by volume.
I. Section 9.0
In this action, the EPA is proposing to move and renumber the
current section 7.0 (Quality Control) to a new section 9.0 titled
``Quality Control,'' and to make clarifying and technical revisions to
the section. We are proposing to add an introductory note that
addresses maintaining and documenting quality control compliance
required in Method 23. We would add a new subsection that clarifies the
recordkeeping and reporting necessary to demonstrate compliance with
quality control requirements of this method. We are also proposing to
add specifications for conducting pre-sampling, pre-extraction, and
pre-analysis spike recoveries of isotopically-labeled standards and to
add specifications for:
Capillary gas chromatography columns;
[[Page 2240]]
Preparing and analyzing batch blanks;
Determining the method detection limit; and
Assessing field train proof blanks.
We are also proposing to move language from the current section 9.0
to a proposed new section 12.0.
J. Section 10.0
In this action, the EPA is proposing to renumber and move the text
in section 6.0 (Calibration) of the current method to a new section
10.0 titled ``Calibration and Standardization,'' and to make clarifying
and technical revisions to the specifications for calibrating the
sampling and the HRGC/HRMS systems. We are proposing to add
specifications for tuning the HRGC/HRMS system, to move the
specification for HRMS resolution (currently in section 5) to this
proposed section, to add procedures for assessing the relative standard
deviation for the mean instrument response, and to add procedures for
determining the signal-to-noise ratio of the MS to bring Method 23 up
to date with current laboratory practice. We are also proposing to add
requirements for ion abundance ratio limits, initial calibrations, and
resolution checks under the daily performance check to serve as
performance indicators for analysis quality. We are also proposing to
move language in the current section 10.0 to a proposed new section
16.0.
K. Section 11.0
In this action, the EPA is proposing to renumber and move the text
in section 5.0 (Analysis) of the current method to a new section 11.0
titled ``Analysis Procedure,'' and to make clarifying and technical
revisions to the current specifications for sample extraction and
sample cleanup and fractionation. We are also proposing to add a new
subsection describing how sample extract aliquots are prepared for
cleanup and analysis.
We are also proposing to add the specifications and recommendations
for analysis procedures shown in Table 11 of this preamble.
Table 11--Proposed Additional Specifications for Section 11.0
------------------------------------------------------------------------
Description Proposed section
------------------------------------------------------------------------
Preparing and operating the extraction 11.1.7 through 11.1.9.
apparatus.
Cooling the extraction apparatus........... 11.2.1.
Performing an initial extract concentration 11.2.2.
Cooling the sample extract................. 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 PAHs 11.3.1.
and PCDEs.
Sample cleanup and fractionation for PCDD/ 11.3.2.
DFs and PCBs.
Addressing unresolved compounds............ 11.4.1.2.1.
Retention time for PCBs.................... 11.4.3.4.5.
Chlorodiphenyl ether interference of PCDD/ 11.4.3.4.8.
DFs.
MS lock channels........................... 11.4.3.4.9.
Calculations of target mass and mass per 11.4.3.5.1 and 11.4.3.5.2.
dry standard cubic meter.
Quantifying indigenous PCDD/DFs............ 11.4.3.5.3.
Reporting options compound concentrations.. 11.4.3.5.4 through
11.4.3.5.6.
Identification criteria for PAHs........... 11.4.3.4.10.
------------------------------------------------------------------------
L. Section 12.0
In this action, the EPA is proposing to renumber and move the text
in section 9.0 (Calculations) of the current method to a new section
12.0 titled ``Data Analysis and Calculations,'' and to revise the
equation variable list. We are proposing to revise the equations shown
in Table 12 of this preamble to incorporate isotope dilution
calculations.
Table 12--Proposed Equation Revisions for Section 12.0
------------------------------------------------------------------------
Current equation Description Proposed section
------------------------------------------------------------------------
23-2.......................... Average relative 12.3
response factor
(RRF) for each
compound.
23-6.......................... Concentration of 12.7
individual target
compound i in the
extract by isotope
dilution.
23-9.......................... Recovery of Labeled 12.10
Compound Standards.
23-10......................... Estimated detection 12.11
limit.
23-11......................... Total concentration.. 12.12
------------------------------------------------------------------------
We are also proposing to remove and replace the current equations
in Method 23 with the equations shown in Table 13 of this preamble to
accommodate the proposed changes to the method procedures.
Table 13--Proposed Additional Equations for Section 12.0
------------------------------------------------------------------------
Equation Description Proposed section
------------------------------------------------------------------------
23-1.......................... Individual compound 12.2
RRF for each
calibration level.
23-3.......................... Percent relative 12.4
standard deviation
of the RRFs for a
compound over the
five calibration
levels.
23-4.......................... Standard deviation of 12.5
the RRFs for a
compound over the
five calibration
levels.
23-5.......................... 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.
23-7.......................... Concentration of 12.8
individual target
compound i in the
sample extract.
[[Page 2241]]
23-8.......................... Concentration of the 12.9
Individual Target
Compound or Group i
in the Emission Gas.
------------------------------------------------------------------------
M. Section 13.0
In this action, the EPA is proposing to add a new section 13.0
titled ``Method Performance,'' that would include the specifications
shown in Table 14 of this preamble.
Table 14--Proposed Method Performance Specifications for Section 13.0
------------------------------------------------------------------------
Description Proposed section
------------------------------------------------------------------------
Quality control checks of filters, 13.1, 13.2, and 13.14.
adsorbent resin, glass wool, and batch
blanks.
Field train proof blanks................... 13.2.
GC column systems used to measure PCDD/F, 13.3 through 13.6.
PAH, and PCB target compounds.
Acceptability of detection limits.......... 13.7.
Tuning HRGC/HRMS systems................... 13.8.
MS lock channels........................... 13.9.
Initial and continuing calibrations........ 13.10 and 13.11.
Identification of target compounds......... 13.12 and 13.13.
Pre-sampling, -extraction, and -analysis 13.15 and 13.16.
spike recoveries.
Pre-analysis spike sensitivity requirements 13.17.
Modifications of the method................ 13.18 and 13.19.
