United States Office of Pesticides June. 1990 Environmental Protection Toxic Substances Agency Washington. DC 20460 Toxic Substances &EPA Guidelines for Reporting Test Results of HDD and HDF Determinations in Commercial Products (40 CFR Parts 707 and 766) ------- Guidelines for Reporting Test Results of HDD and HDF Determinations in Commercial Products (40 CFR Parts 707 and 766) Final Report By David H. Steele Thomas Dux For U.S. Environmental Protection Agency Office of Pesticides and Toxic Substances Field Studies Branch 401 M Street, S.W. Washington, D.C. 20460 Ms. Janet Remmers, Work Assignment Manager Dr. Joseph Breen, Program Manager Work Assignment No. 33 EPA Prime Contract No. 68-02-4252 MRI Project No. 8833-A01 June 22,1990 ------- DISCLAIMER This document has been reviewed and approved for publication by the Office of Toxic Substances, Office of Pesticides and Toxic Substances, U.S. Environ- mental Protection Agency. The use of trade names or commercial products does not constitute Agency endorsement or recommendation for use. ------- PREFACE This report provides guidance to the chemical industry for the reporting of results from the testing of chemical products to the Office of Pesticides and Toxic Substances as specified in 40 CFR, Parts 707 and 766, Polyhalogenated Dibenzo-p-dioxin/Dibenzofuran Testing and Reporting Require- ments, Final Rule (Fed. Reg. 52 (108), 21412-21452, June 5, 1987). This report is the third in a series of guidance documents prepared to assist with compliance to the Rule. The first document, "Guidelines for the Determination of Halogenated Dibenzo-p-Dioxins and Dibenzofurans in Chemical Products" (EPA-560/5-87/007), September 1987), was prepared as guidance to the chemical industry in the development of analytical methods and in the preparation of sampling plans, analytical protocols, and quality assurance plans. The second guidance document, "Guidelines for Review of Test Plans Submitted for the Determination of HDDs and HDFs in Commercial Products (40 CFR, Parts 707 and 766)" (Midwest Research Institute, Revised Final Report, February 26, 1988), was prepared specifically for use by EPA's expert panel in the review of protocols. However, this document should also be of use to the chemical industry as guidance to the criteria which will be used to review their protocols. These reporting guidelines were prepared by Midwest Research Institute (Mr. David Steele, Work Assignment Leader, and Mr. Thomas Dux, Chemical Sciences Department Quality Assurance Coordinator) for the Office of Toxic Substances/Field Studies Branch as part of Work Assignment 33 (Analyt- ical Methodologies for Halogenated Dioxins and Dibenzofurans in Commercial Products) under EPA Contract No. 68-02-4252, Ms. Janet Remmers, Work Assign- ment Manager, and Dr. Joseph Breen, Project Officer. Valuable input for this guidance document was provided by the members of the Expert Panel, appointed by EPA to review analytical protocols and data generated under the Rule. The Expert Panel members are Dr. Aubry Dupuy, Jr., Dr. David Firestone, Mr. Robert Harless, Dr. Doug Kuehl, and Dr. Wayne Sovocool. MIDWEST RESEARCH INSTITUTE Approved: Paul C. Constan Program Manager Jack Balsinger ality Assurance Coordinator Jeftn E. Going, Ph.D. fi rector Chemical Sciences Department ii ------- TABLE OF CONTENTS Page Preface 11 I. Introduction 1 II. Summary of Requirements for Reporting Test Results 2 III. Guidelines for Reporting Test Results 3 IV. Conclusion 8 iii ------- I. INTRODUCTION The Code of Federal Regulations, Title 40 Parts 707 and 766 (40 CFR 707 and 766), published June 5, 1987, presents a Final Rule for testing and reporting the concentrations of halogenated dibenzo-p-dioxins (HDDs) and halogenated dibenzofurans (HDFs) in a group of chemical products selected for testing based on the possibility of contamination by HDDs and HDFs. This Rule, promulgated under Sections 4 and 8 of the Toxic Substances Control Act (TSCA), 15 U.S.C. 2603, requires manufacturers and importers of 12 commercial organic chemicals to test for the presence of HDDs and HDFs which are either chlorinated or brominated at the 2,3,7,8 and up to three additional positions on the molecules. Testing will be required for 20 additional chemicals not currently manufactured or imported in the United States if their manufacture or