EPA Method 23-Determination of Polychlorinated Dibenzo-p-Dioxins and Polychlorinated Dibenzofurans From Stationary Sources, 2234-2277 [2019-27842]

Download as PDF 2234 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules 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 Environmental Protection Agency. ACTION: Proposed rule. AGENCY: 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 performancebased 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: a-and-r-docket@epa.gov. Include Docket ID No. EPA–HQ–OAR– 2016–0677 in the subject line of the message. lotter on DSKBCFDHB2PROD with PROPOSALS2 SUMMARY: VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 • 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: merrill.raymond@epa.gov. 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, PO 00000 Frm 00002 Fmt 4701 Sfmt 4702 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 E:\FR\FM\14JAP2.SGM 14JAP2 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules by email at merrill.raymond@epa.gov 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-idenforcement-brieffrequently-askedquestions. 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 2235 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? 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 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 Category NAICSY a Industry .................................. lotter on DSKBCFDHB2PROD with PROPOSALS2 a North 332410 332410 562213 322110 325211 327310 324122 331314 327120 331410 Examples of regulated entities Fossil fuel steam generators. Industrial, commercial, institutional steam generating units. Municipal Waste Combustors. Hazardous Waste Combustors. Polyvinyl Chloride Resins Manufacturing. Portland cement plants. Asphalt Shingle and Coating Materials Manufacturing. Secondary aluminum plants. Clay Building Material and Refractories Manufacturing. Nonferrous Metal (except Aluminum) Smelting and Refining. 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. VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 B. Where can I get a copy of this document and other related information? ttn/emc/methods/. The TTN provides information and technology exchange in various areas of air pollution control. 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/ II. Background PO 00000 Frm 00003 Fmt 4701 Sfmt 4702 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 E:\FR\FM\14JAP2.SGM 14JAP2 lotter on DSKBCFDHB2PROD with PROPOSALS2 2236 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules 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 VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 samples for laboratory analysis and ASTM D4840–99(2018)e1 includes a standard guide for sample chain-ofcustody 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/measurementsmodeling/methoddevelopment#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 preextraction 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 PO 00000 Frm 00004 Fmt 4701 Sfmt 4702 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 performancebased 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 E:\FR\FM\14JAP2.SGM 14JAP2 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules current section 3.0 to a proposed new section 7.0. move language from the current section 4.0 to a proposed new section 8.0. D. Section 4.0 E. Section 5.0 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 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. 2237 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 Filter holder .................................................................................................................................................. Condenser ................................................................................................................................................... Water circulating bath .................................................................................................................................. Absorbent module ........................................................................................................................................ Fitting cap .................................................................................................................................................... Wash bottles ................................................................................................................................................ Filter storage container ................................................................................................................................ Field balance ............................................................................................................................................... Aluminum foil ............................................................................................................................................... Glass sample storage containers ................................................................................................................ Extraction thimble ........................................................................................................................................ Pasteur pipette ............................................................................................................................................. GC oven ....................................................................................................................................................... Temperature monitor for GC oven .............................................................................................................. GC Flow system .......................................................................................................................................... Capillary column .......................................................................................................................................... Mass spectrometer ...................................................................................................................................... Mass spectrometer data system ................................................................................................................. 2.1.1 2.1.2 2.1.3 2.1.4 2.2.1 2.2.2 2.2.4 2.2.5 2.2.6 2.2.9 2.3.4 2.3.5 2.3.10.1 2.3.10.2 2.3.10.3 2.3.10.4 2.3.11 2.3.12 Proposed section 6.1.3 6.1.7 6.1.8 6.1.9 6.2.1 6.2.2 6.2.4 6.2.5 6.2.6 6.2.8 6.3.3.3 6.4.1 6.5.1.1 6.5.1.2 6.5.1.3 6.5.2 6.5.3 6.5.4 TABLE 3—PROPOSED ADDITIONAL SPECIFICATIONS FOR SECTION 6.0 Description Proposed section lotter on DSKBCFDHB2PROD with PROPOSALS2 Probe liner ..................................................................................................................................................................................... Filter heating system ..................................................................................................................................................................... Filter temperature sensor .............................................................................................................................................................. Sample transfer line ....................................................................................................................................................................... Impingers ....................................................................................................................................................................................... Soxhlet extraction apparatus ......................................................................................................................................................... Moisture trap of extraction apparatus ............................................................................................................................................ Kuderna-Danish concentrator ........................................................................................................................................................ Heating mantle ............................................................................................................................................................................... Chromatography column ............................................................................................................................................................... Injection port .................................................................................................................................................................................. PCDD/PCDF column system ......................................................................................................................................................... PAH column system ...................................................................................................................................................................... PCB column system ...................................................................................................................................................................... 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; VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 • 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 PO 00000 Frm 00005 Fmt 4701 Sfmt 4702 6.1.2 6.1.4 6.1.5 6.1.6 6.1.10 6.3.3.1 6.3.3.2 6.3.4 6.3.3.4 6.4.2 6.5.1.4 6.5.2.1 6.5.2.2 6.5.2.3 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 E:\FR\FM\14JAP2.SGM 14JAP2 2238 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules 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 Filter ............................................................................................................................................................. Adsorbent resin ............................................................................................................................................ Glass wool ................................................................................................................................................... Water ........................................................................................................................................................... Methylene chloride ....................................................................................................................................... Sodium sulfate ............................................................................................................................................. Basic alumina .............................................................................................................................................. Silica gel ...................................................................................................................................................... Carbon/Celite® ............................................................................................................................................. Nitrogen ....................................................................................................................................................... Proposed section 3.1.1 3.1.2 3.1.3 3.1.4 3.2.2 3.3.2 3.3.13 3.3.14 3.3.17 3.3.18 7.1 7.2 7.3 7.4 7.6 7.8.2 7.8.9.1.2 7.8.9.3 7.8.9.4 7.8.10 TABLE 5—PROPOSED ADDITIONAL SPECIFICATIONS FOR SECTION 7.0 Description Proposed section High-boiling alkanes used as keeper solvents .............................................................................................................................. Liquid column packing materials ................................................................................................................................................... Acidic alumina ................................................................................................................................................................................ Florisil® .......................................................................................................................................................................................... Helium ............................................................................................................................................................................................ Spiking standards .......................................................................................................................................................................... Pre-sampling recovery standard solution ...................................................................................................................................... Filter recovery spike standard solution .......................................................................................................................................... Pre-extraction recovery standard solution ..................................................................................................................................... Pre-analysis recovery standard solution ....................................................................................................................................... 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 7.8.8 7.8.9 7.8.9.1.1 7.8.9.2 7.9.1 7.9.2 7.9.3 7.9.4 7.9.5 7.9.6 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 ...................................................................................................................................................... Benzene ......................................................................................................................................................................................... Ethyl acetate .................................................................................................................................................................................. Nonane .......................................................................................................................................................................................... Cyclohexane .................................................................................................................................................................................. Hydrogen ....................................................................................................................................................................................... Internal standard solution .............................................................................................................................................................. Surrogate standard solution .......................................................................................................................................................... Recovery standard solution ........................................................................................................................................................... We are also proposing to move the current section 7.0 to a proposed new section 9.0. lotter on DSKBCFDHB2PROD with PROPOSALS2 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. 3.1.6 3.3.7 3.3.8 3.3.11 3.3.12 3.3.19 3.3.20 3.3.21 3.3.22 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 Glassware cleaning ..................................................................................................................................... Assembling the adsorbent module .............................................................................................................. Maintaining the sampling train components ................................................................................................ Silica Gel ...................................................................................................................................................... VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 PO 00000 Frm 00006 Fmt 4701 Sfmt 4702 E:\FR\FM\14JAP2.SGM 4.1.1.1 4.1.1.2 4.1.1.3 4.1.1.4 14JAP2 Proposed section 8.1.1.1 8.1.1.2 8.1.1.3 8.1.1.4 2239 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules TABLE 7—CROSSWALK FOR PROPOSED REVISIONS TO CURRENT METHOD SECTIONS—Continued Description Current section Checking and packing filters ....................................................................................................................... Field preparation of the sampling train ........................................................................................................ Impinger assembly ....................................................................................................................................... Sampling probe and nozzle 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 4.1.1.5 4.1.3.1 4.1.3.2 4.1.3.4 Proposed section 8.1.1.5 8.1.3.1 8.1.3.2 8.1.3.4 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 ............................................................................................................................................................... Sampling time for continuous processes ...................................................................................................................................... Sampling time for batch processes ............................................................................................................................................... Filter assembly ............................................................................................................................................................................... Orientation of the condenser and adsorbent module .................................................................................................................... Monitoring the filter temperature ................................................................................................................................................... Monitoring the adsorbent module temperature ............................................................................................................................. 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 8.1.2.1 8.1.2.2 8.1.2.3 8.1.3.3 8.1.3.4 8.1.5.1 8.1.5.2 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 Adsorbent module sample preparation ....................................................................................................... Preparation of Container No. 2 ................................................................................................................... Rinsing of the filter holder and condenser .................................................................................................. Weighing impinger water ............................................................................................................................. Preparation of Container No. 3 ................................................................................................................... Silica gel ...................................................................................................................................................... 4.2.2 4.1.1.2 4.1.1.3 4.1.1.5 4.1.3.1 4.1.3.2 Proposed section 8.2.5 8.2.6 8.2.7 8.2.8 8.2.9 8.2.10 TABLE 10—PROPOSED ADDITIONAL SPECIFICATIONS FOR SECTION 8.2 Description Proposed section lotter on DSKBCFDHB2PROD with PROPOSALS2 Conducting a post-test leak check ................................................................................................................................................ Storage conditions for Container No. 1 ......................................................................................................................................... Field sample handling, storage, and transport .............................................................................................................................. Sample chain of custody ............................................................................................................................................................... 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 VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 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 PO 00000 Frm 00007 Fmt 4701 Sfmt 4702 8.2.1 8.2.4 8.2.11 8.2.12 requirements of this method. We are also proposing to add specifications for conducting pre-sampling, preextraction, and pre-analysis spike recoveries of isotopically-labeled standards and to add specifications for: • Capillary gas chromatography columns; E:\FR\FM\14JAP2.SGM 14JAP2 2240 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules • 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 apparatus ............................................................................................ Cooling the extraction apparatus ....................................................................................................................... Performing an initial extract concentration ........................................................................................................ Cooling the sample extract ................................................................................................................................ Recommended minimum volume for PCDD/PCDF analysis ............................................................................. Further concentration of sample (if needed) for cleanup and analysis ............................................................. Sample cleanup and fractionation for PAHs and PCDEs ................................................................................. Sample cleanup and fractionation for PCDD/DFs and PCBs ........................................................................... Addressing unresolved compounds ................................................................................................................... Retention time for PCBs .................................................................................................................................... Chlorodiphenyl ether interference of PCDD/DFs ............................................................................................... MS lock channels ............................................................................................................................................... Calculations of target mass and mass per dry standard cubic meter ............................................................... Quantifying indigenous PCDD/DFs .................................................................................................................... Reporting options compound concentrations .................................................................................................... Identification criteria for PAHs ........................................................................................................................... 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 11.1.7 through 11.1.9. 11.2.1. 11.2.2. 11.2.3. 11.2.3. 11.2.4. 11.3.1. 11.3.2. 11.4.1.2.1. 11.4.3.4.5. 11.4.3.4.8. 11.4.3.4.9. 11.4.3.5.1 and 11.4.3.5.2. 11.4.3.5.3. 11.4.3.5.4 through 11.4.3.5.6. 11.4.3.4.10. 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 23–2 ................... 23–6 ................... 23–9 ................... 23–10 ................. 23–11 ................. Average relative response factor (RRF) for each compound ....................................................................... Concentration of individual target compound i in the extract by isotope dilution ......................................... Recovery of Labeled Compound Standards ................................................................................................. Estimated detection limit ............................................................................................................................... Total concentration ........................................................................................................................................ We are also proposing to remove and replace the current equations in Method Proposed section 23 with the equations shown in Table 13 of this preamble to accommodate the 12.3 12.7 12.10 12.11 12.12 proposed changes to the method procedures. lotter on DSKBCFDHB2PROD with PROPOSALS2 TABLE 13—PROPOSED ADDITIONAL EQUATIONS FOR SECTION 12.0 Equation 23–1 23–3 23–4 23–5 Description ................... ................... ................... ................... 23–7 ................... VerDate Sep<11>2014 Proposed section Individual compound RRF for each calibration level .................................................................................... Percent relative standard deviation of the RRFs for a compound over the five calibration levels .............. Standard deviation of the RRFs for a compound over the five calibration levels ........................................ Percent difference of the RRF of the continuing calibration verification compared to the average RRF from the initial calibration for each target compound. Concentration of individual target compound i in the sample extract ........................................................... 19:55 Jan 13, 2020 Jkt 250001 PO 00000 Frm 00008 Fmt 4701 Sfmt 4702 E:\FR\FM\14JAP2.SGM 14JAP2 12.2 12.4 12.5 12.6 12.8 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules 2241 TABLE 13—PROPOSED ADDITIONAL EQUATIONS FOR SECTION 12.0—Continued Equation Description 23–8 ................... Concentration of the Individual Target Compound or Group i in the Emission Gas .................................... M. Section 13.0 Performance,’’ that would include the specifications shown in Table 14 of this preamble. In this action, the EPA is proposing to add a new section 13.0 titled ‘‘Method Proposed section 12.9 TABLE 14—PROPOSED METHOD PERFORMANCE SPECIFICATIONS FOR SECTION 13.0 Description Proposed section Quality control checks of filters, adsorbent resin, glass wool, and batch blanks ...................................................................... Field train proof blanks ............................................................................................................................................................... GC column systems used to measure PCDD/F, PAH, and PCB target compounds ................................................................ Acceptability of detection limits ................................................................................................................................................... Tuning HRGC/HRMS systems ................................................................................................................................................... MS lock channels ....................................................................................................................................................................... Initial and continuing calibrations ................................................................................................................................................ Identification of target compounds .............................................................................................................................................. Pre-sampling, -extraction, and –analysis spike recoveries ........................................................................................................ Pre-analysis spike sensitivity requirements ................................................................................................................................ Modifications of the method ........................................................................................................................................................ 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. lotter on DSKBCFDHB2PROD with PROPOSALS2 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-pDibenzodioxins 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. 13.1, 13.2, and 13.14. 13.2. 13.3 through 13.6. 13.7. 13.8. 13.9. 13.10 and 13.11. 13.12 and 13.13. 13.15 and 13.16. 13.17. 13.18 and 13.19. • 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, He´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 Fortification and Recovery Standards Solutions. Table 2—Composition of the Initial Calibration Solutions ........................ Table 23–7. Composition of the Sample Fortification and Recovery Standard Solutions for PCDDs and PCDFs. Table 23–11. Composition of the Initial Calibration Standard Solutions for PCDDs and PCDFs. VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 PO 00000 Frm 00009 Fmt 4701 Sfmt 4702 E:\FR\FM\14JAP2.SGM 14JAP2 2242 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules TABLE 15—PROPOSED REVISIONS TO METHOD 23 TABLES—Continued Current method Proposed method Table 3—Elemental Compositions and Exact Masses of the Ions Monitored by High Resolution Mass Spectrometry for PCDD’s and PCDF’s. Table 4—Acceptable Ranges for Ion-Abundance Ratios of PCDD’s and PCDF’s. Table 5—Minimum Requirements for Initial and Daily Calibration Response Factors. Table 23–4. Elemental Compositions and Exact Masses of the Ions Monitored by High-Resolution Mass Spectrometry for PCDDs and PCDFs. Table 23–15. Recommended Ion Type and Acceptable Ion Abundance Ratios. Table 23–14. Minimum Requirements for Initial and 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 23–1 ........................ 23–2 ........................ 23–3 ........................ 23–5 ........................ 23–6 ........................ 23–8 ........................ 23–9 ........................ 23–10 ...................... 23–12 ...................... 23–13 ...................... 23–16 ...................... 23–17 ...................... 23–18 ...................... 23–19 ...................... 23–20 ...................... Description Polychlorinated Dibenzo-p-dioxin and Polychlorinated Dibenzofuran Target Analytes. Polycyclic Aromatic Hydrocarbon Target Analytes. Polychlorinated Biphenyl Target Analytes. Elemental Compositions and Exact Masses of the Ions Monitored by High-Resolution Mass Spectrometry for PAHs. Elemental Compositions and Exact Masses of the Ions Monitored by High-Resolution Mass Spectrometry for PCBs. Composition of the Sample Fortification and Recovery Standard Solutions for PAHs. Composition of the Sample Fortification and Recovery Standard Solutions for PCBs. Sample Storage Conditions and Laboratory Hold Times. Composition of the Initial Calibration Standard Solutions for PAHs. Composition of the Initial Calibration Standard Solutions for PCBs. Typical DB5–MS Column Conditions. Assignment of Pre-extraction Standards for Quantitation of Target PCBs. Estimated Method Detection Limits for PCDDs and PCDFs. Target Detection Limits for PAHs. Estimated Method Detection Limits for PCBs. lotter on DSKBCFDHB2PROD with PROPOSALS2 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 § 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 § 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 VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 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. PO 00000 Frm 00010 Fmt 4701 Sfmt 4702 VI. Statutory and Executive Order Reviews Additional information about these statutes and Executive Orders can be found at https://www2.epa.gov/lawsregulations/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 E:\FR\FM\14JAP2.SGM 14JAP2 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules 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. lotter on DSKBCFDHB2PROD with PROPOSALS2 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. VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 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, PO 00000 Frm 00011 Fmt 4701 Sfmt 4702 2243 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 1. The authority citation for part 60 continues to read as follows: ■ Authority: 42 U.S.C. 7401 et seq. 2. In § 60.17: a. Redesignate paragraphs (h)(167) through (h)(209) as (h)(168) through (h)(210); ■ b. Add paragraph (h)(167); and ■ c. Revise newly redesignated paragraph (h)(192). The addition and revision read as follows: ■ ■ § 60.17 Incorporations by reference. * * * * * (h) * * * (167) ASTM D4840–99(2018)e1 Standard Guide for Sample Chain-ofCustody 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. * * * * * ■ 3. In § 60.2125, revise paragraphs (g)(2) and (j)(2) to read as follows: E:\FR\FM\14JAP2.SGM 14JAP2 2244 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules § 60.2125 How do I conduct the initial and annual performance test? Appendix A–7 to Part 60—Test Methods 19 through 25E * * * * * * (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.) * * * * * ■ 4. In § 60.2690, revise paragraphs (g)(2) and (j)(2) to read as follows: § 60.2690 How do I conduct the initial and annual performance test? lotter on DSKBCFDHB2PROD with PROPOSALS2 * * * * * (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 * * * * * ■ 5. Revise Method 23 of appendix A– 7 to part 60 and to read as follows: VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 * * * * 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 ‘‘performancebased’’ and includes acceptability criteria for assessing sampling and analytical procedures. Users may PO 00000 Frm 00012 Fmt 4701 Sfmt 4702 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 midpoint 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 E:\FR\FM\14JAP2.SGM 14JAP2 lotter on DSKBCFDHB2PROD with PROPOSALS2 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules 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-pdioxin (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 VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 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 triPCDFs 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 PO 00000 Frm 00013 Fmt 4701 Sfmt 4702 2245 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-pdioxin Toxic Equivalent Factor(s) (2,3,7,8-TeCDD–TEF). A procedure that expresses the toxicity of PCDDs, PCDFs, E:\FR\FM\14JAP2.SGM 14JAP2 2246 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules 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 columnchromatographic 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. lotter on DSKBCFDHB2PROD with PROPOSALS2 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 VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 atoms in positions 2,3,7,8 have toxicities comparable to that of 2,3,7,8TeCDD. 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 PO 00000 Frm 00014 Fmt 4701 Sfmt 4702 with a heating system capable of maintaining a probe gas temperature of 120 ± 14 °C (248 ± 25 °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 °C (572 °F). Use a quartz glass liner and integrated quartz nozzle for stack temperatures between 300 and 1,200 °C (572 and 2,192 °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, leakfree 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 °C (248 ± 25 °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 °C (5.4 °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 leakfree, 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 °C ± 14 °C (248 °F ± 25 °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, waterjacketed, 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. E:\FR\FM\14JAP2.SGM 14JAP2 lotter on DSKBCFDHB2PROD with PROPOSALS2 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules 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 < 20 °C (68 °F). 6.1.9 Adsorbent Module. Use a water-jacketed glass container to hold up to 40 grams (g) of the solid adsorbent. Figure 23–2 of this method shows a schematic diagram of the adsorbent module. Other physical configurations of the adsorbent resin module/condenser assembly are acceptable if the configuration contains the requisite amount of solid adsorbent and maintains the minimum length-towidth adsorbent bed ratio of two-to-one. Orient the adsorbent module vertically to facilitate condensate drainage. The connecting fittings must form leak-free, vacuum-tight seals. Include a coarse glass frit in the adsorbent module to retain the adsorbent. 6.1.10 Impingers. Use five impingers connected in series with leak-free ground glass fittings or any similar leakfree noncontaminating fittings. The first impinger must be a short-stem stem (water-dropout) design or equivalent. The second, fourth, and fifth impingers must be of the Greenburg-Smith design, modified by replacing the tip with a 1.3 cm (1–2 in.) inside diameter (ID) glass tube extending to approximately 1.3 cm (1–2 in.) from the bottom of the flask. The third impinger must be of the Greenburg-Smith design with the standard tip. The second and third impingers must contain known quantities of water, and the fifth impinger must contain a known weight of silica gel or equivalent desiccant. Alternatively, you may omit the first impinger if you do not expect excess moisture in the sample gas. 6.2 Sample Recovery Equipment. 6.2.1 Fitting Caps. Use leak-free ground glass fittings or any similar leakfree non-contaminating fitting to cap the sections of the sampling train exposed to the sample gas. Alternatively, use PTFE tape or contaminant-free aluminum foil for this purpose (see Section 6.2.6 of this method). 6.2.2 Wash Bottles. Use PTFE bottles. 6.2.3 Probe-Liner, Probe-Nozzle, and Filter-Holder Brushes. Use inert bristle brushes with precleaned stainless steel or PTFE handles. Extensions of the probe brush must be made of stainless steel or PTFE and be at least as long as VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 the probe. Use brushes that are properly sized and shaped to remove accumulated material from the nozzle and probe liner if used. 6.2.4 Filter Storage Container. Use a sealed filter holder, wide-mouth amber glass jar with PTFE-lined cap, or glass petri dish sealed with PTFE tape. Purchase precleaned amber glass jars and petri dishes or clean according to the glassware cleaning procedures listed in Section 8.1.1.1 of this method. 6.2.5 Field Balance. Use a weighing device capable of measurements to an accuracy of 0.5g. 6.2.6 Aluminum Foil. Use heavy duty aluminum foil cleaned by rinsing three times with hexane or toluene and stored in a pre-cleaned glass petri dish or glass jar. Do not use aluminum foil to wrap or contact filter samples due to the possibility of reaction between the sample and the aluminum. 6.2.7 Adsorbent Storage Containers. Use an air-tight container to store silica gel. 6.2.8 Glass Sample Storage Containers. Recover samples in amber glass bottles, 500- or 1000-milliliters (mL) with leak-free PTFE-lined caps. Either purchase precleaned bottles or clean containers according to glassware cleaning procedures listed in Section 8.1.1.1 of this method. 6.3 Sample Extraction Equipment. 6.3.1 Sample Containers. Use 125and 250-mL amber glass bottles with PTFE-lined caps. 6.3.2 Test Tubes. Use glass test tubes or small (e.g., 5 to 10 mL) amber vials. 6.3.3 Soxhlet/Dean-Stark Extraction Apparatus. 6.3.3.1 Soxhlet Apparatus. Use 200mL capacity capable of holding 43 × 123-millimeter (mm) extraction thimbles, with receiving flask (typically round-bottom). 6.3.3.2 Moisture Trap. Use DeanStark or Barret with fluoropolymer stopcock trap to fit between the Soxhlet extractor body and the condenser as shown in Figure 23–3 of this method. Note: Dean-Stark or Barret traps are used to remove water with extraction solvents that are less dense and insoluble in water. 6.3.3.3 Extraction Thimble. Use quartz, glass, or glass fiber thimble, typically 43 × 123 mm to fit Soxhlet apparatus. 6.3.3.4 Heating Mantle. Use a hemispherical shaped heating mantle to fit round-bottom flask. 6.3.4 Kuderna-Danish Concentrator. Use an apparatus consisting of a threeball Snyder column, a flask with leakfree joint to accept the three-ball Snyder column at the top, a leak-free joint to PO 00000 Frm 00015 Fmt 4701 Sfmt 4702 2247 receive a graduated concentration tube at the bottom and a heating mantle. 6.3.5 Nitrogen Evaporative Concentrator. Use a nitrogen evaporative concentrator equipped with a water bath with the temperature controlled in the range of 30 to 60 °C (86 to 140 °F) (N-Evap Organomation Associates, Inc., South Berlin, MA, or equivalent). 6.3.6 Separatory Funnels. Use glass or PTFE 2-liter separatory funnels. 6.4 Glass Liquid Chromatography Columns. 6.4.1 Pasteur Pipettes. Use disposable pipettes, or glass serological pipettes typically 150 mm long × 6 mm ID. 6.4.2 Chromatography Columns. 200 to 300 mm long × 20 mm ID with 250mL reservoir. 6.5 Analytical Equipment. 6.5.1 Gas Chromatograph. Use a gas chromatograph consisting of the following components: 6.5.1.1 Oven. Use an oven capable of maintaining the separation column at the proper operating temperature ± 1.0 °C (1.8 °F) and performing programmed increases in temperature at rates of at least 20 °C/min with isothermal hold. 6.5.1.2 Temperature Monitor. Use a temperature monitor to measure column oven temperature to ± 1.0 °C (1.8 °F). 6.5.1.3 Flow System. Use an electronic pressure control or equivalent gas metering system to control carrier gas flow or pressure. 6.5.1.4 Use a split/splitless injection port in the splitless mode or on-column injection port for the capillary column. 6.5.2 Capillary Gas Chromatography Columns. Use different columns for the analysis of the different target compound classes in this method, if needed. Perform the resolution checks in Sections 10.2.3.4 and 10.2.3.5 of this method to document the required resolution. Compound separation must meet the resolution specifications in Section 10.2.3.4 of this method and the identification specifications found in Section 11.4.3.4 of this method. 6.5.2.1 Recommended column systems for measuring PCDDs/PCDFs should be capable of achieving separation of the 17 PCDD/PCDF target compounds from the nearest eluting congener with no more than 10 percent peak overlap. The system must meet the performance specifications for compound separation and quantitation in calibration, performance check, and isotopically labeled standards added to field samples. Use a variety of bondedphase capillary gas chromatography columns to meet these requirements, if needed. E:\FR\FM\14JAP2.SGM 14JAP2 2248 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules lotter on DSKBCFDHB2PROD with PROPOSALS2 Note: Fishman, et al. (see Section 16.3 of this method) demonstrated that all TEF isomers can be fully differentiated from closely eluting isomers using either of two sets of non-polar and polar stationary phase combinations. One set consisted of 5-percent phenyl methylpolysiloxane (DB–5, HP–5MS, Rtx–5MS, Equity–5) and 50-percent cyanopropylmethyl, 50-percent phenylmethylsiloxane (DB–225, SP 2331) GC columns and the other set consisted of 5percent phenyl, 94-percent methyl, 1-percent vinyl silicone bonded-phase (DB–5MS, ZB– 5MS, VF–5MS, CP–Sil 8 CB LowBleed/MS) with 50-percent cyanopropylmethyl, 50percent phenylmethylsiloxane (SP–2331). 6.5.2.2 Use column systems for measuring PAHs that can achieve separation of anthracene and phenanthrene at m/z 178 such that the valley between the peaks does not exceed 50 percent of the taller of the two peaks, and benzo[b]fluoranthene and benzo[k]fluoranthene such that the valley between the peaks is less than 60 percent of the height of the taller peak. These requirements are achievable using a 30-m narrow bore (0.25 mm ID) 5percent phenyl polysilphenylenesiloxane (BPX5 or equivalent) bondedphase, fused-silica capillary column. 6.5.2.3 PCB Columns. 6.5.2.3.1 Use column systems for measuring PCBs that can achieve unique resolution and identification of the toxics for determination of a TEQPCB using TEFs (American Society of Mechanical Engineers 1984). Isomers may be unresolved if they have the same TEF and response factor and if these unresolved isomers are uniquely resolved from all other congeners. These requirements are achievable using several 30-meter (m) narrow bore (0.25 mm ID) columns including 8-percent phenyl polycarborane-siloxane (HT8), DB–XLB, and poly (50-percent n-octyl/ 50-percent methyl siloxane) (SPB– Octyl). 6.5.2.3.2 If using an SPB-Octyl column for PCB analysis, the column should also uniquely resolve isomers 34 from 23 and 187 from 182. Resolution for these PCBs is shown by the valley between the peaks not exceeding 40 percent of the taller of the two peaks that result when these congeners are analyzed in the same calibration sample. 6.5.3 Mass Spectrometer. Use 28 to 70 electron volt impact ionization capable of repetitive selective monitoring of 12 exact m/z values with a mass resolution defined in section 10.2.1 of this method for fragments in the range of 300 to 350 m/z. The deviation between each monitored mass lock m/z and the monoisotopic m/z (Tables 23–4, 23–5, and 23–6 of this method for PCDDs/PCDFs, PAHs, and VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 PCBs, respectively) must be less than 5 parts per million. 6.5.4 Mass Spectrometer Data System. Use a data system compatible with the mass spectrometer and capable of sequencing and monitoring multiple groups of selected ions. 6.5.5 Analytical Balance. Use an analytical balance to measure within 0.1 milligram (mg). 7.0 Reagents, Media, and Standards Note: The quality checks described in this section are recommended but not required. They are provided to help ensure data will meet the required performance specifications in Section 13 of this method. 7.1 Filter. Glass fiber filters, without organic binder, exhibiting at least 99.95 percent efficiency (<0.05 percent penetration) on 0.3-micron dioctyl phthalate smoke particles. 7.1.1 Extraction. Conduct a quality control check on the filter lot prior to the field test to demonstrate that filters are free from contamination or interference. Perform Soxhlet extraction on a minimum of three filters with toluene for 16 hours. After extraction, allow the Soxhlet apparatus to cool. Remove the filters and remove the solvent from the filters under clean conditions (e.g., a clean nitrogen stream). 7.1.2 Analysis. Analyze the individual extracts of a minimum of three filters from each lot used for sampling according to the procedures in Section 11 of this method. The blank filter check analysis must meet the performance requirements in Section 13.14 of this method. 7.2 Adsorbent Resin. Amberlite® XAD–2 resin. All adsorbent resin must meet the cleanliness criteria in Section 13.14 of this method for all target compounds on the analysis list (i.e., native PCDD/PCDF, PCB, and/or PAH) following the same extraction, concentration, cleanup, and analysis steps as field samples. This method recommends using the procedures provided in appendix B to this method to clean the resin before use, if needed. However, this method allows alternative cleanup procedures that use automated extraction equipment if the adsorbent meets the required performance criteria in Section 13.14 of this method. 7.2.1 Conduct a quality control check on the cleaned adsorbent using HRGC/HRMS techniques following procedures in Section 11 of this method. The cleaned adsorbent must meet the criteria in Section 13.14 of this method. A batch blank conducted on the filter and adsorbent lot combination used for a test can serve this purpose. PO 00000 Frm 00016 Fmt 4701 Sfmt 4702 7.2.2 Storage. Store adsorbent in its original purchase container, a clean wide-mouth amber glass container with a PTFE-lined cap, or in glass adsorbent modules tightly sealed with glass caps. 7.3 Glass Wool. Clean the glass wool to meet the specifications in Section 13.14 of this method. Using sequential immersion in three clean aliquots of toluene, drying in a 110 °C (230 °F) oven, and storing in a toluene-rinsed glass jar with a PTFE-lined screw cap can meet these requirements. 7.4 Water. Use deionized or distilled water meeting requirements in Section 13.14 of this method and store in its original container or in a toluene-rinsed glass container with a PTFE-lined screw cap. 7.5 Silica Gel. Indicating type, 6–16 mesh. If previously used, dry at 175 °C (347 °F) for two hours. Use new silica gel as received. As an alternative, use other types of desiccants (equivalent or better), subject to the approval of the Administrator. 7.6 Methylene Chloride. Pesticide grade or better. 7.7 Sample Recovery Reagents. 7.7.1 Acetone. Pesticide grade or better. 7.7.2 Toluene. Pesticide grade or better. 7.8 Sample Extraction and Cleanup. 7.8.1 Potassium Hydroxide. American Chemical Society (ACS) grade, 2 percent (weight/volume) in water. 7.8.2 Sodium Sulfate. Granulated or powdered, reagent grade. Use as received, include in batch blank evaluation prior to use, or purify as necessary prior to use by rinsing with methylene chloride or toluene and oven drying. The batch blank must meet the requirements in Section 13.14 of this method. Store the cleaned material in a glass container with a PTFE-lined screw cap. 7.8.3 Sulfuric Acid. Reagent grade. 7.8.4 Sodium Hydroxide. 1.0 N. Weigh 40 g of sodium hydroxide into a 1-liter volumetric flask. Dilute to 1 liter with water. 7.8.5 Hexane. Pesticide grade or better. 7.8.6 Methanol. Pesticide grade or better. 7.8.7 Toluene. Pesticide grade or better. 7.8.8 High-Boiling Alkanes Used as Keeper Solvents (e.g., tetradecane, nonane, decane). Pesticide grade. Note: Lower homologous series alkanes (nonane or decane) are necessary for higher volatility targets such as MoCBs and naphthalene to maintain retention during concentration procedures. However, do not take samples to E:\FR\FM\14JAP2.SGM 14JAP2 lotter on DSKBCFDHB2PROD with PROPOSALS2 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules dryness when using these lower alkane homologs. 7.8.9 Liquid Column Chromatography Packing Materials. Use the following column chromatography packing materials, as needed, to prepare sample extracts and remove interfering compounds. Commercially prepacked cleaning columns may be available for this purpose. All procedures for preparing column chromatography packing materials are recommendations shown to meet the performance specifications required for the recovery of labeled compounds described in Section 13 of this method. 7.8.9.1 Alumina. Use either acidic or basic alumina in the cleanup of sample extracts. Use the same type of alumina for all samples in an analytical sequence, including those used to demonstrate batch blank performance. 7.8.9.1.1 Acidic Alumina (SigmaAldrich® 199966 or equivalent). Brockmann activity grade 1, 100–200 mesh. Prior to use, activate the alumina by heating for 12 hours at 130 °C (266 °F). Store in a desiccator. You may use pre-activated alumina purchased from a supplier as received. 7.8.9.1.2 Basic Alumina (SigmaAldrich® 19943 or equivalent). Brockmann activity grade 1. Activate by heating to 600 °C (1,112 °F) for a minimum of 24 hours. Do not heat to over 700 °C (1,292 °F) because this can lead to reduced capacity for retaining the analytes. Store at 130 °C (266 °F) in a covered flask. Use within five days of baking. Use prepacked alumina columns immediately after opening the vacuum sealed pouch or container. 7.8.9.2 Florisil®. Activated, 60–100 mesh recommended. Heat previously activated Florisil® in a glass container loosely covered with aluminum foil in an oven at 130 to 150 °C (266 to 302 °F) for a minimum of 24 hours. Upon cooling, store activated Florisil® silica prior to use in a desiccator. 7.8.9.3 Silica Gel. Use either activated, acidic or basic silica gel in the cleanup of sample extracts. Use the same type of silica gel for all samples in an analytical sequence, including those used to demonstrate batch blank performance. 7.8.9.3.1 Activated Silica Gel. Supelco® 1–3651, Bio-Sil® A, 100–200 mesh (or equivalent). Prior to use, rinse with methylene chloride and activate the silica gel by heating for at least 1 hour at 180 °C (356 °F). After cooling, rinse the silica gel sequentially with methanol and toluene. Heat the rinsed silica gel at 50 °C (122 °F) for 10 minutes, then increase the temperature gradually to 180 °C (356 °F) over 25 minutes and maintain the gel at this VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 temperature for 90 minutes. Cool in a desiccator to room temperature and store in a glass container with a PTFElined screw cap. 7.8.9.3.2 Acidic Silica Gel (30 percent weight/weight). Combine 100 g of activated silica gel with 44 g of concentrated sulfuric acid in a clean screw-capped glass container and agitate thoroughly. Disperse the solids with a stirring rod until obtaining a uniform mixture. Store the mixture in a glass container with a PTFE-lined screw cap. 7.8.9.3.3 Basic Silica Gel. Combine 30 g of 1 N sodium hydroxide with 100 g of activated silica gel in a clean screwcapped glass container and agitate thoroughly. Disperse solids with a stirring rod until obtaining a uniform mixture. Store the mixture in glass container with a PTFE-lined screw cap. 7.8.9.4 Carbon/Celite® 545 (or equivalent solid support). Use a carbonbased column cleanup material (e.g., one of the many Carbopack® B or C) to remove impurities from the samples prior to analysis. Thoroughly mix 9.0 g Carbopack® C and 41.0 g Celite® 545 to produce an 18-percent weight/weight mixture. Activate the mixture at 130 °C (266 °F) for a minimum of 6 hours. Store in a desiccator. 