------------------------------------------------------------------------
N. Section 14.0
In this action, the EPA is proposing to add 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
In this action, the EPA is proposing to add 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
In this action, the EPA is proposing to renumber and move the text
in section 10.0 (Bibliography) of the current method to a new section
16.0 titled ``References.'' We are proposing to delete previous
reference numbers 3 and 4 that are no longer relevant and to add new
citations for the following references:
Fishman, V.N., Martin, G.D. and Lamparski, L.L. Comparison
of a variety of gas chromatographic columns with different polarities
for the separation of chlorinated dibenzo-p-dioxins and dibenzofurans
by high-resolution mass spectrometry. Journal of Chromatography A 1139
(2007) 285-300.
International Agency for Research on Cancer. Environmental
Carcinogens Methods of Analysis and Exposure Measurement, Volume 11--
Polychlorinated Dioxins and Dibenzofurans. IARC Scientific Publications
No. 108, 1991.
Stieglitz, L., Zwick, G., Roth, W. Investigation of
different treatment techniques for PCDD/PCDF in fly ash. Chemosphere
15: 1135-1140; 1986.
Triangle Laboratories. Case Study: Analysis of Samples for
the Presence of Tetra Through Octachloro-p-Dibenzodioxins and
Dibenzofurans. Research Triangle Park, NC. 1988. 26 p.
U.S. Environmental Protection Agency. Office of Air
Programs Publication No. APTD-0576: Maintenance, Calibration, and
Operation of Isokinetic Source Sampling Equipment. Research Triangle
Park, NC. March 1972.
U.S. Environmental Protection Agency. Method 1625C-
Semivolatile Organic Compounds by Isotope Dilution GCMS.
U.S. Environmental Protection Agency. Method 1613B-Tetra-
through Octa-Chlorinated Dioxins and Furans by Isotope Dilution HRGC/
HRMS.
U.S. Environmental Protection Agency. Method 1668C-
Chlorinated Biphenyl Congeners in Water, Soil, Sediment, Biosolids, and
Tissue by HRGC/HRMS.
Tondeur, Y., Nestrick, T., Silva, H[eacute]ctor A.,
Vining, B., Hart, J. Analytical procedures for the determination of
polychlorinated-p-dioxins, polychlorinated dibenzofurans, and
hexachlorobenzene in pentachlorophenol. Chemosphere Volume 80, Issue 2,
June 2010, pages 157-164.
Q. Section 17.0
In this action, the EPA is proposing to add a new section 17 titled
``Tables, Diagrams, Flow Charts, and Validation Data,'' that will
contain all tables, diagrams, flow charts, and validation data
referenced in Method 23. We are proposing to revise Figures 23-1 and
23-2 and to rename and/or renumber the current Method 23 tables as
shown in Table 15 of this preamble.
Table 15--Proposed Revisions to Method 23 Tables
------------------------------------------------------------------------
Current method Proposed method
------------------------------------------------------------------------
Table 1--Composition of the Sample Table 23-7. Composition of the
Fortification and Recovery Standards Sample Fortification and
Solutions. Recovery Standard Solutions
for PCDDs and PCDFs.
Table 2--Composition of the Initial Table 23-11. Composition of the
Calibration Solutions. Initial Calibration Standard
Solutions for PCDDs and PCDFs.
[[Page 2242]]
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 PCDDs and PCDFs.
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. Daily Calibration Response
Factors for Isotopically
Labeled and Native Compounds.
------------------------------------------------------------------------
We are also proposing to add Figure 23-3 (Soxhlet/Dean-Stark
Extractor) and Figure 23-4 (Sample Preparation Flow Chart) and to add
the tables specified in Table 16 of this preamble.
Table 16--Additional Proposed Tables to Method 23
------------------------------------------------------------------------
Proposed 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 PAHs.
23-6.............................. Elemental Compositions and Exact
Masses of the Ions Monitored by
High-Resolution Mass Spectrometry
for PCBs.
23-8.............................. Composition of the Sample
Fortification and Recovery Standard
Solutions for PAHs.
23-9.............................. Composition of the Sample
Fortification and Recovery Standard
Solutions for PCBs.
23-10............................. Sample Storage Conditions and
Laboratory Hold Times.
23-12............................. Composition of the Initial
Calibration Standard Solutions for
PAHs.
23-13............................. Composition of the Initial
Calibration Standard Solutions for
PCBs.
23-16............................. Typical DB5-MS Column Conditions.
23-17............................. Assignment of Pre-extraction
Standards for Quantitation of
Target PCBs.
23-18............................. Estimated Method Detection Limits
for PCDDs and PCDFs.
23-19............................. Target Detection Limits for PAHs.
23-20............................. Estimated Method Detection Limits
for PCBs.
------------------------------------------------------------------------
V. Summary of Proposed 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 propose to incorporate by reference ASTM
D4840-99(2018)e1, Standard Guide for Sample Chain-of-Custody
Procedures, and to amend the reference to ASTM D6911-15, Guide for
Packaging and Shipping Environmental Samples for Laboratory Analysis,
to include for use in Method 23.
In Subpart CCCC, we propose to revise Sec. 60.2125(g)(2) and
(j)(2) to realign the requirement for quantifying isomers to the
reorganized section 11.4.2.4 in the proposed revision of Method 23.
In Subpart DDDD, we propose to revise Sec. 60.2690(g)(2) and
(j)(2) to realign the requirement for identifying isomers to the
reorganized section 11.4.2.4 in the proposed revision 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), we propose to replace California Air
Resources Board (CARB) Method 428 with Method 23 for the measurement of
PCB emissions from roof monitors not employing wet roof scrubbers.
In 40 CFR 63.1208, we propose to remove 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 propose to replace CARB Method 429
with Method 23 for measuring the emissions of PAH from ferromanganese
electric arc furnaces.
In Subpart AAAAAAA, Table 3, we propose to replace the requirement
for analysis of PAH by SW-846 Method 8270 with a requirement to use
Method 23. Specifically, we are deleting ``with analysis by SW 846
Method 8270D'' in row 6 of Table 3. Since revisions to Method 23
propose to eliminate the use of methylene chloride, we also propose to
remove footnote ``b'' in Table 3.
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 propose to add Method 23 as an alternative to
SW-846 Method 0023A.
VI. Statutory and Executive Order Reviews
Additional information about these statutes and Executive Orders
can be found at https://www2.epa.gov/laws-regulations/laws-and-executive-orders.