importation should resume. EPA will conduct in-depth reviews of all test data submitted under the Rule. These reviews will require the submission of any and all records and data which support the test results. EPA authority for requesting this information stems from 40 CFR Part 766.10, "All new data, documentation, records, protocols, specimens, and reports generated as a result of testing under Subpart B of this Part must be fully developed and retained in accordance with Part 792 of the chapter. These items must be made available during an inspection or submitted to EPA upon request of EPA or its authorized representative." EPA reviews of the first data submittals under the Rule have indicated a discrepancy between the level and type of information which has been reported by different members of the regulated community. This demon- strates a need for EPA to provide guidance on the type of information which needs to be submitted to comply with Rule requirements. This document deals specifically with the reporting of results from the sampling activities and subsequent analytical determination of HDDs and HDFs in the chemical products listed in the Rule. Section II presents a summary of the Rule reporting requirements for test results. Section III contains a detailed listing and description of the type of information needed for EPA to conduct a full review of test results. This document is provided as guidance only and should not be con- sidered comprehensive. Each submitter is responsible for the submission of the appropriate information based on the approved protocols under which the testing is performed. Different protocols will result in different types of records. This document should also not be used as guidance to the kinds of records which must be developed and maintained for total compliance to the Rule. For example, other documentation and records, in addition to those discussed in this document, must be maintained to be in compliance with TSCA Good Laboratory Practice (GLP) requirements. These may be found in the TSCA GLP Standards (40 CFR 792). ------- II. SUMMARY OF REQUIREMENTS FOR REPORTING TEST RESULTS Requirements pertinent to the reporting of HDD/HDF test results are summarized below. The section of the Rule containing the requirement is given in parentheses after the requirement. It should be noted that the Rule con- tains other reporting requirements which are not directly related to test results. These are not addressed in this document. The Rule should be consulted for these additional requirements. A. All information submitted to EPA must bear the applicable CFR section number and must be addressed to: Document Control Office (TS-790), Office of Pesticides and Toxic Substances, Environmental Protection Agency, 401 M Street, S.W., Washington, D.C. 20460. (766.7) B. All new data, documentation, records, protocols, specimens, and reports generated as a result of testing must be made available during an inspection or submitted to EPA upon request of EPA or its authorized representative. (766.10) C. Sponsors are responsible for ensuring that laboratories con- ducting the testing abide by the TSCA GLP standards. At the time test data are submitted, manufacturers must submit a certification to EPA that the laboratory performing the testing adhered to the TSCA GLPs. (766.10) D. The results of the Limit of Quantitation (LOQ) demonstration for each of the analytes specified in the Rule must be pre- sented. This requires fortification of two samples with isotopically labeled internal standards of each of the analytes at the LOQ specified in 766.27. This fortification is done at the beginning of sample preparation. The LOQ is demonstrated by a recovery of the internal standard between 50% and 150% of the amount spiked and a relative percent difference between the two samples of less than 20%. (766.18) E. Analysis results for all the HDDs and HDFs specified in the test protocol must be submitted. Only the chlorinated and brominated congeners specified in 766.27 need to be quantified. (766.27) F. Test results must be reported to EPA no later than 270 days after EPA's transmission of comments or 180 days after a final protocol is submitted to EPA, whichever is shorter. (766.35) ------- III. GUIDELINES FOR REPORTING TEST RESULTS EPA will conduct an in-depth review of all data