7.8.10 Nitrogen. 99.999 percent (ultra-high) purity. 7.9 Sample Analysis. 7.9.1 Helium. 99.999 percent (ultrahigh) purity. 7.9.2 Spiking Standards. Prepare spiking standards quantitatively at a convenient concentration (e.g.,10 nanograms (ng)/mL) or use commercial standards if available, to enable accurate spiking of a labeled standard at various stages of the sample preparation. You may adjust the spiking concentrations from those recommended in Tables 23– 7, 23–8 and 23–9 of this method to accommodate the concentration of target compounds anticipated in samples if the performance criteria in Section 13 of this method are met. 7.9.3 Pre-Sampling Recovery Standard Solution. Prepare stock standard solutions in nonane to enable spiking of the isotopically labelled compounds for target compound classes in Tables 23–7, 23–8, and 23–9 of this method at the mass shown under the heading ‘‘Pre-sampling Adsorbent Standards.’’ 7.9.4 Pre-extraction Filter Recovery Spike Standard Solution. Prepare stock standard solutions in nonane to enable spiking of the isotopically labelled compounds for target compound classes in Tables 23–7, 23–8, and 23–9 of this method at the mass shown under the PO 00000 Frm 00017 Fmt 4701 Sfmt 4702 2249 heading ‘‘Pre-extraction Filter Recovery Spike Standards.’’ 7.9.5 Pre-extraction Recovery Standard Solution. Prepare stock standard solutions in nonane to enable spiking of the isotopically labelled compounds for target compound classes in Tables 23–7, 23–8, and 23–9 of this method at the mass shown under the heading ‘‘Pre-extraction Standards.’’ 7.9.6 Pre-analysis Standard Solution. Prepare stock standard solutions in nonane to enable spiking of the isotopically labelled compounds for target compound classes in Tables 23– 7, 23–8, and 23–9 of this method at the mass shown under the heading ‘‘Preanalysis Standards.’’ 8.0 Sample Collection, Preservation and Storage 8.1 Sampling. This method involves collection and recovery of trace concentrations of semivolatile organic compounds. Therefore, train field sampling and recovery staff in the best practices for handling and using organic solvents in field environments to recover and protect samples from contamination. 8.1.1 Pretest Preparation. 8.1.1.1 Cleaning Glassware. Clean glassware thoroughly before using. This section provides a recommended procedure, but any protocol that consistently results in contaminationfree glassware meeting the batch blank criteria in Section 13.2 of this method is acceptable. 8.1.1.1.1 Soak all glassware in hot soapy water (Alconox® or equivalent). 8.1.1.1.2 Rinse with hot tap water. 8.1.1.1.3 Rinse with deionized/ distilled water. 8.1.1.1.4 Rinse with methanol. 8.1.1.1.5 Rinse with toluene. 8.1.1.1.6 Baking glassware at 300 °C (572 °F) for a minimum of 2 hours may be necessary to remove contaminants or interferents from particularly dirty samples. Cool glassware after baking. Note: Repeated baking of glassware may cause active sites on the glass surface that may irreversibly absorb target compounds. 8.1.1.1.7 Cover glassware openings with clean glass fitting caps or cleaned aluminum foil (see Section 6.2.6 of this method). 8.1.1.1.8 Rinse glassware immediately before use with acetone and toluene. Note: To prepare heavily soiled glassware, remove surface residuals from the glassware by soaking in hot soapy water, rinsing with hot water, then soaking with a non-chromic acid oxidizing cleaning reagent in a strong acid (e.g., NOCHROMIX® prepared according to manufacturer’s directions). After the acid soak, rinse with hot water and repeat the E:\FR\FM\14JAP2.SGM 14JAP2 2250 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules lotter on DSKBCFDHB2PROD with PROPOSALS2 cleaning procedures in Section 8.1.1.1 of this method. 8.1.1.2 Adsorbent Module. Load the modules in a clean area to avoid contamination. Spike modules before the sampling event, but do not spike the modules in the field. Fill a module with 20 to 40 g of XAD–2. Add the presampling standard spike for each of the compound classes to be measured to the top quarter of the adsorbent bed. Add sufficient spike (picograms (pg)/module) to result in the final theoretical concentrations specified in Tables 23–7, 23–8, and 23–9 of this method for PCDDs/PCDFs, PAHs, and PCBs, respectively. For samples with known or anticipated target compound concentration significantly higher or lower than the specified amount in these tables, add a pre-sampling spike amount appropriate to the expected native compound concentration, but no less than 10 times the EDL. Follow the XAD–2 with cleaned glass wool and tightly cap both ends of the module. For analysis that include PAH, use spiked modules within 14 days of preparation. See Table 23–10 of this method for storage conditions. 8.1.1.3 Sampling Train. Figure 23–1 of this method shows the complete sampling train. Follow the best practices by maintaining all sampling train components according to the procedure described in APTD–0576 Maintenance, Calibration, and Operation of Isokinetic Source-sampling Equipment (U.S. EPA 1972). 8.1.1.4 Silica Gel. Weigh several 200 to 300 g portions of silica gel in an airtight container to the nearest 0.5 g. Record the total weight of the silica gel plus container on the outside of each container. As an alternative, directly weigh the silica gel in its impinger or sampling holder just prior to sampling. 8.1.1.5 Filter. Check each filter against light for irregularities and flaws or pinhole leaks. Pack the filters flat in a clean glass container. Do not mark filters with ink or any other contaminating substance. 8.1.2 Preliminary Determinations. Use the procedures specified in Section 8.2 of Method 5 of appendix A–3 to 40 CFR part 60. 8.1.2.1 Sample Volume. Unless otherwise specified in an applicable rule, permit, or other requirement, sample for a minimum of 2 minutes at each traverse point. This method recommends sampling a minimum of 2.5 dry standard cubic meters (dscm). 8.1.2.2 For continuously operating processes, use the same sampling time at each traverse point. To avoid timekeeping errors, use an integer, or an VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 integer plus one-half minute, for each traverse point. 8.1.2.3 For batch processes, determine the minimum operating cycle duration, dividing the sampling time evenly between the required numbers of traverse points. After sampling all traverse points once, sample each point again for the same duration of time per sampling point in reverse order until the operating cycle is completed. Sample all traverse points at least once during each test run. 8.1.3 Preparation of Sampling Train. 8.1.3.1 During field preparation and assembly of the sampling train, keep all train openings where contamination can enter sealed until just prior to assembly or until sampling is about to begin. To protect the adsorbent module from radiant heat and sunlight, you must wrap the module with aluminum foil or other suitable material capable of shielding the module from light. The XAD–2 adsorbent resin temperature must never exceed 50 °C (122 °F) because thermal decomposition will occur. Clean and prepare a complete set of sampling train components that will contact the sample for each sampling run, including one complete set to be used as a field train proof blank as described in Section 9.6 of this method. 8.1.3.2 Place approximately 100 mL of water in the second and third impingers but leave the first and fourth impingers empty. Transfer approximately 200 g or more of silica gel from its container to the fifth impinger. Weigh each impinger and the adsorbent module, including the fitting caps, to the nearest 0.5 g using the field balance and record the weight for moisture determination. Remove the aluminum foil from the adsorbent module before weighing. Keep the module out of direct sunlight and rewrap the module with foil immediately after recording the module weight. 8.1.3.3 Using tweezers or clean disposable surgical gloves, place a filter in the filter holder. Be sure that the filter is properly centered, and the gasket properly placed, to prevent the sample gas stream from circumventing the filter. Check the filter for tears after completing the assembly. 8.1.3.4 Prepare the inside of the sampling probe and nozzle by brushing each component while rinsing three times each with acetone and toluene. Install the selected nozzle. You may use connecting systems described in Section 6.1.2 of this method. Mark the probe with heat resistant tape or by some other method to denote the proper distance into the stack or duct for each sampling point. Assemble the train as shown in PO 00000 Frm 00018 Fmt 4701 Sfmt 4702 Figure 23–1 of this method. Orient the adsorbent module vertically so condensed moisture drains into the first impinger. See APTD–0576 Maintenance, Calibration, and Operation of Isokinetic Source-sampling Equipment (U.S. EPA 1972) for details. 8.1.3.5 Turn on the recirculation pump to the adsorbent module and condenser coil and begin monitoring the temperature of the gas entering the adsorbent module. Ensure proper temperature of the gas entering the adsorbent module before proceeding. 8.1.4 Leak-Check Procedure. Same as Section 8.4 of Method 5 of appendix A–3 to 40 CFR part 60. 8.1.5 Sampling Train Operation. Same as Sections 8.5.1 through 8.5.9 of Method 5 of appendix A–3 to 40 CFR part 60. 8.1.5.1 Monitor the filter temperature sensor and record the filter temperature during sampling to ensure a sample gas temperature exiting the filter of 120 °C ± 14 °C (248 °F ± 25 °F), or such other temperature as specified by an applicable subpart of the standards or approved by the Administrator for an application of this method. 8.1.5.2 During testing, you must record the temperature of the gas entering the XAD–2 adsorbent module. The temperature of the gas must not exceed 20 °C (68 °F) for efficient capture of the target compounds. 8.2 Sample Recovery. Begin the cleanup procedure as soon as the probe is removed from the stack at the end of the sampling period. Seal the nozzle end of the sampling probe with PTFE tape or clean (e.g., toluene rinsed) aluminum foil. This method recommends using clean glassware prepared following Section 8.1.1.1 of this method for each sample set in a test series. 8.2.1 When the probe can be safely handled, wipe off all external particulate matter near the tip of the probe. Conduct a post-test leak check. Remove the probe from the train and close off both ends with PTFE tape or clean aluminum foil. Seal off the inlet to the train with PTFE tape, a ground glass cap, or clean aluminum foil. 8.2.2 Transfer the probe and impinger assembly to the cleanup area. This method recommends cleaning and enclosing this area to minimize the chances of losing or contaminating the sample. To avoid sample contamination and unnecessary exposure to toxic chemicals, smoking or eating in the sample recovery area shall not be allowed. 8.2.3 Inspect the train prior to and during disassembly. Note and record E:\FR\FM\14JAP2.SGM 14JAP2 lotter on DSKBCFDHB2PROD with PROPOSALS2 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules any abnormal conditions (e.g., broken filters, colored impinger liquid). Recover and prepare samples for shipping as follows in Sections 8.2.4 through 8.2.12 of this method. 8.2.4 Container No. 1. Either seal the filter holder or carefully remove the filter from the filter holder and place it in its identified container. If it is necessary to remove the filter, use a pair of cleaned tweezers to handle the filter. If necessary fold the filter such that the particulate cake is inside the fold. Carefully transfer to the container any particulate matter and filter fibers that adhere to the filter holder gasket by using a dry inert bristle brush and a sharp-edged blade. Seal the container and store cool (≤ 20 ± 3 °C, 68 ± 5 °F) for transport to the laboratory. 8.2.5 Adsorbent Module Sample. Remove the module from the train, tightly cover both ends with fitting caps and PTFE tape, remove the foil, drain the recirculating water from the module, weigh and record the module weight, and label the adsorbent module. Moisture measurement in the field using the Method 23 train requires weighing the adsorbent module before the sampling run and after sampling as part of the sample recovery. 8.2.6 Container No. 2. Quantitatively recover material deposited in the nozzle, the front half of the filter holder, and the cyclone, if used, by brushing while rinsing three times with acetone followed by three rinses with toluene. Collect all the rinses in Container No. 2. 8.2.7 Rinse the back half of the filter holder three times with acetone followed by three rinses with toluene. Rinse the sample transfer line between the filter and the condenser three times with acetone followed by three rinses with toluene. If using a separate condenser and adsorbent module, rinse the condenser three times with acetone followed by three rinses with toluene. Collect all the rinses in Container No. 2 and mark the level of the liquid on the container. 8.2.8 Moisture Weight. Weigh the adsorbent module, impingers, and silica gel impinger to within ± 0.5 g using the field balance and record the weights. This information is required to calculate the moisture content of the effluent gas. For PCDD/PCDF-only measurements, discard the liquid after measuring and recording the weight. 8.2.9 Container No. 3. You must save and analyze impinger water samples if PAHs and/or PCBs are the target compounds. Quantitatively recover impinger water samples for analysis if PAHs and/or PCBs are the target compounds by rinsing three times with acetone followed by three rinses VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 with toluene. Collect impinger water and rinses in Container No. 3 and mark the level of the liquid on the container. 8.2.10 Silica Gel. Note the color of the indicating silica gel to determine if it has been completely spent and report its condition on the field data sheet. 8.2.11 Field Sample Handling, Preservation, Storage, and Transport. Store all field samples temporarily in cool (≤ 20 ± 3 °C, 68 ± 5 °F) and dark conditions prior to transport to the laboratory. Ship samples cool (≤ 20 ± 3 °C, 68 ± 5 °F), shielded from ultraviolet light. In addition, follow the procedures in ASTM D6911–15 (Guide for Packaging and Shipping Environmental Samples for Laboratory Analysis) for all samples, where appropriate. To avoid contamination of the samples, pay special attention to cleanliness during transport, field handling, sampling, recovery, and laboratory analysis, as well as during preparation of the adsorbent cartridges. 8.2.12 Sample Custody. Proper procedures and documentation for sample chain of custody are critical to ensuring data integrity. Follow the chain of custody procedures in ASTM D4840–99(2018)e1 (Standard Guide for Sample Chain-of-Custody Procedures) for all samples (including field samples and blanks). 8.3 Sample Storage Conditions and Laboratory Hold Times. 8.3.1 Table 23–10 of this method summarizes the sample storage conditions and laboratory hold times. 8.3.2 Store sampling train rinses and filter samples in the dark at 6 °C (43 °F) or less from the time the laboratory receives the samples until analysis. 8.3.3 You may store adsorbent samples for PCDDs/PCDFs or PCBs prior to extraction in the dark at 6 °C (43 °F) or less for up to one year from the time the laboratory receives the samples. 8.3.4 Protect adsorbent samples destined for PAH analysis from ultraviolet light. You may store adsorbent samples for PAH analysis at 6 °C (43 °F) or less for up to 30 days from the time the laboratory receives the samples. 8.3.5 Analyze PAH extracts within 45 days of extraction. 8.3.6 You may store sample aliquots including archived extracts of PCDD/ PCDF, PAH and/or PCB samples in the dark at ¥10 °C (14 °F) or less for up to one year. 9.0 Quality Control Note: In recognition of advances that are occurring in sampling and analytical technology, and to allow the test team to overcome analyte sensitivity and matrix interferences, this method allows certain PO 00000 Frm 00019 Fmt 4701 Sfmt 4702 2251 options to increase sample collection volume and to improve separations and the quality of the analysis results for target analytes. It is the laboratory’s responsibility to establish the conditions for optimum sample extraction, cleanup, and concentration to meet the performance criteria in this method. However, you may not change the fundamental sampling and analysis techniques, isokinetic sampling with an adsorbent collection media followed by sample extraction, and HRMS detection and isotopic dilution quantification procedures. Section 13 of this method specifies the performance criteria to ensure that options employed for a sample set and analytes of interest are equal to or better than the specificity of the techniques in this method. This method recommends performing a media blank (i.e., batch blank) assessment to evaluate an individual laboratory’s performance against the performance criteria in this method. At a minimum, evaluate changes within the alternatives allowed in this method using a media blank sample to re-demonstrate that the performance criteria are achieved. 9.1 Record and report data and information that will allow an independent reviewer to validate the determination of each target compound concentration. At a minimum, record and report the data as described in Sections 9.1.1 through 9.1.7 of this method. 9.1.1 Sample numbers and other sample identifiers. Each sample must have a unique identifier. 9.1.2 Field sample volume. 9.1.3 Field sampling date. 9.1.4 Extraction dates. 9.1.5 Analysis dates and times. 9.1.6 Analysis sequence/run chronology. 9.1.7 Quantitation Reports. 9.1.7.1 This method does not consider EPC-flagged data to be zero concentrations. Calculate the EPC separately for each quantitation ion, if present, and report the lower value as the EPC. 9.1.7.2 In determining compliance with any PCDD and PCDF standard developed using zero for values that are below the detection level of the method, including federal emission standards using Method 23 promulgated under 40 CFR parts 60 and 63 prior to [DATE OF PUBLICATION OF THE FINAL RULE], use zero for the determination of total and weighted concentrations when the target compound is not detected. For all other circumstances, unless otherwise specified in applicable regulations, permits, or other requirements, when a target compound is measured at or below EDL, use EDL as the concentration for calculating compliance. 9.1.7.3 You must report your EDLs with analysis results. E:\FR\FM\14JAP2.SGM 14JAP2 lotter on DSKBCFDHB2PROD with PROPOSALS2 2252 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules 9.1.8 Performance criteria results (See Section 13 of this method). 9.2 Isotopically Labeled Spike Recovery Results. 9.2.1 Pre-sampling Adsorbent Spike and Pre-extraction Filter Spike Recoveries. Pre-sampling adsorbent and pre-extraction filter spike recoveries must demonstrate on a per sample basis that recovery of the labeled standard achieved the requirements in Section 13 of this method. Recoveries below the acceptable range for the pre-sampling spikes may be an indication of breakthrough in the sampling train. 9.2.1.1 If the recovery of all the presampling adsorbent spike standards is below 70 percent, the sampling runs are not valid, and you must repeat the invalid runs. As an alternative, you do not have to repeat the invalid sampling runs if the average pre-sampling adsorbent spike recovery is 25 percent or more and you divide the final results by the average fraction of pre-sampling adsorbent spike recovery. 9.2.1.2 If the recovery of the preextraction filter spike is below 70 percent, the filter sampling extraction recovery is not valid, and you must flag the test run results. 9.2.2 Pre-extraction Spike Recoveries. Pre-extraction spike recoveries must demonstrate on a per sample basis that recovery of the labeled standard achieved the requirements in Section 13 of this method. Recoveries below the acceptable range for preextraction spikes are an indication that sample preparation procedures did not adequately address sample and or sample matrix processing to recover native target compounds. 9.2.3 Pre-analysis Spike Recoveries. Pre-analysis spike recoveries must demonstrate on a per sample basis that adequate labeled standard signal meets the requirements in Section 13 of this method. Add pre-analysis standards to every sample (including blanks, quality control samples, and calibration solutions) in a known concentration. You may analyze archive samples to attempt meeting requirements for the compounds that do not meet the preanalysis recovery criteria. Recoveries below the acceptable range for preanalysis spikes are an indication that sample injection or instrument drift has failed beyond the ability to correct using pre-analysis standard results. 9.3 Capillary GC columns must be able to achieve the separation resolution specified in Sections 13.3, 13.4, and/or 13.5 of this method for the target compounds analyzed in test samples. 9.4 Batch Blank Samples. Evaluate chromatographic separation performance, spiking errors, and VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 continuing calibration checks using a batch blank sample prepared from typical filter and absorbent media, spiked with isotopically labeled compounds and extracted identically to the procedures used to prepare samples. Analyze batch blank samples at least once during each analytical sequence or every 24 hours, whichever period is shorter. Section 13.2 of this method describes the performance criteria for field train proof blank assessment samples and batch blank samples. 9.5 Detection Limits. Calculate the EDL using the equation in Section 12.11 of this method. If the field train proof blank or the batch blank results are above the EDL, calculate and report the test-specific and compound-specific DLs equal to the sum of the EDL and the larger of the batch or field train proof blank results. If the field train proof blank and the batch blank results are equal to or less than the EDL, report the test-specific and compound-specific DLs as the EDL. 9.6 Field Train Proof Blank Assessment. Conduct at least one field train proof blank for each test series at a single facility. A field train proof blank train consists of a fully assembled train at the sampling site. Prepare and assemble the blank train in a manner identical to that described in Sections 8.1.3 and 8.1.4 of this method. The blank train must remain assembled for the same average amount of time samples are collected. Recover the blank train as described in Section 8.2 of this method. Follow all subsequent steps for blank train sample preparation and analysis used for field train samples including data reporting. 10.0 Calibration and Standardization 10.1 Sampling System. Same as Sections 6.1 and 10.1 through 10.7 of Method 5 of appendix A–3 to 40 CFR part 60. 10.2 HRGC/HRMS System. 10.2.1 Mass Resolution. Tune the HRMS instrument to a mass resolution (R) of at least 10,000 at 5 percent of the peak height or 25,000 at 50 percent of the peak height where resolution is calculated as an R = M/DM, where M is the resolving power and DM is the peak width. You may use peak matching and the chosen perfluoro-kerosene (PFK) or perfluorotributylamine (FC43) reference peak to verify that the exact mass is within 5 ppm of the required value. Assess the resolution at three m/z ranges representing the low, mid and high m/z range of the masses used to measure the target compound class. 10.2.2 Initial Calibration. Calibrate the HRGC/HRMS system using a minimum of five concentrations over a PO 00000 Frm 00020 Fmt 4701 Sfmt 4702 range that brackets typical field sample concentrations and the concentration of isotopically labeled standards in spiked samples. Tables 23–11, 23–12, and/or 23–13 of this method, as applicable to the compound classes analyzed, show the calibration concentrations recommended by this method. Perform calibration and subsequent analyses on an absolute mass (pg/microliter (mL)) basis. The recommended calibration range ensures isotopic labels can be accurately distinguished from native compounds and provides the initial response factors that are corrected by isotopic recovery. 10.2.2.1 Lock Channels. Tables 23– 4, 23–5, and 23–6 of this method provide the recommended mass spectrometer lock channels for PCDD/ PCDFs, PAHs, and PCBs, respectively. You may use PFK or FC43 as your lock mass standard. 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 during analysis. 10.2.2.2 The relative standard deviation (RSD) for the mean response factor from each of the unlabeled analytes and isotopically labeled compounds used in an analysis must be less than or equal to the values in Table 23–14 of this method. 10.2.2.3 The signal-to-noise (S/N) ratio for the MS signal present in every selected ion current profile must be greater than or equal to 10 in all concentrations of calibration standards for unlabeled targets and isotopically labeled standards. The ion abundance ratios must be within the control limits in Table 23–15 of this method. 10.2.3 Daily Performance Check. 10.2.3.1 Continuing Calibration Check. Inject a mid-level calibration standard C4 from Table 23–11, 23–12, or 23–13 of this method for the compound class being analyzed at least once every 24 hours during an analysis sequence. Calculate the RRF for each compound and compare each RRF to the corresponding mean RRF obtained during the initial calibration. The analyzer performance is acceptable if the measured RRFs for the labeled compounds for a 24-hour period are within the limits of the values shown in Table 23–14 of this method. The RRF for each native compound measured in a CCV must not deviate from the initial calibration by more than the limits shown in this table. 10.2.3.2 The ion abundance ratios must be within the allowable control limits shown in Table 23–15 of this method. E:\FR\FM\14JAP2.SGM 14JAP2 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules lotter on DSKBCFDHB2PROD with PROPOSALS2 10.2.3.3 Repeat the initial calibration when there is a failure to meet the requirements for acceptable continuing calibration check analysis. 10.2.3.4 Column Separation Check. Use the results from a continuing calibration check sample to verify and document the resolution required in Sections 13.3, 13.4, or 13.5 of this method for the compound classes analyzed with this method. 10.2.3.5 If you use a confirmation column, perform the resolution check in Section 10.2.3.4 of this method to document the required resolution on the confirmation column. 11.0 Analysis Procedure 11.1 Sample Extraction and Concentration. The sample extraction procedures in this method are the same for PCDD, PCDF, PCB and PAH targets. Figure 23–4 provides a flow chart showing sample container combination and extraction steps. Do not allow samples and extracts destined for PAH or PCB analysis to concentrate to dryness because the lower molecular weight PAHs and the mono- through trichlorobiphenyls may be totally or partially lost. 11.1.1 Optional Soxhlet Precleaning. Place an extraction thimble (see Section 6.3.3.3 of this method) and a plug of glass wool into the Soxhlet apparatus equipped with a Dean-Stark trap, charge the apparatus with toluene, and reflux for a minimum of 3 hours. Remove the toluene and discard it. Remove the extraction thimble from the extraction system and place it in a glass beaker to catch the solvent rinses from sample transfer to the extraction thimble. Retain the clean glass wool plug. Alternatively, confirm that the batch blank for reagents, materials, and media meets the performance requirements in Section 13 of this method. 11.1.2 Container No. 1 (Filter) Preparation. Spike the filter with the appropriate pre-extraction filter recovery standard solution(s) shown in Tables 23–7, 23–8, and 23–9 of this method taking care that all spike liquid is distributed on the filter. Allow the filter to air dry, then transfer the filter and the contents of Container No. 1 directly to the glass extraction thimble in the glass solvent rinse catch beaker so that the filter will be completely immersed in the solvent during extraction. 11.1.3 Adsorbent Module. Transfer the adsorbent material to the glass extraction thimble in the glass solvent rinse catch beaker. Rinse the module into the thimble in the beaker with the contents of Container No. 1. Alternatively, suspend the adsorbent VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 module directly over the extraction thimble in a beaker, then, using a wash bottle containing methanol, flush the XAD–2 into the thimble onto the filter. Thoroughly rinse the interior of the glass module that contained the XAD– 2 with toluene. 11.1.4 Container No. 2 (Acetone and Toluene Rinses). Concentrate the sample to a volume of no less than 5 mL. Concentrate samples containing toluene using a heating mantle and three-ball Snyder column or a rotary evaporator. Rinse sample Container No. 2 three times with small portions of toluene and add these to the concentrated solution and concentrate further to no less than 5 mL. This residue contains particulate matter removed in the rinse of the train probe and nozzle. Rinse the concentrated material from Container No. 2 into the glass extraction thimble containing the filter and the XAD–2 resin. 11.1.5 Transfer the solvent contained in the collection beaker to the extraction apparatus solvent reservoir. Rinse the beaker into the Soxhlet extraction apparatus solvent reservoir three times with small portions of toluene. 11.1.6 Container No. 3 (Impinger Water and Rinses). For PAH and PCB analysis, transfer the contents of Container No. 3 to a separatory funnel. Adjust to pH 2 with 6 N sulfuric acid, if necessary. Rinse the sample container with three successive 10-mL aliquots of the toluene and these rinses to the separatory funnel. Extract the sample by vigorously shaking the separatory funnel for 5 minutes. After complete separation of the phases, remove the solvent and filter it through a bed of precleaned, dry sodium sulfate into the Soxhlet extraction apparatus solvent reservoir. Repeat the extraction step two additional times. Adjust the pH to 11 with 6 N sodium hydroxide, re-extract the impinger water and rinses, and filter it through a bed of precleaned, dry sodium sulfate into the Soxhlet extraction apparatus solvent reservoir. Rinse the sodium sulfate into the extraction apparatus solvent reservoir with fresh solvent and discard the desiccant. 11.1.7 Add the appropriate preextraction spikes for the compound classes being analyzed (Tables 23–7, 23– 8, and 23–9 of this method) to the extraction thimble containing the combined filter and adsorbent sample fractions. Cover the contents of the extraction thimble with the cleaned glass wool plug to prevent the XAD–2 resin from splashing into the solvent reservoir of the extractor. Place the PO 00000 Frm 00021 Fmt 4701 Sfmt 4702 2253 extraction thimble into the Soxhlet extraction apparatus. 11.1.8 Pour additional toluene to fill the reservoir approximately two-thirds capacity. Add PTFE boiling chips and assemble the apparatus. 11.1.9 Adjust the heat source to cause the extractor to cycle approximately three times per hour. Extract the sample for sufficient time to meet the pre-extraction spike recovery performance criteria in Section 13 of this method. The solvent should cycle completely through the system a minimum of 48 times. Note: Samples containing high carbon particulate loading, such as those collected downstream of an activated carbon injection system, may require extended extraction time or treatment such as those described in Stieglitz 1986. 11.2 Sample Aliquots for Cleanup and Analysis. 11.2.1 After extraction, allow the Soxhlet apparatus to cool. 11.2.2 Initial Extract Concentration. You may perform an initial concentration of the sample extract using the techniques (e.g., Kuderna Danish, rotary evaporation, nitrogen blowdown) found to recover preextraction isotopically labeled compounds sufficient to meet the performance criteria in Section 13 of this method. Concentrate initial extracts in toluene using a heating mantle and three-ball Snyder column or a rotary evaporator. Concentrate the field train proof blank and batch blank samples in the same manner as samples. Note: For samples requiring PCB or PAH analysis, you should perform the initial concentration using a three-ball Snyder column on the original extraction receiver flask. To meet isotopically label spike recoveries for low molecular weight PAHs and PCBs, do not evaporate samples to dryness. 11.2.3 Allow the sample to cool. You should use a minimum of one half of the sample extract for PCDD/PCDF analysis. You may archive the remaining sample extract or further split the extract for PCB and/or PAH analysis and archive. 11.2.4 If necessary, further concentrate the sample for cleanup and analysis using concentration techniques (e.g., Kuderna Danish, rotary evaporation, nitrogen blowdown) found to recover pre-extraction isotopically labeled compounds sufficient to meet the performance criteria in Section 13 of this method. 11.3 Sample Cleanup and Fractionation. You may process a separate aliquot/split of the sample extract for each of the compound classes E:\FR\FM\14JAP2.SGM 14JAP2 2254 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules analyzed by this method. Sample cleanup for each compound class may include techniques in addition to column chromatography such as acid/ base back-extraction or highperformance liquid chromatography (HPLC) to isolate target compounds from interferences. This section includes a description of column chromatography shown to meet the performance criteria in Sections 9.2 and 13 of this method. The following sample cleanup and fractionation procedures are recommended but not required. You may modify cleanup column dimensions to meet manual or automated cleanup procedures as technology changes and improves. You must evaluate the cleanup and fractionation procedures used to confirm acceptable recovery of isotopically labeled standards. The alternative procedures must provide sufficient cleanup to meet method identification criteria (Section 11.4.3.4 of this method) and recovery criteria (Section 9.2 of this method). Section 13 of this method summarizes the method performance requirements. Note: Recommendations in this section provide a cleanup approach that may allow multiple compound class measurement from a single aliquot of the original sample extract. Typically, Florisil® and alumina are used to separate PAH and chlorobiphenyl ether compounds from PCDD and PCDF target compounds. Use acid, neutral, and basic silica gel and cleanup procedures to remove nonpolar and polar interferences from samples destined for PCB and PCDD/PCDF analysis. Use Carbopack®/Celite® (or other equivalent carbon-based column material) to remove other nonpolar interferences. 11.3.1 PAH and PCDEs Fractionation and Cleanup. You may use a Florisil® column to remove PAHs and PCDEs from a sample. You may also fractionate samples using Florisil® as the first cleanup step to separate PAH for analysis. lotter on DSKBCFDHB2PROD with PROPOSALS2 Note: High concentrations of PAHs may interfere with mass spectrometer lock mass or saturate the source, leading to failure of performance criteria for PCDD/PCDF or PCB analysis. 11.3.1.1 Pack a 6-mm ID chromatographic column or equivalent diameter glass pipet with a glass wool plug followed by approximately 1.5 g (approximately 2 mL) of activated Florisil®. Add approximately 1 cm (approximately 1 mL) of anhydrous sodium sulfate followed by a glass wool plug to the head of the column. Preelute the column with 10 mL of methylene chloride followed by 10 mL of hexane and discard the eluate. 11.3.1.2 When the solvent is within 1 mm of the packing, transfer the VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 concentrated extract (up to 5 mL) to the top of the Florisil® column, rinse the sample container twice with 1 to 2 mL of hexane, adding each rinse to the column, and elute the column with 35 mL of 5-percent dichloromethane in hexane. This fraction (Fraction 1) should contain target PCBs, and selected hydrocarbons and chlorinated monoaromatic compounds. 11.3.1.3 Elute the column with 35 mL of 15-percent of dichloromethane in hexane and collect the eluate. This fraction (Fraction 2) should contain target PCDD/PCDF compounds. 11.3.1.4 Elute the column with 50 mL of 50-percent dichloromethane in hexane. The fraction (Fraction 3) should contain target PAHs. 11.3.1.5 If necessary to remove any remaining polar organic compounds, elute the column with 70 mL of 15percent acetone in hexane. 11.3.2 PCDD/PCDF and PCB Fractionation and Cleanup. You may remove PAHs from the original aliquot of extract used for PCDD/PCDF analysis as described in Section 11.3.1 of this method. Design the column cleanup chromatography for PCDD/PCDFs and PCBs such that two consecutive fractions are collected (one with PCDD/ PCDFs and one with PCBs) without impacting the DLs. Depending on the source and sample matrix of the original sample, one or more of the following column cleanup approaches may be necessary to remove polyhalogenated diphenyl ethers. You may use any number of permutations found in the referenced literature for this cleanup if the pre-extraction standard recoveries from field and batch blank samples meet the associated performance criteria in Section 13 of this method. Alternatively, you may use an automated cleanup approach that meets the labeled spike recovery requirements in Section 13 of this method. 11.3.2.1 Silica Gel Column Chromatography. Pack one end of a glass column, approximately 20 mm ID x 230 mm long, with glass wool. Add in sequence to the glass column, 1 g of silica gel, 2 g of sodium hydroxide impregnated silica gel, 1 g of silica gel, 4 g of acid-modified silica gel, 1 g of silica gel, and 1 cm layer of anhydrous sodium sulfate. Pre-elute the column with 30 to 50 mL of hexane leaving a small quantity of hexane above the sodium sulfate layer. Discard the preelution hexane. Add the sample extract, dissolved in 5 mL of hexane to the head of the column. Allow the sample to flow into the column leaving a small quantity of hexane above the sodium sulfate layer. Rinse the extract container with two additional 5-mL rinses of hexane PO 00000 Frm 00022 Fmt 4701 Sfmt 4702 and apply each rinse to the column separately as the previous addition elutes. Elute the column with an additional 90 mL of hexane and retain the entire eluate. Concentrate this solution to a volume of about 1 mL using the nitrogen evaporative concentrator (see Section 6.3.5 of this method). 11.3.2.2 Silver Nitrate Silica Gel Column Chromatography. Pack a column (6 mm ID, 150 mm in length) sequentially with 1 g of silica gel and 1 g of 10-percent silver nitrate silica gel followed by a layer of about 10 mm of sodium sulfate (anhydrous). Wash the column sufficiently with hexane, elute until the liquid level reaches to the upper end of the column, and then load the sample solution that is concentrated under vacuum to be about 5 mL. Wash the inner side several times with a small amount of hexane, elute with 200 mL of hexane at a flow rate about 2.5 mL/min (approximately one drop per second) to elute PCDDs. 11.3.2.3 Multi-layer Silica Gel Column Chromatography. You may use a multi-layer silica gel column in place of separate silica columns. Pack a column of 20 mm ID and 300 mm in length sequentially by the dry pack method with 0.9 g of silica gel, 3.0 g of 2-percent potassium hydroxide silica gel, 0.9 g of silica gel, 4.5 g of 44-percent sulfuric acid silica gel, 6.0 g of 22percent sulfuric acid silica gel, 0.9 g of silica gel, 3.0 g of 10-percent silver nitrate silica gel, 2.0 g of silica gel and 6.0 g of sodium sulfate (anhydrous). Wash the column sufficiently with hexane, elute until the liquid level reaches to the upper end of the column, and then load the sample solution. Wash the inner side of the transfer vessel several times with a small amount of hexane, elute with 150–200 mL of hexane at a flow rate about 2.5 mL/min (approximately one drop per second) to elute PCDDs/PCDFs. 11.3.2.4 Basic Alumina Column Chromatography. Pack a column (20 mm ID, 300 mm in length) with approximately 6 to 12 g of basic alumina. Pre-elute the column with 50 to 100 mL of hexane. Transfer the concentrated extract from the previous column cleanup to the top of the basic alumina column. Allow the sample to flow into the column leaving a small quantity of solvent above the top of the bed. Rinse the extract container with two additional 1-mL rinses of hexane and apply each rinse to the column separately as the previous addition elutes. Elute the column with 100 mL hexane to remove the interferences. Elute the PCDDs/PCDFs from the column with 20 to 40 mL of 50-percent E:\FR\FM\14JAP2.SGM 14JAP2 lotter on DSKBCFDHB2PROD with PROPOSALS2 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules methylene chloride in hexane. The ratio of methylene chloride to hexane may vary depending on the activity of the alumina used in the column preparation. Do not let the head of the column go without solvent. The first 100 mL hexane eluate is not used for subsequent PCDD/PCDF analysis. The eluate is concentrated to approximately 0.5 mL using the nitrogen evaporative concentrator. 11.3.2.5 Carbopack® C/Celite® 545 Column or Equivalent. Cut both ends from a 10 mL disposable Pasteur pipette (see Section 6.4.1 of this method) to produce a 10 cm column. Fire-polish both ends and flare both ends if desired. Insert a glass wool plug at one end and pack the column with 0.55 g of Carbopack®/Celite® (see Section 7.8.9.4 of this method) to form an adsorbent bed approximately 2 cm long. Insert a glass wool plug on top of the bed to hold the adsorbent in place. Pre-elute the column with 5 mL of toluene followed by 2 mL of methylene chloride:methanol:toluene (15:4:1 v/v), 1 mL of methylene chloride:cyclohexane (1:1 v/v), and 5 mL of hexane. If the flow rate of eluate exceeds 0.5 mL/minute, discard the column. Do not let the head of the column go without solvent. Add the sample extract to the column. Rinse the sample container twice with 1 mL portions of hexane and apply separately to the column. Apply 2 mL of hexane to the head of the column to complete the transfer. Elute the interfering compounds with two 3 mL portions of hexane, 2 mL of methylene chloride:cyclohexane (1:1 v/v), and 2 mL of methylene chloride:methanol:toluene (15:4:1 v/v). Discard the eluate. Invert the column and elute the PCDDs/PCDFs with 20 mL of toluene. If carbon particles are present in the eluate, filter through glass-fiber filter paper. Concentrate the eluate to approximately 0.5 mL using the nitrogen evaporative concentrator for further cleanup or analysis by HRGC/HRMS. 11.4 PCDD, PCDF, PCB and PAH Analysis. 11.4.1 Analyze the sample with an HRGC/HRMS using the instrumental parameters in Sections 11.4.2 and 11.4.3 of this method. 11.4.1.1 Immediately prior to analysis, add an aliquot (typically 20 microliters (ml)) of the pre-analysis standard solution(s) from Table 23–7, 23–8, or 23–9 of this method to each sample as appropriate for the compounds you are measuring by this method. 11.4.1.2 Inject an aliquot of the sample extract into the GC. You may VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 perform separate analyses using different GC columns for each of the target compound classes. A 1-ml aliquot of the extract is typically injected into the GC. Perform calibration and analysis for each target compound class using the same sample injection volume and concentration calculations. 11.4.1.2.1 If target compounds are not resolved sufficient from other target compounds or interferences in the sample to meet the requirements in Section 10.2.3.4 or 10.2.3.5 of this method, as applicable to the compound class being analyzed, or as otherwise specified in an applicable regulation, permit, or other requirement, analyze another aliquot of the sample using an alternative column that provides elution order to uniquely quantify the target compounds subject to interference on the first GC column. 11.4.1.2.2 You may use column systems other than those recommended in this method provided the analyst is able to demonstrate, using calibration and performance checks, that the alternative column system is able to meet the applicable specifications of Section 10.2.3.4 or 10.2.3.5 of this method. 11.4.2 Example Gas Chromatograph Operating Conditions. 11.4.2.1 Injector. Configured for capillary column, splitless, 250 °C (482 °F). 11.4.2.2 Carrier Gas. Helium, 1 to 2 mL/min. 11.4.2.3 Oven. Optimize the GC temperature program to achieve the required separation and target compound recovery for the GC column in use. Table 23–16 of this method presents the typical conditions for a DB5–MS column. 11.4.3 High-Resolution Mass Spectrometer. 11.4.3.1 Ionization Mode. Electron ionization. 11.4.3.2 Source Temperature. Maintain the source temperature in the range of 250 to 300 °C (482 to 572 °F). 11.4.3.3 Ion Monitoring Mode. Tables 23–4, 23–5, and 23–6 of this method summarize the various ions to be monitored for PCDD/PCDFs, PAHs, and PCBs, respectively. 11.4.3.4 Identification Criteria for Target Compounds. Use the following identification criteria for the characterization of target compounds in this method. The available native and isotopically labeled standards allow the unique identification of all PCDD/PCDF, PAH, and selected PCB congeners required in this method. Also see Sections 13.12 and 13.13 of this method for identification criteria for PCDD/ PO 00000 Frm 00023 Fmt 4701 Sfmt 4702 2255 PCDF/PCB and PAH target compounds, respectively. 11.4.3.4.1 For PCDD/PCDFs and PCBs, Table 23–15 of this method provides the integrated ion abundance ratio of primary and secondary target compound ions for the identification of target compounds. When the ion abundance ratio for a target analyte is outside the performance criteria, you may reanalyze samples on an alternative GC column to resolve chemical interferences, tune the mass spectrometer to operate at a higher mass resolution to discriminate against the interference(s), and/or reprocess an archived sample through the cleanup procedure to remove the interference(s). Report analysis results that do not meet the identification criteria as an estimated maximum possible concentration (EPC). Calculate the EPC separately for each quantitation ion, if present, and report the lower value as the EPC. This method does not consider EPC-flagged data to be zero concentrations. Note: Some EPCs are caused by poor ion statistics when the concentration of the target compound is at or near the DL. If you use the primary ion to determine and report the target compound concentration in these cases, reanalysis of samples is not necessary. 11.4.3.4.2 The retention time for the analytes must be within 3 seconds of the corresponding 13 C-labeled preextraction standard. 11.4.3.4.3 The signals for the two exact masses in Tables 23–4 and 23–6 of this method for PCDD/PCDFs and PCBs, respectively, must be present and must reach their maximum response within two seconds of each other. 11.4.3.4.4 Identify and quantify specific target compounds or isomers that do not have corresponding 13 Clabeled standards by comparing to the pre-extraction labeled standard of the same compound class with the nearest retention time to target compound. 11.4.3.4.5 For the identification of specific PCB isomers, the retention time of the native congener must be within 0.006 relative retention time (RRT) units of the pre-extraction isotopically labeled standard. 11.4.3.4.6 For qualitative identification, the S/N ratio for the GC signal present in every selected ion current profile for native compound response must be greater than or equal to 2.5. The ion abundance ratios must be within the control limits in Table 23–15 of this method for the compound class measured. 11.4.3.4.7 The confirmation of 2,3,7,8–TeCDD and 2,3,7,8–TeCDF must satisfy the separation criteria in Section E:\FR\FM\14JAP2.SGM 14JAP2 lotter on DSKBCFDHB2PROD with PROPOSALS2 2256 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules 10.2.3.4 of this method and all the identification criteria specified in Sections 11.4.3.4.1 through 11.4.3.4.6 of this method. 11.4.3.4.8 Chlorodiphenyl Ether Interference. If chromatographic peaks are detected at the retention time of any PCDDs/PCDF in any of the m/z channels used to monitor chlorodiphenyl ethers, there is evidence of a positive interference and you may opt to flag data noting the interference and keep the value to calculate PCDD/PCDF concentration as EPC or conduct a complete reanalysis to remove or shift the interference. This method recommends alumina (see Section 11.3.2.4 of this method) and Florisil® (see Section 11.3.1 of this method) liquid column chromatography packing materials for removal of chlorodiphenyl ethers during sample cleanup. 11.4.3.4.9 Set the mass spectrometer lock channels as specified in Tables 23– 4, 23–5, and 23–6 of this method for PCDD/PCDFs, PAHs, and PCBs, respectively. Monitor the quality control check channels to verify instrument stability during the analysis. If the signal varies by more than 25 percent from the average response, flag results for all isomers at corresponding retention time as QCF. You have the option to conduct additional cleanup procedures on an archived portion of the sample if the archive is available, or dilution the original sample and reanalysis or follow other quality review that demonstrates the target analyte and its corresponding isotopically labeled standard are equally affected by the change in the control check channels. When you conduct a complete reanalysis, reanalyze all concentration calculations based on the reanalyzed sample. 11.4.3.4.10 Identification Criteria for PAHs. The RRT between each native and labeled compound must be within 0.006 RRT units. The signals for the characteristic ion listed in Table 23–5 of this method must be present. 11.4.3.5 Quantitation. Measure the response of each native target compound and the corresponding preextraction standard. Use the equation in Section 12.7 of this method to sum the peak areas for the two quantitation ions monitored for each analyte and calculate the mass of the target compound(s) in the injection using the CCV RF. Use the pre-extraction recovery standard compounds to correct the homologous congener results for variations in recovery from the extraction, cleanup, and concentration steps of the analysis. Recovery of preextraction standards must meet minimum specifications (in Section 9.2. VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 of this method) to ensure that the method performance and reliability have not been compromised by unacceptable losses during sample processing. Table 23–17 of this method shows the assignments for single isotopically labeled compounds for use in calculating the response factor and the concentrations of PCBs. Recoveries of all labeled standards must meet the minimum recovery specifications in this method and unacceptably low recoveries are an indication of the sample processing step that caused the low recoveries. 11.4.3.5.1 Use Eq. 23–7 to calculate the mass of each target compound or group in the extract. 11.4.3.5.2 Use Eq. 23–8 to calculate the mass per dscm of each target compound or group in the sample. 11.4.3.5.3 Quantify indigenous PCDD and PCDF in its homologous series using the corresponding native and pre-extraction standard response in its homologous series. For example, use 13C -2,3,7,8-tetra chlorinated 12 dibenzodioxin to calculate the concentrations of all other tetra chlorinated isomers. 11.4.3.5.4 As an option or as required or specified in applicable regulations, permits, or other requirements, you may quantify any or all other PCB congeners as resolved or coeluting combinations using the response of the nearest eluting native target PCB and the response of the preextraction isotopic label assigned in appendix A to this method. 