MIDWEST RESEARCH INSTITUTE
GUIDELINES FOR REVIEW OF TEST PLANS SUBMITTED FOR DETERMINATION OF
HDDs AND HDFs IN COMMERCIAL PRODUCTS (40 CFR, PART 766)
Work Assignment 41
FINAL REPORT
EPA Contract No. 63-02-3338
MRI Project No.8501-A(41)
April 24, 1S86
For
U.S. Environmental Protection Agency
Office of Toxic Substances
Field Studies Branch, TS-798
401 M Street, S.W.
Washington, DC 20460
Attn: Mr. Thomas Murray, Work Assignment Manager
Dr. Joseph Breen, Dro,ject Officer
MIDWEST RESEARCH INSTITUTE 425 VOLKER BOULEVARD, KANSAS CITY, MISSOURI 64110 • 816 753-7600
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GUIDELINES FOR REVIEW OF TEST PLANS SUBMITTED FOR DETERMINATION OF
HDDs AND HDFs IN COMMERCIAL PRODUCTS (40 CFR, PART 766)
Work Assignment 41
FINAL REPORT
EPA Contract No. 68-02-3938
MRI Project No.8501-A(41)
April 24, 1986
For
U.S. Environmental Protection Agency
Office of Toxic Substances
Fiield Studies Branch, TS-798
1 401 M Street, S.W.
Washington, DC 20460
Attn: Mr. T|homas Murray, Work Assignment Manager
Dr. Joseph Breen, Project Officer
MIDWEST RESEARCH INSTITUTE 425 VOLKER BOULEVARD, KANSAS CITY, MISSOURI 64110 • 816 753-7600
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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.
Environmental Protection Agency. The use of trade names or commercial products
does not constitute Agency endorsement or recommendation f,ç use.
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PREFACE
This report provides guidance for the review of analytical testing
procedures to be submitted by the chemical industry to the Office of Pesti-
cides and Toxic Substances as specified in 40 CFR, Part 766: Polyhalogenated
Dibenzo- —dioxin/Dibenzofurans Testing and Reporting Requirements, Proposed
Rule (Fed. Reg. 50 (244), 51794-51823, December 19, 1985). This document
provides a format for documenting and evaluating the test plans for con-
formance with the proposed rule. These guidelines were prepared for the
OTS/Field Studies Branch as part of Work Assignment 41 (Analytical Methodol-
ogies for Halogenated Oloxins and Dibenzofurans in Commercial Products) under
EPA Contract No. 68-02-3938.
This report was prepared by Dr. John S. Stanley with assistance from
Mr. Jack Balsinger.
MIDWEST RESEARCH INSTITUTE
Paul C. Constant
Program Manager
Approved:
Jack Balsinger
Qu ty ssurance Coordinator
J’ 1i’n E. Going, Director
Chemical Sciences Department
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TABLE OF CONTENTS
Page
I. Introduction 1
II. Summary of 40 CFR 766 Testing Requirements. . . . 1
A. General Analytical Method Consideration 3
B. Detection Method 3
C. Method Sensitivity 4
0. Quality Assurance/Quality Control (QA/QC)
Procedures . 4
E. Analytical Standards . . 4
III. Submission of Testing Protocols . . 4
IV. Review of the Testing Protocols 9
V. References 10
Appendix A - Testing Protocol Summary and Review Forms 11
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I. INTRODUCTION
The Code of Federal Regulations, Title 40, Part 766 (40 CFR 766),
published December 19, 1985, presents a proposed rule for testing and report-
ing the levels of halogenated dibenzo- -dioxins (HDD) and dibenzofurans (HDFs)
in commercial products.
This rule proposes, under Section 4 of the Toxic Substances Control
Act (ISCA), 15 U.S.C. 2603, to require manufacturers and importers of 14 com-
mercial organic chemicals to test for the presence of certain HODs and HDFs.
In addition, this testing will be required for 20 other commercial organic
chemicals not currently manufactured or imported commercially in the United
States if their manufacture or importation should resume.