submitted under the Rule. The information required for EPA review consists of all raw data needed to completely trace the sample from field activities to final data and allow the reviewer to independently calculate the sample results. Sufficient infor- mation should be given so that a^-reviewer can determine whether the test protocol was followed in the field, sample preparation laboratory, and analy- sis laboratory. The reviewer should be able to calculate final test results from sample size, internal standard fortification amounts, sample dilution or concentration factors, instrument calibration factors, and raw instrument output (e.g., areas of chromatographic peaks). The information which is needed for review is presented in the remainder of this section. This listing should not be considered to be com- prehensive since each test protocol will be different and will have different types of records. The submittal should be made in report form and should contain all of the elements described below: A. A cover letter, properly addressed to the Office of Pesticides and Toxic Substances Document Control Officer, with the appro- priate CFR reference should be submitted. This letter should specifically cite the approved test protocol used for the study, and detail any pertinent time extensions in regard to the reporting requirements. B. A title page and complete table of contents outlining the submittal including all appendices and attachments. C. A certification from the submitter that the laboratory performing the testing adhered to TSCA GLPs, given in 40 CFR Part 792, August 17, 1989. D. A summary section. This section should summarize the overall test results in terms of the objectives of the study. It should detail any additional work which is warranted by results which do not meet the data quality objectives defined by the Rule. It should also describe any additional reporting required as a result of the testing and the time frame for subsequent reports. E. A section discussing the sampling of the chemical product. This section should contain all of the following elements. 1. A statement as to whether the sampling protocol was followed. 2. A discussion of any deviations from the sampling protocol and the reasons for the deviations. ------- 3. A discussion of any problems encountered in sampling, the resolution of the problems, and any possible impact the problems may have on the quality of the data. 4. A statement describing the transfer of samples from the sampling location to the analytical laboratory. 5. An inventory of all samples which were taken, the amount of sample, and the disposition of the sample (shipped for analysis, archived on site, etc.). F. A section discussing the preparation of the samples for chemical analysis. This section should contain all of the following elements. 1. A statement as to whether the analytical protocol was followed. 2. A discussion of any deviations from the analytical proto- col, the reasons for the deviations, and any possible impact which the deviations may have on the quality of the data. 3. A discussion of any options in the analytical protocol which were taken. Examples of options might include cleanup procedures or fortification levels. 4. A discussion of any problems encountered in sample preparation, the resolution of the problems, and any possible impact the problems may have on the quality of the data. G. A section discussing the instrumental analysis of the prepared chemical product. This section should include the following elements. 1. A statement as to whether the protocol was followed. 2. A discussion of any deviations from the protocol and the reasons for the deviations. 3. A discussion of any options in the protocol which were taken. Examples of options might include instrumentation, injection volumes, etc. 4. A discussion of any problems encountered during sample analysis, the resolution of the problems, and any possible impact on data quality. H. A summary of all initial calibration and continuing calibration results. These should be presented in tables. Quality control information should be calculated and included in this section. ------- This include average response factors, percent relative standard deviation, and relative percent difference. Data for any analyte which does not meet the required criteria should be clearly