11.4.3.5.5 As an option or as required or specified in applicable regulations, permits, or other requirements, report the total concentration of congeners at a given level of chlorination (homolog; i.e., total TrCB, total PeCB, total HxCB) by summing the concentrations of all congeners identified in the retention time window for the homologs as assigned in appendix A to this method. 11.4.3.5.6 As an option or if required in an applicable regulation, permit or other requirement, total chlorinated biphenyls (CBs) may be reported by summing all congeners identified at all window-defined congeners (WDCs) as assigned in appendix A to this method. 12.0 Data Analysis and Calculations Note: Same as Section 12 of Method 5 of appendix A–3 to 40 CFR part 60, with the following additions. 12.1 Nomenclature. Aai = Integrated ion current (area) of the noise for the primary and secondary m/z values at the retention time of the analyte. PO 00000 Frm 00024 Fmt 4701 Sfmt 4702 A*ci = Integrated ion current (area) of the primary and secondary m/z values of the pre-extraction (internal) standard i in the calibration standard. A1l = Integrated ion current of the primary m/z values for the isotopically labeled compound (assigned in Tables 23–4, 23–5, and 23–6 of this method). A1n = Integrated ion current of the primary m/z values for the target native compound. A2l = Integrated ion current of the secondary m/z’s for the isotopically labeled compound. For PAH A2l = 0. A2n = Integrated ion current of the secondary m/z values for the target native compound. For PAH A2n = 0. Cl = The concentration of the labeled compound used to perform isotope recovery correction, pg/mL. Tables 23–4, 23–5, and 23–17 of this method provide the compound mass assignments. Cn = The concentration of the target native compound, pg/mL. Ci = Concentration of target native compound i in the sample, pg/mL. Cidscm = Concentration of target native compound i in the emission gas, pg/ dscm. Ciext = Concentration of target native compound i in the extract, pg. CT = Total concentration of target compounds in the sample, pg/mL. D = Difference in the RRF of the continuing calibration verification compared to the average RRF of the initial calibration, percent (%). dscm = Dry standard cubic meters of gas volume sample measured by the dry gas meter, corrected to standard conditions. Hai = Summed heights of the noise at the retention time of the analyte in the two analyte channels. H*ci = Summed heights of the noise at the primary and secondary m/z’s of the pre-extraction standard i in the calibration standard. mi = Mass of compound i, pg. m*i = Mass of pre-extraction (internal standard) compound i, pg. n = Number of values. NOAAT = National Oceanic and Atmospheric Administration isotopic labeled congener for PCB of interest. R* = Recovery of labeled compound standards, %. RRFi = Relative response factor of a target compound at calibration level i. RRFccv = Relative response factor of a target compound in the continuing calibration verification. RSD = Relative standard deviation, in this case, of RRFs over the five calibration levels, %. SDRRF = Standard deviation of initial calibration RRFs. Vext = Extract volume, mL. E:\FR\FM\14JAP2.SGM 14JAP2 RSD = SDRRF X 100°1: RRF R* found = cone. . cone. spiked Estimated Detectable Limit EDL Eq. 23-3 Eq. 23-4 lotter on DSKBCFDHB2PROD with PROPOSALS2 12.6 Percent Difference of the RRF of the Continuing Calibration Verification Compared to the Average RRF from the Initial Calibration for Each Target Compound. The requirement for the continuing calibration verification percent difference is in Section 13.11 and Table 23–14 of this method. D = RRFccvRRF 0 RRF X 1001/o Eq. 23-5 12.7 Concentration of Individual Target Compound i in the Extract by Isotope Dilution (pg/mL). This equation VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 100% Eq. 23-9 12.11 (EDL). ?O 12.5 Standard Deviation of the RRFs for a Compound Over the Five Calibration Levels. X = 2.5 (Hai)m*i H*ci RRFi Eq. 23-10 12.12 Total Concentration. Note: Unless otherwise specified in applicable regulations, permits or other requirements, count any target compounds reported as non-detected as EDL when calculating the concentration of target compounds in the sample. 13.0 Method Performance 13.1 Residual Toluene Quality Check. If adsorbent resin is cleaned or recleaned by the laboratory, a quality control check for residual toluene must be ≤1,000 mg/g of adsorbent. See appendix B to this method for procedures to assess residual toluene. 13.2 Field Train Proof Blank and Batch Blank Sample Assessment. Conduct at least one field train proof blank for each test series at a single facility or sampling location. Analyze at PO 00000 Frm 00025 Fmt 4701 Sfmt 4702 E:\FR\FM\14JAP2.SGM 14JAP2 EP14JA20.010</GPH> EP14JA20.009</GPH> Eq. 23-2 12.4 Percent RSD of the RRFs for a Compound Over the Five Calibration Levels. The requirement for the initial calibration RSD is in Section 13.10 and Table 23–14 of this method. Ciext -Eq. 23-8 dscm 12.10 Recovery of Labeled Compound Standards. Use this equation to determine the recovery of any labeled compounds, including pre-sampling spikes, pre-extraction filter spike, preextraction spikes, pre-analysis spikes. The recovery performance criteria for these spikes is in Sections 13.15, 13.16, and 13.17 of this method. EP14JA20.008</GPH> = ~ Lf= 1 RRFi Cidscm -_ EP14JA20.007</GPH> RRF 12.9 Mass of the Individual Target Compound or Group i in the Emission Gas (pg/dscm). EP14JA20.006</GPH> 12.3 Average RRF for Each Compound Over the Five Calibration Levels. Eq. 23-6 12.8 Concentration of the Individual Target Compound i in the Sample Extract (pg). EP14JA20.005</GPH> Eq. 23-1 Cz (A1n+A2n) ] (A1z+A2z)RRF CCV EP14JA20.004</GPH> (A1z+A2z)Cn =[ EP14JA20.003</GPH> = (Aln + A2n)Cz Ci least one batch blank sample during an analytical sequence or every 24 hours, whichever is shorter. Native target compound concentrations must be less than or equal to three times the EDL of the method or 10 times lower than the quantitation limit required by the end use of the data, whichever is higher. If blank assessment fails this criterion, flag sample data from this test with explanation that the blank samples failed the method criteria. 13.3 GC column systems used to measure PCDD/PCDFs must meet the column separation requirements in Section 6.5.2.1 of this method and the applicable requirements in Sections 10.2.3.4 and 11.4.3.4 of this method using calibration and batch blank performance checks. Failure to meet this chromatographic resolution criterion requires data from this analysis to be flagged explaining the potential bias of the results. A mid-concentration standard containing all of the native target PCDD/PCDFs may be used to demonstrate this requirement. 13.4 GC column systems used to measure PAHs must meet the column separation requirements in Section 6.5.2.2 of this method and the applicable requirements in Sections 10.2.3.4 and 11.4.3.4 of this method using calibration and batch blank performance checks. Failure to meet this chromatographic resolution criterion requires data from this analysis to be flagged explaining the potential bias of the results. 13.5 GC systems used to measure PCBs must meet the column separation requirements in Section 6.5.2.3 of this method and the applicable requirements in Sections 10.2.3.4 and 11.4.3.4 of this method of this method using calibration and batch blank performance checks, and be able to achieve unique resolution and identification of the toxics for determination of a TEQPCB using TEFs (American Society of Mechanical Engineers 1984). 13.6 Confirmation Column. If target compounds are not sufficiently resolved from other target compounds or interferences in the sample to meet the requirements for target compounds in Sections 13.3, 13.4, and/or 13.5 of this method, analyze another aliquot of the sample in a separate run using an alternative column that provides elution order to uniquely quantify the target compounds subject to interference on the first GC column. 13.7 Detection Limits. If the DLs as determined in Section 9.5 of this method meet the target DLs shown in Tables 23–18, 23–19, and 23–20 of this method for the target compounds determined with this method, the DLs EP14JA20.002</GPH> RR Fi corrects for the target native compound recovery by its labeled pre-extraction spike analog. To accomplish this the pre-extraction spike, labeled compound levels must remain constant. EP14JA20.001</GPH> WHOT = World Health Organization acronym used to designate WHO isotopic labeled toxic analog. WDC = Window-defined congener representing an isotopically labeled PCB that defines the beginning or end of a retention time window bracketing a PCB homolog level of chlorination. 12.2 Individual Compound RRF for Each Calibration Level i. The equation for the response factor of each target native compound relative to its labeled pre-extraction spike analog includes the integrated ion current of both the primary and secondary m/z values for each compound in the calibration standard. Use this equation to calculate the RRF for the continuing calibration verification for comparison to the average RRF from the initial calibration. 2257 EP14JA20.000</GPH> Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules lotter on DSKBCFDHB2PROD with PROPOSALS2 2258 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules are considered acceptable. If the compound specific DLs are less than 50 percent of the emission standard, the DLs are acceptable. If the DL requirements are not met, you must flag native compound data that fails to meet these criteria and provide a description of the impact on the data as part of the quality narrative for the sample analyses. 13.8 Tune. Tune the HRGC/HRMS to meet the isotopic ratio criteria listed in Table 23–15 of this method. 13.9 Lock Channels. MS lock and quality control channels recommended in Tables 23–4, 23–5, and 23–6 of this method for PCDD/PCDFs, PCBs, or PAHs, respectively, must not vary >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. VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 13.12.3 The Retention time (RT) for the analytes must be within 3 seconds of the corresponding labeled preextraction 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, 2,3,4,6,7,8HxCDF, 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 ≤ three times the EDL of the method or 10 times lower than the quantitation limit required by the end use of the data, whichever is higher. Note: You must analyze batch blank samples at least once during each analytical sequence or every 24 hours, whichever is shorter. 13.15 Pre-sampling Spike Recovery and Pre-extraction Filter Spike Recovery. Recoveries of all pre-sampling isotopically labeled spike compounds standards added to the sample and all pre-extraction filter recovery spike compounds added to the filter must be PO 00000 Frm 00026 Fmt 4701 Sfmt 4702 between 70 and 130 percent (Tables 23– 7, 23–8, and 23–9 of this method). 13.15.1 If the recovery of the presampling spike is below 70 percent, the sampling runs are not valid, and you must repeat the invalid runs. As an alternative, you do not have to repeat the invalid sampling runs if the average pre-sampling adsorbent spike recovery is 25 percent or more and you divide the final results by the average fraction of pre-sampling adsorbent spike recovery. 13.15.2 If the recovery of the preextraction filter spike is below 70 percent, the sampling recovery is not valid, and you must flag the test run results. 13.16 Pre-extraction Spike Recovery. Recoveries of all pre-extraction isotopically labeled spike compounds standards added to the sample must be between 20 to 130 percent for PCDD/ PCDFs and PAHs (Tables 23–7 and 23– 8 of this method) and between 20 to 145 percent for PCBs (Table 23–9 of this method). 13.17 Pre-analysis Spike Sensitivity. Response of all pre-analysis isotopically labeled spike compounds must show a S/N for every selected ion current profile of ≥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-guidelinedocuments. 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 E:\FR\FM\14JAP2.SGM 14JAP2 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules hoods and bench operations. The laboratory must also comply with any sewage discharge permits and regulations. The EPA’s Environmental Management Guide for Small Laboratories (EPA 233–B–98–001) provides an overview of requirements. 15.2 Samples containing hydrogen chloride or sulfuric acid to pH <2 are hazardous and must be neutralized before being poured down a drain or must be handled as hazardous waste. 15.3 For further information on waste management, consult The Waste Management Manual for Laboratory Personnel and Less is Better-Laboratory Chemical Management for Waste Reduction, available from the American Chemical Society’s Department of Government Relations and Science Policy, 1155 16th Street NW, Washington, DC 20036. 16.0 Bibliography 1. American Society of Mechanical Engineers. Analytical Procedures to Assay Stack Effluent Samples and Residual Combustion Products for Polychlorinated Dibenzo-p-Dioxins (PCDD) and Polychlorinated Dibenzofurans (PCDF). Prepared for the U.S. Department of Energy and U.S. Environmental Protection Agency. Washington, DC. December 1984. 23 p. 2. American Society of Mechanical Engineers. Sampling for the Determination of Chlorinated Organic Compounds in Stack Emissions. Prepared for U.S. Department of Energy and U.S. Environmental Protection Agency. Washington DC. December 1984. 25 p. 3. Fishman, V.N., Martin, G.D. and Lamparski, L.L., Comparison of a variety of gas chromatographic columns with different polarities for the separation of chlorinated dibenzo-p-dioxins and dibenzofurans by high-resolution mass spectrometry, Journal of Chromatography A 1139 (2007) 285– 300. 4. International Agency for Research on Cancer. Environmental Carcinogens Methods of Analysis and Exposure Measurement, Volume 11— Polychlorinated Dioxins and Dibenzofurans. IARC Scientific Publications No. 108, 1991. 5. Stieglitz, L., Zwick, G., Roth, W. Investigation of different treatment techniques for PCDD/PCDF in fly ash. Chemosphere 15: 1135–1140; 1986. 6. Triangle Laboratories. Case Study: Analysis of Samples for the Presence of Tetra Through Octachloro-pDibenzodioxins and Dibenzofurans. Research Triangle Park, NC. 1988. 26 p. 7. U.S. Environmental Protection Agency. Method 8290—The Analysis of Polychlorinated Dibenzo-p-dioxin and Polychlorinated Dibenzofurans by HighResolution Gas Chromatography/High- 2259 Resolution Mass Spectrometry. In: Test Methods for Evaluating Solid Waste. Washington, DC. SW–846. 8. U.S. Environmental Protection Agency. Office of Air Programs Publication No. APTD–0576: Maintenance, Calibration, and Operation of Isokinetic Source Sampling Equipment. Research Triangle Park, NC. March 1972. 9. U.S. Environmental Protection Agency. Method 1625C-Semivolatile Organic Compounds by Isotope Dilution GCMS. 10. U.S. Environmental Protection Agency. Method 1613B-Tetra- through Octa-Chlorinated Dioxins and Furans by Isotope Dilution HRGC/HRMS. 11. U.S. Environmental Protection Agency. Method 1668C-Chlorinated Biphenyl Congeners in Water, Soil, Sediment, Biosolids, and Tissue by HRGC/HRMS.12. Tondeur, Y., Nestrick, T., Silva, He´ctor A., Vining, B., Hart, J. Analytical procedures for the determination of polychlorinated-pdioxins, polychlorinated dibenzofurans, and hexachlorobenzene in pentachlorophenol, Chemosphere Volume 80, Issue 2, June 2010 pages 157–164. 17.0 Tables, Diagrams, Flowcharts, and Validation Data TABLE 23–1—POLYCHLORINATED DIBENZO-P-DIOXIN AND POLYCHLORINATED DIBENZOFURAN TARGET ANALYTES CAS a registry number lotter on DSKBCFDHB2PROD with PROPOSALS2 Polychlorinated dibenzo-p-dioxins 2,3,7,8-TeCDD .................................................................................................................. 1746–01–6 1,2,3,7,8-PeCDD ............................................................................................................... 40321–76–4 1,2,3,4,7,8-HxCDD ............................................................................................................ 39227–28–6 1,2,3,6,7,8-HxCDD ............................................................................................................ 57653–85–7 1,2,3,7,8,9-HxCDD ............................................................................................................ 19408–74–3 1,2,3,4,6,7,8-HpCDD ......................................................................................................... 35822–46–9 Total TeCDD ..................................................................................................................... 41903–57–5 Total PeCDD ..................................................................................................................... 36088–22–9 Total HxCDD ..................................................................................................................... 34465–4608 Total HpCDD ..................................................................................................................... Total OCDD ....................................................................................................................... 37871–00–4 3268–87–9 a Polychlorinated dibenzofurans 2,3,7,8TeCDF. 1,2,3,7,8PeCDF. 2,3,4,7,8PeCDF. 1,2,3,4,7,8HxCDF. 1,2,3,6,7,8HxCDF. 1,2,3,7,8,9HxCDF. 2,3,4,6,7,8HxCDF. 1,2,3,4,6,7,8HpCDF. 1,2,3,4,7,8,9HpCDF. Total TeCDF Total PeCDF Total HxCDF Total HpCDF Total OCDF .. Chemical Abstract Service. VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 PO 00000 Frm 00027 Fmt 4701 Sfmt 4702 E:\FR\FM\14JAP2.SGM 14JAP2 CAS a registry No. 51207–31–9 57117–41–6 57117–31–4 70648–26–9 57117–44–9 72918–21–9 60851–34–5 67562–39–4 55673–89–7 55722–27–5 30402–15–4 55684–94–1 38998–75–3 39001–02–0 2260 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules TABLE 23–2—POLYCYCLIC AROMATIC HYDROCARBON TARGET ANALYTES Polycyclic aromatic hydrocarbons Naphthalene ............................................................ 2-Methylnapthalene ................................................ Acenaphthylene ...................................................... Acenaphthene ......................................................... Fluorene .................................................................. Anthracene .............................................................. Phenanthrene ......................................................... Fluoranthene ........................................................... Pyrene ..................................................................... Benzo[a]anthracene ................................................ a Polycyclic aromatic hydrocarbons CAS a registry No. 91–20–3 91–57–6 208–96–8 83–32–9 86–73–7 120–12–7 85–01–8 206–44–0 129–00–0 56–55–3 CAS a registry No. Chrysene ................................................................ Benzo[b]fluoranthene ............................................. Benzo[k]fluoranthene ............................................. Perylene ................................................................. Benzo[a]pyrene ...................................................... Benzo[e]pyrene ...................................................... Benzo[g,h,i]perylene ............................................... Indeno[1,2,3-cd]pyrene .......................................... Dibenz[a,h]anthracene ........................................... 218–01–9 205–99–2 207–08–9 198–55–8 50–32–8 192–92–2 191–24–2 193–39–5 53–70–3 Chemical Abstract Service. TABLE 23–3—POLYCHLORINATED BIPHENYL TARGET ANALYTES BZ No.a PCB congener 2,4′-DiCB ..................................... 2,2′,5-TrCB .................................. 2,4,4′-TrCB .................................. 2,2′,3,5′-TeCB ............................. 2,2′,5,5′-TeCB ............................. 2,3′,4,4′-TeCB ............................. 3,3′,4,4′-TeCB ............................. 3,4,4′,5-TeCB .............................. 2,2′,4,5,5′-PeCB .......................... 2,3,3′,4,4′-PeCB .......................... 2,3,4,4′,5-PeCB ........................... 2,3′,4,4′,5-PeCB .......................... 2′,3,4,4′,5-PeCB .......................... 3,3′,4,4′,5-PeCB .......................... a BZ CASb Registry No. 8 18 28 44 52 66 77 81 101 105 114 118 123 126 34883–43–7 37680–65–2 7012–37–5 41464–39–5 35693–99–3 32598–10–0 32598–13–3 70362–50–4 37680–73–2 32598–14–4 74472–37–0 31508–00–6 65510–44–3 57465–28–8 CAS b Registry No. BZ No.a PCB congener 2,2′,3,3′,4,4′-HxCB ..................... 2,2′,3,4,4′,5′-HxCB ..................... 2,2′,4,4′,5,5′-HxCB ..................... 2,3,3′,4,4′,5-HxCB ...................... 2,3,3′,4,4′,5′-HxCB ..................... 2,3′,4,4′,5,5′-HxCB ..................... 3,3′,4,4′,5,5′-HxCB ..................... 2,2′,3,3′,4,4′,5-HpCB .................. 2,2′,3,4,4′,5,5′-HpCB .................. 2,2′,3,4′,5,5′,6-HpCB .................. 2,3,3′,4,4′,5,5′-HpCB .................. 2,2′,3,3′,4,4′,5,6-OcCB ............... 2,2′,3,3′,4,4′,5,5′,6-NoCB ........... 2,2′,3,3′,4,4′,5,5′,6,6′-DeCB ....... 128 138 153 156 157 167 169 170 180 187 189 195 206 209 38380–07–3 35065–28–2 35065–27–1 38380–08–4 69782–90–7 52663–72–6 32774–16–6 35065–30–6 35065–29–3 52663–68–0 39635–31–9 52663–78–2 40186–72–9 2051–24–3 No.: Ballschmiter and Zell 1980, or International Union of Pure and Applied Chemistry (IUPAC) number. Abstract Service. b Chemical TABLE 23–4—ELEMENTAL COMPOSITIONS AND EXACT MASSES OF THE IONS MONITORED BY HIGH-RESOLUTION MASS SPECTROMETRY FOR PCDDS AND PCDFS lotter on DSKBCFDHB2PROD with PROPOSALS2 Mass a 263.9871 292.9825 303.9016 305.8987 313.9839 315.9419 316.9745 317.9389 319.8965 321.8936 325.9839 327.8847 330.9792 331.9368 333.9339 339.8597 341.8567 354.9792 351.9000 353.8970 355.8546 357.8516 367.8949 369.8919 375.9807 375.8364 409.7974 373.8208 375.8178 375.9807 Ion type b ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... LOCK LOCK M M+2 QC M M+2 M+2 M M+2 QC M QC M M+2 M+2 M+4 LOCK M+2 M+4 M+2 M+4 M+2 M+4 QC M+2 M+2 M+2 M+4 QC Elemental composition Target analyte b C5F10N .............................. C7F11 ................................ C12H435Cl4O ..................... C12H435Cl37O ................... C6F12N .............................. 13C H 35Cl O .................. 12 4 4 13C H 35Cl O .................. 12 4 4 13C H 35Cl 37ClO ........... 12 4 3 C12H435ClO2 ..................... C12H435Cl337ClO2 ............. C7F12N .............................. C12H437Cl4O2 ................... C7F13 ................................ 13C H 35Cl O 12 4 4 2 ................ 13C H 35Cl37ClO 12 4 2 ........... C12H335Cl437ClO .............. C12H335Cl337Cl2O ............. C9F13 ................................ 13C H 35Cl 37ClO ........... 12 3 4 13C H 35Cl3537Cl O ........ 12 3 2 C12H335Cl337ClO2 ............. C12H335Cl337Cl2O2 ........... 13C H 35Cl 37ClO .......... 12 3 4 2 13C H 35Cl 37Cl O ........ 12 3 3 2 2 C8F14N .............................. C12H435Cl537ClO .............. C12H335Cl637ClO .............. C12H235Cl537ClO .............. C12H235Cl437Cl2O ............. C8F14N .............................. FC43 ................................. PFK ................................... TeCDF .............................. TeCDF .............................. FC43 ................................. TeCDF (S) ........................ TeCDF (S) ........................ TeCDF (S) ........................ TeCDD .............................. TeCDD .............................. FC43 ................................. TeCDD (S) ........................ PFK ................................... TeCDD (S) ........................ TeCDD (S) ........................ PeCDF .............................. PeCDF .............................. PFK ................................... PeCDF (S) ........................ PeCDF (S) ........................ PeCDD .............................. PeCDD .............................. PeCDD (S) ........................ PeCDD (S) ........................ FC43 ................................. HxCDPE ........................... HpCPDE ........................... HxCDF .............................. HxCDF .............................. FC43 ................................. Mass a 383.8639 385.8610 389.8157 391.8127 392.9760 401.8559 403.8529 425.9775 445.7555 407.7818 409.7789 417.8253 419.8220 423.7766 425.7737 430.9729 435.8169 437.8140 442.9728 479.7165 430.9729 441.7428 443.7399 457.7377 459.7348 463.9743 469.7779 471.7750 513.6775 442.9728 Ion typeb .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. M M+2 M+2 M+4 LOCK M+2 M+4 QC M+4 M+2 M+4 M M+2 M+2 M+4 QC M+2 M+4 LOCK M+4 LOCK M+2 M+4 M+2 M+4 QC M+2 M+4 M+4 QC Elemental composition 35Cl O .................. 6 35 37 12H2 Cl5 ClO ........... C12H235Cl537ClO2 ............. C12H235Cl437Cl2O2 ........... 13C 12H2 13C C9F15 ................................ 13C H 35Cl 37ClO .......... 12 2 5 2 13C H 35Cl 37Cl O .......... 12 2 4 2 C9F16N .............................. C12H235Cl637Cl2O ............. C12H35Cl637ClO ................ C12H35Cl537Cl2O .............. 13C H35Cl O ................... 12 7 13C H35Cl 37ClO ............. 12 6 C12H35Cl637ClO2 .............. C12H35Cl537Cl2O2 ............. C9F17 ................................ 13C H35Cl 37ClO 12 6 2 ........... 13C H35Cl 37Cl O .......... 12 5 2 2 C10F17 ............................... C12H35Cl737Cl2O .............. C9F17 ................................ C1235Cl737ClO ................... C1235Cl637Cl2O ................. C1235Cl737ClO2 ................. C1235Cl637Cl2O2 ............... C9F18N .............................. 13C 35Cl 37ClO .............. 12 7 2 13C 35Cl 37Cl O 12 6 2 2 ............ C1235Cl837Cl2O2 ............... C10F17 ............................... Target analyte b HxCDF (S). HxCDF (S). HxCDD. HxCDD. PFK. HxCDD (S). HxCDD (S). FC43. OCDPE. HpCDF. HpCDF. HpCDF (S). HpCDF (S). HpCDD. HpCDD. PFK. HpCDD (S). HpCDD (S). PFK. NCPDE. PFK. OCDF. OCDF. OCDD. OCDD. FC43. OCDD (S). OCDD (S). DCDPE. PFK. a The following nuclidic masses were used to calculate exact masses: H = 1.007825, C = 12.000000, 13C = 13.003355, F = 18.9984, O = 15.994915, 34.968853, 37Cl = 36.965903. b (S) = Labeled Standard. QC = Ion selected for monitoring instrument stability during the HRGC/HRMS analysis. VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 PO 00000 Frm 00028 Fmt 4701 Sfmt 4702 E:\FR\FM\14JAP2.SGM 14JAP2 35Cl = Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules 2261 TABLE 23–5—ELEMENTAL COMPOSITIONS AND EXACT MASSES OF THE IONS MONITORED BY HIGH-RESOLUTION MASS SPECTROMETRY FOR PAHS Aromatic ring No. 2 ........................................... 2 2 2 2 2 2 2 2 ........................................... ........................................... ........................................... ........................................... ........................................... ........................................... ........................................... ........................................... 2 3 3 3 3 3 ........................................... ........................................... ........................................... ........................................... ........................................... ........................................... 3 ........................................... 4 ........................................... 4 ........................................... 4 ........................................... 4 4 4 4 4 4 4 5 5 5 5 5 5 ........................................... ........................................... ........................................... ........................................... ........................................... ........................................... ........................................... ........................................... ........................................... ........................................... ........................................... ........................................... ........................................... 6 ........................................... 6 ........................................... 5 ........................................... 5 ........................................... 6 ........................................... 6 ........................................... Mass a 128.0624 130.9920 134.0828 142.078 148.0984 152.0624 158.0828 154.078 160.078 166.078 169.988 172.0984 178.078 184.0984 178.078 184.078 202.078 204.9888 208.0984 202.078 205.078 213.9898 218.9856 228.0936 230.9856 234.114 228.0936 234.114 252.0936 258.114 252.32 258.114 252.0936 256.1072 256.1072 252.0936 252.0936 264.1692 268.9824 263.9871 276.0936 282.114 278.1092 280.9824 284.1296 276.0936 288.1344 313.9839 Ion type b M LOCK M M M M M M M M QC M M M M M M QC M M M QC LOCK M LOCK M M M M M M M M M M M M M QC LOCK M M M LOCK M M M QC Elemental composition C10H8 ............................................................... 13C 12C H ....................................................... 6 4 8 C11H10 .............................................................. 13C 12C H 6 5 10 ..................................................... C12H8 ................................................................ 13C 12C H ....................................................... 6 6 8 C12H10 .............................................................. 13C 12C H 6 6 10 ..................................................... C13H10 .............................................................. 13C 12C H ........................................................ 6 7 C14H10 .............................................................. 13C 12C H 6 8 10 .................................................... C14H10 .............................................................. 13C 12C H 6 8 10 ..................................................... C16H10 .............................................................. 13C 12C H 6 10 10 .................................................... C16H10 .............................................................. 13C 12C H 3 13 10 .................................................... C18H12 .............................................................. 13C C H 6 12 12 ....................................................... C18H12 .............................................................. 13C 12C H 6 12 12 .................................................... C20H12 .............................................................. 13C 12C H 6 14 12 .................................................... C20H12 .............................................................. 13C 127C H 6 14 12 .................................................. C20H12 .............................................................. 13C 12C H 4 16 12 .................................................... 13C 12C H 4 16 12 .................................................... C20H12 .............................................................. C20H12 .............................................................. C20D12 .............................................................. C22H12 .............................................................. 13C 12C H 6 16 12 .................................................... C22H14 .............................................................. 13C 12C H 6 16 14 .................................................... C22H12 .............................................................. 13C 12C H 12 10 12 .................................................. a Isotopic b LOCK masses used for accurate mass calculation: 1H = 1.0078, 12C = 12.0000, = Lock-Mass Ion PFK or FC43. QC = Quality Control Check Ion. 13C Target analyte Naphthalene. PFK/FC43. 13C -Naphthalene. 6 2-Methylnaphthalene. 13C -2-Methylnaphthalene. 6 Acenaphthylene. 13C -Acenaphthylene. 6 Acenaphthene. 13C -Acenaphthene. 6 Fluorene. PFK/FC43. 13C -Fluorene. 6 Phenanthrene. 13C -Phenanthrene. 6 Anthracene. 13C -Anthracene. 6 Fluoranthene. PFK. 13C -Fluoranthene. 6 Pyrene. 13C -Pyrene. 3 FC43. FC43. Benzo[a]anthracene. PFK. 13C -Benzo[a]anthracene. 6 Chrysene. 13C -Chrysene. 6 Benzo[b]fluoranthene. 13C -Benzo[b]fluoranthene. 6 Benzo[k]fluoranthene. 13C -Benzo[k]fluoranthene. 6 Benzo[e]pyrene. 13C -Benzo[e]pyrene. 4 13C -Benzo[a]pyrene. 4 Benzo[a]pyrene. Perylene. d12-Perylene. PFK. FC43. Indeno[1,2,3-cd]pyrene. 13C -Indeno[1,2,3,cd]pyrene. 6 Dibenz[a,h]anthracene. PFK. 13C -Dibenz[a,h]anthracene. 6 Benzo[g,h,i]perylene. 13C -Benzo[g,h,i]perylene. 12 FC43. = 13.0034, 2H = 2.0141. TABLE 23–6—ELEMENTAL COMPOSITIONS AND EXACT MASSES OF THE IONS MONITORED BY HIGH-RESOLUTION MASS SPECTROMETRY FOR PCBS Chlorine substitution Fn-1; Cl-1 ............................. lotter on DSKBCFDHB2PROD with PROPOSALS2 Fn-2; Cl-2,3 .......................... Fn-3; Cl-3,4,5 ....................... VerDate Sep<11>2014 21:08 Jan 13, 2020 Mass a 188.0393 190.0363 200.0795 202.0766 218.9856 222.0003 223.9974 225.9944 234.0406 236.0376 242.9856 255.9613 257.9584 268.0016 269.9986 255.9613 257.9584 259.9554 268.0016 269.9986 280.9825 289.9224 291.9194 Jkt 250001 Ion type b M M+2 M M+2 LOCK M M+2 M+4 M M+2 C4 F9 M M+2 M M+2 M M+2 M+4 M M+2 LOCK M M+2 PO 00000 Elemental composition 35Cl 12C 12H9 12C 12H9 ...................................................... ...................................................... ...................................................... 12H9 12C H 37Cl ...................................................... 12 9 C4F9 .................................................................. 12C H 35C 12 8 l2 ..................................................... 12C H 35Cl 12 8 37 Cl .............................................. 12C H 37Cl 12 8 2 .................................................... 13C H 35Cl 12 8 2 .................................................... 13C H 35 Cl Cl .............................................. 12 8 37 C4 F9 ................................................................ 12C H 35C 12 7 l3 ..................................................... 12C H 35C 37Cl .............................................. 12 7 l2 13C H 35Cl 12 7 3 .................................................... 13C H 35Cl 37Cl ............................................. 12 7 2 12C H 35Cl 12 7 3 .................................................... 12C H 35Cl 37Cl ............................................. 12 7 2 12C H 35Cl37Cl .............................................. 12 7 2 13C H 35Cl 12 7 3 .................................................... 13C H 35Cl .............................................. 12 7 2 C6F11 ................................................................ 12C H 35Cl 12 6 4 .................................................... 12C H 35Cl 37Cl .............................................. 12 6 3 13C Frm 00029 37Cl 35Cl Fmt 4701 Sfmt 4702 E:\FR\FM\14JAP2.SGM Target analyte Cl-1 PCB Cl-1P CB 13C Cl-1 PCB 12 13C Cl-1 PCB 12 PFK Cl-2 PCB Cl-2 PCB Cl-2 PCB 13C Cl-2 PCB 12 13C Cl-2 PCB 12 PFK Cl-3 PCB Cl-3 PCB 13C 12 Cl-3 PCB 13C 12 Cl-3 PCB Cl-3 PCB Cl-3 PCB Cl-3 PCB 13C 12 Cl-3 PCB 13C 12 Cl-3 PCB PFK Cl-4 PCB Cl-4 PCB 14JAP2 2262 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules TABLE 23–6—ELEMENTAL COMPOSITIONS AND EXACT MASSES OF THE IONS MONITORED BY HIGH-RESOLUTION MASS SPECTROMETRY FOR PCBS—Continued Chlorine substitution Fn-4; Cl-4,5,6 ....................... Fn-5; Cl-5,6,7 ....................... lotter on DSKBCFDHB2PROD with PROPOSALS2 Fn-6; Cl-7,8,9,10 .................. Mass a 293.9165 301.9626 303.9597 323.8834 325.8804 327.8775 337.9207 339.9178 289.9224 291.9194 293.9165 301.9626 303.9597 323.8834 325.8804 327.8775 330.9792 337.9207 339.9178 359.8415 361.8385 363.8356 371.8817 373.8788 323.8834 325.8804 327.8775 337.9207 339.9178 354.9792 359.8415 361.8385 363.8356 371.8817 373.8788 393.8025 395.7995 397.7966 405.8428 407.8398 454.9728 393.8025 395.7995 397.7966 405.8428 407.8398 427.7635 429.7606 431.7576 439.8038 441.8008 454.9728 427.7635 429.7606 431.7576 439.8038 441.8008 442.9728 454.9728 461.7246 463.7216 465.7187 473.7648 475.7619 495.6856 499.6797 501.6767 507.7258 509.7229 511.7199 Ion type b M+4 M M+2 M M+2 M+4 M+2 M+4 M M+2 M+4 M+2 M+4 M M+2 M+4 LOCK M+2 M+4 M+2 M+4 M+6 M+2 M+4 M M+2 M+4 M+2 M+4 LOCK M+2 M+4 M+6 M+2 M+4 M+2 M+4 M+6 M+2 M+4 QC M+2 M+4 M+6 M+2 M+4 M+2 M+4 M+6 M+2 M+4 QC M+2 M+4 M+6 M+2 M+4 QC LOCK M+2 M+4 M+6 M+2 M+4 M+2 M+4 M+6 M+2 M+4 M+6 Elemental composition 35 37Cl ........................................... 12H6 Cl2 2 13C H 35Cl ..................................................... 12 6 4 13C H 35Cl 37Cl ............................................. 12 6 3 12C H 35Cl 12 5 5 .................................................... 12C H 35Cl 37Cl ............................................. 12 5 4 12C H 35Cl 37Cl ........................................... 12 5 3 2 13C H 35Cl 37Cl ............................................. 12 5 4 13C H 35Cl 37Cl 12 5 3 2 ........................................... 12C H 35Cl 12 6 4 .................................................... 12C H 35Cl 37Cl ............................................. 12 6 3 12C H 35Cl 37Cl ........................................... 12 6 2 2 13C H 35Cl 37Cl ............................................. 12 6 3 13C H 35C 37Cl 12 6 l2 2 ........................................... 12C H 35Cl 12 5 5 .................................................... 12C H 35Cl 37Cl ............................................. 12 5 4 12C H 35Cl 37Cl .......................................... 12 5 3 2 C7F15 ................................................................ 13C H 35Cl 37Cl ............................................. 12 5 4 13C H 35Cl 37Cl 12 5 3 2 ........................................... 13C H 35Cl ..................................................... 12 4 5 13C H 35Cl 37Cl ........................................... 12 4 4 2 12C H 35Cl 37Cl ........................................... 12 4 3 3 13C H 35Cl 37Cl ............................................. 12 4 5 13C H 35Cl 37Cl ........................................... 12 4 4 2 12C H 35Cl 12 5 5 .................................................... 12C H 35Cl 37Cl ............................................. 12 5 4 12C H 35Cl 37Cl ........................................... 12 5 3 2 13C H 35Cl 37Cl ............................................. 12 5 4 13C H 35Cl 37Cl ........................................... 12 5 3 2 C9F13 ................................................................ 12C H 35Cl 37Cl ............................................. 12 4 5 12C H 35Cl 37Cl ........................................... 12 4 4 2 12C H 35Cl 37Cl ........................................... 12 4 3 3 13C H 35Cl 37Cl ............................................. 12 4 5 13C H 35Cl 37Cl ........................................... 12 4 4 2 12C H 35Cl 37Cl ............................................. 12 3 6 12C H 35Cl 37Cl ........................................... 12 3 5 2 12C H 35Cl 12 3 4 .................................................... 13C H 35Cl 37Cl ............................................. 12 3 6 13C H 35Cl 37Cl ........................................... 12 3 5 2 C11F17 ............................................................... 12C H 35Cl 37Cl ............................................. 12 3 6 12C H 35Cl 37Cl ........................................... 12 3 5 2 12C H 35Cl 12 3 4 .................................................... 13C H 35Cl 37Cl ............................................. 12 3 6 13C H 35Cl 37Cl ........................................... 12 3 5 2 12C H 35Cl 37Cl ............................................. 12 2 7 12C H 35Cl 37Cl ........................................... 12 2 6 2 12C H 35Cl 37Cl ........................................... 12 2 5 3 13C H 35Cl 37Cl ............................................. 12 2 7 13C H 35Cl 37Cl 12 2 6 2 ........................................... C11F17 ............................................................... 12C H 35Cl 37Cl ............................................. 12 2 7 12C H 35Cl 37Cl 12 2 6 2 ........................................... 12C H 35Cl 37Cl 12 2 5 3 ........................................... 13C H 35Cl 37Cl ............................................. 12 2 7 13C H 35Cl 37Cl 12 2 6 2 ........................................... C10F17 ............................................................... C11F17 ............................................................... 12C H 35Cl 37Cl ............................................. 12 1 8 12C H 35Cl 37Cl 12 1 7 2 ........................................... 12C H 35Cl 37Cl 12 1 6 3 ........................................... 13C H 35Cl 37Cl ............................................. 12 1 8 13C H 35Cl 37Cl 12 1 7 2 ........................................... 13C H 35Cl 37Cl ............................................. 12 4 9 12C 35Cl 37Cl ................................................. 12 7 3 12C 35Cl 37Cl ................................................. 12 6 4 13C H 35Cl 37Cl ............................................. 12 4 9 13C H 35Cl 37Cl 12 4 8 2 ........................................... 13C H 35Cl 37Cl 12 4 8 4 ........................................... 12C Target analyte Cl-4 PCB 13C Cl-4 PCB 12 13C Cl-4 PCB 12 Cl-5 PCB Cl-5 PCB Cl-5 PCB 13C Cl-5 PCB 12 13C Cl-5 PCB 12 Cl-4 PCB Cl-4 PCB Cl-4 PCB 13C Cl-4 PCB 12 13C Cl-4 PCB 12 Cl-5 PCB Cl-5 PCB Cl-5 PCB PFK 13C Cl-5 PCB 12 13C Cl-5 PCB 12 37Cl Cl-6 PCB Cl-6 PCB Cl-6 PCB 13C Cl-6 PCB 12 13C Cl-6 PCB 12 Cl-5 PCB Cl-5 PCB Cl-5 PCB 13C Cl-5 PCB 12 13C Cl-5 PCB 12 PFK Cl-6 PCB Cl-6 PCB Cl-6 PCB 13C Cl-6 PCB 12 13C Cl-6 PCB 12 Cl-7 PCB Cl-7 PCB 37Cl Cl-7 PCB 3 13C Cl-7 PCB 12 13C Cl-7 PCB 12 PFK Cl-7 PCB Cl-7 PCB 37Cl Cl-7 PCB 3 13C Cl-7 PCB 12 13C Cl-7 PCB 12 Cl-8 PCB Cl-8 PCB Cl-8 PCB 13C Cl-8 PCB 12 13C Cl-8 PCB 12 PFK Cl-8 PCB Cl-8 PCB Cl-8 PCB 13C Cl-8 PCB 12 13C Cl-8 PCB 12 PFK PFK Cl-9 PCB Cl-9 PCB Cl-9 PCB 13C Cl-9 PCB 12 13C Cl-9 PCB 12 Cl-10 PCB Cl-10 PCB Cl-10 PCB 13C Cl-10 PCB 12 13C Cl-10 PCB 12 13C Cl-10 PCB 12 a Isotopic masses used for accurate mass calculation: 1H = 1.0078, 12C = 12.0000, 13C = 13.0034, 35Cl = 34.9689, 37Cl = 36.9659, 19F = 18.9984. An interference with PFK m/z 223.9872 may preclude meeting 10:1 S/N for the DiCB congeners at optional Calibration Level 1 (Table 23–12). If this interference occurs, 10:1 S/N must be met at the Calibration Level 2. b LOCK = Lock-Mass Ion PFK or FC43. QC = Quality Control Check Ion. VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 PO 00000 Frm 00030 Fmt 4701 Sfmt 4702 E:\FR\FM\14JAP2.SGM 14JAP2 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules 2263 TABLE 23–7—COMPOSITION OF THE SAMPLE FORTIFICATION AND RECOVERY STANDARD SOLUTIONS FOR PCDDS AND PCDFS a Compound Amount (pg/μL of final extract) b Spike recovery (percent) 50 50 50 50 50 70–130 70–130 70–130 70–130 70–130 100 100 70–130 70–130 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 200 200 20–130 20–130 20–130 20–130 20–130 20–130 20–130 20–130 20–130 20–130 20–130 20–130 20–130 20–130 20–130 20–130 20–130 100 100 100 100 S/N≥10 S/N≥10 S/N≥10 S/N≥10 100 100 20–130 20–130 Pre-sampling Adsorbent Standards 13C 12-1,2,3,4-TeCDD 13C 12-1,2,3,4,7-PeCDD ................................................................................................................................................ ............................................................................................................................................. 12-1,2,3,4,6-PeCDF ............................................................................................................................................. 13C -1,2,3,4,6,9-HxCDF .......................................................................................................................................... 12 13C -1,2,3,4,6,8,9-HpCDF ....................................................................................................................................... 12 13C Pre-extraction Filter Recovery Spike Standards 13C 12-1,2,7,8-TeCDF 13C 12-1,2,3,4,6,8-HxCDD ................................................................................................................................................. .......................................................................................................................................... Pre-extraction Standards 13C 12-2,3,7,8-TeCDD 13C 12-2,3,7,8-TeCDF ................................................................................................................................................ ................................................................................................................................................. 12-1,2,3,7,8-PeCDD ............................................................................................................................................. 13C -1,2,3,7,8-PeCDF ............................................................................................................................................. 12 13C -2,3,4,7,8-PeCDF ............................................................................................................................................. 12 13C -1,2,3,4,7,8-HxCDD .......................................................................................................................................... 12 13C -1,2,3,6,7,8-HxCDD .......................................................................................................................................... 12 13C -1,2,3,7,8,9-HxCDD .......................................................................................................................................... 12 13C -1,2,3,4,7,8-HxCDF .......................................................................................................................................... 12 13C -1,2,3,6,7,8-HxCDF .......................................................................................................................................... 12 13C -2,3,4,6,7,8-HxCDF .......................................................................................................................................... 12 13C -1,2,3,7,8,9-HxCDF .......................................................................................................................................... 12 13C -1,2,3,4,6,7,8-HpCDD ....................................................................................................................................... 12 13C -1,2,3,4,6,7,8-HpCDF ....................................................................................................................................... 12 13C -1,2,3,4,7,8,9-HpCDF ....................................................................................................................................... 12 13C -OCDD .............................................................................................................................................................. 12 13C -OCDF .............................................................................................................................................................. 12 13C Pre-analysis Standards 13C 12-1,3,6,8-TeCDD 13C 12-1,2,3,4-TeCDF ................................................................................................................................................ ................................................................................................................................................. 13C -1,2,3,4,6,7-HxCDD .......................................................................................................................................... 12 13C -1,2,3,4,6,7,9-HpCDD ....................................................................................................................................... 12 Alternate Recovery Standards 13C 12-1,3,7,8-TeCDD 13C 12-1,2,4,7,8-PeCDD ................................................................................................................................................ ............................................................................................................................................. 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 1μL 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 Compound Amount (pg/μL of final extract) b Spike recovery (percent) 100 100 70–130 70–130 100 70–130 100 100 100 100 100 100 100 100 100 100 100 100 20–130 20–130 20–130 20–130 20–130 20–130 20–130 20–130 20–130 20–130 20–130 20–130 Pre-sampling Adsorbent Standards 13C -Benzo[c]fluorene .............................................................................................................. 6 13C -Benzo[j]fluoranthene ...................................................................................................... 12 Pre-extraction Filter Recovery Spike Standards d10-Anthracene ........................................................................................................................ lotter on DSKBCFDHB2PROD with PROPOSALS2 Pre-extraction Standards 13C -Naphthalene .................................................................................................................... 6 13C -2-Methylnaphthalene ....................................................................................................... 6 13C -Acenaphthylene ............................................................................................................... 6 13C -Acenaphthene ................................................................................................................. 6 13C -Fluorene .......................................................................................................................... 6 13C -Phenanthrene .................................................................................................................. 6 13C -Anthracene ...................................................................................................................... 6 13C -Fluoranthene ................................................................................................................... 6 13C -Pyrene ............................................................................................................................. 3 13C -Benzo[a]anthracene ........................................................................................................ 6 13C -13Chrysene ...................................................................................................................... 6 13C -Benzo[b]fluoranthene ...................................................................................................... 6 VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 PO 00000 Frm 00031 Fmt 4701 Sfmt 4702 E:\FR\FM\14JAP2.SGM 14JAP2 2264 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules TABLE 23–8—COMPOSITION OF THE SAMPLE FORTIFICATION AND RECOVERY STANDARD SOLUTIONS FOR PAHS a— Continued Compound Amount (pg/μL of final extract) b Spike recovery (percent) 100 100 100 100 100 100 100 20–130 20–130 20–130 20–130 20–130 20–130 20–150 100 100 100 S/N≥10 S/N≥10 S/N≥10 13C -Benzo[k]fluoranthene ....................................................................................................... 6 13C -Benzo[e]pyrene ............................................................................................................... 4 13C -Benzo[a]pyrene ............................................................................................................... 4 d12-Perylene ............................................................................................................................ 13C -Indeno[1,2,3-cd]pyrene .................................................................................................... 6 13C -Dibenz[a,h]anthracene .................................................................................................... 6 13C -Benzo[g,h,i]perylene ...................................................................................................... 12 Pre-analysis Standards d10-Acenaphthene ................................................................................................................... d10-Pyrene ............................................................................................................................... d12-Benzo[e]pyrene ................................................................................................................. 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 BZ No.b Compound Amount (pg/μL of final extract) c Spike recovery (percent) 100 100 100 100 70–130 70–130 70–130 70–130 100 70–130 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 20–145 100 100 S/N≥10 S/N≥10 Pre-sampling Adsorbent Standards 13C -3,3′-DiCB .............................................................................................. 