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. Executive Order 13771: Reducing Regulations and Controlling
Regulatory Costs
This action is expected to be an Executive Order 13771 deregulatory
action. This proposed rule is expected to provide meaningful burden
reduction by improving the accuracy of Method 23, improving data
quality, and providing source testers flexibility by providing a
performance-based approach and incorporating approved alternative
procedures into the regulatory measurement method. This proposed action
does not impose any requirements on owners/operators to
[[Page 2243]]
use Method 23 but provides instruction on how to use Method 23 if
required to do so by an EPA source category regulation.
C. Paperwork Reduction Act (PRA)
This proposed action does not impose an information collection
burden under the PRA. The revisions being proposed in this action to
Method 23 do not add information collection requirements but make
corrections, clarifications and updates to existing testing
methodology.
D. Regulatory Flexibility Act (RFA)
I certify that this proposed action will not have a significant
economic impact on a substantial number of small entities under the
RFA. This action will not impose any requirements on small entities.
The proposed revisions to Method 23 do not impose any requirements on
regulated entities. Rather the proposed changes improve the quality of
the results when required by other rules to use Method 23. Revisions
proposed for Method 23 allow contemporary advances in analysis
techniques to be used. Further, the proposed changes in Method 23
analysis procedures reduce the impact of this method by bringing it
into alignment with other agency methods.
E. Unfunded Mandates Reform Act (UMRA)
This proposed action does not contain any unfunded mandate of $100
million or more as described in UMRA, 2 U.S.C. 1531-1538. The proposed
action imposes no enforceable duty on any State, local or tribal
governments or the private sector.
F. Executive Order 13132: Federalism
This proposed 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.
G. Executive Order 13175: Consultation and Coordination With Indian
Tribal Governments
This proposed 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.
H. 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 proposed 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.
I. Executive Order 13211: Actions That Significantly Affect Energy
Supply, Distribution or Use
This proposed action is not subject to Executive Order 13211,
because it is not a significant regulatory action under Executive Order
12866.
J. National Technology Transfer and Advancement Act (NTTAA)
This proposed action involves technical standards. The EPA proposes
to 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 the American society
for Testing and Materials. The standard may be obtained from https://www.astm.org or from the ASTM at 100 Barr Harbor Drive, P.O. box C700,
West Conshohocken, PA 19428-2959.
K. Executive Order 12898: Federal Actions To Address Environmental
Justice in Minority Populations and Low-Income Populations
This proposed action will not have potential disproportionately
high and adverse human health or environmental effects on minority,
low-income or indigenous populations because it does not establish or
revise a standard that provides protection to human health or the
environment.
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
compounds, 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 compounds, Test methods, Waste management.
Dated: December 17, 2019.
Andrew R. Wheeler,
Administrator.
For the reasons stated in the preamble, the Environmental
Protection Agency proposes to amend 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.
0
2. In Sec. 60.17:
0
a. Redesignate paragraphs (h)(167) through (h)(209) as (h)(168) through
(h)(210);
0
b. Add paragraph (h)(167); and
0
c. Revise newly redesignated paragraph (h)(192).
The addition and revision read as follows:
Sec. 60.17 Incorporations by reference.
* * * * *
(h) * * *
(167) ASTM D4840-99(2018)e1 Standard Guide for Sample Chain-of-
Custody Procedures, approved August 2018, IBR approved for appendix A-
8: Method 30B, IBR approved for Appendix A-7: Method 23.
* * * * *
(192) 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 and appendix A-8: Method
30B.
* * * * *
0
3. In Sec. 60.2125, revise paragraphs (g)(2) and (j)(2) to read as
follows:
[[Page 2244]]
Sec. 60.2125 How do I conduct the initial and annual performance
test?
* * * * *
(g) * * * (2) Quantify isomers meeting identification criteria 2,
3, 4, and 5 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 2, 3, 4, and 5
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.)
* * * * *
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 2, 3, 4, and 5
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 2, 3, 4, and 5
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 and 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 measuring emissions of
polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans
(PCDDs/PCDFs), polychlorinated biphenyls (PCBs), and/or polycyclic
aromatic hydrocarbons (PAHs) in emissions from stationary sources.
Using this method, you can measure these analyte groups individually or
in any combination using a single sample acquisition. Tables 23-1
through 23-3 of this method list the applicable targets analytes for
Method 23.
1.2 Scope. This method describes the sampling and analytical
procedures used to measure selected PCDDs, PCDFs, PCBs, and PAHs from
stationary source air emissions. However, Method 23 incorporates by
reference some of the specifications (e.g., equipment and supplies) and
procedures (e.g., sampling and analytical) from other methods in this
part that are essential to conducting Method 23. To obtain reliable
samples, source sampling teams should be trained and experienced with
the following additional EPA test methods: Method 1, Method 2, Method
3, Method 4, and Method 5 of appendices A-1, A-2, and A-3 to 40 CFR
part 60. Laboratory analysis teams should be trained and experienced
with Method 1668C found at: https://www.epa.gov/sites/production/files/2015-09/documents/method_1668c_2010.pdf and Method 1613B of 40 CFR part
136 appendix A.
1.3 The high-resolution gas chromatography and high-resolution mass
spectrometry (HRGC/HRMS) portions of this method are for use by
laboratory analysts experienced with HRGC/HRMS analysis of PCDDs,
PCDFs, PCBs, and PAHs 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, PCBs, and PAHs 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 particle 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.
3.0 Definitions
3.1 Alternate Recovery Standards. A group of isotopically labeled
compounds that is not otherwise designated in this method for quality
control purposes. Use alternative recovery standards to assess the
recovery of a compound class relative to a step in the sampling and
analysis procedure that is not already assessed as a mandatory part of
this method.
3.2 Batch Blank Sample. A laboratory blank sample composed of clean
filter and XAD-2 media processed and analyzed using the same procedures
as a field sample.
3.3 Benzo[a]pyrene Toxic Equivalent Factor (B[a]P-TEF). 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.
3.4 Continuing Calibration Verification Standard (CCV). The mid-
point calibration standard used to verify calibration. Prepare CCV
standards from a second source, when possible.
3.5 Congener. An individual compound with a common structure
(dioxin, furan, or biphenyl), only differing by the number of chlorine
atoms attached to the structure.
3.6 Estimated Detection Limit (EDL). The minimum qualitatively
recognizable signal above background for a target compound. The EDL is
a
[[Page 2245]]
mathematically-derived detection limit (MDL) specific to each sample
analysis based on the noise signal measured near the mass of a target
compound or target isomer group. Being sample specific, the EDL is
affected by sample size, dilution, etc.