identified in the table. The use of instrument cali- bration which does not meet criteria must be justified in terms of overall data quality and impact on the sample results. I. A section presenting the results for the chemical product samples. These results should be presented in a table. Results which do not meet data quality objectives should be flagged and discussed in the text. Internal standard recovery statistics such as average recovery for a specific analyte, standard deviation, and relative standard deviation should be calculated and presented. An example table of sample results is shown in Table 1. J. A section detailing the quality control results from the sample analysis. This section should contain all of the following elements. 1. The results of the limit of quantitation determination as specified in 40 CFR Part 766.27. The results from these spiked duplicate samples should be presented in a table which contains the internal standard spiking levels, the internal standard recoveries (% of amount spiked) for each analyte in each sample, and the calculated relative percent difference of the recoveries from the two samples for each analyte. Any value which does not meet the spiking level (LOQ), recovery (50% to 150%), or precision (±20%) requirements of the Rule must be clearly identified in the table and discussed in the accompanying text. If the sensitivity requirements defined in 40 CFR Part 766.27 are not met, a discussion should be included which details the reasons the associated sample results should be accepted by EPA. An example table for a limit of quanti- tation determination has been provided (Table 2). 2. The results of any matrix spikes of the chemical product. These results should also be presented in a table. Any value which does not meet the data quality objectives specified in the test protocol should be clearly identi- fied and the impact on data quality discussed in the text. 3. The recoveries of all isotopically labeled internal stan- dards should be presented in a table. This table should include the data from all blanks, samples, and spikes. Results which do not meet data quality objectives should be flagged and discussed in the text. Statistics such as average recovery for a specific analyte, standard devia- tion, and relative standard deviation should be calculated and presented. ------- All raw data and documentation should be Included In the form of one or more appendices to the report. Information which should be included is listed below. This list should not be considered to be comprehensive since each test protocol will be different and will have different types of records. 1. Complete records of field sampling • Field sampling logbook pages or sampling forms giving the sample identifiers, the person conducting the sampling, the location of the samples, the sampling method, the data, and the time of sampling • Calibration records of sampling equipment, before and after sampling Shipping forms • Preparation, manufacturer, lot number, and expiration date of any reagents used in sampling Any sampling problems 2. Sample shipment records Sample traceability forms • Field inventory sheets • Documentation of laboratory receipt indicating who received the samples, when, and the conditions upon receipt 3. Complete standard preparation records for reference standards for both internal standard addition and instrument calibration • Standard preparation notebook pages or forms giving the standard identifier, the person preparing the standards, the amount weighed, and all subsequent dilutions • Balance calibration records Supplier, lot number, purity, and expiration dates for reference materials and all reagents • Verification of standards by comparison to independently prepared standard or certified standards ------- 4. Sample preparation records • Sample preparation notebook pages or forms giving the name of the analyst, the date, the samples prepared, all sample preparation operations, and reference to the approved test protocol All additions of internal standards All sample preparation problems Initial sample size and all subsequent dilutions and concentrations Balance calibration records for the balance used in sample weighing All reagents and their preparation 5. Sample analysis records Complete information on the instrumental system including