12 13C -2,4′,5-TrCB ........................................................................................... 12 13C -2,2′,3,5′,6-PeCB ................................................................................... 12 13C -2,2′,4,4′,5,5′-HxCB ............................................................................... 12 11L 31L 95L 153L Pre-extraction Filter Recovery Spike Standards 13C -2,3,3′,4,5,5′-HxCB 12 ................................................................................ 159L lotter on DSKBCFDHB2PROD with PROPOSALS2 Pre-extraction Standards 13C -2-MoCB (WDC) .................................................................................... 12 13C -4-MoCB (WDC) .................................................................................... 12 13C -2,2′-DiCB (WDC) .................................................................................. 12 13C -4,4′-DiCB (WDC) .................................................................................. 12 13C -2,2′,6-TrCB (WDC) ............................................................................... 12 13C -3,4′,4′-TrCB (WDC) .............................................................................. 12 13C -2,2′,6,6′-TeCB (WDC) .......................................................................... 12 13C -3,3′,4,4′-TeCB (WDC) (WHOT) (NOAAT) ........................................... 12 13C -3,4,4′,5-TeCB (WHOT) ......................................................................... 12 13C -2,2′,4,6,6′-PeCB (WDC) ....................................................................... 12 13C -2,3,3′,4,4′-PeCB (WHOT) .................................................................... 12 13C -2,3,4,4′,5-PeCB (WHO) ........................................................................ 12 13C -2,3′,4,4′,5-PeCB (WHOT) .................................................................... 12 13C -2′,3,4,4′,5-PeCB (WHOT) .................................................................... 12 13C -3,3′,4,4′,5-PeCB (WDC) (WHOT) ........................................................ 12 13C -2,2′,4,4′,6,6′-HxCB (WDC) ................................................................... 12 13C -2,3,3′,4,4′,5-HxCB (WHOT) ................................................................. 12 13C -2,3,3′,4,4′,5′-HxCB (WHOT) ................................................................. 12 13C -2,3′,4,4′,5,5′-HxCB (WHOT) ................................................................. 12 13C -3,3′,4,4′,5,5′-HxCB (WDC) (WHOT) (NOAAT) .................................... 12 13C -2,2′,3,3′,4,4′,5′-HpCB (NOAAT) ........................................................... 12 13C -2,2′,3,4,4′,5,5′-HpCB (NOAAT) ............................................................ 12 13C -2,2′,3,4′,5,6,6′-HpCB (WDC) ................................................................ 12 13C -2,3,3′,4,4′,5,5′-HpCB (WDC) (WHOT) ................................................. 12 13C -2,2′,3′,3′,5,5′,6,6′-OcCB (WDC) ........................................................... 12 13C -2,3′,3′,4,4′,5,5′,6-OcCB (WDC) ............................................................ 12 13C -2,2′,3,3′,4,4′,5,5′,6-NoCB (WDC) ......................................................... 12 13C -2,2′,3,3′,4,5,5′,6,6′-NoCB (WDC) ......................................................... 12 13C -DeCB (WDC) ........................................................................................ 12 1L 3L 4L 15L 19L 37L 54L 77L 81L 104L 105L 114L 118L 123L 126L 155L 156L 157L 167L 169L 170L 180L 188L 189L 202L 205L 206L 208L 209L Pre-analysis Standards 13C -2,5-DiCB ............................................................................................... 12 13C -2,2′,5,5′-TeCB (NOAAT) ...................................................................... 12 VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 PO 00000 Frm 00032 Fmt 4701 9L 52L Sfmt 4702 E:\FR\FM\14JAP2.SGM 14JAP2 2265 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules TABLE 23–9—COMPOSITION OF THE SAMPLE FORTIFICATION AND RECOVERY STANDARD SOLUTIONS FOR PCBS a— Continued BZ No.b Compound 13C -2,2′,4,5,5′-PeCBl (NOAAT) .................................................................. 12 13C -2,2′,3,4,4′,5′-HxCB (NOAAT) ............................................................... 12 13C -2,2′,3,3′,4,4′,5,5′-OcCB ........................................................................ 12 Amount (pg/μL of final extract) c Spike recovery (percent) 100 100 100 S/N≥10 S/N≥10 S/N≥10 100 100 100 20–130 20–130 20–130 100 100 100 20–130 20–130 20–130 101L 138L 194L Optional Cleanup Spiking Standards 13C -2-MoCB (NOAAT) ................................................................................ 12 13C -2,2′,4,5,5′-PeCB ................................................................................... 12 13C -2,2′,3,3′,5,5′,6,6′-OcCB ........................................................................ 12 28L 111L 178L Alternate Recovery Standards 13C -2,3′,4′,5-TeCB ....................................................................................... 12 13C -2,3,4,4′-TeCB ....................................................................................... 12 13C -3,3′,4,5,5′-PeCB ................................................................................... 12 70L 60L 127L 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 ............................... ≤20 ± 5 °C, (68 ± 9 °F) .................... ≤20 ± 5 °C, (68 ± 9 °F) .................... ≤20 ± 5 °C, (68 ± 9 °F). Laboratory Storage Conditions Sampling Train Rinses and Filters .... Adsorbent ........................................... Extract and Archive ............................ ≤6 °C (43 °F) .................................... ≤6 °C (43 °F) .................................... <¥10 °C (14 °F) ............................... ≤6 °C (43 °F) .................................... ≤6 °C (43 °F) .................................... <¥10 °C (14 °F) ............................... ≤6 °C (43 °F). ≤6 °C (43 °F). <¥10 °C (14 °F). Laboratory Hold Times Extract and Archive ............................ One year ........................................... 45 Days ............................................ One year. a All samples must be stored in the dark. b Hold times begin from the time the laboratory receives the samples. TABLE 23–11—COMPOSITION OF THE INITIAL CALIBRATION STANDARD SOLUTIONS FOR PCDDS AND PCDFS a [pg/μL] Cal 1 (optional) Standard compound Target (Unlabeled) Analytes .................... Pre-sampling Adsorbent Standards ......... Pre-extraction Filter Recovery Standards Pre-extraction Standards ......................... Pre-analysis Standards ............................ Alternate Recovery Standards ................. a Assumes Cal 2 0.50 50 50 50 50 50 Cal 3 1.0 50 50 50 50 50 Cal 4 5.0 50 50 50 50 50 Cal 5 10.0 50 50 50 50 50 Cal 7 (optional) Cal 6 25 50 50 50 50 50 50 50 50 50 50 50 100 50 50 50 50 50 1 μL injection volume. TABLE 23–12—COMPOSITION OF THE INITIAL CALIBRATION STANDARD SOLUTIONS FOR PAHS a lotter on DSKBCFDHB2PROD with PROPOSALS2 [pg/μL] Cal 1 (optional) Standard compound Target (Unlabeled) Analytes .................... Pre-sampling Adsorbent Standards ......... Pre-extraction Filter Recovery Standards Pre-extraction Standards ......................... Pre-analysis Standards ............................ a Assumes VerDate Sep<11>2014 Cal 2 1 100 100 100 100 Cal 3 2 100 100 100 100 Cal 4 4 100 100 100 100 Cal 5 20 100 100 100 100 80 100 100 100 100 1 μL injection volume. 19:55 Jan 13, 2020 Jkt 250001 PO 00000 Frm 00033 Fmt 4701 Sfmt 4702 E:\FR\FM\14JAP2.SGM 14JAP2 Cal 6 400 100 100 100 100 Cal 7 (optional) 1,000 100 100 100 100 2266 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules TABLE 23–13—COMPOSITION OF THE INITIAL CALIBRATION STANDARD SOLUTIONS FOR PCBS a [pg/μL] Cal 1 (optional) Standard compound Target (Unlabeled) Analytes .................... Pre-sampling Adsorbent Standard(s) ...... Pre-extraction Filter Recovery Standards Pre-extraction Standards ......................... Pre-analysis Standards ............................ Alternate Standards ................................. a Assumes Cal 2 0.50 100 100 100 100 100 Cal 3 1 100 100 100 100 100 Cal 4 5 100 100 100 100 100 Cal 5 10 100 100 100 100 100 Cal 7 (optional) Cal 6 50 100 100 100 100 100 400 100 100 100 100 100 2,000 100 100 100 100 100 1 μL injection volume. TABLE 23–14—MINIMUM REQUIREMENTS FOR INITIAL AND DAILY CALIBRATION RESPONSE FACTORS FOR ISOTOPICALLY LABELED AND NATIVE COMPOUNDS Relative response factors Analyte group Initial calibration RSD Daily and continuing calibration (percent difference) Native (Unlabeled) Analytes ........................................................................................................ Pre-sampling Adsorbent Standard(s) .......................................................................................... Pre-extraction Filter Recovery Standards ................................................................................... Pre-extraction Standards ............................................................................................................. Pre-analysis Standards ................................................................................................................ Alternative Recovery Standards .................................................................................................. 10 20 20 20 20 20 25 25 25 30 30 30 TABLE 23–15—RECOMMENDED ION TYPE AND ACCEPTABLE ION ABUNDANCE RATIOS No. of chlorine atoms Ion type 1 ......................................................................................................................... 2 ......................................................................................................................... 3 ......................................................................................................................... 4 ......................................................................................................................... 5 ......................................................................................................................... 6 ......................................................................................................................... 6 a ...................................................................................................................... 7 ......................................................................................................................... 7 b ...................................................................................................................... 8 ......................................................................................................................... 9 ......................................................................................................................... 10 ....................................................................................................................... a Used b Used only for only for Theoretical ratio M/M+2 M/M+2 M/M+2 M/M+2 M+2/M+4 M+2/M+4 M/M+2 M+2/M+4 M/M+2 M+2/M+4 M+2/M+4 M+4/M+6 3.13 1.56 1.04 0.77 1.55 1.24 0.51 1.05 0.44 0.89 0.77 1.16 Control limits Upper Lower 2.66 1.33 0.88 0.65 1.32 1.05 0.43 0.89 0.37 0.76 0.65 0.99 3.60 1.79 1.20 0.89 1.78 1.43 0.59 1.21 0.51 1.02 0.89 1.33 13C-HxCDF. 13C-HpCDF. TABLE 23–16—TYPICAL DB5–MS COLUMN CONDITIONS Analyte Column parameter lotter on DSKBCFDHB2PROD with PROPOSALS2 Injector temperature Initial oven temperature. Initial hold time (minutes). Temperature program. PCDD/PCDF PAH PCB 250 °C .................................................. 100 °C .................................................. 320 °C .................................................. 100 °C .................................................. 270 °C. 100 °C. 2 ........................................................... 2 ........................................................... 2. 100 to 190 °C at 40 °C/min, then 190 to 300 °C at 3°C/min. 100 to 300 °C at 8°C/min ..................... 100 to 150 °C at 15 °C/min, then 150 to 290 °C at 2.5 °C/min. TABLE 23–17—ASSIGNMENT OF PRE-EXTRACTION STANDARDS FOR QUANTITATION OF TARGET PCBS b BZ No. a PCB congener 2,4′-DiCB (NOAAT) ......................................................... 2,2′,5-TrCB (NOAAT) ...................................................... 2,4,4′-TrCB (NOAAT) ...................................................... 2,2′,3,5′-TeCB (NOAAT) .................................................. VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 PO 00000 13C -2,2′-DiCB .............................................................. 12 13C -2,2′,6-TrCB ........................................................... 12 13C -2,2′,6-TrCB ........................................................... 12 13C -2,2′,6,6′-TeCB ...................................................... 12 8 18 28 52 Frm 00034 Labeled analog Fmt 4701 Sfmt 4702 E:\FR\FM\14JAP2.SGM 14JAP2 BZ No. 4L 19L 19L 54L 2267 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules TABLE 23–17—ASSIGNMENT OF PRE-EXTRACTION STANDARDS FOR QUANTITATION OF TARGET PCBS b—Continued BZ No. a PCB congener 2,2′,5,5′-TeCB (NOAAT) .................................................. 2,3′,4,4′-TeCB (NOAAT) .................................................. 3,3′,4,4′-TeCB (NOAAT) (WHOT) ................................... 3,4,4′,5-TeCB (WHOT) .................................................... 2,2′,4,5,5′-PeCB (NOAAT) .............................................. 2,3,3′,4,4′-PeCB (NOAAT) (WHOT) ................................ 2,3,4,4′,5-PeCB (WHOT) ................................................. 2,3′,4,4′,5-PeCB (WHOT) ................................................ 2′,3,4,4′,5-PeCB (WHOT) ................................................ 3,3′,4,4′,5-PeCB (NOAAT) (WHOT) ................................ 2,2′,3,3′,4,4′-HxCB (NOAAT) ........................................... 2,2′,3,4,4′,5′-HxCB (NOAAT) ........................................... 2,2′,4,4′,5,5′-HxCB (NOAAT) ........................................... 2,3,3′,4,4′,5-HxCB (WHOT) ............................................. 2,3,3′,4,4′,5′-HxCB (WHOT) ............................................ 2,3′,4,4′,5,5′-HxCB (WHOT) ............................................ 3,3′,4,4′,5,5′-HxCB (NOAAT) (WHOT) ............................ 2,2′,3,3′,4,4′,5-HpCB (NOAA) .......................................... 2,2′,3,4,4′,5,5′-HpCB (NOAAT) ....................................... 2,2′,3,4′,5,5′,6-HpCB (NOAAT) ....................................... 2,3,3′,4,4′,5,5′-HpCB (WHOT) ......................................... 2,2′,3,3′,4,4′,5,6-OcCB (NOAAT) .................................... 2,2′,3,3′,4,4′,5,5′,6-NoCB (NOAAT) ................................ 2,2′,3,3′,4,4′,5,5′,6,6′-DeCB (NOAAT) ............................. Labeled analog BZ No. 13C -2,2′,6,6′-TeCB ...................................................... 12 13C -2,2′,6,6′-TeCB ...................................................... 12 13C -3,3′,4,4′-TeCB ...................................................... 12 13C -3,4,4’’,5-TeCB ....................................................... 12 13C -2,2′,4,5,5′-PeCB ................................................... 12 13C -2,3,3′,4,4′-PeCB ................................................... 12 13C -2,3,4,4′,5-PeCB .................................................... 12 13C -2,3′,4,4′,5-PeCB ................................................... 12 13C -2′,3,4,4′,5-PeCB ................................................... 12 13C -3,3′,4,4′,5-PeCB ................................................... 12 13C -2,2′,4,4′,6,6′-HxCB ............................................... 12 13C -2,2′, 4,4′,6,6′-HxCB .............................................. 12 13C -2,2′, 4,4′,6,6′-HxCB .............................................. 12 13C -2,3,3′,4,4′,5-HxCB ................................................ 12 13C -2,3,3′,4,4′,5′-HxCB ............................................... 12 13C -2,3′,4,4′,5,5′-HxCB ............................................... 12 13C -3,3′,4,4′,5,5′-HxCB ............................................... 12 13C -2,2′,3,3′,4,4′,5′-HpCB ........................................... 12 13C -2,2′,3,4,4′,5,5′-HpCB ............................................ 12 13C -2,2′,3,4′,5,6,6′-HpCB ............................................ 12 13C -2,3,3′,4,4′,5,5′-HpCB ............................................ 12 13C -2,2′ 3,3′,5,5′,6,6′-OcCB ........................................ 12 13C -2,2′,3,3′,4,4′,5,5′,6-NoCB ..................................... 12 13C -DeCB .................................................................... 12 52 66 77 81 101 105 114 118 123 126 128 138 153 156 157 167 169 170 180 187 189 195 206 209 54L 54L 77L 81L 104L 105L 114L 118L 123L 126L 155L 155L 155L 156L 157L 167L 169L 170L 180L 188L 189L 202L 206L 209L a BZ No.: Ballschmiter and Zell 1980, or IUPAC number. assume the use of the SPB-Octyl column. In the event you choose another column, you may select the labeled standard having the same number of chlorine substituents and the closest retention time to the target analyte in question as the labeled standard to use for quantitation. b Assignments TABLE 23–18—ESTIMATED METHOD DETECTION LIMITS FOR PCDDS AND PCDFS Target MDL a (ng/sample) TEQ–DL (ng/sample) Total OCDD ................................................................................................................................................. Total OCDF .................................................................................................................................................. 1,2,3,4,6,7,8-HpCDD ................................................................................................................................... 1,2,3,4,6,7,8-HpCDF .................................................................................................................................... 1,2,3,4,7,8-HxCDD ....................................................................................................................................... 1,2,3,4,7,8-HxCDF ....................................................................................................................................... 1,2,3,4,7,8,9-HpCDF .................................................................................................................................... 1,2,3,6,7,8-HxCDD ....................................................................................................................................... 1,2,3,6,7,8-HxCDF ....................................................................................................................................... 1,2,3,7,8-PeCDD .......................................................................................................................................... 1,2,3,7,8-PeCDF .......................................................................................................................................... 1,2,3,7,8,9-HxCDD ....................................................................................................................................... 1,2,3,7,8,9-HxCDF ....................................................................................................................................... 2,3,4,6,7,8-HxCDF ....................................................................................................................................... 2,3,4,7,8-PeCDF .......................................................................................................................................... 2,3,7,8-TeCDD ............................................................................................................................................. 2,3,7,8-TeCDF ............................................................................................................................................. Mean DL ............................................................................................................................................... Sum of DL ............................................................................................................................................ 1.75E–01 5.38E–02 2.36E–02 4.88E–02 9.26E–03 6.60E–02 2.46E–02 1.06E–02 7.72E–03 3.52E–02 1.46E–02 2.70E–02 6.24E–03 1.88E–02 1.29E–02 2.70E–02 1.80E–02 2.34E–02 2.90E–01 5.00E–05 1.51E–05 2.16E–04 4.82E–04 8.50E–04 6.48E–03 2.40E–04 9.86E–04 7.06E–04 3.46E–02 4.20E–04 2.60E–03 5.54E–04 1.82E–03 3.70E–03 2.68E–02 1.75E–03 5.48E–03 4.11E–02 a Detection Limits are based on a survey of laboratories MDL data from Information Collection Requests from the Industrial Boiler and Utility MACT rulemaking process. MDL assumes half of the sample was archived before concentration. lotter on DSKBCFDHB2PROD with PROPOSALS2 TABLE 23–19—TARGET DETECTION LIMITS FOR PAHS a Target MDL (ng/sample) Naphthalene ................................................................................................................................................................................... 2-Methylnaphthalene ..................................................................................................................................................................... Acenaphthylene ............................................................................................................................................................................. Acenaphthene ................................................................................................................................................................................ Fluorene ......................................................................................................................................................................................... Phenanthrene ................................................................................................................................................................................ Anthracene ..................................................................................................................................................................................... Fluoranthene .................................................................................................................................................................................. Pyrene ............................................................................................................................................................................................ Benzo[a]anthracene ....................................................................................................................................................................... 110.5 36.3 31.4 11.3 12.8 19.9 11.8 9.0 7.6 6.2 VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 PO 00000 Frm 00035 Fmt 4701 Sfmt 4702 E:\FR\FM\14JAP2.SGM 14JAP2 2268 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules TABLE 23–19—TARGET DETECTION LIMITS FOR PAHS a—Continued Target MDL (ng/sample) Chrysene ........................................................................................................................................................................................ Benzo[b]fluoranthene ..................................................................................................................................................................... Benzo[k]fluoranthene ..................................................................................................................................................................... Benzo[e]pyrene .............................................................................................................................................................................. Benzo[a]pyrene .............................................................................................................................................................................. Perylene ......................................................................................................................................................................................... Indeno[1,2,3-cd]pyrene .................................................................................................................................................................. Dibenz[a,h]anthracene ................................................................................................................................................................... Benzo[g,h,i]perylene ...................................................................................................................................................................... Mean DL ................................................................................................................................................................................. Sum of DL .............................................................................................................................................................................. 6.2 7.8 6.4 3.3 15.9 28.3 7.2 6.8 6.8 23 435 a Detection limits are based on a survey of laboratories MDL data from Information Collection Requests form the Coke Oven and Electric Power Generating unit MACT rulemaking process. TABLE 23–20—ESTIMATED METHOD DETECTION LIMITS FOR PCBS a Target BZ No. 2,4′-DiCB ................................................................................................................................................................. 2,2′,5-TrCB .............................................................................................................................................................. 2,4,4′-TrCB .............................................................................................................................................................. 2,2′,3,5′-TeCB .......................................................................................................................................................... 2,2′,5,5′-TeCB .......................................................................................................................................................... 2,3′,4,4′-TeCB .......................................................................................................................................................... 3,3′,4,4′-TeCB .......................................................................................................................................................... 3,4,4′,5-TeCB ........................................................................................................................................................... 2,2′,4,5,5′-PeCB ....................................................................................................................................................... 2,3,3′,4,4′-PeCB ....................................................................................................................................................... 2,3,4,4′,5-PeCB ....................................................................................................................................................... 2,3′,4,4′,5-PeCB ....................................................................................................................................................... 2′,3,4,4′,5-PeCB ....................................................................................................................................................... 3,3′,4,4′,5-PeCB ....................................................................................................................................................... 2,2′,3,3′,4,4′-HxCB ................................................................................................................................................... 2,2′,3,4,4′,5′-HxCB ................................................................................................................................................... 2,2′,4,4′,5,5′-HxCB ................................................................................................................................................... 2,3,3′,4,4′,5-HxCB .................................................................................................................................................... 2,3,3′,4,4′,5′-HxCB ................................................................................................................................................... 2,3′,4,4′,5,5′-HxCB ................................................................................................................................................... 3,3′,4,4′,5,5′-HxCB ................................................................................................................................................... 2,2′,3,3′,4,4′,5-HpCB ................................................................................................................................................ 2,2′,3,4,4′,5,5′-HpCB ................................................................................................................................................ 2,2′,3,4′,5,5′,6-HpCB ................................................................................................................................................ 2,3,3′,4,4′,5,5′-HpCB ................................................................................................................................................ 2,2′,3,3′,4,4′,5,6-OcCB ............................................................................................................................................. 2,2′,3,3′,4,4′,5,5′,6-NoCB ......................................................................................................................................... 2,2′,3,3′,4,4′,5,5′,6,6′-DeCB ..................................................................................................................................... Mean DL ........................................................................................................................................................... Sum of DL ........................................................................................................................................................ 8 18 28 44 52 66 77 81 101 105 114 118 123 126 128 138 153 156 157 167 169 170 180 187 189 195 206 209 ........................ ........................ a Detection lotter on DSKBCFDHB2PROD with PROPOSALS2 30 32 44 80 30 34 28 36 94 34 30 60 34 32 58 72 60 46 46 26 30 24 60 34 26 44 32 32 42 1,188 Limits are based on information from EPA Method 1668C, assuming half of the sample extract is archived before concentration. BILLING CODE 6560–50–P VerDate Sep<11>2014 Target detection limit (pg/sample) 19:55 Jan 13, 2020 Jkt 250001 PO 00000 Frm 00036 Fmt 4701 Sfmt 4702 E:\FR\FM\14JAP2.SGM 14JAP2 2269 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules stack Wall tl Thelmocouple / Thetmocouple Thermocouple Healedl:IOX I ype S Pillot TUbe Manometer Reci1tulalioo Pump Va:uum Une ( D!}'_~ ) ~ VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 PO 00000 Frm 00037 Fmt 4701 Sfmt 4725 E:\FR\FM\14JAP2.SGM 14JAP2 EP14JA20.011</GPH> lotter on DSKBCFDHB2PROD with PROPOSALS2 F.1gure 23 - 1• Method 23 Sampling Train 2270 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules Silanized Glass Wool •~---Water Jacket ~---coarse Glass Frit VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 PO 00000 Frm 00038 Fmt 4701 Sfmt 4725 E:\FR\FM\14JAP2.SGM 14JAP2 EP14JA20.012</GPH> lotter on DSKBCFDHB2PROD with PROPOSALS2 Figure 23-2. Condenser and Adsorbent Module Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules 2271 VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 PO 00000 Frm 00039 Fmt 4701 Sfmt 4725 E:\FR\FM\14JAP2.SGM 14JAP2 EP14JA20.013</GPH> lotter on DSKBCFDHB2PROD with PROPOSALS2 Figure 23-3. So:xhlet/Dean-Stark Extractor 2272 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules Particulate Matter Filter Container 1 Nozzle, Probe, Cyclone (if used) Front.Back Half Filter Holder and support, rinses Container 2 I '' Concentrate Adsorbent Module, Module Rinses PAH and PCB only lmpinger Water and Rinses Container 3 ,. I Spike Filter with Filter Pre-extraction lsotopically-Labeled Analogs Extract with Toluene ' I Combine in Extraction Thimble I • Spike with Pre-extraction lsotopically-Labeled Analogs ' ' Soxhlet Extraction Toluene I Concentrate , ' -- I Aliquots for Analysis and Archive , I Clean up Archive BILLING CODE 6560–50–P VerDate Sep<11>2014 21:27 Jan 13, 2020 Jkt 250001 PO 00000 Frm 00040 Fmt 4701 Sfmt 4702 E:\FR\FM\14JAP2.SGM 14JAP2 EP14JA20.014</GPH> lotter on DSKBCFDHB2PROD with PROPOSALS2 Figure 23-4. Sample Preparation Flow Chart Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules 2273 Appendix A to Method 23 COMPLETE LIST OF 209 PCB CONGENERS AND THEIR ISOMERS WITH CORRESPONDING ISOTOPE DILUTION QUANTITATION STANDARDS a BZ b No. Pre-extraction standard BZ b No. Unlabeled target analyte BZ b No. Pre-extraction standard MoCBs 13C 12-2-MoCB 13C 12-2-MoCB 13C .................... .................... -4-MoCB .................... 12 1L 1L 3L BZ b No. Unlabeled target analyte DiCBs 2-MoCB .............................. 3-MoCB .............................. 4-MoCB .............................. 1 2 3 13C 12-2,2′-DiCB 13C 12-2,2′-DiCB 13C 12-2,2′-DiCB 13C -2,2′-DiCB 12 13C -2,2′-DiCB 12 13C -2,2′-DiCB 12 13C -2,2′-DiCB 12 13C -2,2′-DiCB 12 13C -2,2′-DiCB 12 13C -2,2′-DiCB 12 13C -2,2′-DiCB 12 13C -4,4′-DiCB 12 ................. ................. ................. ................. ................. ................. ................. ................. ................. ................. ................. ................. 4L 4L 4L 4L 4L 4L 4L 4L 4L 4L 4L 15L 2,2′-DiCB ........................... 2,3-DiCB ............................ 2,3′-DiCB ........................... 2,4-DiCB ............................ 2,4′-DiCB ........................... 2,5-DiCB ............................ 2,6-DiCB ............................ 3,3′-DiCB ........................... 3,4-DiCB ............................ 3,4′-DiCB ........................... 3,5-DiCB ............................ 4,4′-DiCB ........................... 4 5 6 7 8 9 10 11 12 13 14 15 19L 19L 19L 19L 19L 19L 19L 19L 19L 37L 37L 37L 2,4,4′-TrCB ........................ 2,4,5-TrCB ......................... 2,4,6-TrCB ......................... 2,4′,5-TrCB ........................ 2,4′,6-TrCB ........................ 2′,3,4-TrCB ........................ 2′,3,5-TrCB ........................ 3,3′,4-TrCB ........................ 3,3′,5-TrCB ........................ 3,4,4′-TrCB ........................ 3,4,5-TrCB ......................... 3,4′,5-TrCB ........................ 28 29 30 31 32 33 34 35 36 37 38 39 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 77L 77L 77L 77L 81L 2,3,4,5-TeCB ..................... 2,3,4,6-TeCB ..................... 2,3,4′,5-TeCB .................... 2,3,4′,6-TeCB .................... 2,3,5,6-TeCB ..................... 2,3′,4,4′-TeCB .................... 2,3′,4,5-TeCB .................... 2,3′,4,5′-TeCB .................... 2,3′,4,6-TeCB .................... 2,3′,4′,5-TeCB .................... 2,3′,4′,6-TeCB .................... 2,3′,5,5′-TeCB .................... 2,3′,5′,6-TeCB .................... 2,4,4′,5-TeCB .................... 2,4,4′,6-TeCB .................... 2′,3,4,5-TeCB .................... 3,3′,4,4′-TeCB .................... 3,3′,4,5-TeCB .................... 3,3′,4,5′-TeCB .................... 3,3′,5,5′-TeCB .................... 3,4,4′,5-TeCB .................... 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 105L 105L 105L 105L 105L 105L 105L 105L 105L 114L 114L 114L 114L 118L 118L 118L 118L 118L 123L 123L 123L 126L 126L 2,3,3′,4,4′-PeCB ................ 2,3,3′,4,5-PeCB ................. 2,3,3′,4′,5-PeCB ................ 2,3,3′,4,5′-PeCB ................ 2,3,3′,4,6-PeCB ................. 2,3,3′,4′,6-PeCB ................ 2,3,3′,5,5′-PeCB ................ 2,3,3′,5,6-PeCB ................. 2,3,3′,5′,6-PeCB ................ 2,3,4,4′,5-PeCB ................. 2,3,4,4′,6-PeCB ................. 2,3,4,5,6-PeCB .................. 2,3,4′,5,6-PeCB ................. 2,3′,4,4′,5-PeCB ................ 2,3′,4,4′,6-PeCB ................ 2,3′,4,5,5′-PeCB ................ 2,3′,4,5,′6-PeCB ................ 2′,3,3′,4,5-PeCB ................ 2′,3,4,4′,5-PeCB ................ 2′,3,4,5,5′-PeCB ................ 2′,3,4,5,6′-PeCB ................ 3,3′,4,4′,5-PeCB ................ 3,3′,4,5,5′-PeCB ................ 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 TrCBs 13C 12-2,2′,6-TrCB 13C 12-2,2′,6-TrCB 13C 12-2,2′,6-TrCB 13C 12-2,2′,6-TrCB 13C 12-2,2′,6-TrCB 13C 12-2,2′,6-TrCB 13C 12-2,2′,6-TrCB 13C 12-2,2′,6-TrCB 13C 12-2,2′,6-TrCB 13C 12-2,2′,6-TrCB 13C 12-2,2′,6-TrCB 13C 12-2,2′,6-TrCB ............... ............... ............... ............... ............... ............... ............... ............... ............... ............... ............... ............... 19L 19L 19L 19L 19L 19L 19L 19L 19L 19L 19L 19L 2,2′,3-TrCBTrCB ................ 2,2′,4-TrCB ........................ 2,2′,5-TrCB ........................ 2,2′,6-TrCB ........................ 2,3,3′-TrCB ........................ 2,3,4-TrCB ......................... 2,3,4′-TrCB ........................ 2,3,5- TrCB ........................ 2,3,6- TrCB ........................ 2,3′,4-TrCB ........................ 2,3′,5-TrCB ........................ 2,3′,6-TrCB ........................ 16 17 18 19 20 21 22 23 23 25 26 27 13C 12-3,4,4′-TrCB 13C 12-3,4,4′-TrCB .............. .............. 12-3,4,4′-TrCB .............. 13C -3,4,4′-TrCB .............. 12 13C -3,4,4′-TrCB .............. 12 13C -3,4,4′-TrCB .............. 12 13C -3,4,4′-TrCB .............. 12 13C -3,4,4′-TrCB .............. 12 13C -3,4,4′-TrCB .............. 12 13C -3,4′,4′-TrCB ............. 12 13C -3,4′,4′-TrCB ............. 12 13C -3,4′,4′-TrCB ............. 12 13C TeCBs 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C -2,2′,6,6′-TeCB 12 13C -2,2′,6,6′-TeCB 12 13C -2,2′,6,6′-TeCB 12 13C -2,2′,6,6′-TeCB 12 13C -2,2′,6,6′-TeCB 12 13C -2,2′,6,6′-TeCB 12 13C -2,2′,6,6′-TeCB 12 13C -2,2′,6,6′-TeCB 12 13C -2,2′,6,6′-TeCB 12 13C -2,2′,6,6′-TeCB 12 13C -2,2′,6,6′-TeCB 12 13C -2,2′,6,6′-TeCB 12 13C -2,2′,6,6′-TeCB 12 13C -2,2′,6,6′-TeCB 12 13C -2,2′,6,6′-TeCB 12 13C -2,2′,6,6′-TeCB 12 .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 54L 2,2′,3,3′-TeCB 2,2′,3,4-TeCB 2,2′,3,4′-TeCB 2,2′,3,5-TeCB 2,2′,3,5′-TeCB 2,2′,3,6-TeCB 2,2′,3,6′-TeCB 2,2′,4,4′-TeCB 2,2′,4,5-TeCB 2,2′,4,5′-TeCB 2,2′,4,6-TeCB 2,2′,4,6′-TeCB 2,2′,5,5′-TeCB 2,2′,5,6′-TeCB 2,2′,6,6′-TeCB 2,3,3′,4′-TeCB 2,3,3′,4′-TeCB 2,3,3′,5-TeCB 2,3,3′,5′-TeCB 2,3,3′,6-TeCB 2,3,4,4′-TeCB .................... .................... .................... .................... .................... .................... .................... .................... .................... .................... .................... .................... .................... .................... .................... .................... .................... .................... .................... .................... .................... 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C 12-2,2′,6,6′-TeCB 13C 12-3,3′,4,4′-TeCB 13C 12-3,3′,4,4′-TeCB 13C 12-3,3′,4,4′-TeCB 13C 12-3,3′,4,4′-TeCB 13C 12-3,4,4′,5-TeCB .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... lotter on DSKBCFDHB2PROD with PROPOSALS2 PeCBs 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB 13C 12-2,2′,4,6,6′-PeCB VerDate Sep<11>2014 ....... ....... ....... ....... ....... ....... ....... ....... ....... ....... ....... ....... ....... ....... ....... ....... ....... ....... ....... ....... ....... ....... ....... 104L 104L 104L 104L 104L 104L 104L 104L 104L 104L 104L 104L 104L 104L 104L 104L 104L 104L 104L 104L 104L 104L 104L 21:27 Jan 13, 2020 2,2′,3,3′,4-PeCB ................ 2,2′,3,3′,5-PeCB ................ 2,2′,3,3′,6-PeCB ................ 2,2′,3,4,4′-PeCB ................ 2,2′,3,4,5-PeCB ................. 2,2′,3,4,5′-PeCB ................ 2,2′,3,4,6-PeCB ................. 2,2′,3,4,6′-PeCB ................ 2,2′,3,4′,5-PeCB ................ 2,2′,3,4′,6-PeCB ................ 2,2′,3,5,5′-PeCB ................ 2,2′,3,5,6-PeCB ................. 2,2′,3,5,6′-PeCB ................ 2,2′,3,5′,6-PeCB ................ 2,2′,3,6,6′-PeCB ................ 2,2′,3′,4,5-PeCB ................ 2,2′,3′,4,6-PeCB ................ 2,2′,4,4′,5-PeCB ................ 2,2′,4,4′,6-PeCB ................ 2,2′,4,5,5′-PeCB ................ 2,2′,4,5,6′-PeCB ................ 2,2′,4,5,′6-PeCB ................ 2,2′,4,6,6′-PeCB ................ Jkt 250001 PO 00000 Frm 00041 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 Fmt 4701 13C 12-2,3,3′,4,4′-PeCB 13C 12-2,3,3′,4,4′-PeCB ...... ...... 12-2,3,3′,4,4′-PeCB ...... 13C -2,3,3′,4,4′-PeCB ...... 12 13C -2,3,3′,4,4′-PeCB ...... 12 13C -2,3,3′,4,4′-PeCB ...... 12 13C -2,3,3′,4,4′-PeCB ...... 12 13C -2,3,3′,4,4′-PeCB ...... 12 13C -2,3,3′,4,4′-PeCB ...... 12 13C -2,3,4,4′,5-PeCB ....... 12 13C -2,3,4,4′,5-PeCB ....... 12 13C -2,3,4,4′,5-PeCB ....... 12 13C -2,3,4,4′,5-PeCB ....... 12 13C -2,3′,4,4′,5-PeCB ...... 12 13C -2,3′,4,4′,5-PeCB ...... 12 13C -2,3′,4,4′,5-PeCB ...... 12 13C -2,3′,4,4′,5-PeCB ...... 12 13C -2,3′,4,4′,5-PeCB ...... 12 13C -2′,3,4,4′,5-PeCB ...... 12 13C -2′,3,4,4′,5-PeCB ...... 12 13C -2′,3,4,4′,5-PeCB ...... 12 13C -3,3′,4,4′,5-PeCB ...... 12 13C -3,3′,4,4′,5-PeCB ...... 12 13C Sfmt 4702 E:\FR\FM\14JAP2.SGM 14JAP2 2274 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules COMPLETE LIST OF 209 PCB CONGENERS AND THEIR ISOMERS WITH CORRESPONDING ISOTOPE DILUTION QUANTITATION STANDARDS a—Continued BZ b No. Pre-extraction standard Unlabeled target analyte BZ b No. BZ b No. Pre-extraction standard Unlabeled target analyte BZ b No. HxCBs 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... 155L 155L 155L 155L 155L 155L 155L 155L 155L 155L 155L 155L 155L 155L 155L 155L 155L 155L 155L 155L 155L 2,2′,3,3′,4,4′-HxCB ............ 2,2′,3,3′,4,5-HxCB ............. 2,2′,3,3′,4,5′-HxCB ............ 2,2′,3,3′,4,6-HxCB ............. 2,2′,3,3′,4,6′-HxCB ............ 2,2′,3,3′,5,5′-HxCB ............ 2,2′,3,3′,5,6-HxCB ............. 2,2′,3,3′,5,6′-HxCB ............ 2,2′,3,3′,6,6′-HxCB ............ 2,2′,3,4,4′,5-HxCB ............. 2,2′,3,4,4′,5′-HxCB ............ 2,2′,3,4,4′,6-HxCB ............. 2,2′,3,4,4′,6′-HxCB ............ 2,2′,3,4,5,5′-HxCB ............. 2,2′,3,4,5,6-HxCB .............. 2,2′,3,4,5,6′-HxCB ............. 2,2′,3,4,5′,6-HxCB ............. 2,2′,3,4,6,6′-HxCB ............. 2,2′,3,4′,5,5′-HxCB ............ 2,2′,3,4′,5,6-HxCB ............. 2,2′,3,4′,5,6′-HxCB ............ 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,2′,4,4′,6,6′-HxCB 13C 12-2,3,3′,4,4′,5- 13C 12-2,3,3′,4,4′,5′-HxCB 13C 12-2,3,3′,4,4′,5′-HxCB 13C 12-2,3,3′,4,4′,5′-HxCB 13C 12-2,3,3′,4,4′,5′-HxCB 13C 12-2,3,3′,4,4′,5′-HxCB 13C 12-2,3,3′,4,4′,5′-HxCB 13C 12-2,3,3′,4,4′,5′-HxCB 13C 12-2,3,3′,4,4′,5′-HxCB 13C 12-2,3,3′,4,4′,5′-HxCB 13C 12-2,3,3′,4,4′,5′-HxCB 13C 12-2,3′,4,4′,5,5′-HxCB 13C 12-2,3′,4,4′,5,5′-HxCB 13C 12-3,3′,4,4′,5,5′-HxCB HxCB .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. 155L 155L 155L 155L 155L 155L 155L 156L 157L 157L 157L 157L 157L 157L 157L 157L 157L 157L 167L 167L 169L 2,2′,3,4′,5′,6-HxCB ............ 2,2′,3,4′,6,6′-HxCB ............ 2,2′,3,5,5′,6-HxCB ............. 2,2′,3,5,6,6′-HxCB ............. 2,2′,4,4′,5,5′-HxCB ............ 2,2′,4,4′,5′,6-HxCB ............ 2,2′,4,4′,6,6′-HxCB ............ 2,3,3′,4,4′,5-HxCB ............. 2,3,3′,4,4′,5′-HxCB ............ 2,3,3′,4,4′,6-HxCB ............. 2,3,3′,4,5,5′-HxCB ............. 2,3,3′,4,5,6-HxCB .............. 2,3,3′,4,5′,6-HxCB ............. 2,3,3′,4′,5,5′-HxCB ............ 2,3,3′,4′,5,6-HxCB ............. 2,3,3′,4′,5′,6-HxCB ............ 2,3,3′,5,5′,6-HxCB ............. 2,3,4,4′,5,6-HxCB .............. 2,3′,4,4′,5,5′-HxCB ............ 2,3′,4,4′,5′,6-HxCB ............ 3,3′,4,4′,5,5′-HxCB ............ 149 150 151 152 153 154 155 156 157 158 158 160 161 162 163 164 165 166 167 168 169 188L 188L 188L 188L 188L 188L 188L 189L 189L 189L 189L 189L 2,2′,3,4,4′,5,6′-HpCB ......... 2,2′,3,4,4′,5′,6-HpCB ......... 2,2′,3,4,4′,5′,6-HpCB ......... 2,2′,3,4,4′,6,6′-HpCB ......... 2,2′,3,4,5,5′,6-HpCB .......... 2,2′,3,4′,5,5′,6-HpCB ......... 2,2′,3,4′,5,6,6′-HpCB ......... 2,3,3′,4,4′,5,5′-HpCB ......... 2,3,3′,4,4′,5,6-HpCB .......... 2,3,3′,4,4′,5′,6-HpCB ......... 2,3,3′,4,5,5′,6-HpCB .......... 2,3,3′,4′,5,5′,6-HpCB ......... 182 183 184 185 186 187 188 189 190 191 192 193 HpCBs 13C 12-2,2′,3,4′,5,6,6′-HpCB 13C 12-2,2′,3,4′,5,6,6′-HpCB 13C 12-2,2′,3,4′,5,6,6′-HpCB 13C 12-2,2′,3,4′,5,6,6′-HpCB 13C 12-2,2′,3,4′,5,6,6′-HpCB 13C 12-2,2′,3,4′,5,6,6′-HpCB 13C 12-2,2′,3,4′,5,6,6′-HpCB 13C 12-2,2′,3,4′,5,6,6′-HpCB 13C 12-2,2′,3,4′,5,6,6′-HpCB 13C 12-2,2′,3,4′,5,6,6′-HpCB 13C 12-2,2′,3,4′,5,6,6′-HpCB 13C 12-2,2′,3,4′,5,6,6′-HpCB 188L 188L 188L 188L 188L 188L 188L 188L 188L 188L 188L 188L 2,2′,3,3′,4,4′,5-HpCB ......... 2,2′,3,3′,4,4′,6-HpCB ......... 2,2′,3,3′,4,5,5′-HpCB ......... 2,2′,3,3′,4,5,6-HpCB .......... 2,2′,3,3′,4,5,6′-HpCB ......... 2,2′,3,3′,4,5′,6-HpCB ......... 2,2′,3,3′,4,6,6′-HpCB ......... 2,2′,3,3′,4′,5,6-HpCB ......... 2,2′,3,3′,5,5′,6-HpCB ......... 2,2′,3,3′,5,6,6′-HpCB ......... 2,2′,3,4,4′,5,5′-HpCB ......... 2,2′,3,4,4′,5,6-HpCB .......... 170 171 172 173 174 175 176 177 178 179 180 181 13C 12-2,2′,3,4′,5,6,6′-HpCB 13C 12-2,2′,3,4′,5,6,6′-HpCB 13C 12-2,2′,3,4′,5,6,6′-HpCB 13C 12-2,2′,3,4′,5,6,6′-HpCB 13C 12-2,2′,3,4′,5,6,6′-HpCB 13C 12-2,2′,3,4′,5,6,6′-HpCB 13C 12-2,2′,3,4′,5,6,6′-HpCB 13C 12-2,3,3′,4,4′,5,5′-HpCB 13C 12-2,3,3′,4,4′,5,5′-HpCB 13C 12-2,3,3′,4,4′,5,5′-HpCB 13C 12-2,3,3′,4,4′,5,5′-HpCB 13C 12-2,3,3′,4,4′,5,5′-HpCB OcCBs 13C 12-2,2′,3,3′,5,5′,6,6′OcCB. 13C -2,2′,3,3′,5,5′,6,6′12 OcCB. 13C -2,2′,3,3′,5,5′,6,6′12 OcCB. 202L 2,2′,3,3′,4,4′,5,5′-OcCB ..... 194 202L 2,2′,3,3′,4,4′,5,6-OcCB ...... 195 202L 2,2′,3,3′,4,4′,5,6′-OcCB ..... 196 13C 202L 2,2′,3,3′,4,4′,6,6′-OcCB ..... 197 13C 202L 2,2′,3,3′,4,5,5′,6-OcCB ...... 198 202L 2,2′,3,3′,4,5,5′,6′-OcCB ..... 199 202L 2,2′,3,3′,4,5,6,6′-OcCB ...... 200 202L 2,2′,3,3′,4,5′,6,6′-OcCB ..... 201 202L 2,2′,3,3′,5,5′,6,6′-OcCB ..... 202 205L 2,2′,3,4,4′,5,5′,6-OcCB ...... 203 205L 2,2′,3,4,4′,5,6,6′-OcCB ...... 204 205L 2,3,3′,4,4′,5,5′,6-OcCB ...... 205 12-2,2′,3,3′,5,5′,6,6′OcCB. lotter on DSKBCFDHB2PROD with PROPOSALS2 NoCBs 12-2,2′,3,3′,5,5′,6,6′OcCB. 13C -2,2′,3,3′,5,5′,6,6′12 OcCB. 13C -2,2′,3,3′,5,5′,6,6′12 OcCB. 13C -2,2′,3,3′,5,5′,6,6′12 OcCB. 13C -2,2′,3,3′,5,5′,6,6′12 OcCB. 13C -2,3′,3′,4,4′,5,5′,612 OcCB. 13C -2,3′,3′,4,4′,5,5′,612 OcCB. 13C -2,3′,3′,4,4′,5,5′,612 OcCB. 13C 12-2,2′,3,3′,4,4′,5,5′,6NoCB. 13C -2,2′,3,3′,4,4′,5,5′,612 NoCB. 13C -2,2′,3,3′,4,5,5′,6,6′12 NoCB. 206L 2,2′,3,3′,4,4′,5,5′,6-NoCB .. 206 206L 2,2′,3,3′,4,4′,5,6,6′-NoCB .. 207 208L 2,2′,3,3′,4,5,5′,6,6′- NoCB 208 DeCB 13C 12-DeCB ....................... 209L 2,2′,3,3′,4,4′,5,5′,6,6′-DeCB 209 a Assignments assume the use of the SPB-Octyl column. In the event you choose another column, you may select the labeled standard having the same number of chlorine substituents and the closest retention time to the target analyte in question as the labeled standard to use for quantitation. b BZ No.: Ballschmiter and Zell 1980, also referred to as IUPAC number. VerDate Sep<11>2014 21:27 Jan 13, 2020 Jkt 250001 PO 00000 Frm 00042 Fmt 4701 Sfmt 4702 E:\FR\FM\14JAP2.SGM 14JAP2 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules Appendix B to Method 23 Preparation of XAD–2 Adsorbent Resin 1.0 Scope and Application XAD–2® resin, as supplied by the original manufacturer, is impregnated with a bicarbonate solution to inhibit microbial growth during storage. Remove both the salt solution and any residual extractable chemicals used in the polymerization process before use. Prepare the resin by a series of water and organic extractions, followed by careful drying. 2.0 Extraction 2.1 You may perform the extraction using a Soxhlet extractor or other apparatus that generates resin meeting the requirements in Section 13.14 of Method 23. Use an all-glass thimble containing an extra-coarse frit for extraction of the resin. The frit is recessed 10–15 mm above a crenellated ring at the bottom of the thimble to facilitate drainage. Because the resin floats on methylene chloride, carefully retain the resin in the extractor cup with a glass wool plug and stainless-steel screen. This process involves sequential extraction with the following recommended solvents in the listed order. • Water initial rinse: Place resin in a suitable container, soak for approximately 5 min with Type II water, remove fine floating resin particles and discard the water. Fill with Type II water a second time, let stand overnight, remove fine floating resin particles and discard the water. • Hot water: Extract with water for 8 hr. • Methyl alcohol: Extract for 22 hr. • Methylene chloride: Extract for 22 hr. • Toluene: Extract for 22 hr. • Toluene (fresh): Extract for 22 hr. lotter on DSKBCFDHB2PROD with PROPOSALS2 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 VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 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 °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 PO 00000 Frm 00043 Fmt 4701 Sfmt 4702 2275 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 mg/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-ml 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 °C. • Detector: Flame ionization detector or an MS installed on a GC able to separate methylene chloride and toluene. • Oven Temperature Profile: Typically, 30 °C for 4 min; programmed to rise at 20 °C/min until the oven reaches 250 °C; return to 30 °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 ml/mL (22 ml/100 mL) of methylene chloride. This concentration corresponds to maximum acceptable toluene concentration in the dry adsorbent of 1,000 mg/g of adsorbent. If the adsorbent exceeds this level, continue drying until the excess toluene is removed. BILLING CODE 6560–50–P E:\FR\FM\14JAP2.SGM 14JAP2 2276 Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules Gas take off Ni-S■n C\'liM■r Ll....ld 1110 .II H■a1Sourc■ BILLING CODE 6560–50–C 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. * * * * * ■ 8. In § 63.1208, revise paragraph (b)(1) to read as follows: PART 63—NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS FOR SOURCE CATEGORIES 6. The authority citation for part 63 continues to read as follows: ■ Authority: 42 U.S.C. 7401 et seq. 7. In § 63.849, revise paragraphs (a)(13) and (a)(14) to read as follows: lotter on DSKBCFDHB2PROD with PROPOSALS2 ■ § 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) VerDate Sep<11>2014 19:55 Jan 13, 2020 Jkt 250001 § 63.1208 What are the test methods? * * * * * (b) * * * (1) Dioxins and furans. (i) To determine compliance with the PO 00000 Frm 00044 Fmt 4701 Sfmt 4702 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 § 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. * * * * * ■ 9. In § 63.1625, revise paragraph (b)(10) to read as follows: E:\FR\FM\14JAP2.SGM 14JAP2 EP14JA20.015</GPH> Figure A-1. XAD-2 fluidized-bed drying apparatus Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / Proposed Rules § 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. * * * * * ■ 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 * * * lotter on DSKBCFDHB2PROD with PROPOSALS2 * * * 6. Measuring the PAH emissions. VerDate Sep<11>2014 19:55 Jan 13, 2020 You must use * * * * * EPA test method 23. Jkt 250001 * * * * * PART 266—STANDARDS FOR THE MANAGEMENT OF SPECIFIC HAZARDOUS WASTES AND SPECIFIC TYPES OF HAZARDOUS WASTE MANAGEMENT FACILITIES 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. 12. In § 266.104, revise paragraph (e)(1) to read as follows: ■ § 266.104 Standards to control organic emissions. * * * * * (e) * * * (1) During the trial burn (for new facilities or an interim status facility PO 00000 Frm 00045 Fmt 4701 Sfmt 9990 2277 applying for a permit) or compliance test (for interim status facilities), determine emission rates of the tetraocta congeners of chlorinated dibenzop-dioxins and dibenzofurans (CDDs/ CDFs) using Method 0023A, Sampling Method for Polychlorinated Dibenzo-pDioxins and Polychlorinated Dibenzofurans Emissions from Stationary Sources, EPA Publication SW–826, as incorporated by reference in § 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 E:\FR\FM\14JAP2.SGM 14JAP2