3.7 Estimated Possible Concentration (EPC). Report the results as
EPC when the ion abundance ratio for a target analyte is outside the
performance criteria. Calculate the EPC separately for each
quantitation ion, if present, and report the lower value as the EPC.
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.
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 Polychlorinated Biphenyl (PCB) Isomers. Any or all 209
chlorinated biphenyl congeners and their isomers. 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.
3.10.1 Monochlorobiphenyl (MoCB). Any or all three monochlorinated
biphenyl isomers.
3.10.2 Dichlorobiphenyl (DiCB). Any or all 12 dichlorinated
biphenyl isomers.
3.10.3 Trichlorobiphenyl (TrCB). Any or all 24 trichlorinated
biphenyl isomers.
3.10.4 Tetrachlorobiphenyl (TeCB). Any or all 42 tetrachlorinated
biphenyl isomers.
3.10.5 Pentachlorobiphenyl (PeCB). Any or all 46 pentachlorinated
biphenyl isomers.
3.10.6 Hexachlorobiphenyl (HxCB). Any or all 42 hexachlorinated
biphenyl isomers.
3.10.7 Heptachlorobiphenyl (HpCB). Any or all 24 heptachlorinated
biphenyl isomers.
3.10.8 Octachlorobiphenyl (OcCB). Any or all 12 octachlorinated
biphenyl isomers.
3.10.9 Nonachlorobiphenyl (NoCB). Any or all three nonachlorinated
biphenyl isomers.
3.10.10 Decachlorobiphenyl (DeCB). Biphenyl fully chlorinated with
ten chlorine atom substituents replacing hydrogen in the parent
compound.
3.11 Polychlorinated dibenzo-p-dioxin (PCDD) isomers. Any or all 75
chlorinated dibenzo-p-dioxin isomers. There are 11 required target PCDD
analytes listed in Table 23-1 of this method. This method does not
measure mono- through tri-PCDDs and includes non-2,3,7,8 substituted
congeners in the total homolog categories.
3.11.1 Tetrachlorodibenzo-p-dioxin (TeCDD). Any or all 22
tetrachlorinated dibenzo-p-dioxin isomers.
3.11.2 Pentachlorodibenzo-p-dioxin (PeCDD). Any or all 14
pentachlorinated dibenzo-p-dioxin isomers.
3.11.3 Hexachlorodibenzo-p-dioxin (HxCDD). Any or all 10
hexachlorinated dibenzo-p-dioxin isomers.
3.11.4 Heptachlorodibenzo-p-dioxin (HpCDD). Any or all two
heptachlorinated dibenzo-p-dioxin isomers.
3.11.5 Octachlorodibenzo-p-dioxin (OCDD). Dibenzodioxin fully
chlorinated with eight chlorine atom substituents replacing hydrogen in
the parent compound.
3.12 Polychlorinated dibenzofuran (PCDF) isomers. Any or all
chlorinated dibenzofuran isomers. There are 14 required target PCDF
analytes listed in Table 23-1 of this method. This method does not
measure mono- through tri-PCDFs and includes non-2,3,7,8 substituted
congeners in the total homolog categories.
3.12.1 Tetrachlorodibenzofuran (TeCDF). Any or all 38
tetrachlorinated dibenzofuran isomers.
3.12.2 Pentachlorodibenzofuran (PeCDF). Any or all 28
pentachlorinated dibenzofuran isomers.
3.12.3 Hexachlorodibenzofuran (HxCDF). Any or all 16
hexachlorinated dibenzofuran isomers.
3.12.4 Heptachlordibenzofuran (HpCDF). Any or all four
heptachlorinated dibenzofuran isomers.
3.12.5 Octachlorodibenzofuran (OCDF). Dibenzofuran fully
chlorinated with eight chlorine atom substituents replacing hydrogen in
the parent compound.
3.13 Polychlorinated diphenyl ethers (PCDEs). Any or all
chlorinated substituted diphenyl ethers.
3.13.1 Hexachlorodiphenyl ether (HxCDPE). Any or all 42
hexachlorinated diphenyl ether isomers.
3.13.2 Heptachlorodiphenyl ether (HpCDPE). Any or all 24
heptachlorinated diphenyl ether isomers.
3.13.3 Octachlorodiphenyl ether (OCDPE). Any or all 12
octachlorinated diphenyl ether isomers.
3.13.4 Nonachlorodiphenyl ether (NCDPE). Any or all three
nonachlorinated diphenyl ether isomers.
3.13.5 Decachlorodiphenyl ether (DCDPE).
3.14 Polycyclic Aromatic Hydrocarbons (PAHs). 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 spike mixture and
by following the other requirements for target PAH compounds in this
method.
3.15 Pre-analysis Standard(s). A group of isotopically labeled
compounds added at a known amount immediately prior to analysis and
used to correct instrument response, injection errors, instrument drift
and to determine the recovery of the pre-extraction isotopically
labeled spike compounds. Add pre-analysis standards to every sample
(including blank, quality control sample, and calibration solutions) at
a known amount.
3.16 Pre-extraction Filter Recovery Standard(s). 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(s) to the filter samples just
prior extraction.
3.17 Pre-extraction Standard(s). A group of isotopically labeled
compounds added in a known amount to the XAD-2 adsorbent sample
immediately before extraction to correct the quantity of the native
target compounds present in the sample for extraction, cleanup, and
concentration recovery. These isotopically labeled compounds constitute
a matrix spike in each sample.
3.18 Pre-sampling Adsorbent Standard(s). A group of isotopically
labeled compounds added in a known amount to the XAD-2 adsorbent prior
to sampling used to indicate the sample collection and recovery
efficiency of the method.
3.19 Pre-transport Standard(s). Spiking compound(s) 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 recovery samples. 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.
3.20 Relative Response Factor (RRF). The response of the mass
spectrometer to a known amount of an analyte relative to a known amount
of an isotopically labeled standard.
3.21 2,3,7,8-Tetrachlorodibenzo-p-dioxin Toxic Equivalent Factor(s)
(2,3,7,8-TeCDD-TEF). A procedure that expresses the toxicity of PCDDs,
PCDFs,
[[Page 2246]]
and PCBs in terms of the most toxic dioxin, as specified in applicable
regulations, permits, or other requirements.