manufacturer, model number, chromatographic column, chromatography conditions, data system, and pertinent maintenance which affects the sample results Complete list of all standards and samples in the order of analysis • Instrument logbook pages for the days on which sample analyses were conducted All chromatograms, peak areas, ion masses (m/z) etc., needed to calculate the calibration information (e.g., relative retention times, ion abundance ratio factors, etc.), and the sample results Complete traceable documentation of data reduction and validation procedures including formulas, tables of mass area ratios, hand calculations for situations where the data system was inadequate, explanations for rejected data, calculations of internal standard recoveries, etc. ------- IV. CONCLUSION A description of the information needed for a submittal of test data in response to the Rule should help the regulated community prepare a complete document resulting in an efficient and timely review of the information. If the submittal follows the format given in the Section II, the data should be clearly presented and address all the testing objectives of the Rule. ------- Table 1. Example of Sample Results PCODs/PCOFs in Commercial Product (ng/g) vo Analytes 2,3,7,8-TCDD 1,2,3,7,8-PeCOD 1,2,3,4,7,8-HxCDD 1,2,3,6,7,8-HxCDD 1,2,3,7,8,9-HxCDO 1,2,3,4,6,7,8-HpCDD 2,3,7,8-TCOF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCOF 1,2,3,4,7,8-HxCOF 1, 2,3,6, 7,8-HxCOF 2,3,4,6,7,8-HxCDF 1,2,3,7,8,9-HxCDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF Internal standard ]*C-2,3,7,8-TCDD *C- ,2,3,7,8-PeCDD *C- ,2,3,6,7,8-HxCDD |C- ,2,3,4,6,7,8-HpCOD *C-2,3,7,8-TCDF *C- ,2,3,7,8-PeCDF *C- ,2,3,6,7,8-HxCDF 13C- ,2,3,4,6,7,8-HpCOF Spike level ng/g 10 50 50 50 10 50 . 50 50 Blank8 < 0.05 < 0.1 < 1.2 < 1.2 < 1.2 < 14 < 0.05 < 2.2 < 2.2 < 12.6 < 12.6 < 12.6 < 12.6 < 25.0 < 25.0 63.2 92.1 96.2 87.4 117 104 104 109 Sample identification number 109 1.6 2.2 25.1 NDd 66.3 56.4 1.9 36.4 22.6 950 260 460 382 1310 2250 92.1 83.6 114 96.2 83.4 80.2 93.6 124 234 1.2 3.1 33.5 ND 52.3 88.3 2.2 64.5 36.1 725 225 523 399 1560 2190 93.6 125 134 90.6 53.1 63.2 63.8 112 573 1.1 2.6 20.1 ND 44.1 103 1.6 46.3 15.8 668 146 356 363 1450 2400 Percent 49. 5f 95.2 149 73.5 72.3 64.5 94.9 101 638 0.8 1.9 23.6 ND 89.3 64.1 2.6 12.6 25.9 852 360 498 264 1340 2110 recovery 81.6 92.5 131 87.4 74.9. 43. 9f 86.4 107 552 1.5 .17 30.9 ND 50.1 22.3 1.8 55.3 21.6 645 259 550 346 1220 2560 123 88.6 87.6 99.4 134 59.3 78.2 112 698 1.1 2.1 28.2 ND 93.2 98.5 4.5 33.6 33.3 889 189 390 452 1610 2890 95.2 66.1 74.2 123 88.4 96.2 101 115 226 1.4 2.4 27.6 ND 33.4 55.6 3.4 52.1 19.8 753 230 462 299 1460 2360 166f 102 89.3 87.2 99.5 114 77.1 88.3 Average 1.2 2.3 27.0 NAe 61.2 69.7 2.6 43.0 25.0 783 238 463 358 142 2400 100.1 93.3 111.3 93.9 86.5 74.4 85.0 108.5 SDb 0.3 0.5 4.5 NA 22.8 28.6 1.0 17.1 7.3 116 67.0 69.7 62.7 140 260 36.3 18.0 28.1 15.3 25.5 24.0 12.8 11.4 RSOC 22.2 20.4 16.7 NA 37.2 41.1 40.6 39.9 29.3 14.8 28.1 15.1 17.5 9.8 11.0 36.2 19.3 25.2 16.2 29.4 32.2 15.1 10.5 Range 0.8-1.6 1.7-3.1 20.1-33.5 NA 33.4-93.2 22-3-103 1.6-4.5 12.6-64.5 15.8-36.1 645-950 146-360 356-550 264-452 1220-1610 2110-2890 49.5-166 66.1-125 74.2-152 73.5-123 53.1-134 43.9-114 63.8-101 88.3-124 "Blank results are not included in statistics. Values are limits of quantitation (ng/g) based on a 1.0-g sample size. bSD = Standard deviation •JRSD = Relative standard deviation dND = Not detected above LOO required by 40 CFR 766.27. eNA = Not applicable — values are beneath LOO. 'Outside 501-1501 range specified by Rule. ------- Table 2. Example of Limit of Quantitation Determination Limit of Quantitation Determination—Sample 573 Internal standard i3C12-2,3,7,8-TCDD i3C12-l,2,3,7,8-PeCDD >3C12-l,2,3,6,7,8-HxCDD i3C12-lt2s3,4,6,7,8-HpCDD i3C12-2,3,7,8-TCDF '3C12-l,2,3,7,8-PeCDF i3C12-l,2,3,6,7,8-HxCDF >3C12-l,2,3,4,6,7,8-HpCDF Spike level (ng/g) 0.1 0.5 2.5 100 1.0 5.0 25.0 1000 % Recovery Signal : noise 12:1 50:1 50:1 1000:1 50:1 50:1 100:1 1000:1 First sample 63.1 90.2 123 62.4 61.6 45. 6C 105 102 Second sample 72.4 115 145 72.6 63.4 51.2 89 121 Average 67.8 102 134 67.5 62.5 48.4 97.1 112 %R& 13.7 24. 3b 16.4 15.1 2.9 11.6 16.3 16.9 *%R = Range percent = [(high-low)/average)! x 100. D0utside the QA objective of ±20%. C0utside the QA objective of 50%-150# recovery. ------- |