Agencies

ENVIRONMENTAL PROTECTION AGENCY

[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 II





Environmental Protection Agency





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40 CFR Parts 60, 63, and 266





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

Federal Register / Vol. 85, No. 9 / Tuesday, January 14, 2020 / 
Proposed Rules

[[Page 2234]]


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

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

[[Page 2235]]

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

[[Page 2237]]

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

[[Page 2239]]

 
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 < 20 [deg]C (68 [deg]F).
    6.1.9 Adsorbent Module. Use a water-jacketed glass container to 
hold up to 40 grams (g) of the solid adsorbent. Figure 23-2 of this 
method shows a schematic diagram of the adsorbent module. Other 
physical configurations of the adsorbent resin module/condenser 
assembly are acceptable if the configuration contains the requisite 
amount of solid adsorbent and maintains the minimum length-to-width 
adsorbent bed ratio of two-to-one. Orient the adsorbent module 
vertically to facilitate condensate drainage. The connecting fittings 
must form leak-free, vacuum-tight seals. Include a coarse glass frit in 
the adsorbent module to retain the adsorbent.
    6.1.10 Impingers. Use five impingers connected in series with leak-
free ground glass fittings or any similar leak-free noncontaminating 
fittings. The first impinger must be a short-stem stem (water-dropout) 
design or equivalent. The second, fourth, and fifth impingers must be 
of the Greenburg-Smith design, modified by replacing the tip with a 1.3 
cm (1-2 in.) inside diameter (ID) glass tube extending to approximately 
1.3 cm (1-2 in.) from the bottom of the flask. The third impinger must 
be of the Greenburg-Smith design with the standard tip. The second and 
third impingers must contain known quantities of water, and the fifth 
impinger must contain a known weight of silica gel or equivalent 
desiccant. Alternatively, you may omit the first impinger if you do not 
expect excess moisture in the sample gas.
    6.2 Sample Recovery Equipment.
    6.2.1 Fitting Caps. Use leak-free ground glass fittings or any 
similar leak-free non-contaminating fitting to cap the sections of the 
sampling train exposed to the sample gas. Alternatively, use PTFE tape 
or contaminant-free aluminum foil for this purpose (see Section 6.2.6 
of this method).
    6.2.2 Wash Bottles. Use PTFE bottles.
    6.2.3 Probe-Liner, Probe-Nozzle, and Filter-Holder Brushes. Use 
inert bristle brushes with precleaned stainless steel or PTFE handles. 
Extensions of the probe brush must be made of stainless steel or PTFE 
and be at least as long as the probe. Use brushes that are properly 
sized and shaped to remove accumulated material from the nozzle and 
probe liner if used.
    6.2.4 Filter Storage Container. Use a sealed filter holder, wide-
mouth amber glass jar with PTFE-lined cap, or glass petri dish sealed 
with PTFE tape. Purchase precleaned amber glass jars and petri dishes 
or clean according to the glassware cleaning procedures listed in 
Section 8.1.1.1 of this method.
    6.2.5 Field Balance. Use a weighing device capable of measurements 
to an accuracy of 0.5g.
    6.2.6 Aluminum Foil. Use heavy duty aluminum foil cleaned by 
rinsing three times with hexane or toluene and stored in a pre-cleaned 
glass petri dish or glass jar. Do not use aluminum foil to wrap or 
contact filter samples due to the possibility of reaction between the 
sample and the aluminum.
    6.2.7 Adsorbent Storage Containers. Use an air-tight container to 
store silica gel.
    6.2.8 Glass Sample Storage Containers. Recover samples in amber 
glass bottles, 500- or 1000-milliliters (mL) with leak-free PTFE-lined 
caps. Either purchase precleaned bottles or clean containers according 
to glassware cleaning procedures listed in Section 8.1.1.1 of this 
method.
    6.3 Sample Extraction Equipment.
    6.3.1 Sample Containers. Use 125- and 250-mL amber glass bottles 
with PTFE-lined caps.
    6.3.2 Test Tubes. Use glass test tubes or small (e.g., 5 to 10 mL) 
amber vials.
    6.3.3 Soxhlet/Dean-Stark Extraction Apparatus.
    6.3.3.1 Soxhlet Apparatus. Use 200-mL capacity capable of holding 
43 x 123-millimeter (mm) extraction thimbles, with receiving flask 
(typically round-bottom).
    6.3.3.2 Moisture Trap. Use Dean-Stark or Barret with fluoropolymer 
stopcock trap to fit between the Soxhlet extractor body and the 
condenser as shown in Figure 23-3 of this method. Note: Dean-Stark or 
Barret traps are used to remove water with extraction solvents that are 
less dense and insoluble in water.
    6.3.3.3 Extraction Thimble. Use quartz, glass, or glass fiber 
thimble, typically 43 x 123 mm to fit Soxhlet apparatus.
    6.3.3.4 Heating Mantle. Use a hemispherical shaped heating mantle 
to fit round-bottom flask.
    6.3.4 Kuderna-Danish Concentrator. Use an apparatus consisting of a 
three-ball Snyder column, a flask with leak-free joint to accept the 
three-ball Snyder column at the top, a leak-free joint to receive a 
graduated concentration tube at the bottom and a heating mantle.
    6.3.5 Nitrogen Evaporative Concentrator. Use a nitrogen evaporative 
concentrator equipped with a water bath with the temperature controlled 
in the range of 30 to 60 [deg]C (86 to 140 [deg]F) (N-Evap Organomation 
Associates, Inc., South Berlin, MA, or equivalent).
    6.3.6 Separatory Funnels. Use glass or PTFE 2-liter separatory 
funnels.
    6.4 Glass Liquid Chromatography Columns.
    6.4.1 Pasteur Pipettes. Use disposable pipettes, or glass 
serological pipettes typically 150 mm long x 6 mm ID.
    6.4.2 Chromatography Columns. 200 to 300 mm long x 20 mm ID with 
250-mL reservoir.
    6.5 Analytical Equipment.
    6.5.1 Gas Chromatograph. Use a gas chromatograph consisting of the 
following components:
    6.5.1.1 Oven. Use an oven capable of maintaining the separation 
column at the proper operating temperature  1.0 [deg]C (1.8 
[deg]F) and performing programmed increases in temperature at rates of 
at least 20 [deg]C/min with isothermal hold.
    6.5.1.2 Temperature Monitor. Use a temperature monitor to measure 
column oven temperature to  1.0 [deg]C (1.8 [deg]F).
    6.5.1.3 Flow System. Use an electronic pressure control or 
equivalent gas metering system to control carrier gas flow or pressure.
    6.5.1.4 Use a split/splitless injection port in the splitless mode 
or on-column injection port for the capillary column.
    6.5.2 Capillary Gas Chromatography Columns. Use different columns 
for the analysis of the different target compound classes in this 
method, if needed. Perform the resolution checks in Sections 10.2.3.4 
and 10.2.3.5 of this method to document the required resolution. 
Compound separation must meet the resolution specifications in Section 
10.2.3.4 of this method and the identification specifications found in 
Section 11.4.3.4 of this method.
    6.5.2.1 Recommended column systems for measuring PCDDs/PCDFs should 
be capable of achieving separation of the 17 PCDD/PCDF target compounds 
from the nearest eluting congener with no more than 10 percent peak 
overlap. The system must meet the performance specifications for 
compound separation and quantitation in calibration, performance check, 
and isotopically labeled standards added to field samples. Use a 
variety of bonded-phase capillary gas chromatography columns to meet 
these requirements, if needed.


[[Page 2248]]


    Note:  Fishman, et al. (see Section 16.3 of this method) 
demonstrated that all TEF isomers can be fully differentiated from 
closely eluting isomers using either of two sets of non-polar and 
polar stationary phase combinations. One set consisted of 5-percent 
phenyl methylpolysiloxane (DB-5, HP-5MS, Rtx-5MS, Equity-5) and 50-
percent cyanopropylmethyl, 50-percent phenylmethylsiloxane (DB-225, 
SP 2331) GC columns and the other set consisted of 5-percent phenyl, 
94-percent methyl, 1-percent vinyl silicone bonded-phase (DB-5MS, 
ZB-5MS, VF-5MS, CP-Sil 8 CB LowBleed/MS) with 50-percent 
cyanopropylmethyl, 50-percent phenylmethylsiloxane (SP-2331).

    6.5.2.2 Use column systems for measuring PAHs that can achieve 
separation of anthracene and phenanthrene at m/z 178 such that the 
valley between the peaks does not exceed 50 percent of the taller of 
the two peaks, and benzo[b]fluoranthene and benzo[k]fluoranthene such 
that the valley between the peaks is less than 60 percent of the height 
of the taller peak. These requirements are achievable using a 30-m 
narrow bore (0.25 mm ID) 5-percent phenyl polysilphenylene-siloxane 
(BPX5 or equivalent) bonded-phase, fused-silica capillary column.
    6.5.2.3 PCB Columns.
    6.5.2.3.1 Use column systems for measuring PCBs that can achieve 
unique resolution and identification of the toxics for determination of 
a TEQPCB using TEFs (American Society of Mechanical 
Engineers 1984). Isomers may be unresolved if they have the same TEF 
and response factor and if these unresolved isomers are uniquely 
resolved from all other congeners. These requirements are achievable 
using several 30-meter (m) narrow bore (0.25 mm ID) columns including 
8-percent phenyl polycarborane-siloxane (HT8), DB-XLB, and poly (50-
percent n-octyl/50-percent methyl siloxane) (SPB-Octyl).
    6.5.2.3.2 If using an SPB-Octyl column for PCB analysis, the column 
should also uniquely resolve isomers 34 from 23 and 187 from 182. 
Resolution for these PCBs is shown by the valley between the peaks not 
exceeding 40 percent of the taller of the two peaks that result when 
these congeners are analyzed in the same calibration sample.
    6.5.3 Mass Spectrometer. Use 28 to 70 electron volt impact 
ionization capable of repetitive selective monitoring of 12 exact m/z 
values with a mass resolution defined in section 10.2.1 of this method 
for fragments in the range of 300 to 350 m/z. The deviation between 
each monitored mass lock m/z and the monoisotopic m/z (Tables 23-4, 23-
5, and 23-6 of this method for PCDDs/PCDFs, PAHs, and PCBs, 
respectively) must be less than 5 parts per million.
    6.5.4 Mass Spectrometer Data System. Use a data system compatible 
with the mass spectrometer and capable of sequencing and monitoring 
multiple groups of selected ions.
    6.5.5 Analytical Balance. Use an analytical balance to measure 
within 0.1 milligram (mg).

7.0 Reagents, Media, and Standards

    Note:  The quality checks described in this section are 
recommended but not required. They are provided to help ensure data 
will meet the required performance specifications in Section 13 of 
this method.

    7.1 Filter. Glass fiber filters, without organic binder, exhibiting 
at least 99.95 percent efficiency (<0.05 percent penetration) on 0.3-
micron dioctyl phthalate smoke particles.
    7.1.1 Extraction. Conduct a quality control check on the filter lot 
prior to the field test to demonstrate that filters are free from 
contamination or interference. Perform Soxhlet extraction on a minimum 
of three filters with toluene for 16 hours. After extraction, allow the 
Soxhlet apparatus to cool. Remove the filters and remove the solvent 
from the filters under clean conditions (e.g., a clean nitrogen 
stream).
    7.1.2 Analysis. Analyze the individual extracts of a minimum of 
three filters from each lot used for sampling according to the 
procedures in Section 11 of this method. The blank filter check 
analysis must meet the performance requirements in Section 13.14 of 
this method.
    7.2 Adsorbent Resin. Amberlite[supreg] XAD-2 resin. All adsorbent 
resin must meet the cleanliness criteria in Section 13.14 of this 
method for all target compounds on the analysis list (i.e., native 
PCDD/PCDF, PCB, and/or PAH) following the same extraction, 
concentration, cleanup, and analysis steps as field samples. This 
method recommends using the procedures provided in appendix B to this 
method to clean the resin before use, if needed. However, this method 
allows alternative cleanup procedures that use automated extraction 
equipment if the adsorbent meets the required performance criteria in 
Section 13.14 of this method.
    7.2.1 Conduct a quality control check on the cleaned adsorbent 
using HRGC/HRMS techniques following procedures in Section 11 of this 
method. The cleaned adsorbent must meet the criteria in Section 13.14 
of this method. A batch blank conducted on the filter and adsorbent lot 
combination used for a test can serve this purpose.
    7.2.2 Storage. Store adsorbent in its original purchase container, 
a clean wide-mouth amber glass container with a PTFE-lined cap, or in 
glass adsorbent modules tightly sealed with glass caps.
    7.3 Glass Wool. Clean the glass wool to meet the specifications in 
Section 13.14 of this method. Using sequential immersion in three clean 
aliquots of toluene, drying in a 110 [deg]C (230 [deg]F) oven, and 
storing in a toluene-rinsed glass jar with a PTFE-lined screw cap can 
meet these requirements.
    7.4 Water. Use deionized or distilled water meeting requirements in 
Section 13.14 of this method and store in its original container or in 
a toluene-rinsed glass container with a PTFE-lined screw cap.
    7.5 Silica Gel. Indicating type, 6-16 mesh. If previously used, dry 
at 175 [deg]C (347 [deg]F) for two hours. Use new silica gel as 
received. As an alternative, use other types of desiccants (equivalent 
or better), subject to the approval of the Administrator.
    7.6 Methylene Chloride. Pesticide grade or better.
    7.7 Sample Recovery Reagents.
    7.7.1 Acetone. Pesticide grade or better.
    7.7.2 Toluene. Pesticide grade or better.
    7.8 Sample Extraction and Cleanup.
    7.8.1 Potassium Hydroxide. American Chemical Society (ACS) grade, 2 
percent (weight/volume) in water.
    7.8.2 Sodium Sulfate. Granulated or powdered, reagent grade. Use as 
received, include in batch blank evaluation prior to use, or purify as 
necessary prior to use by rinsing with methylene chloride or toluene 
and oven drying. The batch blank must meet the requirements in Section 
13.14 of this method. Store the cleaned material in a glass container 
with a PTFE-lined screw cap.
    7.8.3 Sulfuric Acid. Reagent grade.
    7.8.4 Sodium Hydroxide. 1.0 N. Weigh 40 g of sodium hydroxide into 
a 1-liter volumetric flask. Dilute to 1 liter with water.
    7.8.5 Hexane. Pesticide grade or better.
    7.8.6 Methanol. Pesticide grade or better.
    7.8.7 Toluene. Pesticide grade or better.
    7.8.8 High-Boiling Alkanes Used as Keeper Solvents (e.g., 
tetradecane, nonane, decane). Pesticide grade. Note: Lower homologous 
series alkanes (nonane or decane) are necessary for higher volatility 
targets such as MoCBs and naphthalene to maintain retention during 
concentration procedures. However, do not take samples to

[[Page 2249]]

dryness when using these lower alkane homologs.
    7.8.9 Liquid Column Chromatography Packing Materials. Use the 
following column chromatography packing materials, as needed, to 
prepare sample extracts and remove interfering compounds. Commercially 
prepacked cleaning columns may be available for this purpose. All 
procedures for preparing column chromatography packing materials are 
recommendations shown to meet the performance specifications required 
for the recovery of labeled compounds described in Section 13 of this 
method.
    7.8.9.1 Alumina. Use either acidic or basic alumina in the cleanup 
of sample extracts. Use the same type of alumina for all samples in an 
analytical sequence, including those used to demonstrate batch blank 
performance.
    7.8.9.1.1 Acidic Alumina (Sigma-Aldrich[supreg] 199966 or 
equivalent). Brockmann activity grade 1, 100-200 mesh. Prior to use, 
activate the alumina by heating for 12 hours at 130 [deg]C (266 
[deg]F). Store in a desiccator. You may use pre-activated alumina 
purchased from a supplier as received.
    7.8.9.1.2 Basic Alumina (Sigma-Aldrich[supreg] 19943 or 
equivalent). Brockmann activity grade 1. Activate by heating to 600 
[deg]C (1,112 [deg]F) for a minimum of 24 hours. Do not heat to over 
700 [deg]C (1,292 [deg]F) because this can lead to reduced capacity for 
retaining the analytes. Store at 130 [deg]C (266 [deg]F) in a covered 
flask. Use within five days of baking. Use prepacked alumina columns 
immediately after opening the vacuum sealed pouch or container.
    7.8.9.2 Florisil[supreg]. Activated, 60-100 mesh recommended. Heat 
previously activated Florisil[supreg] in a glass container loosely 
covered with aluminum foil in an oven at 130 to 150 [deg]C (266 to 302 
[deg]F) for a minimum of 24 hours. Upon cooling, store activated 
Florisil[supreg] silica prior to use in a desiccator.
    7.8.9.3 Silica Gel. Use either activated, acidic or basic silica 
gel in the cleanup of sample extracts. Use the same type of silica gel 
for all samples in an analytical sequence, including those used to 
demonstrate batch blank performance.
    7.8.9.3.1 Activated Silica Gel. Supelco[supreg] 1-3651, Bio-
Sil[supreg] A, 100-200 mesh (or equivalent). Prior to use, rinse with 
methylene chloride and activate the silica gel by heating for at least 
1 hour at 180 [deg]C (356 [deg]F). After cooling, rinse the silica gel 
sequentially with methanol and toluene. Heat the rinsed silica gel at 
50 [deg]C (122 [deg]F) for 10 minutes, then increase the temperature 
gradually to 180 [deg]C (356 [deg]F) over 25 minutes and maintain the 
gel at this temperature for 90 minutes. Cool in a desiccator to room 
temperature and store in a glass container with a PTFE-lined screw cap.
    7.8.9.3.2 Acidic Silica Gel (30 percent weight/weight). Combine 100 
g of activated silica gel with 44 g of concentrated sulfuric acid in a 
clean screw-capped glass container and agitate thoroughly. Disperse the 
solids with a stirring rod until obtaining a uniform mixture. Store the 
mixture in a glass container with a PTFE-lined screw cap.
    7.8.9.3.3 Basic Silica Gel. Combine 30 g of 1 N sodium hydroxide 
with 100 g of activated silica gel in a clean screw-capped glass 
container and agitate thoroughly. Disperse solids with a stirring rod 
until obtaining a uniform mixture. Store the mixture in glass container 
with a PTFE-lined screw cap.
    7.8.9.4 Carbon/Celite[supreg] 545 (or equivalent solid support). 
Use a carbon-based column cleanup material (e.g., one of the many 
Carbopack[supreg] B or C) to remove impurities from the samples prior 
to analysis. Thoroughly mix 9.0 g Carbopack[supreg] C and 41.0 g 
Celite[supreg] 545 to produce an 18-percent weight/weight mixture. 
Activate the mixture at 130 [deg]C (266 [deg]F) for a minimum of 6 
hours. Store in a desiccator.
    7.8.10 Nitrogen. 99.999 percent (ultra-high) purity.
    7.9 Sample Analysis.
    7.9.1 Helium. 99.999 percent (ultra-high) purity.
    7.9.2 Spiking Standards. Prepare spiking standards quantitatively 
at a convenient concentration (e.g.,10 nanograms (ng)/mL) or use 
commercial standards if available, to enable accurate spiking of a 
labeled standard at various stages of the sample preparation. You may 
adjust the spiking concentrations from those recommended in Tables 23-
7, 23-8 and 23-9 of this method to accommodate the concentration of 
target compounds anticipated in samples if the performance criteria in 
Section 13 of this method are met.
    7.9.3 Pre-Sampling Recovery Standard Solution. Prepare stock 
standard solutions in nonane to enable spiking of the isotopically 
labelled compounds for target compound classes in Tables 23-7, 23-8, 
and 23-9 of this method at the mass shown under the heading ``Pre-
sampling Adsorbent Standards.''
    7.9.4 Pre-extraction Filter Recovery Spike Standard Solution. 
Prepare stock standard solutions in nonane to enable spiking of the 
isotopically labelled compounds for target compound classes in Tables 
23-7, 23-8, and 23-9 of this method at the mass shown under the heading 
``Pre-extraction Filter Recovery Spike Standards.''
    7.9.5 Pre-extraction Recovery Standard Solution. Prepare stock 
standard solutions in nonane to enable spiking of the isotopically 
labelled compounds for target compound classes in Tables 23-7, 23-8, 
and 23-9 of this method at the mass shown under the heading ``Pre-
extraction Standards.''
    7.9.6 Pre-analysis Standard Solution. Prepare stock standard 
solutions in nonane to enable spiking of the isotopically labelled 
compounds for target compound classes in Tables 23-7, 23-8, and 23-9 of 
this method at the mass shown under the heading ``Pre-analysis 
Standards.''

