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)
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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
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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.
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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
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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
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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).
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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)
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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.
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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.
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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.
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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
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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.
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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.
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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.
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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.
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