4.0 Interferences
4.1 PCBs and PCDEs have similar molecular weight and
chromatographic properties to PCDDs and PCDFs. PCBs produce an
interfering mass-to-charge ratio (m/z) when losing chlorine
(Cl2) or Cl4 upon fragmenting during ionization
processes. PCDEs also produce interfering m/z values when losing
Cl2 in the PCDF homolog group with two fewer chlorine atoms
(i.e., an octachlorinated PCDE can interfere with a hexachlorinated
PCDF). The latter interferences are potentially detected by monitoring
an m/z corresponding to the potentially interfering PCDE; however, the
fragmentation patterns of all PCDEs may not be known, complicating any
attempt to quantify the extent of ether interference.
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 batch blank samples. Use high purity reagents, solvents,
and standards to minimize interference problems in sample analysis.
4.4 PAHs 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 PCDDs, PCDFs, PCBs, and/or PAHs.
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 PCDDs and PCDFs containing chlorine atoms in positions
2,3,7,8 have toxicities comparable to that of 2,3,7,8-TeCDD.
5.2 PCBs 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 PCDDs, PCDFs, PCBs, and PAHs.
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. 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 or borosilicate
glass or titanium. Stainless steel nozzles should not be used.
6.1.2 Probe Liner. Use either polytetrafluoroethylene (PTFE),
borosilicate, or quartz glass probe liners with a heating system
capable of maintaining a probe gas temperature of 120 14
[deg]C (248 25 [deg]F) during sampling, or such other
temperature as specified by an applicable subpart of the standards or
as approved by the Administrator. Use a PTFE ferrule or single-use PTFE
coated O-ring to achieve the seal at the nozzle end of the probe for
stack temperatures up to about 300 [deg]C (572 [deg]F). Use a quartz
glass liner and integrated quartz nozzle for stack temperatures between
300 and 1,200 [deg]C (572 and 2,192 [deg]F).
6.1.3 Filter Holder. Use a filter holder of borosilicate glass with
a PTFE frit or PTFE-coated wire filter support. The holder design
should provide a positive seal against leakage from the outside or
around the filter. The holder should be durable, easy to load, leak-
free in normal applications, and positioned immediately following the
probe and cyclone bypass (or cyclone, if used) with the active side of
the filter perpendicular to the source of the flow.
6.1.4 Filter Heating System. Use any heating system capable of
monitoring and maintaining the temperature around the filter to ensure
that the sample gas temperature exiting the filter is 120
14 [deg]C (248 25 [deg]F) during sampling or such other
temperature as specified by an applicable subpart of the standards or
approved by the Administrator for a particular application.
6.1.5 Filter Temperature Sensor. Install a temperature sensor
capable of measuring temperature to within 3 [deg]C (5.4
[deg]F) so that the sensing tip protrudes at least 1.3 centimeters (cm)
(1-2 in.) into the sample gas exiting the filter. Encase the sensing
tip of the sensor in glass or PTFE if needed.
6.1.6 Sample Transfer Line. The sample transfer line transports
gaseous emissions from the heated filter holder to the condenser and
must be heat traced and constructed of glass or PTFE with connecting
fittings that form leak-free, vacuum-tight connections without using
sealing greases or tapes. Keep the sample transfer lines as short as
possible and maintain the lines at a temperature of 120 [deg]C 14 [deg]C (248 [deg]F 25 [deg]F) using active
heating when necessary. Orient the sample transfer lines with the
downstream end lower than the upstream end so that any condensate will
flow away from the filter and into the condenser.
6.1.7 Condenser. Glass, water-jacketed, coil-type with compatible
fittings. Orient the condenser to cause moisture to flow down to the
adsorbent module to facilitate condensate drainage. Figure 23-2 of this
method shows a schematic diagram of the condenser.
[[Page 2247]]
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 measuring the gas
temperature at the entrance to the adsorbent module. Maintain this
temperature at 25 percent from the
average response. You may use PFK or perfluorotributylamine (FC43) as
your lock mass standard. You may choose lock masses within a SIM
descriptor window that demonstrates the least interference. Monitor the
quality control check channels specified in these tables to verify
instrument stability during the analysis. Flag data resulting from
failure to maintain lock channel signal or quality control check signal
during analysis (QCF).
13.10 Initial Calibration.
13.10.1 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.
13.10.2 The S/N in every selected ion current profile must be >=10
for all unlabeled targets and labeled standards in the calibration
samples.
13.10.3 The ion abundance ratios must be within the control limits
in Table 23-15 of this method.
13.11 Continuing Calibration.
13.11.1 The RRF for each unlabeled and labeled compound measured in
a continuing calibration verification must not deviate from the initial
calibration by more than the limits shown in Table 23-14 of this
method.
13.11.2 The ion abundance ratios must be within the control limits
in Table 23-15 of this method.
13.12 Compound Identification for PCDD/PCDFs and PCBs.
13.12.1 Target compounds must have ion abundance ratios within the
control limits in Table 23-15 of this method. When the ion abundance
ratio for a target analyte is outside the performance criteria, report
the results as EPC (see Section 3.7 of this method). PAH target
compounds have single ion identifiers with no ion abundance ratio
requirement.
13.12.2 Report analysis results that do not meet the identification
criteria as an EPC.
13.12.3 The Retention time (RT) for the analytes must be within 3
seconds of the corresponding labeled pre-extraction standard.
13.12.4 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.
13.12.5 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.
13.12.6 For the identification of specific PCB isomers, the
retention time of the native congener must be within 0.006 RRT units of
the pre-extraction standard RRT.
13.12.7 The chromatographic overlap of 2,3,4,7,8-PeCDF,
2,3,4,6,7,8-HxCDF, and 1,2,3,7,8,9-HxCDF peaks with interference peaks
must not exceed 25 percent.
13.12.8 Identify and quantify isomers that do not have
corresponding labeled pre-extraction standards by comparing to the pre-
extraction labeled standard of the same compound class with the nearest
RT to the target compound.
13.12.9 If chromatographic peaks are detected at the RT of any
PCDD/PCDF in any of the m/z channels used to monitor chlorophenyl
ethers, 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 PAHs.
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 Filter, Adsorbent Resin, Glass Wool, Water and Laboratory
Batch Blank Quality Control Check. Target levels must be =10. Poor sensitivity compared to initial
calibration response may indicate injection errors or instrument drift.