8.0 Sample Collection, Preservation and Storage

    8.1 Sampling. This method involves collection and recovery of trace 
concentrations of semivolatile organic compounds. Therefore, train 
field sampling and recovery staff in the best practices for handling 
and using organic solvents in field environments to recover and protect 
samples from contamination.
    8.1.1 Pretest Preparation.
    8.1.1.1 Cleaning Glassware. Clean glassware thoroughly before 
using. This section provides a recommended procedure, but any protocol 
that consistently results in contamination-free glassware meeting the 
batch blank criteria in Section 13.2 of this method is acceptable.
    8.1.1.1.1 Soak all glassware in hot soapy water (Alconox[supreg] or 
equivalent).
    8.1.1.1.2 Rinse with hot tap water.
    8.1.1.1.3 Rinse with deionized/distilled water.
    8.1.1.1.4 Rinse with methanol.
    8.1.1.1.5 Rinse with toluene.
    8.1.1.1.6 Baking glassware at 300 [deg]C (572 [deg]F) for a minimum 
of 2 hours may be necessary to remove contaminants or interferents from 
particularly dirty samples. Cool glassware after baking.

    Note:  Repeated baking of glassware may cause active sites on 
the glass surface that may irreversibly absorb target compounds.

    8.1.1.1.7 Cover glassware openings with clean glass fitting caps or 
cleaned aluminum foil (see Section 6.2.6 of this method).
    8.1.1.1.8 Rinse glassware immediately before use with acetone and 
toluene.

    Note:  To prepare heavily soiled glassware, remove surface 
residuals from the glassware by soaking in hot soapy water, rinsing 
with hot water, then soaking with a non-chromic acid oxidizing 
cleaning reagent in a strong acid (e.g., NOCHROMIX[supreg] prepared 
according to manufacturer's directions). After the acid soak, rinse 
with hot water and repeat the

[[Page 2250]]

cleaning procedures in Section 8.1.1.1 of this method.

    8.1.1.2 Adsorbent Module. Load the modules in a clean area to avoid 
contamination. Spike modules before the sampling event, but do not 
spike the modules in the field. Fill a module with 20 to 40 g of XAD-2. 
Add the pre-sampling standard spike for each of the compound classes to 
be measured to the top quarter of the adsorbent bed. Add sufficient 
spike (picograms (pg)/module) to result in the final theoretical 
concentrations specified in Tables 23-7, 23-8, and 23-9 of this method 
for PCDDs/PCDFs, PAHs, and PCBs, respectively. For samples with known 
or anticipated target compound concentration significantly higher or 
lower than the specified amount in these tables, add a pre-sampling 
spike amount appropriate to the expected native compound concentration, 
but no less than 10 times the EDL. Follow the XAD-2 with cleaned glass 
wool and tightly cap both ends of the module. For analysis that include 
PAH, use spiked modules within 14 days of preparation. See Table 23-10 
of this method for storage conditions.
    8.1.1.3 Sampling Train. Figure 23-1 of this method shows the 
complete sampling train. Follow the best practices by maintaining all 
sampling train components according to the procedure described in APTD-
0576 Maintenance, Calibration, and Operation of Isokinetic Source-
sampling Equipment (U.S. EPA 1972).
    8.1.1.4 Silica Gel. Weigh several 200 to 300 g portions of silica 
gel in an air-tight container to the nearest 0.5 g. Record the total 
weight of the silica gel plus container on the outside of each 
container. As an alternative, directly weigh the silica gel in its 
impinger or sampling holder just prior to sampling.
    8.1.1.5 Filter. Check each filter against light for irregularities 
and flaws or pinhole leaks. Pack the filters flat in a clean glass 
container. Do not mark filters with ink or any other contaminating 
substance.
    8.1.2 Preliminary Determinations. Use the procedures specified in 
Section 8.2 of Method 5 of appendix A-3 to 40 CFR part 60.
    8.1.2.1 Sample Volume. Unless otherwise specified in an applicable 
rule, permit, or other requirement, sample for a minimum of 2 minutes 
at each traverse point. This method recommends sampling a minimum of 
2.5 dry standard cubic meters (dscm).
    8.1.2.2 For continuously operating processes, use the same sampling 
time at each traverse point. To avoid timekeeping errors, use an 
integer, or an integer plus one-half minute, for each traverse point.
    8.1.2.3 For batch processes, determine the minimum operating cycle 
duration, dividing the sampling time evenly between the required 
numbers of traverse points. After sampling all traverse points once, 
sample each point again for the same duration of time per sampling 
point in reverse order until the operating cycle is completed. Sample 
all traverse points at least once during each test run.
    8.1.3 Preparation of Sampling Train.
    8.1.3.1 During field preparation and assembly of the sampling 
train, keep all train openings where contamination can enter sealed 
until just prior to assembly or until sampling is about to begin. To 
protect the adsorbent module from radiant heat and sunlight, you must 
wrap the module with aluminum foil or other suitable material capable 
of shielding the module from light. The XAD-2 adsorbent resin 
temperature must never exceed 50 [deg]C (122 [deg]F) because thermal 
decomposition will occur. Clean and prepare a complete set of sampling 
train components that will contact the sample for each sampling run, 
including one complete set to be used as a field train proof blank as 
described in Section 9.6 of this method.
    8.1.3.2 Place approximately 100 mL of water in the second and third 
impingers but leave the first and fourth impingers empty. Transfer 
approximately 200 g or more of silica gel from its container to the 
fifth impinger. Weigh each impinger and the adsorbent module, including 
the fitting caps, to the nearest 0.5 g using the field balance and 
record the weight for moisture determination. Remove the aluminum foil 
from the adsorbent module before weighing. Keep the module out of 
direct sunlight and rewrap the module with foil immediately after 
recording the module weight.
    8.1.3.3 Using tweezers or clean disposable surgical gloves, place a 
filter in the filter holder. Be sure that the filter is properly 
centered, and the gasket properly placed, to prevent the sample gas 
stream from circumventing the filter. Check the filter for tears after 
completing the assembly.
    8.1.3.4 Prepare the inside of the sampling probe and nozzle by 
brushing each component while rinsing three times each with acetone and 
toluene. Install the selected nozzle. You may use connecting systems 
described in Section 6.1.2 of this method. Mark the probe with heat 
resistant tape or by some other method to denote the proper distance 
into the stack or duct for each sampling point. Assemble the train as 
shown in Figure 23-1 of this method. Orient the adsorbent module 
vertically so condensed moisture drains into the first impinger. See 
APTD-0576 Maintenance, Calibration, and Operation of Isokinetic Source-
sampling Equipment (U.S. EPA 1972) for details.
    8.1.3.5 Turn on the recirculation pump to the adsorbent module and 
condenser coil and begin monitoring the temperature of the gas entering 
the adsorbent module. Ensure proper temperature of the gas entering the 
adsorbent module before proceeding.
    8.1.4 Leak-Check Procedure. Same as Section 8.4 of Method 5 of 
appendix A-3 to 40 CFR part 60.
    8.1.5 Sampling Train Operation. Same as Sections 8.5.1 through 
8.5.9 of Method 5 of appendix A-3 to 40 CFR part 60.
    8.1.5.1 Monitor the filter temperature sensor and record the filter 
temperature during sampling to ensure a sample gas temperature exiting 
the filter of 120 [deg]C  14 [deg]C (248 [deg]F  25 [deg]F), or such other temperature as specified by an 
applicable subpart of the standards or approved by the Administrator 
for an application of this method.
    8.1.5.2 During testing, you must record the temperature of the gas 
entering the XAD-2 adsorbent module. The temperature of the gas must 
not exceed 20 [deg]C (68 [deg]F) for efficient capture of the target 
compounds.
    8.2 Sample Recovery. Begin the cleanup procedure as soon as the 
probe is removed from the stack at the end of the sampling period. Seal 
the nozzle end of the sampling probe with PTFE tape or clean (e.g., 
toluene rinsed) aluminum foil. This method recommends using clean 
glassware prepared following Section 8.1.1.1 of this method for each 
sample set in a test series.
    8.2.1 When the probe can be safely handled, wipe off all external 
particulate matter near the tip of the probe. Conduct a post-test leak 
check. Remove the probe from the train and close off both ends with 
PTFE tape or clean aluminum foil. Seal off the inlet to the train with 
PTFE tape, a ground glass cap, or clean aluminum foil.
    8.2.2 Transfer the probe and impinger assembly to the cleanup area. 
This method recommends cleaning and enclosing this area to minimize the 
chances of losing or contaminating the sample. To avoid sample 
contamination and unnecessary exposure to toxic chemicals, smoking or 
eating in the sample recovery area shall not be allowed.
    8.2.3 Inspect the train prior to and during disassembly. Note and 
record

[[Page 2251]]

any abnormal conditions (e.g., broken filters, colored impinger 
liquid). Recover and prepare samples for shipping as follows in 
Sections 8.2.4 through 8.2.12 of this method.
    8.2.4 Container No. 1. Either seal the filter holder or carefully 
remove the filter from the filter holder and place it in its identified 
container. If it is necessary to remove the filter, use a pair of 
cleaned tweezers to handle the filter. If necessary fold the filter 
such that the particulate cake is inside the fold. Carefully transfer 
to the container any particulate matter and filter fibers that adhere 
to the filter holder gasket by using a dry inert bristle brush and a 
sharp-edged blade. Seal the container and store cool (<= 20  3 [deg]C, 68  5 [deg]F) for transport to the 
laboratory.
    8.2.5 Adsorbent Module Sample. Remove the module from the train, 
tightly cover both ends with fitting caps and PTFE tape, remove the 
foil, drain the recirculating water from the module, weigh and record 
the module weight, and label the adsorbent module. Moisture measurement 
in the field using the Method 23 train requires weighing the adsorbent 
module before the sampling run and after sampling as part of the sample 
recovery.
    8.2.6 Container No. 2. Quantitatively recover material deposited in 
the nozzle, the front half of the filter holder, and the cyclone, if 
used, by brushing while rinsing three times with acetone followed by 
three rinses with toluene. Collect all the rinses in Container No. 2.
    8.2.7 Rinse the back half of the filter holder three times with 
acetone followed by three rinses with toluene. Rinse the sample 
transfer line between the filter and the condenser three times with 
acetone followed by three rinses with toluene. If using a separate 
condenser and adsorbent module, rinse the condenser three times with 
acetone followed by three rinses with toluene. Collect all the rinses 
in Container No. 2 and mark the level of the liquid on the container.
    8.2.8 Moisture Weight. Weigh the adsorbent module, impingers, and 
silica gel impinger to within  0.5 g using the field 
balance and record the weights. This information is required to 
calculate the moisture content of the effluent gas. For PCDD/PCDF-only 
measurements, discard the liquid after measuring and recording the 
weight.
    8.2.9 Container No. 3. You must save and analyze impinger water 
samples if PAHs and/or PCBs are the target compounds. Quantitatively 
recover impinger water samples for analysis if PAHs and/or PCBs are the 
target compounds by rinsing three times with acetone followed by three 
rinses with toluene. Collect impinger water and rinses in Container No. 
3 and mark the level of the liquid on the container.
    8.2.10 Silica Gel. Note the color of the indicating silica gel to 
determine if it has been completely spent and report its condition on 
the field data sheet.
    8.2.11 Field Sample Handling, Preservation, Storage, and Transport. 
Store all field samples temporarily in cool (<= 20  3 
[deg]C, 68  5 [deg]F) and dark conditions prior to 
transport to the laboratory. Ship samples cool (<= 20  3 
[deg]C, 68  5 [deg]F), shielded from ultraviolet light. In 
addition, follow the procedures in ASTM D6911-15 (Guide for Packaging 
and Shipping Environmental Samples for Laboratory Analysis) for all 
samples, where appropriate. To avoid contamination of the samples, pay 
special attention to cleanliness during transport, field handling, 
sampling, recovery, and laboratory analysis, as well as during 
preparation of the adsorbent cartridges.
    8.2.12 Sample Custody. Proper procedures and documentation for 
sample chain of custody are critical to ensuring data integrity. Follow 
the chain of custody procedures in ASTM D4840-99(2018)e1 (Standard 
Guide for Sample Chain-of-Custody Procedures) for all samples 
(including field samples and blanks).
    8.3 Sample Storage Conditions and Laboratory Hold Times.
    8.3.1 Table 23-10 of this method summarizes the sample storage 
conditions and laboratory hold times.
    8.3.2 Store sampling train rinses and filter samples in the dark at 
6 [deg]C (43 [deg]F) or less from the time the laboratory receives the 
samples until analysis.
    8.3.3 You may store adsorbent samples for PCDDs/PCDFs or PCBs prior 
to extraction in the dark at 6 [deg]C (43 [deg]F) or less for up to one 
year from the time the laboratory receives the samples.
    8.3.4 Protect adsorbent samples destined for PAH analysis from 
ultraviolet light. You may store adsorbent samples for PAH analysis at 
6 [deg]C (43 [deg]F) or less for up to 30 days from the time the 
laboratory receives the samples.
    8.3.5 Analyze PAH extracts within 45 days of extraction.
    8.3.6 You may store sample aliquots including archived extracts of 
PCDD/PCDF, PAH and/or PCB samples in the dark at -10 [deg]C (14 [deg]F) 
or less for up to one year.

9.0 Quality Control

    Note:  In recognition of advances that are occurring in sampling 
and analytical technology, and to allow the test team to overcome 
analyte sensitivity and matrix interferences, this method allows 
certain options to increase sample collection volume and to improve 
separations and the quality of the analysis results for target 
analytes. It is the laboratory's responsibility to establish the 
conditions for optimum sample extraction, cleanup, and concentration 
to meet the performance criteria in this method. However, you may 
not change the fundamental sampling and analysis techniques, 
isokinetic sampling with an adsorbent collection media followed by 
sample extraction, and HRMS detection and isotopic dilution 
quantification procedures. Section 13 of this method specifies the 
performance criteria to ensure that options employed for a sample 
set and analytes of interest are equal to or better than the 
specificity of the techniques in this method. This method recommends 
performing a media blank (i.e., batch blank) assessment to evaluate 
an individual laboratory's performance against the performance 
criteria in this method. At a minimum, evaluate changes within the 
alternatives allowed in this method using a media blank sample to 
re-demonstrate that the performance criteria are achieved.

    9.1 Record and report data and information that will allow an 
independent reviewer to validate the determination of each target 
compound concentration. At a minimum, record and report the data as 
described in Sections 9.1.1 through 9.1.7 of this method.
    9.1.1 Sample numbers and other sample identifiers. Each sample must 
have a unique identifier.
    9.1.2 Field sample volume.
    9.1.3 Field sampling date.
    9.1.4 Extraction dates.
    9.1.5 Analysis dates and times.
    9.1.6 Analysis sequence/run chronology.
    9.1.7 Quantitation Reports.
    9.1.7.1 This method does not consider EPC-flagged data to be zero 
concentrations. Calculate the EPC separately for each quantitation ion, 
if present, and report the lower value as the EPC.
    9.1.7.2 In determining compliance with any PCDD and PCDF standard 
developed using zero for values that are below the detection level of 
the method, including federal emission standards using Method 23 
promulgated under 40 CFR parts 60 and 63 prior to [DATE OF PUBLICATION 
OF THE FINAL RULE], use zero for the determination of total and 
weighted concentrations when the target compound is not detected. For 
all other circumstances, unless otherwise specified in applicable 
regulations, permits, or other requirements, when a target compound is 
measured at or below EDL, use EDL as the concentration for calculating 
compliance.
    9.1.7.3 You must report your EDLs with analysis results.

[[Page 2252]]

    9.1.8 Performance criteria results (See Section 13 of this method).
    9.2 Isotopically Labeled Spike Recovery Results.
    9.2.1 Pre-sampling Adsorbent Spike and Pre-extraction Filter Spike 
Recoveries. Pre-sampling adsorbent and pre-extraction filter spike 
recoveries must demonstrate on a per sample basis that recovery of the 
labeled standard achieved the requirements in Section 13 of this 
method. Recoveries below the acceptable range for the pre-sampling 
spikes may be an indication of breakthrough in the sampling train.
    9.2.1.1 If the recovery of all the pre-sampling adsorbent spike 
standards is below 70 percent, the sampling runs are not valid, and you 
must repeat the invalid runs. As an alternative, you do not have to 
repeat the invalid sampling runs if the average pre-sampling adsorbent 
spike recovery is 25 percent or more and you divide the final results 
by the average fraction of pre-sampling adsorbent spike recovery.
    9.2.1.2 If the recovery of the pre-extraction filter spike is below 
70 percent, the filter sampling extraction recovery is not valid, and 
you must flag the test run results.
    9.2.2 Pre-extraction Spike Recoveries. Pre-extraction spike 
recoveries must demonstrate on a per sample basis that recovery of the 
labeled standard achieved the requirements in Section 13 of this 
method. Recoveries below the acceptable range for pre-extraction spikes 
are an indication that sample preparation procedures did not adequately 
address sample and or sample matrix processing to recover native target 
compounds.
    9.2.3 Pre-analysis Spike Recoveries. Pre-analysis spike recoveries 
must demonstrate on a per sample basis that adequate labeled standard 
signal meets the requirements in Section 13 of this method. Add pre-
analysis standards to every sample (including blanks, quality control 
samples, and calibration solutions) in a known concentration. You may 
analyze archive samples to attempt meeting requirements for the 
compounds that do not meet the pre-analysis recovery criteria. 
Recoveries below the acceptable range for pre-analysis spikes are an 
indication that sample injection or instrument drift has failed beyond 
the ability to correct using pre-analysis standard results.
    9.3 Capillary GC columns must be able to achieve the separation 
resolution specified in Sections 13.3, 13.4, and/or 13.5 of this method 
for the target compounds analyzed in test samples.
    9.4 Batch Blank Samples. Evaluate chromatographic separation 
performance, spiking errors, and continuing calibration checks using a 
batch blank sample prepared from typical filter and absorbent media, 
spiked with isotopically labeled compounds and extracted identically to 
the procedures used to prepare samples. Analyze batch blank samples at 
least once during each analytical sequence or every 24 hours, whichever 
period is shorter. Section 13.2 of this method describes the 
performance criteria for field train proof blank assessment samples and 
batch blank samples.
    9.5 Detection Limits. Calculate the EDL using the equation in 
Section 12.11 of this method. If the field train proof blank or the 
batch blank results are above the EDL, calculate and report the test-
specific and compound-specific DLs equal to the sum of the EDL and the 
larger of the batch or field train proof blank results. If the field 
train proof blank and the batch blank results are equal to or less than 
the EDL, report the test-specific and compound-specific DLs as the EDL.
    9.6 Field Train Proof Blank Assessment. Conduct at least one field 
train proof blank for each test series at a single facility. A field 
train proof blank train consists of a fully assembled train at the 
sampling site. Prepare and assemble the blank train in a manner 
identical to that described in Sections 8.1.3 and 8.1.4 of this method. 
The blank train must remain assembled for the same average amount of 
time samples are collected. Recover the blank train as described in 
Section 8.2 of this method. Follow all subsequent steps for blank train 
sample preparation and analysis used for field train samples including 
data reporting.

10.0 Calibration and Standardization

    10.1 Sampling System. Same as Sections 6.1 and 10.1 through 10.7 of 
Method 5 of appendix A-3 to 40 CFR part 60.
    10.2 HRGC/HRMS System.
    10.2.1 Mass Resolution. Tune the HRMS instrument to a mass 
resolution (R) of at least 10,000 at 5 percent of the peak height or 
25,000 at 50 percent of the peak height where resolution is calculated 
as an R = M/[Delta]M, where M is the resolving power and [Delta]M is 
the peak width. You may use peak matching and the chosen perfluoro-
kerosene (PFK) or perfluorotributylamine (FC43) reference peak to 
verify that the exact mass is within 5 ppm of the required value. 
Assess the resolution at three m/z ranges representing the low, mid and 
high m/z range of the masses used to measure the target compound class.
    10.2.2 Initial Calibration. Calibrate the HRGC/HRMS system using a 
minimum of five concentrations over a range that brackets typical field 
sample concentrations and the concentration of isotopically labeled 
standards in spiked samples. Tables 23-11, 23-12, and/or 23-13 of this 
method, as applicable to the compound classes analyzed, show the 
calibration concentrations recommended by this method. Perform 
calibration and subsequent analyses on an absolute mass (pg/microliter 
([mu]L)) basis. The recommended calibration range ensures isotopic 
labels can be accurately distinguished from native compounds and 
provides the initial response factors that are corrected by isotopic 
recovery.
    10.2.2.1 Lock Channels. Tables 23-4, 23-5, and 23-6 of this method 
provide the recommended mass spectrometer lock channels for PCDD/PCDFs, 
PAHs, and PCBs, respectively. You may use PFK or FC43 as your lock mass 
standard. 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 during analysis.
    10.2.2.2 The relative standard deviation (RSD) for the mean 
response factor from each of the unlabeled analytes and isotopically 
labeled compounds used in an analysis must be less than or equal to the 
values in Table 23-14 of this method.
    10.2.2.3 The signal-to-noise (S/N) ratio for the MS signal present 
in every selected ion current profile must be greater than or equal to 
10 in all concentrations of calibration standards for unlabeled targets 
and isotopically labeled standards. The ion abundance ratios must be 
within the control limits in Table 23-15 of this method.
    10.2.3 Daily Performance Check.
    10.2.3.1 Continuing Calibration Check. Inject a mid-level 
calibration standard C4 from Table 23-11, 23-12, or 23-13 of this 
method for the compound class being analyzed at least once every 24 
hours during an analysis sequence. Calculate the RRF for each compound 
and compare each RRF to the corresponding mean RRF obtained during the 
initial calibration. The analyzer performance is acceptable if the 
measured RRFs for the labeled compounds for a 24-hour period are within 
the limits of the values shown in Table 23-14 of this method. The RRF 
for each native compound measured in a CCV must not deviate from the 
initial calibration by more than the limits shown in this table.
    10.2.3.2 The ion abundance ratios must be within the allowable 
control limits shown in Table 23-15 of this method.

[[Page 2253]]

    10.2.3.3 Repeat the initial calibration when there is a failure to 
meet the requirements for acceptable continuing calibration check 
analysis.
    10.2.3.4 Column Separation Check. Use the results from a continuing 
calibration check sample to verify and document the resolution required 
in Sections 13.3, 13.4, or 13.5 of this method for the compound classes 
analyzed with this method.
    10.2.3.5 If you use a confirmation column, perform the resolution 
check in Section 10.2.3.4 of this method to document the required 
resolution on the confirmation column.

11.0 Analysis Procedure

    11.1 Sample Extraction and Concentration. The sample extraction 
procedures in this method are the same for PCDD, PCDF, PCB and PAH 
targets. Figure 23-4 provides a flow chart showing sample container 
combination and extraction steps. Do not allow samples and extracts 
destined for PAH or PCB analysis to concentrate to dryness because the 
lower molecular weight PAHs and the mono- through tri-chlorobiphenyls 
may be totally or partially lost.
    11.1.1 Optional Soxhlet Precleaning. Place an extraction thimble 
(see Section 6.3.3.3 of this method) and a plug of glass wool into the 
Soxhlet apparatus equipped with a Dean-Stark trap, charge the apparatus 
with toluene, and reflux for a minimum of 3 hours. Remove the toluene 
and discard it. Remove the extraction thimble from the extraction 
system and place it in a glass beaker to catch the solvent rinses from 
sample transfer to the extraction thimble. Retain the clean glass wool 
plug. Alternatively, confirm that the batch blank for reagents, 
materials, and media meets the performance requirements in Section 13 
of this method.
    11.1.2 Container No. 1 (Filter) Preparation. Spike the filter with 
the appropriate pre-extraction filter recovery standard solution(s) 
shown in Tables 23-7, 23-8, and 23-9 of this method taking care that 
all spike liquid is distributed on the filter. Allow the filter to air 
dry, then transfer the filter and the contents of Container No. 1 
directly to the glass extraction thimble in the glass solvent rinse 
catch beaker so that the filter will be completely immersed in the 
solvent during extraction.
    11.1.3 Adsorbent Module. Transfer the adsorbent material to the 
glass extraction thimble in the glass solvent rinse catch beaker. Rinse 
the module into the thimble in the beaker with the contents of 
Container No. 1. Alternatively, suspend the adsorbent module directly 
over the extraction thimble in a beaker, then, using a wash bottle 
containing methanol, flush the XAD-2 into the thimble onto the filter. 
Thoroughly rinse the interior of the glass module that contained the 
XAD-2 with toluene.
    11.1.4 Container No. 2 (Acetone and Toluene Rinses). Concentrate 
the sample to a volume of no less than 5 mL. Concentrate samples 
containing toluene using a heating mantle and three-ball Snyder column 
or a rotary evaporator. Rinse sample Container No. 2 three times with 
small portions of toluene and add these to the concentrated solution 
and concentrate further to no less than 5 mL. This residue contains 
particulate matter removed in the rinse of the train probe and nozzle. 
Rinse the concentrated material from Container No. 2 into the glass 
extraction thimble containing the filter and the XAD-2 resin.
    11.1.5 Transfer the solvent contained in the collection beaker to 
the extraction apparatus solvent reservoir. Rinse the beaker into the 
Soxhlet extraction apparatus solvent reservoir three times with small 
portions of toluene.
    11.1.6 Container No. 3 (Impinger Water and Rinses). For PAH and PCB 
analysis, transfer the contents of Container No. 3 to a separatory 
funnel. Adjust to pH 2 with 6 N sulfuric acid, if necessary. Rinse the 
sample container with three successive 10-mL aliquots of the toluene 
and these rinses to the separatory funnel. Extract the sample by 
vigorously shaking the separatory funnel for 5 minutes. After complete 
separation of the phases, remove the solvent and filter it through a 
bed of precleaned, dry sodium sulfate into the Soxhlet extraction 
apparatus solvent reservoir. Repeat the extraction step two additional 
times. Adjust the pH to 11 with 6 N sodium hydroxide, re-extract the 
impinger water and rinses, and filter it through a bed of precleaned, 
dry sodium sulfate into the Soxhlet extraction apparatus solvent 
reservoir. Rinse the sodium sulfate into the extraction apparatus 
solvent reservoir with fresh solvent and discard the desiccant.
    11.1.7 Add the appropriate pre-extraction spikes for the compound 
classes being analyzed (Tables 23-7, 23-8, and 23-9 of this method) to 
the extraction thimble containing the combined filter and adsorbent 
sample fractions. Cover the contents of the extraction thimble with the 
cleaned glass wool plug to prevent the XAD-2 resin from splashing into 
the solvent reservoir of the extractor. Place the extraction thimble 
into the Soxhlet extraction apparatus.
    11.1.8 Pour additional toluene to fill the reservoir approximately 
two-thirds capacity. Add PTFE boiling chips and assemble the apparatus.
    11.1.9 Adjust the heat source to cause the extractor to cycle 
approximately three times per hour. Extract the sample for sufficient 
time to meet the pre-extraction spike recovery performance criteria in 
Section 13 of this method. The solvent should cycle completely through 
the system a minimum of 48 times.

    Note: Samples containing high carbon particulate loading, such 
as those collected downstream of an activated carbon injection 
system, may require extended extraction time or treatment such as 
those described in Stieglitz 1986.

    11.2 Sample Aliquots for Cleanup and Analysis.
    11.2.1 After extraction, allow the Soxhlet apparatus to cool.
    11.2.2 Initial Extract Concentration. You may perform an initial 
concentration of the sample extract using the techniques (e.g., Kuderna 
Danish, rotary evaporation, nitrogen blowdown) found to recover pre-
extraction isotopically labeled compounds sufficient to meet the 
performance criteria in Section 13 of this method. Concentrate initial 
extracts in toluene using a heating mantle and three-ball Snyder column 
or a rotary evaporator. Concentrate the field train proof blank and 
batch blank samples in the same manner as samples.

    Note: For samples requiring PCB or PAH analysis, you should 
perform the initial concentration using a three-ball Snyder column 
on the original extraction receiver flask. To meet isotopically 
label spike recoveries for low molecular weight PAHs and PCBs, do 
not evaporate samples to dryness.

    11.2.3 Allow the sample to cool. You should use a minimum of one 
half of the sample extract for PCDD/PCDF analysis. You may archive the 
remaining sample extract or further split the extract for PCB and/or 
PAH analysis and archive.
    11.2.4 If necessary, further concentrate the sample for cleanup and 
analysis using concentration techniques (e.g., Kuderna Danish, rotary 
evaporation, nitrogen blowdown) found to recover pre-extraction 
isotopically labeled compounds sufficient to meet the performance 
criteria in Section 13 of this method.
    11.3 Sample Cleanup and Fractionation. You may process a separate 
aliquot/split of the sample extract for each of the compound classes

[[Page 2254]]

analyzed by this method. Sample cleanup for each compound class may 
include techniques in addition to column chromatography such as acid/
base back-extraction or high-performance liquid chromatography (HPLC) 
to isolate target compounds from interferences. This section includes a 
description of column chromatography shown to meet the performance 
criteria in Sections 9.2 and 13 of this method. The following sample 
cleanup and fractionation procedures are recommended but not required. 
You may modify cleanup column dimensions to meet manual or automated 
cleanup procedures as technology changes and improves. You must 
evaluate the cleanup and fractionation procedures used to confirm 
acceptable recovery of isotopically labeled standards. The alternative 
procedures must provide sufficient cleanup to meet method 
identification criteria (Section 11.4.3.4 of this method) and recovery 
criteria (Section 9.2 of this method). Section 13 of this method 
summarizes the method performance requirements.

    Note:  Recommendations in this section provide a cleanup 
approach that may allow multiple compound class measurement from a 
single aliquot of the original sample extract. Typically, 
Florisil[supreg] and alumina are used to separate PAH and 
chlorobiphenyl ether compounds from PCDD and PCDF target compounds. 
Use acid, neutral, and basic silica gel and cleanup procedures to 
remove nonpolar and polar interferences from samples destined for 
PCB and PCDD/PCDF analysis. Use Carbopack[supreg]/Celite[supreg] (or 
other equivalent carbon-based column material) to remove other 
nonpolar interferences.

    11.3.1 PAH and PCDEs Fractionation and Cleanup. You may use a 
Florisil[supreg] column to remove PAHs and PCDEs from a sample. You may 
also fractionate samples using Florisil[supreg] as the first cleanup 
step to separate PAH for analysis.

    Note:  High concentrations of PAHs may interfere with mass 
spectrometer lock mass or saturate the source, leading to failure of 
performance criteria for PCDD/PCDF or PCB analysis.

    11.3.1.1 Pack a 6-mm ID chromatographic column or equivalent 
diameter glass pipet with a glass wool plug followed by approximately 
1.5 g (approximately 2 mL) of activated Florisil[supreg]. Add 
approximately 1 cm (approximately 1 mL) of anhydrous sodium sulfate 
followed by a glass wool plug to the head of the column. Pre-elute the 
column with 10 mL of methylene chloride followed by 10 mL of hexane and 
discard the eluate.
    11.3.1.2 When the solvent is within 1 mm of the packing, transfer 
the concentrated extract (up to 5 mL) to the top of the 
Florisil[supreg] column, rinse the sample container twice with 1 to 2 
mL of hexane, adding each rinse to the column, and elute the column 
with 35 mL of 5-percent dichloromethane in hexane. This fraction 
(Fraction 1) should contain target PCBs, and selected hydrocarbons and 
chlorinated monoaromatic compounds.
    11.3.1.3 Elute the column with 35 mL of 15-percent of 
dichloromethane in hexane and collect the eluate. This fraction 
(Fraction 2) should contain target PCDD/PCDF compounds.
    11.3.1.4 Elute the column with 50 mL of 50-percent dichloromethane 
in hexane. The fraction (Fraction 3) should contain target PAHs.
    11.3.1.5 If necessary to remove any remaining polar organic 
compounds, elute the column with 70 mL of 15-percent acetone in hexane.
    11.3.2 PCDD/PCDF and PCB Fractionation and Cleanup. You may remove 
PAHs from the original aliquot of extract used for PCDD/PCDF analysis 
as described in Section 11.3.1 of this method. Design the column 
cleanup chromatography for PCDD/PCDFs and PCBs such that two 
consecutive fractions are collected (one with PCDD/PCDFs and one with 
PCBs) without impacting the DLs. Depending on the source and sample 
matrix of the original sample, one or more of the following column 
cleanup approaches may be necessary to remove polyhalogenated diphenyl 
ethers. You may use any number of permutations found in the referenced 
literature for this cleanup if the pre-extraction standard recoveries 
from field and batch blank samples meet the associated performance 
criteria in Section 13 of this method. Alternatively, you may use an 
automated cleanup approach that meets the labeled spike recovery 
requirements in Section 13 of this method.
    11.3.2.1 Silica Gel Column Chromatography. Pack one end of a glass 
column, approximately 20 mm ID x 230 mm long, with glass wool. Add in 
sequence to the glass column, 1 g of silica gel, 2 g of sodium 
hydroxide impregnated silica gel, 1 g of silica gel, 4 g of acid-
modified silica gel, 1 g of silica gel, and 1 cm layer of anhydrous 
sodium sulfate. Pre-elute the column with 30 to 50 mL of hexane leaving 
a small quantity of hexane above the sodium sulfate layer. Discard the 
pre-elution hexane. Add the sample extract, dissolved in 5 mL of hexane 
to the head of the column. Allow the sample to flow into the column 
leaving a small quantity of hexane above the sodium sulfate layer. 
Rinse the extract container with two additional 5-mL rinses of hexane 
and apply each rinse to the column separately as the previous addition 
elutes. Elute the column with an additional 90 mL of hexane and retain 
the entire eluate. Concentrate this solution to a volume of about 1 mL 
using the nitrogen evaporative concentrator (see Section 6.3.5 of this 
method).
    11.3.2.2 Silver Nitrate Silica Gel Column Chromatography. Pack a 
column (6 mm ID, 150 mm in length) sequentially with 1 g of silica gel 
and 1 g of 10-percent silver nitrate silica gel followed by a layer of 
about 10 mm of sodium sulfate (anhydrous). Wash the column sufficiently 
with hexane, elute until the liquid level reaches to the upper end of 
the column, and then load the sample solution that is concentrated 
under vacuum to be about 5 mL. Wash the inner side several times with a 
small amount of hexane, elute with 200 mL of hexane at a flow rate 
about 2.5 mL/min (approximately one drop per second) to elute PCDDs.
    11.3.2.3 Multi-layer Silica Gel Column Chromatography. You may use 
a multi-layer silica gel column in place of separate silica columns. 
Pack a column of 20 mm ID and 300 mm in length sequentially by the dry 
pack method with 0.9 g of silica gel, 3.0 g of 2-percent potassium 
hydroxide silica gel, 0.9 g of silica gel, 4.5 g of 44-percent sulfuric 
acid silica gel, 6.0 g of 22-percent sulfuric acid silica gel, 0.9 g of 
silica gel, 3.0 g of 10-percent silver nitrate silica gel, 2.0 g of 
silica gel and 6.0 g of sodium sulfate (anhydrous). Wash the column 
sufficiently with hexane, elute until the liquid level reaches to the 
upper end of the column, and then load the sample solution. Wash the 
inner side of the transfer vessel several times with a small amount of 
hexane, elute with 150-200 mL of hexane at a flow rate about 2.5 mL/min 
(approximately one drop per second) to elute PCDDs/PCDFs.
    11.3.2.4 Basic Alumina Column Chromatography. Pack a column (20 mm 
ID, 300 mm in length) with approximately 6 to 12 g of basic alumina. 
Pre-elute the column with 50 to 100 mL of hexane. Transfer the 
concentrated extract from the previous column cleanup to the top of the 
basic alumina column. Allow the sample to flow into the column leaving 
a small quantity of solvent above the top of the bed. Rinse the extract 
container with two additional 1-mL rinses of hexane and apply each 
rinse to the column separately as the previous addition elutes. Elute 
the column with 100 mL hexane to remove the interferences. Elute the 
PCDDs/PCDFs from the column with 20 to 40 mL of 50-percent

[[Page 2255]]

methylene chloride in hexane. The ratio of methylene chloride to hexane 
may vary depending on the activity of the alumina used in the column 
preparation. Do not let the head of the column go without solvent. The 
first 100 mL hexane eluate is not used for subsequent PCDD/PCDF 
analysis. The eluate is concentrated to approximately 0.5 mL using the 
nitrogen evaporative concentrator.
    11.3.2.5 Carbopack[supreg] C/Celite[supreg] 545 Column or 
Equivalent. Cut both ends from a 10 mL disposable Pasteur pipette (see 
Section 6.4.1 of this method) to produce a 10 cm column. Fire-polish 
both ends and flare both ends if desired. Insert a glass wool plug at 
one end and pack the column with 0.55 g of Carbopack[supreg]/
Celite[supreg] (see Section 7.8.9.4 of this method) to form an 
adsorbent bed approximately 2 cm long. Insert a glass wool plug on top 
of the bed to hold the adsorbent in place. Pre-elute the column with 5 
mL of toluene followed by 2 mL of methylene chloride:methanol:toluene 
(15:4:1 v/v), 1 mL of methylene chloride:cyclohexane (1:1 v/v), and 5 
mL of hexane. If the flow rate of eluate exceeds 0.5 mL/minute, discard 
the column. Do not let the head of the column go without solvent. Add 
the sample extract to the column. Rinse the sample container twice with 
1 mL portions of hexane and apply separately to the column. Apply 2 mL 
of hexane to the head of the column to complete the transfer. Elute the 
interfering compounds with two 3 mL portions of hexane, 2 mL of 
methylene chloride:cyclohexane (1:1 v/v), and 2 mL of methylene 
chloride:methanol:toluene (15:4:1 v/v). Discard the eluate. Invert the 
column and elute the PCDDs/PCDFs with 20 mL of toluene. If carbon 
particles are present in the eluate, filter through glass-fiber filter 
paper. Concentrate the eluate to approximately 0.5 mL using the 
nitrogen evaporative concentrator for further cleanup or analysis by 
HRGC/HRMS.
    11.4 PCDD, PCDF, PCB and PAH Analysis.
    11.4.1 Analyze the sample with an HRGC/HRMS using the instrumental 
parameters in Sections 11.4.2 and 11.4.3 of this method.
    11.4.1.1 Immediately prior to analysis, add an aliquot (typically 
20 microliters ([micro]l)) of the pre-analysis standard solution(s) 
from Table 23-7, 23-8, or 23-9 of this method to each sample as 
appropriate for the compounds you are measuring by this method.
    11.4.1.2 Inject an aliquot of the sample extract into the GC. You 
may perform separate analyses using different GC columns for each of 
the target compound classes. A 1-[micro]l aliquot of the extract is 
typically injected into the GC. Perform calibration and analysis for 
each target compound class using the same sample injection volume and 
concentration calculations.
    11.4.1.2.1 If target compounds are not resolved sufficient from 
other target compounds or interferences in the sample to meet the 
requirements in Section 10.2.3.4 or 10.2.3.5 of this method, as 
applicable to the compound class being analyzed, or as otherwise 
specified in an applicable regulation, permit, or other requirement, 
analyze another aliquot of the sample using an alternative column that 
provides elution order to uniquely quantify the target compounds 
subject to interference on the first GC column.
    11.4.1.2.2 You may use column systems other than those recommended 
in this method provided the analyst is able to demonstrate, using 
calibration and performance checks, that the alternative column system 
is able to meet the applicable specifications of Section 10.2.3.4 or 
10.2.3.5 of this method.
    11.4.2 Example Gas Chromatograph Operating Conditions.
    11.4.2.1 Injector. Configured for capillary column, splitless, 250 
[deg]C (482 [deg]F).
    11.4.2.2 Carrier Gas. Helium, 1 to 2 mL/min.
    11.4.2.3 Oven. Optimize the GC temperature program to achieve the 
required separation and target compound recovery for the GC column in 
use. Table 23-16 of this method presents the typical conditions for a 
DB5-MS column.
    11.4.3 High-Resolution Mass Spectrometer.
    11.4.3.1 Ionization Mode. Electron ionization.
    11.4.3.2 Source Temperature. Maintain the source temperature in the 
range of 250 to 300 [deg]C (482 to 572 [deg]F).
    11.4.3.3 Ion Monitoring Mode. Tables 23-4, 23-5, and 23-6 of this 
method summarize the various ions to be monitored for PCDD/PCDFs, PAHs, 
and PCBs, respectively.
    11.4.3.4 Identification Criteria for Target Compounds. Use the 
following identification criteria for the characterization of target 
compounds in this method. The available native and isotopically labeled 
standards allow the unique identification of all PCDD/PCDF, PAH, and 
selected PCB congeners required in this method. Also see Sections 13.12 
and 13.13 of this method for identification criteria for PCDD/PCDF/PCB 
and PAH target compounds, respectively.
    11.4.3.4.1 For PCDD/PCDFs and PCBs, Table 23-15 of this method 
provides the integrated ion abundance ratio of primary and secondary 
target compound ions for the identification of target compounds. When 
the ion abundance ratio for a target analyte is outside the performance 
criteria, you may reanalyze samples on an alternative GC column to 
resolve chemical interferences, tune the mass spectrometer to operate 
at a higher mass resolution to discriminate against the 
interference(s), and/or reprocess an archived sample through the 
cleanup procedure to remove the interference(s). Report analysis 
results that do not meet the identification criteria as an estimated 
maximum possible concentration (EPC). Calculate the EPC separately for 
each quantitation ion, if present, and report the lower value as the 
EPC. This method does not consider EPC-flagged data to be zero 
concentrations.

    Note:  Some EPCs are caused by poor ion statistics when the 
concentration of the target compound is at or near the DL. If you 
use the primary ion to determine and report the target compound 
concentration in these cases, reanalysis of samples is not 
necessary.

    11.4.3.4.2 The retention time for the analytes must be within 3 
seconds of the corresponding \13\ C-labeled pre-extraction standard.
    11.4.3.4.3 The signals for the two exact masses in Tables 23-4 and 
23-6 of this method for PCDD/PCDFs and PCBs, respectively, must be 
present and must reach their maximum response within two seconds of 
each other.
    11.4.3.4.4 Identify and quantify specific target compounds or 
isomers that do not have corresponding \13\ C-labeled standards by 
comparing to the pre-extraction labeled standard of the same compound 
class with the nearest retention time to target compound.
    11.4.3.4.5 For the identification of specific PCB isomers, the 
retention time of the native congener must be within 0.006 relative 
retention time (RRT) units of the pre-extraction isotopically labeled 
standard.
    11.4.3.4.6 For qualitative identification, the S/N ratio for the GC 
signal present in every selected ion current profile for native 
compound response must be greater than or equal to 2.5. The ion 
abundance ratios must be within the control limits in Table 23-15 of 
this method for the compound class measured.
    11.4.3.4.7 The confirmation of 2,3,7,8-TeCDD and 2,3,7,8-TeCDF must 
satisfy the separation criteria in Section

[[Page 2256]]

10.2.3.4 of this method and all the identification criteria specified 
in Sections 11.4.3.4.1 through 11.4.3.4.6 of this method.
    11.4.3.4.8 Chlorodiphenyl Ether Interference. If chromatographic 
peaks are detected at the retention time of any PCDDs/PCDF in any of 
the m/z channels used to monitor chlorodiphenyl ethers, there is 
evidence of a positive interference and you may opt to flag data noting 
the interference and keep the value to calculate PCDD/PCDF 
concentration as EPC or conduct a complete reanalysis to remove or 
shift the interference. This method recommends alumina (see Section 
11.3.2.4 of this method) and Florisil[supreg] (see Section 11.3.1 of 
this method) liquid column chromatography packing materials for removal 
of chlorodiphenyl ethers during sample cleanup.
    11.4.3.4.9 Set the mass spectrometer lock channels as specified in 
Tables 23-4, 23-5, and 23-6 of this method for PCDD/PCDFs, PAHs, and 
PCBs, respectively. Monitor the quality control check channels to 
verify instrument stability during the analysis. If the signal varies 
by more than 25 percent from the average response, flag results for all 
isomers at corresponding retention time as QCF. You have the option to 
conduct additional cleanup procedures on an archived portion of the 
sample if the archive is available, or dilution the original sample and 
reanalysis or follow other quality review that demonstrates the target 
analyte and its corresponding isotopically labeled standard are equally 
affected by the change in the control check channels. When you conduct 
a complete reanalysis, reanalyze all concentration calculations based 
on the reanalyzed sample.
    11.4.3.4.10 Identification Criteria for PAHs. The RRT between each 
native and labeled compound must be within 0.006 RRT units. The signals 
for the characteristic ion listed in Table 23-5 of this method must be 
present.
    11.4.3.5 Quantitation. Measure the response of each native target 
compound and the corresponding pre-extraction standard. Use the 
equation in Section 12.7 of this method to sum the peak areas for the 
two quantitation ions monitored for each analyte and calculate the mass 
of the target compound(s) in the injection using the CCV RF. Use the 
pre-extraction recovery standard compounds to correct the homologous 
congener results for variations in recovery from the extraction, 
cleanup, and concentration steps of the analysis. Recovery of pre-
extraction standards must meet minimum specifications (in Section 9.2. 
of this method) to ensure that the method performance and reliability 
have not been compromised by unacceptable losses during sample 
processing. Table 23-17 of this method shows the assignments for single 
isotopically labeled compounds for use in calculating the response 
factor and the concentrations of PCBs. Recoveries of all labeled 
standards must meet the minimum recovery specifications in this method 
and unacceptably low recoveries are an indication of the sample 
processing step that caused the low recoveries.
    11.4.3.5.1 Use Eq. 23-7 to calculate the mass of each target 
compound or group in the extract.
    11.4.3.5.2 Use Eq. 23-8 to calculate the mass per dscm of each 
target compound or group in the sample.
    11.4.3.5.3 Quantify indigenous PCDD and PCDF in its homologous 
series using the corresponding native and pre-extraction standard 
response in its homologous series. For example, use \13\C12-
2,3,7,8-tetra chlorinated dibenzodioxin to calculate the concentrations 
of all other tetra chlorinated isomers.
    11.4.3.5.4 As an option or as required or specified in applicable 
regulations, permits, or other requirements, you may quantify any or 
all other PCB congeners as resolved or coeluting combinations using the 
response of the nearest eluting native target PCB and the response of 
the pre-extraction isotopic label assigned in appendix A to this 
method.
    11.4.3.5.5 As an option or as required or specified in applicable 
regulations, permits, or other requirements, report the total 
concentration of congeners at a given level of chlorination (homolog; 
i.e., total TrCB, total PeCB, total HxCB) by summing the concentrations 
of all congeners identified in the retention time window for the 
homologs as assigned in appendix A to this method.
    11.4.3.5.6 As an option or if required in an applicable regulation, 
permit or other requirement, total chlorinated biphenyls (CBs) may be 
reported by summing all congeners identified at all window-defined 
congeners (WDCs) as assigned in appendix A to this method.

12.0 Data Analysis and Calculations

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

    12.1 Nomenclature.
    Aai = Integrated ion current (area) of the noise for the primary 
and secondary m/z values at the retention time of the analyte.
    A*ci = Integrated ion current (area) of the primary and secondary 
m/z values of the pre-extraction (internal) standard i in the 
calibration standard.
    A1l = Integrated ion current of the primary m/z values 
for the isotopically labeled compound (assigned in Tables 23-4, 23-5, 
and 23-6 of this method).
    A1n = Integrated ion current of the primary m/z values 
for the target native compound.
    A2l = Integrated ion current of the secondary m/z's for 
the isotopically labeled compound. For PAH A2l = 0.
    A2n = Integrated ion current of the secondary m/z values 
for the target native compound. For PAH A2n = 0.
    Cl = The concentration of the labeled compound used to 
perform isotope recovery correction, pg/[mu]L. Tables 23-4, 23-5, and 
23-17 of this method provide the compound mass assignments.
    Cn = The concentration of the target native compound, 
pg/[mu]L.
    Ci = Concentration of target native compound i in the 
sample, pg/[mu]L.
    Cidscm = Concentration of target native compound i in 
the emission gas, pg/dscm.
    Ciext = Concentration of target native compound i in the 
extract, pg.
    CT = Total concentration of target compounds in the 
sample, pg/[mu]L.
    D = Difference in the RRF of the continuing calibration 
verification compared to the average RRF of the initial calibration, 
percent (%).
    dscm = Dry standard cubic meters of gas volume sample measured by 
the dry gas meter, corrected to standard conditions.
    Hai = Summed heights of the noise at the retention time 
of the analyte in the two analyte channels.
    H*ci = Summed heights of the noise at the primary and secondary m/
z's of the pre-extraction standard i in the calibration standard.
    mi = Mass of compound i, pg.
    m*i = Mass of pre-extraction (internal standard) 
compound i, pg.
    n = Number of values.
    NOAAT = National Oceanic and Atmospheric Administration isotopic 
labeled congener for PCB of interest.
    R* = Recovery of labeled compound standards, %.
    RRFi = Relative response factor of a target compound at 
calibration level i.
    RRFccv = Relative response factor of a target compound 
in the continuing calibration verification.
    RSD = Relative standard deviation, in this case, of RRFs over the 
five calibration levels, %.
    SDRRF = Standard deviation of initial calibration RRFs.
    Vext = Extract volume, [mu]L.

[[Page 2257]]

    WHOT = World Health Organization acronym used to designate WHO 
isotopic labeled toxic analog.
    WDC = Window-defined congener representing an isotopically labeled 
PCB that defines the beginning or end of a retention time window 
bracketing a PCB homolog level of chlorination.
    12.2 Individual Compound RRF for Each Calibration Level i. The 
equation for the response factor of each target native compound 
relative to its labeled pre-extraction spike analog includes the 
integrated ion current of both the primary and secondary m/z values for 
each compound in the calibration standard. Use this equation to 
calculate the RRF for the continuing calibration verification for 
comparison to the average RRF from the initial calibration.
[GRAPHIC] [TIFF OMITTED] TP14JA20.000

    12.3 Average RRF for Each Compound Over the Five Calibration 
Levels.
[GRAPHIC] [TIFF OMITTED] TP14JA20.001

    12.4 Percent RSD of the RRFs for a Compound Over the Five 
Calibration Levels. The requirement for the initial calibration RSD is 
in Section 13.10 and Table 23-14 of this method.
[GRAPHIC] [TIFF OMITTED] TP14JA20.002

    12.5 Standard Deviation of the RRFs for a Compound Over the Five 
Calibration Levels.
[GRAPHIC] [TIFF OMITTED] TP14JA20.003

    12.6 Percent Difference of the RRF of the Continuing Calibration 
Verification Compared to the Average RRF from the Initial Calibration 
for Each Target Compound. The requirement for the continuing 
calibration verification percent difference is in Section 13.11 and 
Table 23-14 of this method.
[GRAPHIC] [TIFF OMITTED] TP14JA20.004

    12.7 Concentration of Individual Target Compound i in the Extract 
by Isotope Dilution (pg/[mu]L). This equation corrects for the target 
native compound recovery by its labeled pre-extraction spike analog. To 
accomplish this the pre-extraction spike, labeled compound levels must 
remain constant.
[GRAPHIC] [TIFF OMITTED] TP14JA20.005

    12.8 Concentration of the Individual Target Compound i in the 
Sample Extract (pg).
[GRAPHIC] [TIFF OMITTED] TP14JA20.006

    12.9 Mass of the Individual Target Compound or Group i in the 
Emission Gas (pg/dscm).
[GRAPHIC] [TIFF OMITTED] TP14JA20.007

    12.10 Recovery of Labeled Compound Standards. Use this equation to 
determine the recovery of any labeled compounds, including pre-sampling 
spikes, pre-extraction filter spike, pre-extraction spikes, pre-
analysis spikes. The recovery performance criteria for these spikes is 
in Sections 13.15, 13.16, and 13.17 of this method.
[GRAPHIC] [TIFF OMITTED] TP14JA20.008

    12.11 Estimated Detectable Limit (EDL).
    [GRAPHIC] [TIFF OMITTED] TP14JA20.009
    
    12.12 Total Concentration.
    [GRAPHIC] [TIFF OMITTED] TP14JA20.010
    

    Note: Unless otherwise specified in applicable regulations, 
permits or other requirements, count any target compounds reported 
as non-detected as EDL when calculating the concentration of target 
compounds in the sample.

13.0 Method Performance

    13.1 Residual Toluene Quality Check. If adsorbent resin is cleaned 
or recleaned by the laboratory, a quality control check for residual 
toluene must be <=1,000 [mu]g/g of adsorbent. See appendix B to this 
method for procedures to assess residual toluene.
    13.2 Field Train Proof Blank and Batch Blank Sample Assessment. 
Conduct at least one field train proof blank for each test series at a 
single facility or sampling location. Analyze at least one batch blank 
sample during an analytical sequence or every 24 hours, whichever is 
shorter. Native target compound concentrations must be less than or 
equal to three times the EDL of the method or 10 times lower than the 
quantitation limit required by the end use of the data, whichever is 
higher. If blank assessment fails this criterion, flag sample data from 
this test with explanation that the blank samples failed the method 
criteria.
    13.3 GC column systems used to measure PCDD/PCDFs must meet the 
column separation requirements in Section 6.5.2.1 of this method and 
the applicable requirements in Sections 10.2.3.4 and 11.4.3.4 of this 
method using calibration and batch blank performance checks. Failure to 
meet this chromatographic resolution criterion requires data from this 
analysis to be flagged explaining the potential bias of the results. A 
mid-concentration standard containing all of the native target PCDD/
PCDFs may be used to demonstrate this requirement.
    13.4 GC column systems used to measure PAHs must meet the column 
separation requirements in Section 6.5.2.2 of this method and the 
applicable requirements in Sections 10.2.3.4 and 11.4.3.4 of this 
method using calibration and batch blank performance checks. Failure to 
meet this chromatographic resolution criterion requires data from this 
analysis to be flagged explaining the potential bias of the results.
    13.5 GC systems used to measure PCBs must meet the column 
separation requirements in Section 6.5.2.3 of this method and the 
applicable requirements in Sections 10.2.3.4 and 11.4.3.4 of this 
method of this method using calibration and batch blank performance 
checks, and be able to achieve unique resolution and identification of 
the toxics for determination of a TEQPCB using TEFs 
(American Society of Mechanical Engineers 1984).
    13.6 Confirmation Column. If target compounds are not sufficiently 
resolved from other target compounds or interferences in the sample to 
meet the requirements for target compounds in Sections 13.3, 13.4, and/
or 13.5 of this method, analyze another aliquot of the sample in a 
separate run using an alternative column that provides elution order to 
uniquely quantify the target compounds subject to interference on the 
first GC column.
    13.7 Detection Limits. If the DLs as determined in Section 9.5 of 
this method meet the target DLs shown in Tables 23-18, 23-19, and 23-20 
of this method for the target compounds determined with this method, 
the DLs

[[Page 2258]]

are considered acceptable. If the compound specific DLs are less than 
50 percent of the emission standard, the DLs are acceptable. If the DL 
requirements are not met, you must flag native compound data that fails 
to meet these criteria and provide a description of the impact on the 
data as part of the quality narrative for the sample analyses.
    13.8 Tune. Tune the HRGC/HRMS to meet the isotopic ratio criteria 
listed in Table 23-15 of this method.
    13.9 Lock Channels. MS lock and quality control channels 
recommended in Tables 23-4, 23-5, and 23-6 of this method for PCDD/
PCDFs, PCBs, or PAHs, respectively, must not vary >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 <= three times 
the EDL of the method or 10 times lower than the quantitation limit 
required by the end use of the data, whichever is higher.

    Note:  You must analyze batch blank samples at least once during 
each analytical sequence or every 24 hours, whichever is shorter.

    13.15 Pre-sampling Spike Recovery and Pre-extraction Filter Spike 
Recovery. Recoveries of all pre-sampling isotopically labeled spike 
compounds standards added to the sample and all pre-extraction filter 
recovery spike compounds added to the filter must be between 70 and 130 
percent (Tables 23-7, 23-8, and 23-9 of this method).
    13.15.1 If the recovery of the pre-sampling spike is below 70 
percent, the sampling runs are not valid, and you must repeat the 
invalid runs. As an alternative, you do not have to repeat the invalid 
sampling runs if the average pre-sampling adsorbent spike recovery is 
25 percent or more and you divide the final results by the average 
fraction of pre-sampling adsorbent spike recovery.
    13.15.2 If the recovery of the pre-extraction filter spike is below 
70 percent, the sampling recovery is not valid, and you must flag the 
test run results.
    13.16 Pre-extraction Spike Recovery. Recoveries of all pre-
extraction isotopically labeled spike compounds standards added to the 
sample must be between 20 to 130 percent for PCDD/PCDFs and PAHs 
(Tables 23-7 and 23-8 of this method) and between 20 to 145 percent for 
PCBs (Table 23-9 of this method).
    13.17 Pre-analysis Spike Sensitivity. Response of all pre-analysis 
isotopically labeled spike compounds must show a S/N for every selected 
ion current profile of >=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 <2 
are hazardous and must be neutralized before being poured down a drain 
or must be handled as hazardous waste.
    15.3 For further information on waste management, consult The Waste 
Management Manual for Laboratory Personnel and Less is Better-
Laboratory Chemical Management for Waste Reduction, available from the 
American Chemical Society's Department of Government Relations and 
Science Policy, 1155 16th Street NW, Washington, DC 20036.

16.0 Bibliography

    1. American Society of Mechanical Engineers. Analytical Procedures 
to Assay Stack Effluent Samples and Residual Combustion Products for 
Polychlorinated Dibenzo-p-Dioxins (PCDD) and Polychlorinated 
Dibenzofurans (PCDF). Prepared for the U.S. Department of Energy and 
U.S. Environmental Protection Agency. Washington, DC. December 1984. 23 
p.
    2. American Society of Mechanical Engineers. Sampling for the 
Determination of Chlorinated Organic Compounds in Stack Emissions. 
Prepared for U.S. Department of Energy and U.S. Environmental 
Protection Agency. Washington DC. December 1984. 25 p.
    3. Fishman, V.N., Martin, G.D. and Lamparski, L.L., Comparison of a 
variety of gas chromatographic columns with different polarities for 
the separation of chlorinated dibenzo-p-dioxins and dibenzofurans by 
high-resolution mass spectrometry, Journal of Chromatography A 1139 
(2007) 285-300.
    4. International Agency for Research on Cancer. Environmental 
Carcinogens Methods of Analysis and Exposure Measurement, Volume 11--
Polychlorinated Dioxins and Dibenzofurans. IARC Scientific Publications 
No. 108, 1991.
    5. Stieglitz, L., Zwick, G., Roth, W. Investigation of different 
treatment techniques for PCDD/PCDF in fly ash. Chemosphere 15: 1135-
1140; 1986.
    6. Triangle Laboratories. Case Study: Analysis of Samples for the 
Presence of Tetra Through Octachloro-p-Dibenzodioxins and 
Dibenzofurans. Research Triangle Park, NC. 1988. 26 p.
    7. U.S. Environmental Protection Agency. Method 8290--The Analysis 
of Polychlorinated Dibenzo-p-dioxin and Polychlorinated Dibenzofurans 
by High-Resolution Gas Chromatography/High-Resolution Mass 
Spectrometry. In: Test Methods for Evaluating Solid Waste. Washington, 
DC. SW-846.
    8. U.S. Environmental Protection Agency. Office of Air Programs 
Publication No. APTD-0576: Maintenance, Calibration, and Operation of 
Isokinetic Source Sampling Equipment. Research Triangle Park, NC. March 
1972.
    9. U.S. Environmental Protection Agency. Method 1625C-Semivolatile 
Organic Compounds by Isotope Dilution GCMS.
    10. U.S. Environmental Protection Agency. Method 1613B-Tetra- 
through Octa-Chlorinated Dioxins and Furans by Isotope Dilution HRGC/
HRMS.
    11. U.S. Environmental Protection Agency. Method 1668C-Chlorinated 
Biphenyl Congeners in Water, Soil, Sediment, Biosolids, and Tissue by 
HRGC/HRMS.12. Tondeur, Y., Nestrick, T., Silva, H[eacute]ctor A., 
Vining, B., Hart, J. Analytical procedures for the determination of 
polychlorinated-p-dioxins, polychlorinated dibenzofurans, and 
hexachlorobenzene in pentachlorophenol, Chemosphere Volume 80, Issue 2, 
June 2010 pages 157-164.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

          Table 23-1--Polychlorinated Dibenzo-p-Dioxin and Polychlorinated Dibenzofuran Target Analytes
----------------------------------------------------------------------------------------------------------------
                                             CAS \a\ registry                                   CAS \a\ registry
     Polychlorinated dibenzo-p-dioxins            number        Polychlorinated dibenzofurans         No.
----------------------------------------------------------------------------------------------------------------
2,3,7,8-TeCDD.............................          1746-01-6  2,3,7,8-TeCDF.................         51207-31-9
1,2,3,7,8-PeCDD...........................         40321-76-4  1,2,3,7,8-PeCDF...............         57117-41-6
1,2,3,4,7,8-HxCDD.........................         39227-28-6  2,3,4,7,8-PeCDF...............         57117-31-4
1,2,3,6,7,8-HxCDD.........................         57653-85-7  1,2,3,4,7,8-HxCDF.............         70648-26-9
1,2,3,7,8,9-HxCDD.........................         19408-74-3  1,2,3,6,7,8-HxCDF.............         57117-44-9
1,2,3,4,6,7,8-HpCDD.......................         35822-46-9  1,2,3,7,8,9-HxCDF.............         72918-21-9
Total TeCDD...............................         41903-57-5  2,3,4,6,7,8-HxCDF.............         60851-34-5
Total PeCDD...............................         36088-22-9  1,2,3,4,6,7,8-HpCDF...........         67562-39-4
Total HxCDD...............................         34465-4608  1,2,3,4,7,8,9-HpCDF...........         55673-89-7
Total HpCDD...............................         37871-00-4  Total TeCDF...................         55722-27-5
Total OCDD................................          3268-87-9  Total PeCDF...................         30402-15-4
                                                               Total HxCDF...................         55684-94-1
                                                               Total HpCDF...................         38998-75-3
                                                               Total OCDF....................         39001-02-0
----------------------------------------------------------------------------------------------------------------
\a\ Chemical Abstract Service.


[[Page 2260]]


                           Table 23-2--Polycyclic Aromatic Hydrocarbon Target Analytes
----------------------------------------------------------------------------------------------------------------
                                              CAS \a\ registry       Polycyclic aromatic        CAS \a\ registry
     Polycyclic aromatic  hydrocarbons              No.                  hydrocarbons                 No.
----------------------------------------------------------------------------------------------------------------
Naphthalene................................            91-20-3  Chrysene.....................           218-01-9
2-Methylnapthalene.........................            91-57-6  Benzo[b]fluoranthene.........           205-99-2
Acenaphthylene.............................           208-96-8  Benzo[k]fluoranthene.........           207-08-9
Acenaphthene...............................            83-32-9  Perylene.....................           198-55-8
Fluorene...................................            86-73-7  Benzo[a]pyrene...............            50-32-8
Anthracene.................................           120-12-7  Benzo[e]pyrene...............           192-92-2
Phenanthrene...............................            85-01-8  Benzo[g,h,i]perylene.........           191-24-2
Fluoranthene...............................           206-44-0  Indeno[1,2,3-cd]pyrene.......           193-39-5
Pyrene.....................................           129-00-0  Dibenz[a,h]anthracene........            53-70-3
Benzo[a]anthracene.........................            56-55-3
----------------------------------------------------------------------------------------------------------------
\a\ Chemical Abstract Service.


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


           Table 23-4--Elemental Compositions and Exact Masses of the Ions Monitored by High-Resolution Mass Spectrometry for PCDDs and PCDFs
--------------------------------------------------------------------------------------------------------------------------------------------------------
                   Ion type b        Elemental       Target analyte b                                        Elemental
     Mass a                         composition                              Mass a        Ion typeb        composition           Target analyte b
--------------------------------------------------------------------------------------------------------------------------------------------------------
263.9871.......  LOCK           C5F10N............  FC43..............  383.8639.......  M              13C12H235Cl6O.....  HxCDF (S).
292.9825.......  LOCK           C7F11.............  PFK...............  385.8610.......  M+2            13C12H235Cl537ClO.  HxCDF (S).
303.9016.......  M              C12H435Cl4O.......  TeCDF.............  389.8157.......  M+2            C12H235Cl537ClO2..  HxCDD.
305.8987.......  M+2            C12H435Cl37O......  TeCDF.............  391.8127.......  M+4            C12H235Cl437Cl2O2.  HxCDD.
313.9839.......  QC             C6F12N............  FC43..............  392.9760.......  LOCK           C9F15.............  PFK.
315.9419.......  M              13C12H435Cl4O.....  TeCDF (S).........  401.8559.......  M+2            13C12H235Cl537ClO2  HxCDD (S).
316.9745.......  M+2            13C12H435Cl4O.....  TeCDF (S).........  403.8529.......  M+4            13C12H235Cl437Cl2O  HxCDD (S).
317.9389.......  M+2            13C12H435Cl337ClO.  TeCDF (S).........  425.9775.......  QC             C9F16N............  FC43.
319.8965.......  M              C12H435ClO2.......  TeCDD.............  445.7555.......  M+4            C12H235Cl637Cl2O..  OCDPE.
321.8936.......  M+2            C12H435Cl337ClO2..  TeCDD.............  407.7818.......  M+2            C12H35Cl637ClO....  HpCDF.
325.9839.......  QC             C7F12N............  FC43..............  409.7789.......  M+4            C12H35Cl537Cl2O...  HpCDF.
327.8847.......  M              C12H437Cl4O2......  TeCDD (S).........  417.8253.......  M              13C12H35Cl7O......  HpCDF (S).
330.9792.......  QC             C7F13.............  PFK...............  419.8220.......  M+2            13C12H35Cl637ClO..  HpCDF (S).
331.9368.......  M              13C12H435Cl4O2....  TeCDD (S).........  423.7766.......  M+2            C12H35Cl637ClO2...  HpCDD.
333.9339.......  M+2            13C12H435Cl37ClO2.  TeCDD (S).........  425.7737.......  M+4            C12H35Cl537Cl2O2..  HpCDD.
339.8597.......  M+2            C12H335Cl437ClO...  PeCDF.............  430.9729.......  QC             C9F17.............  PFK.
341.8567.......  M+4            C12H335Cl337Cl2O..  PeCDF.............  435.8169.......  M+2            13C12H35Cl637ClO2.  HpCDD (S).
354.9792.......  LOCK           C9F13.............  PFK...............  437.8140.......  M+4            13C12H35Cl537Cl2O2  HpCDD (S).
351.9000.......  M+2            13C12H335Cl437ClO.  PeCDF (S).........  442.9728.......  LOCK           C10F17............  PFK.
353.8970.......  M+4            13C12H335Cl3537Cl2  PeCDF (S).........  479.7165.......  M+4            C12H35Cl737Cl2O...  NCPDE.
                                 O.
355.8546.......  M+2            C12H335Cl337ClO2..  PeCDD.............  430.9729.......  LOCK           C9F17.............  PFK.
357.8516.......  M+4            C12H335Cl337Cl2O2.  PeCDD.............  441.7428.......  M+2            C1235Cl737ClO.....  OCDF.
367.8949.......  M+2            13C12H335Cl437ClO2  PeCDD (S).........  443.7399.......  M+4            C1235Cl637Cl2O....  OCDF.
369.8919.......  M+4            13C12H335Cl337Cl2O  PeCDD (S).........  457.7377.......  M+2            C1235Cl737ClO2....  OCDD.
                                 2.
375.9807.......  QC             C8F14N............  FC43..............  459.7348.......  M+4            C1235Cl637Cl2O2...  OCDD.
375.8364.......  M+2            C12H435Cl537ClO...  HxCDPE............  463.9743.......  QC             C9F18N............  FC43.
409.7974.......  M+2            C12H335Cl637ClO...  HpCPDE............  469.7779.......  M+2            13C1235Cl737ClO2..  OCDD (S).
373.8208.......  M+2            C12H235Cl537ClO...  HxCDF.............  471.7750.......  M+4            13C1235Cl637Cl2O2.  OCDD (S).
375.8178.......  M+4            C12H235Cl437Cl2O..  HxCDF.............  513.6775.......  M+4            C1235Cl837Cl2O2...  DCDPE.
375.9807.......  QC             C8F14N............  FC43..............  442.9728.......  QC             C10F17............  PFK.
--------------------------------------------------------------------------------------------------------------------------------------------------------
a The following nuclidic masses were used to calculate exact masses: H = 1.007825, C = 12.000000, 13C = 13.003355, F = 18.9984, O = 15.994915, 35Cl =
  34.968853, 37Cl = 36.965903.
b (S) = Labeled Standard. QC = Ion selected for monitoring instrument stability during the HRGC/HRMS analysis.


[[Page 2261]]


 Table 23-5--Elemental Compositions and Exact Masses of the Ions Monitored by High-Resolution Mass Spectrometry
                                                    for PAHs
----------------------------------------------------------------------------------------------------------------
                                                                                Elemental
        Aromatic ring No.              Mass a             Ion type b           composition       Target analyte
----------------------------------------------------------------------------------------------------------------
2................................        128.0624  M                        C10H8............  Naphthalene.
                                         130.9920  LOCK                                        PFK/FC43.
2................................        134.0828  M                        13C612C4H8.......  13C6-Naphthalene.
2................................         142.078  M                        C11H10...........  2-
                                                                                                Methylnaphthalen
                                                                                                e.
2................................        148.0984  M                        13C612C5H10......  13C6-2-
                                                                                                Methylnaphthalen
                                                                                                e.
2................................        152.0624  M                        C12H8............  Acenaphthylene.
2................................        158.0828  M                        13C612C6H8.......  13C6-
                                                                                                Acenaphthylene.
2................................         154.078  M                        C12H10...........  Acenaphthene.
2................................         160.078  M                        13C612C6H10......  13C6-
                                                                                                Acenaphthene.
2................................         166.078  M                        C13H10...........  Fluorene.
                                          169.988  QC                                          PFK/FC43.
2................................        172.0984  M                        13C612C7H........  13C6-Fluorene.
3................................         178.078  M                        C14H10...........  Phenanthrene.
3................................        184.0984  M                        13C6 12C8H10.....  13C6-
                                                                                                Phenanthrene.
3................................         178.078  M                        C14H10...........  Anthracene.
3................................         184.078  M                        13C612C8H10......  13C6-Anthracene.
3................................         202.078  M                        C16H10...........  Fluoranthene.
                                         204.9888  QC                                          PFK.
3................................        208.0984  M                        13C612C10H10.....  13C6-
                                                                                                Fluoranthene.
4................................         202.078  M                        C16H10...........  Pyrene.
4................................         205.078  M                        13C312C13H10.....  13C3-Pyrene.
                                         213.9898  QC                                          FC43.
                                         218.9856  LOCK                                        FC43.
4................................        228.0936  M                        C18H12...........  Benzo[a]anthracen
                                                                                                e.
                                         230.9856  LOCK                                        PFK.
4................................         234.114  M                        13C6C12H12.......  13C6-
                                                                                                Benzo[a]anthrace
                                                                                                ne.
4................................        228.0936  M                        C18H12...........  Chrysene.
4................................         234.114  M                        13C612C12H12.....  13C6-Chrysene.
4................................        252.0936  M                        C20H12...........  Benzo[b]fluoranth
                                                                                                ene.
4................................         258.114  M                        13C612C14H12.....  13C6-
                                                                                                Benzo[b]fluorant
                                                                                                hene.
4................................          252.32  M                        C20H12...........  Benzo[k]fluoranth
                                                                                                ene.
4................................         258.114  M                        13C6127C14H12....  13C6-
                                                                                                Benzo[k]fluorant
                                                                                                hene.
5................................        252.0936  M                        C20H12...........  Benzo[e]pyrene.
5................................        256.1072  M                        13C412C16H12.....  13C4-
                                                                                                Benzo[e]pyrene.
5................................        256.1072  M                        13C412C16H12.....  13C4-
                                                                                                Benzo[a]pyrene.
5................................        252.0936  M                        C20H12...........  Benzo[a]pyrene.
5................................        252.0936  M                        C20H12...........  Perylene.
5................................        264.1692  M                        C20D12...........  d12-Perylene.
                                         268.9824  QC                                          PFK.
                                         263.9871  LOCK                                        FC43.
6................................        276.0936  M                        C22H12...........  Indeno[1,2,3-
                                                                                                cd]pyrene.
6................................         282.114  M                        13C612C16H12.....  13C6-
                                                                                                Indeno[1,2,3,cd]
                                                                                                pyrene.
5................................        278.1092  M                        C22H14...........  Dibenz[a,h]anthra
                                                                                                cene.
                                         280.9824  LOCK                                        PFK.
5................................        284.1296  M                        13C612C16H14.....  13C6-
                                                                                                Dibenz[a,h]anthr
                                                                                                acene.
6................................        276.0936  M                        C22H12...........  Benzo[g,h,i]peryl
                                                                                                ene.
6................................        288.1344  M                        13C1212C10H12....  13C12-
                                                                                                Benzo[g,h,i]pery
                                                                                                lene.
                                         313.9839  QC                                          FC43.
----------------------------------------------------------------------------------------------------------------
a Isotopic masses used for accurate mass calculation: 1H = 1.0078, 12C = 12.0000, 13C = 13.0034, 2H = 2.0141.
b LOCK = Lock-Mass Ion PFK or FC43. QC = Quality Control Check Ion.


 Table 23-6--Elemental Compositions and Exact Masses of the Ions Monitored by High-Resolution Mass Spectrometry
                                                    for PCBs
----------------------------------------------------------------------------------------------------------------
                                                                                Elemental
      Chlorine substitution            Mass a             Ion type b           composition       Target analyte
----------------------------------------------------------------------------------------------------------------
Fn-1; Cl-1.......................        188.0393  M                        12C12H935Cl......  Cl-1 PCB
                                         190.0363  M+2                      12C12H937Cl......  Cl-1P CB
                                         200.0795  M                        13C12H935Cl......  13C12Cl-1 PCB
                                         202.0766  M+2                      12C12H937Cl......  13C12Cl-1 PCB
                                         218.9856  LOCK                     C4F9.............  PFK
Fn-2; Cl-2,3.....................        222.0003  M                        12C12H835Cl2.....  Cl-2 PCB
                                         223.9974  M+2                      12C12H835Cl37 Cl.  Cl-2 PCB
                                         225.9944  M+4                      12C12H837Cl2.....  Cl-2 PCB
                                         234.0406  M                        13C12H835Cl2.....  13C12Cl-2 PCB
                                         236.0376  M+2                      13C12H835 Cl37Cl.  13C12Cl-2 PCB
                                         242.9856  C4 F9                    C4 F9............  PFK
                                         255.9613  M                        12C12H735Cl3.....  Cl-3 PCB
                                         257.9584  M+2                      12C12H735Cl237Cl.  Cl-3 PCB
                                         268.0016  M                        13C12H735Cl3.....  13C12 Cl-3 PCB
                                         269.9986  M+2                      13C12H735Cl2 37Cl  13C12 Cl-3 PCB
Fn-3; Cl-3,4,5...................        255.9613  M                        12C12H735Cl3.....  Cl-3 PCB
                                         257.9584  M+2                      12C12H735Cl2 37Cl  Cl-3 PCB
                                         259.9554  M+4                      12C12H735Cl37Cl2.  Cl-3 PCB
                                         268.0016  M                        13C12H735Cl3.....  13C12 Cl-3 PCB
                                         269.9986  M+2                      13C12H735Cl237Cl.  13C12 Cl-3 PCB
                                         280.9825  LOCK                     C6F11............  PFK
                                         289.9224  M                        12C12H635Cl4.....  Cl-4 PCB
                                         291.9194  M+2                      12C12H635Cl337Cl.  Cl-4 PCB

[[Page 2262]]

 
                                         293.9165  M+4                      12C12H635Cl2       Cl-4 PCB
                                                                             37Cl2.
                                         301.9626  M                        13C12H635Cl4.....  13C12Cl-4 PCB
                                         303.9597  M+2                      13C12H635Cl3 37Cl  13C12Cl-4 PCB
                                         323.8834  M                        12C12H535Cl5.....  Cl-5 PCB
                                         325.8804  M+2                      12C12H535Cl4 37Cl  Cl-5 PCB
                                         327.8775  M+4                      12C12H535Cl3       Cl-5 PCB
                                                                             37Cl2.
                                         337.9207  M+2                      13C12H535Cl4 37Cl  13C12Cl-5 PCB
                                         339.9178  M+4                      13C12H535Cl3       13C12Cl-5 PCB
                                                                             37Cl2.
Fn-4; Cl-4,5,6...................        289.9224  M                        12C12H635Cl4.....  Cl-4 PCB
                                         291.9194  M+2                      12C12H635Cl3 37Cl  Cl-4 PCB
                                         293.9165  M+4                      12C12H635Cl2       Cl-4 PCB
                                                                             37Cl2.
                                         301.9626  M+2                      13C12H635Cl3 37Cl  13C12Cl-4 PCB
                                         303.9597  M+4                      13C12H635Cl2       13C12Cl-4 PCB
                                                                             37Cl2.
                                         323.8834  M                        12C12H535Cl5.....  Cl-5 PCB
                                         325.8804  M+2                      12C12H535Cl4 37Cl  Cl-5 PCB
                                         327.8775  M+4                      12C12H5 35Cl3      Cl-5 PCB
                                                                             37Cl2.
                                         330.9792  LOCK                     C7F15............  PFK
                                         337.9207  M+2                      13C12H535Cl4 37Cl  13C12Cl-5 PCB
                                         339.9178  M+4                      13C12H535Cl3       13C12Cl-5 PCB
                                                                             37Cl2.
                                         359.8415  M+2                      13C12H435Cl5.....  37Cl Cl-6 PCB
                                         361.8385  M+4                      13C12H435Cl4       Cl-6 PCB
                                                                             37Cl2.
                                         363.8356  M+6                      12C12H435Cl3       Cl-6 PCB
                                                                             37Cl3.
                                         371.8817  M+2                      13C12H435Cl5 37Cl  13C12Cl-6 PCB
                                         373.8788  M+4                      13C12H435Cl4       13C12Cl-6 PCB
                                                                             37Cl2.
Fn-5; Cl-5,6,7...................        323.8834  M                        12C12H535Cl5.....  Cl-5 PCB
                                         325.8804  M+2                      12C12H535Cl4 37Cl  Cl-5 PCB
                                         327.8775  M+4                      12C12H535Cl3       Cl-5 PCB
                                                                             37Cl2.
                                         337.9207  M+2                      13C12H535Cl4 37Cl  13C12Cl-5 PCB
                                         339.9178  M+4                      13C12H535Cl3       13C12Cl-5 PCB
                                                                             37Cl2.
                                         354.9792  LOCK                     C9F13............  PFK
                                         359.8415  M+2                      12C12H435Cl5 37Cl  Cl-6 PCB
                                         361.8385  M+4                      12C12H435Cl4       Cl-6 PCB
                                                                             37Cl2.
                                         363.8356  M+6                      12C12H435Cl3       Cl-6 PCB
                                                                             37Cl3.
                                         371.8817  M+2                      13C12H435Cl5 37Cl  13C12Cl-6 PCB
                                         373.8788  M+4                      13C12H435Cl4       13C12Cl-6 PCB
                                                                             37Cl2.
                                         393.8025  M+2                      12C12H335Cl6 37Cl  Cl-7 PCB
                                         395.7995  M+4                      12C12H335Cl5       Cl-7 PCB
                                                                             37Cl2.
                                         397.7966  M+6                      12C12H335Cl4.....  37Cl3 Cl-7 PCB
                                         405.8428  M+2                      13C12H335Cl6 37Cl  13C12Cl-7 PCB
                                         407.8398  M+4                      13C12H335Cl5       13C12Cl-7 PCB
                                                                             37Cl2.
                                         454.9728  QC                       C11F17...........  PFK
Fn-6; Cl-7,8,9,10................        393.8025  M+2                      12C12H335Cl6 37Cl  Cl-7 PCB
                                         395.7995  M+4                      12C12H335Cl5       Cl-7 PCB
                                                                             37Cl2.
                                         397.7966  M+6                      12C12H335Cl4.....  37Cl3 Cl-7 PCB
                                         405.8428  M+2                      13C12H335Cl6 37Cl  13C12Cl-7 PCB
                                         407.8398  M+4                      13C12H335Cl5       13C12Cl-7 PCB
                                                                             37Cl2.
                                         427.7635  M+2                      12C12H235Cl7 37Cl  Cl-8 PCB
                                         429.7606  M+4                      12C12H235Cl6       Cl-8 PCB
                                                                             37Cl2.
                                         431.7576  M+6                      12C12H235Cl5       Cl-8 PCB
                                                                             37Cl3.
                                         439.8038  M+2                      13C12H235Cl7 37Cl  13C12Cl-8 PCB
                                         441.8008  M+4                      13C12H235Cl6       13C12Cl-8 PCB
                                                                             37Cl2.
                                         454.9728  QC                       C11F17...........  PFK
                                         427.7635  M+2                      12C12H235Cl7 37Cl  Cl-8 PCB
                                         429.7606  M+4                      12C12H235Cl6       Cl-8 PCB
                                                                             37Cl2.
                                         431.7576  M+6                      12C12H235Cl5       Cl-8 PCB
                                                                             37Cl3.
                                         439.8038  M+2                      13C12H235Cl7 37Cl  13C12Cl-8 PCB
                                         441.8008  M+4                      13C12H235Cl6       13C12Cl-8 PCB
                                                                             37Cl2.
                                         442.9728  QC                       C10F17...........  PFK
                                         454.9728  LOCK                     C11F17...........  PFK
                                         461.7246  M+2                      12C12H135Cl8 37Cl  Cl-9 PCB
                                         463.7216  M+4                      12C12H135Cl7       Cl-9 PCB
                                                                             37Cl2.
                                         465.7187  M+6                      12C12H135Cl6       Cl-9 PCB
                                                                             37Cl3.
                                         473.7648  M+2                      13C12H135Cl8 37Cl  13C12Cl-9 PCB
                                         475.7619  M+4                      13C12H135Cl7       13C12Cl-9 PCB
                                                                             37Cl2.
                                         495.6856  M+2                      13C12H435Cl9 37Cl  Cl-10 PCB
                                         499.6797  M+4                      12C1235Cl737Cl3..  Cl-10 PCB
                                         501.6767  M+6                      12C1235Cl637Cl4..  Cl-10 PCB
                                         507.7258  M+2                      13C12H435Cl9 37Cl  13C12Cl-10 PCB
                                         509.7229  M+4                      13C12H435Cl8       13C12Cl-10 PCB
                                                                             37Cl2.
                                         511.7199  M+6                      13C12H435Cl8       13C12Cl-10 PCB
                                                                             37Cl4.
----------------------------------------------------------------------------------------------------------------
a Isotopic masses used for accurate mass calculation: 1H = 1.0078, 12C = 12.0000, 13C = 13.0034, 35Cl = 34.9689,
  37Cl = 36.9659, 19F = 18.9984. An interference with PFK m/z 223.9872 may preclude meeting 10:1 S/N for the
  DiCB congeners at optional Calibration Level 1 (Table 23-12). If this interference occurs, 10:1 S/N must be
  met at the Calibration Level 2.
b LOCK = Lock-Mass Ion PFK or FC43. QC = Quality Control Check Ion.