13.18 Requirements for Equivalency. The Administrator considers any
modification of this method, beyond those expressly permitted in this
method as options, to be a major modification subject to application
and approval of alternative test procedures following EPA Guidance
Document 22 currently found at: https://www.epa.gov/emc/emc-guideline-documents.
13.19 Records. As part of the laboratory's quality system, the
laboratory must maintain records of modification 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.
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
[[Page 2259]]
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 =10
13C12-1,2,3,4-TeCDF.......................................... 100 S/N>=10
13C12-1,2,3,4,6,7-HxCDD...................................... 100 S/N>=10
13C12-1,2,3,4,6,7,9-HpCDD.................................... 100 S/N>=10
----------------------------------------------------------------------------------------------------------------
Alternate Recovery Standards
----------------------------------------------------------------------------------------------------------------
13C12-1,3,7,8-TeCDD.......................................... 100 20-130
13C12-1,2,4,7,8-PeCDD........................................ 100 20-130
----------------------------------------------------------------------------------------------------------------
a Changes in the amounts of spike standards added to the sample or its representative extract will necessitate
an adjustment of the calibration solutions to prevent the introduction of inconsistencies. Spike concentration
assumes 1[mu]L sample injection volume for analysis.
b Spike levels assume half of the extract will be archived before cleanup. Spike levels may be adjusted for
different split levels.
Table 23-8--Composition of the Sample Fortification and Recovery Standard Solutions for PAHs a
----------------------------------------------------------------------------------------------------------------
Amount (pg/[mu]L of final Spike recovery
Compound extract) b (percent)
----------------------------------------------------------------------------------------------------------------
Pre-sampling Adsorbent Standards
----------------------------------------------------------------------------------------------------------------
13C6-Benzo[c]fluorene........................................ 100 70-130
13C12-Benzo[j]fluoranthene................................... 100 70-130
----------------------------------------------------------------------------------------------------------------
Pre-extraction Filter Recovery Spike Standards
----------------------------------------------------------------------------------------------------------------
d10-Anthracene............................................... 100 70-130
----------------------------------------------------------------------------------------------------------------
Pre-extraction Standards
----------------------------------------------------------------------------------------------------------------
13C6-Naphthalene............................................. 100 20-130
13C6-2-Methylnaphthalene..................................... 100 20-130
13C6-Acenaphthylene.......................................... 100 20-130
13C6-Acenaphthene............................................ 100 20-130
13C6-Fluorene................................................ 100 20-130
13C6-Phenanthrene............................................ 100 20-130
13C6-Anthracene.............................................. 100 20-130
13C6-Fluoranthene............................................ 100 20-130
13C3-Pyrene.................................................. 100 20-130
13C6-Benzo[a]anthracene...................................... 100 20-130
13C6-13Chrysene.............................................. 100 20-130
13C6-Benzo[b]fluoranthene.................................... 100 20-130
[[Page 2264]]
13C6-Benzo[k]fluoranthene.................................... 100 20-130
13C4-Benzo[e]pyrene.......................................... 100 20-130
13C4-Benzo[a]pyrene.......................................... 100 20-130
d12-Perylene................................................. 100 20-130
13C6-Indeno[1,2,3-cd]pyrene.................................. 100 20-130
13C6-Dibenz[a,h]anthracene................................... 100 20-130
13C12-Benzo[g,h,i]perylene................................... 100 20-150
----------------------------------------------------------------------------------------------------------------
Pre-analysis Standards
----------------------------------------------------------------------------------------------------------------
d10-Acenaphthene............................................. 100 S/N>=10
d10-Pyrene................................................... 100 S/N>=10
d12-Benzo[e]pyrene........................................... 100 S/N>=10
----------------------------------------------------------------------------------------------------------------
a Changes in the amounts of spike standards added to the sample or its representative extract will necessitate
an adjustment of the calibration solutions to prevent the introduction of inconsistencies.
b Spike levels assume half of the extract will be archived before cleanup. You may adjust spike levels for
different split levels.
Table 23-9--Composition of the Sample Fortification and Recovery Standard Solutions for PCBs \a\
----------------------------------------------------------------------------------------------------------------
Amount (pg/[micro]L of final Spike recovery
Compound BZ No.\b\ extract) \c\ (percent)
----------------------------------------------------------------------------------------------------------------
Pre-sampling Adsorbent Standards
----------------------------------------------------------------------------------------------------------------
13C12-3,3'-DiCB..................... 11L 100 70-130
13C12-2,4',5-TrCB................... 31L 100 70-130
13C12-2,2',3,5',6-PeCB.............. 95L 100 70-130
13C12-2,2',4,4',5,5'-HxCB........... 153L 100 70-130
----------------------------------------------------------------------------------------------------------------
Pre-extraction Filter Recovery Spike Standards
----------------------------------------------------------------------------------------------------------------
13C12-2,3,3',4,5,5'-HxCB............ 159L 100 70-130
----------------------------------------------------------------------------------------------------------------
Pre-extraction Standards
----------------------------------------------------------------------------------------------------------------
13C12-2-MoCB (WDC).................. 1L 100 20-145
13C12-4-MoCB (WDC).................. 3L 100 20-145
13C12-2,2'-DiCB (WDC)............... 4L 100 20-145
13C12-4,4'-DiCB (WDC)............... 15L 100 20-145
13C12-2,2',6-TrCB (WDC)............. 19L 100 20-145
13C12-3,4',4'-TrCB (WDC)............ 37L 100 20-145
13C12-2,2',6,6'-TeCB (WDC).......... 54L 100 20-145
13C12-3,3',4,4'-TeCB (WDC) (WHOT) 77L 100 20-145
(NOAAT).
13C12-3,4,4',5-TeCB (WHOT).......... 81L 100 20-145
13C12-2,2',4,6,6'-PeCB (WDC)........ 104L 100 20-145
13C12-2,3,3',4,4'-PeCB (WHOT)....... 105L 100 20-145
13C12-2,3,4,4',5-PeCB (WHO)......... 114L 100 20-145
13C12-2,3',4,4',5-PeCB (WHOT)....... 118L 100 20-145
13C12-2',3,4,4',5-PeCB (WHOT)....... 123L 100 20-145
13C12-3,3',4,4',5-PeCB (WDC) (WHOT). 126L 100 20-145
13C12-2,2',4,4',6,6'-HxCB (WDC)..... 155L 100 20-145
13C12-2,3,3',4,4',5-HxCB (WHOT)..... 156L 100 20-145
13C12-2,3,3',4,4',5'-HxCB (WHOT).... 157L 100 20-145
13C12-2,3',4,4',5,5'-HxCB (WHOT).... 167L 100 20-145
13C12-3,3',4,4',5,5'-HxCB (WDC) 169L 100 20-145
(WHOT) (NOAAT).