[[Page 2263]]


    Table 23-7--Composition of the Sample Fortification and Recovery Standard Solutions for PCDDs and PCDFs a
----------------------------------------------------------------------------------------------------------------
                                                                  Amount (pg/[mu]L of final      Spike recovery
                           Compound                                      extract) b                (percent)
----------------------------------------------------------------------------------------------------------------
                                        Pre-sampling Adsorbent Standards
----------------------------------------------------------------------------------------------------------------
13C12-1,2,3,4-TeCDD..........................................                             50             70-130
13C12-1,2,3,4,7-PeCDD........................................                             50             70-130
13C12-1,2,3,4,6-PeCDF........................................                             50             70-130
13C12-1,2,3,4,6,9-HxCDF......................................                             50             70-130
13C12-1,2,3,4,6,8,9-HpCDF....................................                             50             70-130
----------------------------------------------------------------------------------------------------------------
                                 Pre-extraction Filter Recovery Spike Standards
----------------------------------------------------------------------------------------------------------------
13C12-1,2,7,8-TeCDF..........................................                            100             70-130
13C12-1,2,3,4,6,8-HxCDD......................................                            100             70-130
----------------------------------------------------------------------------------------------------------------
                                            Pre-extraction Standards
----------------------------------------------------------------------------------------------------------------
13C12-2,3,7,8-TeCDD..........................................                            100             20-130
13C12-2,3,7,8-TeCDF..........................................                            100             20-130
13C12-1,2,3,7,8-PeCDD........................................                            100             20-130
13C12-1,2,3,7,8-PeCDF........................................                            100             20-130
13C12-2,3,4,7,8-PeCDF........................................                            100             20-130
13C12-1,2,3,4,7,8-HxCDD......................................                            100             20-130
13C12-1,2,3,6,7,8-HxCDD......................................                            100             20-130
13C12-1,2,3,7,8,9-HxCDD......................................                            100             20-130
13C12-1,2,3,4,7,8-HxCDF......................................                            100             20-130
13C12-1,2,3,6,7,8-HxCDF......................................                            100             20-130
13C12-2,3,4,6,7,8-HxCDF......................................                            100             20-130
13C12-1,2,3,7,8,9-HxCDF......................................                            100             20-130
13C12-1,2,3,4,6,7,8-HpCDD....................................                            100             20-130
13C12-1,2,3,4,6,7,8-HpCDF....................................                            100             20-130
13C12-1,2,3,4,7,8,9-HpCDF....................................                            100             20-130
13C12-OCDD...................................................                            200             20-130
13C12-OCDF...................................................                            200             20-130
----------------------------------------------------------------------------------------------------------------
                                             Pre-analysis Standards
----------------------------------------------------------------------------------------------------------------
13C12-1,3,6,8-TeCDD..........................................                            100            S/N>=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...............  <=20  5  <=20  5  <=20  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         <=6 [deg]C (43       <=6 [deg]C (43       <=6 [deg]C (43 [deg]F).
 Filters.                          [deg]F).             [deg]F).
Adsorbent.......................  <=6 [deg]C (43       <=6 [deg]C (43       <=6 [deg]C (43 [deg]F).
                                   [deg]F).             [deg]F).
Extract and Archive.............  <-10 [deg]C (14      <-10 [deg]C (14      <-10 [deg]C (14 [deg]F).
                                   [deg]F).             [deg]F).
----------------------------------------------------------------------------------------------------------------
                                              Laboratory Hold Times
----------------------------------------------------------------------------------------------------------------
Extract and Archive.............  One year...........  45 Days............  One year.
----------------------------------------------------------------------------------------------------------------
\a\ All samples must be stored in the dark.
\b\ Hold times begin from the time the laboratory receives the samples.


                              Table 23-11--Composition of the Initial Calibration Standard Solutions for PCDDs and PCDFs a
                                                                      [pg/[micro]L]
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                                                  Cal 1                                                                         Cal 7
                      Standard compound                         (optional)     Cal 2        Cal 3        Cal 4        Cal 5        Cal 6      (optional)
--------------------------------------------------------------------------------------------------------------------------------------------------------
Target (Unlabeled) Analytes..................................         0.50          1.0          5.0         10.0           25           50          100
Pre-sampling Adsorbent Standards.............................           50           50           50           50           50           50           50
Pre-extraction Filter Recovery Standards.....................           50           50           50           50           50           50           50
Pre-extraction Standards.....................................           50           50           50           50           50           50           50
Pre-analysis Standards.......................................           50           50           50           50           50           50           50
Alternate Recovery Standards.................................           50           50           50           50           50           50           50
--------------------------------------------------------------------------------------------------------------------------------------------------------
\a\ Assumes 1 [micro]L injection volume.


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


[[Page 2266]]


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


  Table 23-14--Minimum Requirements for Initial and Daily Calibration Response Factors for Isotopically Labeled
                                              and Native Compounds
----------------------------------------------------------------------------------------------------------------
                                                                            Relative response factors
                                                               -------------------------------------------------
                         Analyte group                                                     Daily and continuing
                                                                  Initial calibration     calibration  (percent
                                                                          RSD                  difference)
----------------------------------------------------------------------------------------------------------------
Native (Unlabeled) Analytes...................................                      10                       25
Pre-sampling Adsorbent Standard(s)............................                      20                       25
Pre-extraction Filter Recovery Standards......................                      20                       25
Pre-extraction Standards......................................                      20                       30
Pre-analysis Standards........................................                      20                       30
Alternative Recovery Standards................................                      20                       30
----------------------------------------------------------------------------------------------------------------


                      Table 23-15--Recommended Ion Type and Acceptable Ion Abundance Ratios
----------------------------------------------------------------------------------------------------------------
                                                                                  Control limits
        No. of chlorine atoms                   Ion type            Theoretical  ----------------      Upper
                                                                       ratio           Lower
----------------------------------------------------------------------------------------------------------------
1....................................  M/M+2                                3.13            2.66            3.60
2....................................  M/M+2                                1.56            1.33            1.79
3....................................  M/M+2                                1.04            0.88            1.20
4....................................  M/M+2                                0.77            0.65            0.89
5....................................  M+2/M+4                              1.55            1.32            1.78
6....................................  M+2/M+4                              1.24            1.05            1.43
6 \a\................................  M/M+2                                0.51            0.43            0.59
7....................................  M+2/M+4                              1.05            0.89            1.21
7 \b\................................  M/M+2                                0.44            0.37            0.51
8....................................  M+2/M+4                              0.89            0.76            1.02
9....................................  M+2/M+4                              0.77            0.65            0.89
10...................................  M+4/M+6                              1.16            0.99            1.33
----------------------------------------------------------------------------------------------------------------
\a\ Used only for 13C-HxCDF.
\b\ Used only for 13C-HpCDF.


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


              Table 23-17--Assignment of Pre-extraction Standards for Quantitation of Target PCBs b
----------------------------------------------------------------------------------------------------------------
            PCB congener                    BZ No. \a\              Labeled analog                BZ No.
----------------------------------------------------------------------------------------------------------------
2,4'-DiCB (NOAAT)..................  8                        13C12-2,2'-DiCB...........  4L
2,2',5-TrCB (NOAAT)................  18                       13C12-2,2',6-TrCB.........  19L
2,4,4'-TrCB (NOAAT)................  28                       13C12-2,2',6-TrCB.........  19L
2,2',3,5'-TeCB (NOAAT).............  52                       13C12-2,2',6,6'-TeCB......  54L

[[Page 2267]]

 
2,2',5,5'-TeCB (NOAAT).............  52                       13C12-2,2',6,6'-TeCB......  54L
2,3',4,4'-TeCB (NOAAT).............  66                       13C12-2,2',6,6'-TeCB......  54L
3,3',4,4'-TeCB (NOAAT) (WHOT)......  77                       13C12-3,3',4,4'-TeCB......  77L
3,4,4',5-TeCB (WHOT)...............  81                       13C12-3,4,4'',5-TeCB......  81L
2,2',4,5,5'-PeCB (NOAAT)...........  101                      13C12-2,2',4,5,5'-PeCB....  104L
2,3,3',4,4'-PeCB (NOAAT) (WHOT)....  105                      13C12-2,3,3',4,4'-PeCB....  105L
2,3,4,4',5-PeCB (WHOT).............  114                      13C12-2,3,4,4',5-PeCB.....  114L
2,3',4,4',5-PeCB (WHOT)............  118                      13C12-2,3',4,4',5-PeCB....  118L
2',3,4,4',5-PeCB (WHOT)............  123                      13C12-2',3,4,4',5-PeCB....  123L
3,3',4,4',5-PeCB (NOAAT) (WHOT)....  126                      13C12-3,3',4,4',5-PeCB....  126L
2,2',3,3',4,4'-HxCB (NOAAT)........  128                      13C12-2,2',4,4',6,6'-HxCB.  155L
2,2',3,4,4',5'-HxCB (NOAAT)........  138                      13C12-2,2', 4,4',6,6'-HxCB  155L
2,2',4,4',5,5'-HxCB (NOAAT)........  153                      13C12-2,2', 4,4',6,6'-HxCB  155L
2,3,3',4,4',5-HxCB (WHOT)..........  156                      13C12-2,3,3',4,4',5-HxCB..  156L
2,3,3',4,4',5'-HxCB (WHOT).........  157                      13C12-2,3,3',4,4',5'-HxCB.  157L
2,3',4,4',5,5'-HxCB (WHOT).........  167                      13C12-2,3',4,4',5,5'-HxCB.  167L
3,3',4,4',5,5'-HxCB (NOAAT) (WHOT).  169                      13C12-3,3',4,4',5,5'-HxCB.  169L
2,2',3,3',4,4',5-HpCB (NOAA).......  170                      13C12-2,2',3,3',4,4',5'-    170L
                                                               HpCB.
2,2',3,4,4',5,5'-HpCB (NOAAT)......  180                      13C12-2,2',3,4,4',5,5'-     180L
                                                               HpCB.
2,2',3,4',5,5',6-HpCB (NOAAT)......  187                      13C12-2,2',3,4',5,6,6'-     188L
                                                               HpCB.
2,3,3',4,4',5,5'-HpCB (WHOT).......  189                      13C12-2,3,3',4,4',5,5'-     189L
                                                               HpCB.
2,2',3,3',4,4',5,6-OcCB (NOAAT)....  195                      13C12-2,2' 3,3',5,5',6,6'-  202L
                                                               OcCB.
2,2',3,3',4,4',5,5',6-NoCB (NOAAT).  206                      13C12-                      206L
                                                               2,2',3,3',4,4',5,5',6-
                                                               NoCB.
2,2',3,3',4,4',5,5',6,6'-DeCB        209                      13C12-DeCB................  209L
 (NOAAT).
----------------------------------------------------------------------------------------------------------------
\a\ BZ No.: Ballschmiter and Zell 1980, or IUPAC number.
\b\ Assignments assume the use of the SPB-Octyl column. In the event you choose another column, you may select
  the labeled standard having the same number of chlorine substituents and the closest retention time to the
  target analyte in question as the labeled standard to use for quantitation.


   Table 23-18--Estimated Method Detection Limits for PCDDs and PCDFs
------------------------------------------------------------------------
                                     MDL \a\  (ng/       TEQ-DL  (ng/
             Target                     sample)             sample)
------------------------------------------------------------------------
Total OCDD......................           1.75E-01            5.00E-05
Total OCDF......................           5.38E-02            1.51E-05
1,2,3,4,6,7,8-HpCDD.............           2.36E-02            2.16E-04
1,2,3,4,6,7,8-HpCDF.............           4.88E-02            4.82E-04
1,2,3,4,7,8-HxCDD...............           9.26E-03            8.50E-04
1,2,3,4,7,8-HxCDF...............           6.60E-02            6.48E-03
1,2,3,4,7,8,9-HpCDF.............           2.46E-02            2.40E-04
1,2,3,6,7,8-HxCDD...............           1.06E-02            9.86E-04
1,2,3,6,7,8-HxCDF...............           7.72E-03            7.06E-04
1,2,3,7,8-PeCDD.................           3.52E-02            3.46E-02
1,2,3,7,8-PeCDF.................           1.46E-02            4.20E-04
1,2,3,7,8,9-HxCDD...............           2.70E-02            2.60E-03
1,2,3,7,8,9-HxCDF...............           6.24E-03            5.54E-04
2,3,4,6,7,8-HxCDF...............           1.88E-02            1.82E-03
2,3,4,7,8-PeCDF.................           1.29E-02            3.70E-03
2,3,7,8-TeCDD...................           2.70E-02            2.68E-02
2,3,7,8-TeCDF...................           1.80E-02            1.75E-03
    Mean DL.....................           2.34E-02            5.48E-03
    Sum of DL...................           2.90E-01            4.11E-02
------------------------------------------------------------------------
\a\ Detection Limits are based on a survey of laboratories MDL data from
  Information Collection Requests from the Industrial Boiler and Utility
  MACT rulemaking process. MDL assumes half of the sample was archived
  before concentration.


             Table 23-19--Target Detection Limits for PAHs a
------------------------------------------------------------------------
                       Target                          MDL  (ng/sample)
------------------------------------------------------------------------
Naphthalene.........................................              110.5
2-Methylnaphthalene.................................               36.3
Acenaphthylene......................................               31.4
Acenaphthene........................................               11.3
Fluorene............................................               12.8
Phenanthrene........................................               19.9
Anthracene..........................................               11.8
Fluoranthene........................................                9.0
Pyrene..............................................                7.6
Benzo[a]anthracene..................................                6.2

[[Page 2268]]

 
Chrysene............................................                6.2
Benzo[b]fluoranthene................................                7.8
Benzo[k]fluoranthene................................                6.4
Benzo[e]pyrene......................................                3.3
Benzo[a]pyrene......................................               15.9
Perylene............................................               28.3
Indeno[1,2,3-cd]pyrene..............................                7.2
Dibenz[a,h]anthracene...............................                6.8
Benzo[g,h,i]perylene................................                6.8
    Mean DL.........................................                 23
    Sum of DL.......................................                435
------------------------------------------------------------------------
\a\ Detection limits are based on a survey of laboratories MDL data from
  Information Collection Requests form the Coke Oven and Electric Power
  Generating unit MACT rulemaking process.


        Table 23-20--Estimated Method Detection Limits for PCBs a
------------------------------------------------------------------------
                                                              Target
                                                             detection
                 Target                       BZ No.        limit  (pg/
                                                              sample)
------------------------------------------------------------------------
2,4'-DiCB...............................               8              30
2,2',5-TrCB.............................              18              32
2,4,4'-TrCB.............................              28              44
2,2',3,5'-TeCB..........................              44              80
2,2',5,5'-TeCB..........................              52              30
2,3',4,4'-TeCB..........................              66              34
3,3',4,4'-TeCB..........................              77              28
3,4,4',5-TeCB...........................              81              36
2,2',4,5,5'-PeCB........................             101              94
2,3,3',4,4'-PeCB........................             105              34
2,3,4,4',5-PeCB.........................             114              30
2,3',4,4',5-PeCB........................             118              60
2',3,4,4',5-PeCB........................             123              34
3,3',4,4',5-PeCB........................             126              32
2,2',3,3',4,4'-HxCB.....................             128              58
2,2',3,4,4',5'-HxCB.....................             138              72
2,2',4,4',5,5'-HxCB.....................             153              60
2,3,3',4,4',5-HxCB......................             156              46
2,3,3',4,4',5'-HxCB.....................             157              46
2,3',4,4',5,5'-HxCB.....................             167              26
3,3',4,4',5,5'-HxCB.....................             169              30
2,2',3,3',4,4',5-HpCB...................             170              24
2,2',3,4,4',5,5'-HpCB...................             180              60
2,2',3,4',5,5',6-HpCB...................             187              34
2,3,3',4,4',5,5'-HpCB...................             189              26
2,2',3,3',4,4',5,6-OcCB.................             195              44
2,2',3,3',4,4',5,5',6-NoCB..............             206              32
2,2',3,3',4,4',5,5',6,6'-DeCB...........             209              32
    Mean DL.............................  ..............              42
    Sum of DL...........................  ..............           1,188
------------------------------------------------------------------------
\a\ Detection Limits are based on information from EPA Method 1668C,
  assuming half of the sample extract is archived before concentration.

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Appendix A to Method 23

                   Complete List of 209 PCB Congeners and Their Isomers With Corresponding Isotope Dilution Quantitation Standards \a\
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                                  Unlabeled  target                   Pre-extraction                    Unlabeled  target
    Pre-extraction  standard       BZ \b\  No.         analyte        BZ \b\  No.        standard        BZ \b\  No.         analyte         BZ \b\ No.
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                       MoCBs                      DiCBs
--------------------------------------------------------------------------------------------------------------------------------------------------------
13C12-2-MoCB....................  1L             2-MoCB............  1              13C12-2,2'-DiCB...  4L             2,2'-DiCB.........  4
13C12-2-MoCB....................  1L             3-MoCB............  2              13C12-2,2'-DiCB...  4L             2,3-DiCB..........  5
13C12-4-MoCB....................  3L             4-MoCB............  3              13C12-2,2'-DiCB...  4L             2,3'-DiCB.........  6
                                                                                    13C12-2,2'-DiCB...  4L             2,4-DiCB..........  7
                                                                                    13C12-2,2'-DiCB...  4L             2,4'-DiCB.........  8
                                                                                    13C12-2,2'-DiCB...  4L             2,5-DiCB..........  9
                                                                                    13C12-2,2'-DiCB...  4L             2,6-DiCB..........  10
                                                                                    13C12-2,2'-DiCB...  4L             3,3'-DiCB.........  11
                                                                                    13C12-2,2'-DiCB...  4L             3,4-DiCB..........  12
                                                                                    13C12-2,2'-DiCB...  4L             3,4'-DiCB.........  13
                                                                                    13C12-2,2'-DiCB...  4L             3,5-DiCB..........  14
                                                                                    13C12-4,4'-DiCB...  15L            4,4'-DiCB.........  15
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                                                          TrCBs
--------------------------------------------------------------------------------------------------------------------------------------------------------
13C12-2,2',6-TrCB...............  19L            2,2',3-TrCBTrCB...  16             13C12-3,4,4'-TrCB.  19L            2,4,4'-TrCB.......  28
13C12-2,2',6-TrCB...............  19L            2,2',4-TrCB.......  17             13C12-3,4,4'-TrCB.  19L            2,4,5-TrCB........  29
13C12-2,2',6-TrCB...............  19L            2,2',5-TrCB.......  18             13C12-3,4,4'-TrCB.  19L            2,4,6-TrCB........  30
13C12-2,2',6-TrCB...............  19L            2,2',6-TrCB.......  19             13C12-3,4,4'-TrCB.  19L            2,4',5-TrCB.......  31
13C12-2,2',6-TrCB...............  19L            2,3,3'-TrCB.......  20             13C12-3,4,4'-TrCB.  19L            2,4',6-TrCB.......  32
13C12-2,2',6-TrCB...............  19L            2,3,4-TrCB........  21             13C12-3,4,4'-TrCB.  19L            2',3,4-TrCB.......  33
13C12-2,2',6-TrCB...............  19L            2,3,4'-TrCB.......  22             13C12-3,4,4'-TrCB.  19L            2',3,5-TrCB.......  34
13C12-2,2',6-TrCB...............  19L            2,3,5- TrCB.......  23             13C12-3,4,4'-TrCB.  19L            3,3',4-TrCB.......  35
13C12-2,2',6-TrCB...............  19L            2,3,6- TrCB.......  23             13C12-3,4,4'-TrCB.  19L            3,3',5-TrCB.......  36
13C12-2,2',6-TrCB...............  19L            2,3',4-TrCB.......  25             13C12-3,4',4'-TrCB  37L            3,4,4'-TrCB.......  37
13C12-2,2',6-TrCB...............  19L            2,3',5-TrCB.......  26             13C12-3,4',4'-TrCB  37L            3,4,5-TrCB........  38
13C12-2,2',6-TrCB...............  19L            2,3',6-TrCB.......  27             13C12-3,4',4'-TrCB  37L            3,4',5-TrCB.......  39
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                                                          TeCBs
--------------------------------------------------------------------------------------------------------------------------------------------------------
13C12-2,2',6,6'-TeCB............  54L            2,2',3,3'-TeCB....  40             13C12-2,2',6,6'-    54L            2,3,4,5-TeCB......  61
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,2',3,4-TeCB.....  41             13C12-2,2',6,6'-    54L            2,3,4,6-TeCB......  62
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,2',3,4'-TeCB....  42             13C12-2,2',6,6'-    54L            2,3,4',5-TeCB.....  63
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,2',3,5-TeCB.....  43             13C12-2,2',6,6'-    54L            2,3,4',6-TeCB.....  64
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,2',3,5'-TeCB....  44             13C12-2,2',6,6'-    54L            2,3,5,6-TeCB......  65
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,2',3,6-TeCB.....  45             13C12-2,2',6,6'-    54L            2,3',4,4'-TeCB....  66
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,2',3,6'-TeCB....  46             13C12-2,2',6,6'-    54L            2,3',4,5-TeCB.....  67
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,2',4,4'-TeCB....  47             13C12-2,2',6,6'-    54L            2,3',4,5'-TeCB....  68
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,2',4,5-TeCB.....  48             13C12-2,2',6,6'-    54L            2,3',4,6-TeCB.....  69
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,2',4,5'-TeCB....  49             13C12-2,2',6,6'-    54L            2,3',4',5-TeCB....  70
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,2',4,6-TeCB.....  50             13C12-2,2',6,6'-    54L            2,3',4',6-TeCB....  71
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,2',4,6'-TeCB....  51             13C12-2,2',6,6'-    54L            2,3',5,5'-TeCB....  72
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,2',5,5'-TeCB....  52             13C12-2,2',6,6'-    54L            2,3',5',6-TeCB....  73
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,2',5,6'-TeCB....  53             13C12-2,2',6,6'-    54L            2,4,4',5-TeCB.....  74
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,2',6,6'-TeCB....  54             13C12-2,2',6,6'-    54L            2,4,4',6-TeCB.....  75
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,3,3',4'-TeCB....  55             13C12-2,2',6,6'-    54L            2',3,4,5-TeCB.....  76
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,3,3',4'-TeCB....  56             13C12-3,3',4,4'-    77L            3,3',4,4'-TeCB....  77
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,3,3',5-TeCB.....  57             13C12-3,3',4,4'-    77L            3,3',4,5-TeCB.....  78
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,3,3',5'-TeCB....  58             13C12-3,3',4,4'-    77L            3,3',4,5'-TeCB....  79
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,3,3',6-TeCB.....  59             13C12-3,3',4,4'-    77L            3,3',5,5'-TeCB....  80
                                                                                     TeCB.
13C12-2,2',6,6'-TeCB............  54L            2,3,4,4'-TeCB.....  60             13C12-3,4,4',5-     81L            3,4,4',5-TeCB.....  81
                                                                                     TeCB.
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                                                          PeCBs
--------------------------------------------------------------------------------------------------------------------------------------------------------
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',3,3',4-PeCB..  82             13C12-2,3,3',4,4'-  105L           2,3,3',4,4'-PeCB..  105
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',3,3',5-PeCB..  83             13C12-2,3,3',4,4'-  105L           2,3,3',4,5-PeCB...  106
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',3,3',6-PeCB..  84             13C12-2,3,3',4,4'-  105L           2,3,3',4',5-PeCB..  107
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',3,4,4'-PeCB..  85             13C12-2,3,3',4,4'-  105L           2,3,3',4,5'-PeCB..  108
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',3,4,5-PeCB...  86             13C12-2,3,3',4,4'-  105L           2,3,3',4,6-PeCB...  109
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',3,4,5'-PeCB..  87             13C12-2,3,3',4,4'-  105L           2,3,3',4',6-PeCB..  110
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',3,4,6-PeCB...  88             13C12-2,3,3',4,4'-  105L           2,3,3',5,5'-PeCB..  111
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',3,4,6'-PeCB..  89             13C12-2,3,3',4,4'-  105L           2,3,3',5,6-PeCB...  112
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',3,4',5-PeCB..  90             13C12-2,3,3',4,4'-  105L           2,3,3',5',6-PeCB..  113
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',3,4',6-PeCB..  91             13C12-2,3,4,4',5-   114L           2,3,4,4',5-PeCB...  114
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',3,5,5'-PeCB..  92             13C12-2,3,4,4',5-   114L           2,3,4,4',6-PeCB...  115
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',3,5,6-PeCB...  93             13C12-2,3,4,4',5-   114L           2,3,4,5,6-PeCB....  116
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',3,5,6'-PeCB..  94             13C12-2,3,4,4',5-   114L           2,3,4',5,6-PeCB...  117
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',3,5',6-PeCB..  95             13C12-2,3',4,4',5-  118L           2,3',4,4',5-PeCB..  118
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',3,6,6'-PeCB..  96             13C12-2,3',4,4',5-  118L           2,3',4,4',6-PeCB..  119
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',3',4,5-PeCB..  97             13C12-2,3',4,4',5-  118L           2,3',4,5,5'-PeCB..  120
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',3',4,6-PeCB..  98             13C12-2,3',4,4',5-  118L           2,3',4,5,'6-PeCB..  121
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',4,4',5-PeCB..  99             13C12-2,3',4,4',5-  118L           2',3,3',4,5-PeCB..  122
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',4,4',6-PeCB..  100            13C12-2',3,4,4',5-  123L           2',3,4,4',5-PeCB..  123
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',4,5,5'-PeCB..  101            13C12-2',3,4,4',5-  123L           2',3,4,5,5'-PeCB..  124
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',4,5,6'-PeCB..  102            13C12-2',3,4,4',5-  123L           2',3,4,5,6'-PeCB..  125
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',4,5,'6-PeCB..  103            13C12-3,3',4,4',5-  126L           3,3',4,4',5-PeCB..  126
                                                                                     PeCB.
13C12-2,2',4,6,6'-PeCB..........  104L           2,2',4,6,6'-PeCB..  104            13C12-3,3',4,4',5-  126L           3,3',4,5,5'-PeCB..  127
                                                                                     PeCB.
--------------------------------------------------------------------------------------------------------------------------------------------------------

[[Page 2274]]

 
                                                                          HxCBs
--------------------------------------------------------------------------------------------------------------------------------------------------------
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,3',4,4'-     128            13C12-              155L           2,2',3,4',5',6-     149
                                                  HxCB.                              2,2',4,4',6,6'-                    HxCB.
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,3',4,5-HxCB  129            13C12-              155L           2,2',3,4',6,6'-     150
                                                                                     2,2',4,4',6,6'-                    HxCB.
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,3',4,5'-     130            13C12-              155L           2,2',3,5,5',6-HxCB  151
                                                  HxCB.                              2,2',4,4',6,6'-
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,3',4,6-HxCB  131            13C12-              155L           2,2',3,5,6,6'-HxCB  152
                                                                                     2,2',4,4',6,6'-
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,3',4,6'-     132            13C12-              155L           2,2',4,4',5,5'-     153
                                                  HxCB.                              2,2',4,4',6,6'-                    HxCB.
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,3',5,5'-     133            13C12-              155L           2,2',4,4',5',6-     154
                                                  HxCB.                              2,2',4,4',6,6'-                    HxCB.
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,3',5,6-HxCB  134            13C12-              155L           2,2',4,4',6,6'-     155
                                                                                     2,2',4,4',6,6'-                    HxCB.
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,3',5,6'-     135            13C12-              156L           2,3,3',4,4',5-HxCB  156
                                                  HxCB.                              2,3,3',4,4',5-
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,3',6,6'-     136            13C12-              157L           2,3,3',4,4',5'-     157
                                                  HxCB.                              2,3,3',4,4',5'-                    HxCB.
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,4,4',5-HxCB  137            13C12-              157L           2,3,3',4,4',6-HxCB  158
                                                                                     2,3,3',4,4',5'-
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,4,4',5'-     138            13C12-              157L           2,3,3',4,5,5'-HxCB  158
                                                  HxCB.                              2,3,3',4,4',5'-
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,4,4',6-HxCB  139            13C12-              157L           2,3,3',4,5,6-HxCB.  160
                                                                                     2,3,3',4,4',5'-
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,4,4',6'-     140            13C12-              157L           2,3,3',4,5',6-HxCB  161
                                                  HxCB.                              2,3,3',4,4',5'-
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,4,5,5'-HxCB  141            13C12-              157L           2,3,3',4',5,5'-     162
                                                                                     2,3,3',4,4',5'-                    HxCB.
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,4,5,6-HxCB.  142            13C12-              157L           2,3,3',4',5,6-HxCB  163
                                                                                     2,3,3',4,4',5'-
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,4,5,6'-HxCB  143            13C12-              157L           2,3,3',4',5',6-     164
                                                                                     2,3,3',4,4',5'-                    HxCB.
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,4,5',6-HxCB  144            13C12-              157L           2,3,3',5,5',6-HxCB  165
                                                                                     2,3,3',4,4',5'-
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,4,6,6'-HxCB  145            13C12-              157L           2,3,4,4',5,6-HxCB.  166
                                                                                     2,3,3',4,4',5'-
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,4',5,5'-     146            13C12-              167L           2,3',4,4',5,5'-     167
                                                  HxCB.                              2,3',4,4',5,5'-                    HxCB.
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,4',5,6-HxCB  147            13C12-              167L           2,3',4,4',5',6-     168
                                                                                     2,3',4,4',5,5'-                    HxCB.
                                                                                     HxCB.
13C12-2,2',4,4',6,6'-HxCB.......  155L           2,2',3,4',5,6'-     148            13C12-              169L           3,3',4,4',5,5'-     169
                                                  HxCB.                              3,3',4,4',5,5'-                    HxCB.
                                                                                     HxCB.
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                                                          HpCBs
--------------------------------------------------------------------------------------------------------------------------------------------------------
13C12-2,2',3,4',5,6,6'-HpCB.....  188L           2,2',3,3',4,4',5-   170            13C12-              188L           2,2',3,4,4',5,6'-   182
                                                  HpCB.                              2,2',3,4',5,6,6'-                  HpCB.
                                                                                     HpCB.
13C12-2,2',3,4',5,6,6'-HpCB.....  188L           2,2',3,3',4,4',6-   171            13C12-              188L           2,2',3,4,4',5',6-   183
                                                  HpCB.                              2,2',3,4',5,6,6'-                  HpCB.
                                                                                     HpCB.
13C12-2,2',3,4',5,6,6'-HpCB.....  188L           2,2',3,3',4,5,5'-   172            13C12-              188L           2,2',3,4,4',5',6-   184
                                                  HpCB.                              2,2',3,4',5,6,6'-                  HpCB.
                                                                                     HpCB.
13C12-2,2',3,4',5,6,6'-HpCB.....  188L           2,2',3,3',4,5,6-    173            13C12-              188L           2,2',3,4,4',6,6'-   185
                                                  HpCB.                              2,2',3,4',5,6,6'-                  HpCB.
                                                                                     HpCB.
13C12-2,2',3,4',5,6,6'-HpCB.....  188L           2,2',3,3',4,5,6'-   174            13C12-              188L           2,2',3,4,5,5',6-    186
                                                  HpCB.                              2,2',3,4',5,6,6'-                  HpCB.
                                                                                     HpCB.
13C12-2,2',3,4',5,6,6'-HpCB.....  188L           2,2',3,3',4,5',6-   175            13C12-              188L           2,2',3,4',5,5',6-   187
                                                  HpCB.                              2,2',3,4',5,6,6'-                  HpCB.
                                                                                     HpCB.
13C12-2,2',3,4',5,6,6'-HpCB.....  188L           2,2',3,3',4,6,6'-   176            13C12-              188L           2,2',3,4',5,6,6'-   188
                                                  HpCB.                              2,2',3,4',5,6,6'-                  HpCB.
                                                                                     HpCB.
13C12-2,2',3,4',5,6,6'-HpCB.....  188L           2,2',3,3',4',5,6-   177            13C12-              189L           2,3,3',4,4',5,5'-   189
                                                  HpCB.                              2,3,3',4,4',5,5'-                  HpCB.
                                                                                     HpCB.
13C12-2,2',3,4',5,6,6'-HpCB.....  188L           2,2',3,3',5,5',6-   178            13C12-              189L           2,3,3',4,4',5,6-    190
                                                  HpCB.                              2,3,3',4,4',5,5'-                  HpCB.
                                                                                     HpCB.
13C12-2,2',3,4',5,6,6'-HpCB.....  188L           2,2',3,3',5,6,6'-   179            13C12-              189L           2,3,3',4,4',5',6-   191
                                                  HpCB.                              2,3,3',4,4',5,5'-                  HpCB.
                                                                                     HpCB.
13C12-2,2',3,4',5,6,6'-HpCB.....  188L           2,2',3,4,4',5,5'-   180            13C12-              189L           2,3,3',4,5,5',6-    192
                                                  HpCB.                              2,3,3',4,4',5,5'-                  HpCB.
                                                                                     HpCB.
13C12-2,2',3,4',5,6,6'-HpCB.....  188L           2,2',3,4,4',5,6-    181            13C12-              189L           2,3,3',4',5,5',6-   193
                                                  HpCB.                              2,3,3',4,4',5,5'-                  HpCB.
                                                                                     HpCB.
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                       OcCBs                      NoCBs
--------------------------------------------------------------------------------------------------------------------------------------------------------
13C12-2,2',3,3',5,5',6,6'-OcCB..  202L           2,2',3,3',4,4',5,5  194            13C12-              206L           2,2',3,3',4,4',5,5  206
                                                  '-OcCB.                            2,2',3,3',4,4',5,                  ',6-NoCB.
                                                                                     5',6-NoCB.
13C12-2,2',3,3',5,5',6,6'-OcCB..  202L           2,2',3,3',4,4',5,6- 195            13C12-              206L           2,2',3,3',4,4',5,6  207
                                                  OcCB.                              2,2',3,3',4,4',5,                  ,6'-NoCB.
                                                                                     5',6-NoCB.
13C12-2,2',3,3',5,5',6,6'-OcCB..  202L           2,2',3,3',4,4',5,6  196            13C12-              208L           2,2',3,3',4,5,5',6  208
                                                  '-OcCB.                            2,2',3,3',4,5,5',                  ,6'- NoCB.
                                                                                     6,6'-NoCB.
rrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrr
13C12-2,2',3,3',5,5',6,6'-OcCB..  202L           2,2',3,3',4,4',6,6  197                                            DeCB
                                                  '-OcCB.
rrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrr
13C12-2,2',3,3',5,5',6,6'-OcCB..  202L           2,2',3,3',4,5,5',6- 198            13C12-DeCB........  209L           2,2',3,3',4,4',5,5  209
                                                  OcCB.                                                                 ',6,6'-DeCB.
13C12-2,2',3,3',5,5',6,6'-OcCB..  202L           2,2',3,3',4,5,5',6  199
                                                  '-OcCB.
13C12-2,2',3,3',5,5',6,6'-OcCB..  202L           2,2',3,3',4,5,6,6'- 200
                                                  OcCB.
13C12-2,2',3,3',5,5',6,6'-OcCB..  202L           2,2',3,3',4,5',6,6  201
                                                  '-OcCB.
13C12-2,2',3,3',5,5',6,6'-OcCB..  202L           2,2',3,3',5,5',6,6  202
                                                  '-OcCB.
13C12-2,3',3',4,4',5,5',6-OcCB..  205L           2,2',3,4,4',5,5',6- 203
                                                  OcCB.
13C12-2,3',3',4,4',5,5',6-OcCB..  205L           2,2',3,4,4',5,6,6'- 204
                                                  OcCB.
13C12-2,3',3',4,4',5,5',6-OcCB..  205L           2,3,3',4,4',5,5',6- 205
                                                  OcCB.
--------------------------------------------------------------------------------------------------------------------------------------------------------
\a\ Assignments assume the use of the SPB-Octyl column. In the event you choose another column, you may select the labeled standard having the same
  number of chlorine substituents and the closest retention time to the target analyte in question as the labeled standard to use for quantitation.
\b\ BZ No.: Ballschmiter and Zell 1980, also referred to as IUPAC number.


[[Page 2275]]

Appendix B to Method 23

Preparation of XAD-2 Adsorbent Resin

1.0 Scope and Application

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

2.0 Extraction

    2.1 You may perform the extraction using a Soxhlet extractor or 
other apparatus that generates resin meeting the requirements in 
Section 13.14 of Method 23. Use an all-glass thimble containing an 
extra-coarse frit for extraction of the resin. The frit is recessed 10-
15 mm above a crenellated ring at the bottom of the thimble to 
facilitate drainage. Because the resin floats on methylene chloride, 
carefully retain the resin in the extractor cup with a glass wool plug 
and stainless-steel screen. This process involves sequential extraction 
with the following recommended solvents in the listed order.
     Water initial rinse: Place resin in a suitable container, 
soak for approximately 5 min with Type II water, remove fine floating 
resin particles and discard the water. Fill with Type II water a second 
time, let stand overnight, remove fine floating resin particles and 
discard the water.
     Hot water: Extract with water for 8 hr.
     Methyl alcohol: Extract for 22 hr.
     Methylene chloride: Extract for 22 hr.
     Toluene: Extract for 22 hr.
     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

 BILLING CODE 6560-50-C

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

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