13C12-2,2',3,3',4,4',5'-HpCB (NOAAT) 170L 100 20-145
13C12-2,2',3,4,4',5,5'-HpCB (NOAAT). 180L 100 20-145
13C12-2,2',3,4',5,6,6'-HpCB (WDC)... 188L 100 20-145
13C12-2,3,3',4,4',5,5'-HpCB (WDC) 189L 100 20-145
(WHOT).
13C12-2,2',3',3',5,5',6,6'-OcCB 202L 100 20-145
(WDC).
13C12-2,3',3',4,4',5,5',6-OcCB (WDC) 205L 100 20-145
13C12-2,2',3,3',4,4',5,5',6-NoCB 206L 100 20-145
(WDC).
13C12-2,2',3,3',4,5,5',6,6'-NoCB 208L 100 20-145
(WDC).
13C12-DeCB (WDC).................... 209L 100 20-145
----------------------------------------------------------------------------------------------------------------
Pre-analysis Standards
----------------------------------------------------------------------------------------------------------------
13C12-2,5-DiCB...................... 9L 100 S/N>=10
13C12-2,2',5,5'-TeCB (NOAAT)........ 52L 100 S/N>=10
[[Page 2265]]
13C12-2,2',4,5,5'-PeCBl (NOAAT)..... 101L 100 S/N>=10
13C12-2,2',3,4,4',5'-HxCB (NOAAT)... 138L 100 S/N>=10
13C12-2,2',3,3',4,4',5,5'-OcCB...... 194L 100 S/N>=10
----------------------------------------------------------------------------------------------------------------
Optional Cleanup Spiking Standards
----------------------------------------------------------------------------------------------------------------
13C12-2-MoCB (NOAAT)................ 28L 100 20-130
13C12-2,2',4,5,5'-PeCB.............. 111L 100 20-130
13C12-2,2',3,3',5,5',6,6'-OcCB...... 178L 100 20-130
----------------------------------------------------------------------------------------------------------------
Alternate Recovery Standards
----------------------------------------------------------------------------------------------------------------
\13\C12-2,3',4',5-TeCB.............. 70L 100 20-130
13C12-2,3,4,4'-TeCB................. 60L 100 20-130
13C12-3,3',4,5,5'-PeCB.............. 127L 100 20-130
----------------------------------------------------------------------------------------------------------------
\a\ Changes in the amounts of spike standards added to the sample or its representative extract will necessitate
an adjustment of the calibration solutions to prevent the introduction of inconsistencies.
\b\ BZ No.: Ballschmiter and Zell 1980, or IUPAC number.
\c\ Spike levels assume half of the extract will be archived before cleanup. Spike levels may be adjusted for
different split levels.
Table 23-10--Sample Storage Conditions a and Laboratory Hold Times b
----------------------------------------------------------------------------------------------------------------
Sample type PCDD/PCDF PAH PCB
----------------------------------------------------------------------------------------------------------------
Field Storage and Shipping Conditions
----------------------------------------------------------------------------------------------------------------
All Field Samples............... 5 5 5 [deg]C, (68
[deg]C, (68 9 [deg]F).
minus> 9 [deg]F). minus> 9 [deg]F).
----------------------------------------------------------------------------------------------------------------
Laboratory Storage Conditions
----------------------------------------------------------------------------------------------------------------
Sampling Train Rinses and Water initial rinse: Place resin in a suitable container,
soak for approximately 5 min with Type II water, remove fine floating
resin particles and discard the water. Fill with Type II water a second
time, let stand overnight, remove fine floating resin particles and
discard the water.
Hot water: Extract with water for 8 hr.
Methyl alcohol: Extract for 22 hr.
Methylene chloride: Extract for 22 hr.
Toluene: Extract for 22 hr.
Toluene (fresh): Extract for 22 hr.
Note: You may store the resin in a sealed glass container filled
with toluene prior to the final toluene extraction. It may be
necessary to repeat the final toluene extractions to meet the
requirements in Section 13.14 of Method 23.
2.2 You may use alternative extraction procedures to clean large
batches of resin. Any size extractor may be constructed; the choice
depends on the needs of the sampling programs. The resin is held in a
glass or stainless-steel cylinder between a pair of coarse and fine
screens. Spacers placed under the bottom screen allow for even
distribution of clean solvent. Clean solvent is circulated through the
resin for extraction. A flow rate is maintained upward through the
resin to allow maximum solvent contact and prevent channeling.
2.2.1 Experience has shown that 1 mL/g of resin extracted is the
minimum necessary to extract and clean the resin. The aqueous rinse is
critical to the subsequent organic rinses and may be accomplished by
simply flushing the canister with about 1 liter of distilled water for
every 25 g of resin. A small pump may be useful for pumping the water
through the canister. You should perform the water extraction at the
rate of about 20 to 40 mL/min.
2.2.2 All materials of construction are glass, PTFE, or stainless
steel. Pumps, if used, should not contain extractable materials.
3.0 Drying
3.1 Dry the adsorbent of extraction solvent before use. This
section provides a recommended procedure to dry adsorbent that is wet
with solvent. However, you may use other procedures if the cleanliness
requirements in Sections 13.2 and 13.14 of Method 23 are met.
3.2 Drying Column. A simple column with suitable retainers, as
shown in Figure A-2, will hold all the XAD-2 from the extractor shown
in Figure A-1 or the Soxhlet extractor, with sufficient space for
drying the bed while generating a minimum backpressure in the column.
3.3 Drying Procedure: Dry the adsorbent using clean inert gas.
Liquid nitrogen from a standard commercial liquid nitrogen cylinder has
proven to be a reliable source of large volumes of gas free from
organic contaminants. You may use high-purity tank nitrogen to dry the
resin. However, you should pass the high-purity nitrogen through a bed
of activated charcoal approximately 150 mL in volume prior to entering
the drying apparatus.
3.3.1 Connect the gas vent of a liquid nitrogen cylinder or the
exit of the activated carbon scrubber to the column by a length of
precleaned copper tubing (e.g., 0.95 cm ID) coiled to pass through a
heat source. A convenient heat source is a water bath heated from a
steam line. The final nitrogen temperature should only be warm to the
touch and not over 40 [deg]C.
3.3.2 Allow the toluene to drain from the resin prior to placing
the resin in the drying apparatus.
3.3.3 Flow nitrogen through the drying apparatus at a rate that
does not fluidize or agitate the resin. Continue the nitrogen flow
until the residual solvent is removed.
Note: Experience has shown that about 500 g of resin may be
dried overnight by consuming a full 160-L cylinder of liquid
nitrogen.
4.0 Quality Control Procedures
4.1 Report quality control results for the batch. Re-extract the
batch if the residual extractable organics fail the criteria in Section
13.14 of Method 23.
4.2 Residual Toluene Quality Check. If adsorbent resin is cleaned
or recleaned by the laboratory, perform a quality control check for
residual toluene. The maximum acceptable concentration of toluene is
1000 [micro]g/g of adsorbent. If the adsorbent exceeds this level,
continue drying until the excess toluene is removed.
4.2.1 Extraction. Weigh 1.0 g sample of dried resin into a small
vial, add 3 mL of methylene chloride, cap the vial, and shake it well.
4.2.2 Analysis. Inject a 2-[micro]l sample of the extract into a
gas chromatograph operated to provide separation between the methylene
chloride extraction solvent and toluene.
4.2.2.1 Typical GC conditions to accomplish this performance
requirement include, but are not limited to:
Column: Sufficient to separate extraction solvents used to
verify adsorbent has been sufficiently dried (i.e., gas chromatographic
fused-silica capillary column coated with a slightly polar silicone).
Carrier Gas: Typically, helium at a rate appropriate for
the column selected. Other carrier gases are allowed if the performance
criteria in Method 23 are met.
Injection Port Temperature: 250 [deg]C.
Detector: Flame ionization detector or an MS installed on
a GC able to separate methylene chloride and toluene.
Oven Temperature Profile: Typically, 30 [deg]C for 4 min;
programmed to rise at 20 [deg]C/min until the oven reaches 250 [deg]C;
return to 30 [deg]C after 17 minutes. You may adjust the initial
temperature, hold time, program rate, and final temperature to ensure
separation of extraction solvent from toluene.
4.2.2.2 Compare the results of the analysis to the results from a
toluene calibration standard at a concentration of 0.22 [micro]l/mL (22
[micro]l/100 mL) of methylene chloride. This concentration corresponds
to maximum acceptable toluene concentration in the dry adsorbent of
1,000 [micro]g/g of adsorbent. If the adsorbent exceeds this level,
continue drying until the excess toluene is removed.
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[GRAPHIC] [TIFF OMITTED] TP14JA20.015
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PART 63--NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS
FOR SOURCE CATEGORIES
0
6. The authority citation for part 63 continues to read as follows:
Authority: 42 U.S.C. 7401 et seq.
0
7. In Sec. 63.849, revise paragraphs (a)(13) and (a)(14) to read as
follows:
Sec. 63.849 Test methods and procedures.
* * * * *
(a) * * *
(13) Method 23 of Appendix A-7 of 40 CFR part 60 for the
measurement of Polychlorinated Biphenyls (PCBs) where stack or duct
emissions are sampled; and
(14) Method 23 of appendix A-7 of 40 CFR part 60 and Method 14 or
Method 14A in appendix A to part 60 of this chapter or an approved
alternative method for the concentration of PCB where emissions are
sampled from roof monitors not employing wet roof scrubbers.
* * * * *
0
8. In Sec. 63.1208, revise paragraph (b)(1) to read as follows:
Sec. 63.1208 What are the test methods?
* * * * *
(b) * * *
(1) Dioxins and furans. (i) To determine compliance with the
emission standard for dioxins and furans, you must use:
(A) Method 0023A, Sampling Method for Polychlorinated Dibenzo-p-
Dioxins and Polychlorinated Dibenzofurans emissions from Stationary
Sources, EPA Publication SW-846 (incorporated by reference--see Sec.
63.14); or
(B) Method 23, provided in appendix A, part 60 of this chapter.
(ii) You must sample for a minimum of three hours, and you must
collect a minimum sample volume of 2.5 dscm;
(iii) You may assume that nondetects are present at zero
concentration.
* * * * *
0
9. In Sec. 63.1625, revise paragraph (b)(10) to read as follows:
[[Page 2277]]
Sec. 63.1625 What are the performance test and compliance
requirements for new, reconstructed, and existing facilities?
* * * * *
(b) * * *
(10) Method 23 of appendix A-7 of 40 CFR part 60 to determine PAH.
* * * * *
0
10. In table 3 to subpart AAAAAAA of part 63 revise the entry ``6.
Measuring the PAH emissions'' to read as follows:
Table 3 to Subpart AAAAAAA of Part 63--Test Methods
------------------------------------------------------------------------
For * * * You must use * * *
------------------------------------------------------------------------
* * * * *
6. Measuring the PAH emissions............ EPA test method 23.
------------------------------------------------------------------------
* * * * *
PART 266--STANDARDS FOR THE MANAGEMENT OF SPECIFIC HAZARDOUS WASTES
AND SPECIFIC TYPES OF HAZARDOUS WASTE MANAGEMENT FACILITIES
0
11. The authority citation for part 266 continues to read as follows:
Authority: 42 U.S.C. 1006, 2002(a), 3001-3009, 3014, 3017,
6905, 6906, 6912, 6921, 6922, 6924-6927, 6934, and 6937.
0
12. In Sec. 266.104, revise paragraph (e)(1) to read as follows:
Sec. 266.104 Standards to control organic emissions.
* * * * *
(e) * * *
(1) During the trial burn (for new facilities or an interim status
facility applying for a permit) or compliance test (for interim status
facilities), determine emission rates of the tetra-octa congeners of
chlorinated dibenzo-p-dioxins and dibenzofurans (CDDs/CDFs) using
Method 0023A, Sampling Method for Polychlorinated Dibenzo-p-Dioxins and
Polychlorinated Dibenzofurans Emissions from Stationary Sources, EPA
Publication SW-826, as incorporated by reference in Sec. 266.11 of
this chapter or Method 23, provided in appendix A-7, part 60 of this
chapter.
* * * * *
[FR Doc. 2019-27842 Filed 1-13-20; 8:45 am]
BILLING CODE 6560-50-P