The rule requires that the manufacturers and importers submit ex-
isting data on the levels of HDDs and HOEs in these products to EPA. In addi-
tion, the rule requires that the analytical protocols for testing the commer-
cial products be submitted for review and approval by EPA.
This report deals specifically with the review process for assessing
the applicability of the submitted testing protocols to achieve the limits of
quantitation specified in 40 CFR 766 (0.1 ppb per 2,3,7,8-substituted HOD con-
gener and 1.0 ppb per 2,3,7,8-substituted HDF congener). Section II presents
a summary of the 40 CFR 766 testing requirements. Submission of testing pro-
tocols are discussed in Section III. The proposed review process for testing
protocols is provided in Section IV. Section V lists the pertinent references.
II. SUMMARY OF 40 CFR 766 TESTING REQUIREMENTS
Under Section 4 of TSCA, EPA may require testing of specific chem-
icals or products for contaminants in order to develop health and environ-
mental risk assessments. EPA has determined that it is appropriate for manu-
facturers to test 14 chemicals currently in production and 20 additional
chemicals if production or importation is initiated or resumed for 2,3,7,8-
substituted HODs and HOEs.
The chemicals proposed for testing are listed in Table 1. Table 2
lists 20 chemicals that will require testing if production or importation re-
sumes.
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Table 1. Chemicals Requiring Testing for 2,3,7,8-Substituted
HDDs and HDFs as per 40 CFR 766
Chemical name CAS no.
Tetrabromobisphenol-A 79947
2,4-Dichiorophenoxy acetic acid 94-75-7
2,4-Dichiorophenoxybutyric acid 94-82-6
2 , 3 , 5 ,6-Tetrachloro—2,5-cyc lohexadiene-1,4-dione 118-75-2
2,4,6-Tribromophenol 118-79-8
2,4-Dichlorophenol 120-83-2
Decabromodi phenyl oxide 1163-19-5
Tetrabromobi sphenol-A-bisethoxyl ate 4162—45-2
Tetrabromobisphenol-A-bis-2,3-clibromopropylether 21850-44-2
Allyl ether of tetrabromobisphenol A 25327-89-3
Pentabromodi phenyl oxide 32534-81-9
Octabrornodiphenyl oxide 32536-52-0
1,2-Bi s(tribromophenoxy)ethane 37853-59-1
Tetrabromobisphenol-A diacrylate
Table 2.
HODs
Chemicals Requiring Testing for 2,3,7,8-Substituted
and HDFs if Production or Importation Resumes
C
hemical name
CAS no.
Tetrachlorobisphen
ol-A
79-95-8
3,4,5-Tribromosal i
cylanil ide
87-10-5
2,6-Oichlorophenol
87-65-0
3,4—Dichiorophenol
2,4,5-Trichiorophenol
2 ,6-Dibromo-4-nitrophenol
2 [ 2,4-(Dichlorophenoxy)]—propionic acid
3,5—Dichiorosalicyclic acid
95-77-2
95-95-4
99-28-5
120—36—5
320-72-9
Tetrabromocatechol
488-47-1
2,3—Dichlorophenol
576—24-9
2,5-Dichlorophenol
583-78-8
Pentabromophenol
609-71-9
2,4-Dibromophenol
615—58-7
2,3,6-Trichiorophe
no]
933-75-5
4-Bromo-2, 5-dichl orophenol
3,5-Dibromosalicylani 1 ide
Pentach]orophenyl laurate
Bismethy]ether of tetrabromobisphenol-A
Alkylamine tetrachiorophenate
Tetrabromobisphenol-B
1940-42-7
2577-72-2
3772-94-9
37853-61-5
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EPA has proposed that the manufacturers submit matrix specific
analytical protocols capable of a limit of quantitation (LOQ) of 0.1 ppb
(nanogram/gram) for 2,3,7,8-HOD congeners and 1.0 ppb for 2,3,7,8-HOF con-
geners.
EPA will review the protocols and offer recommendations where
necessary to ensure that the methods are capable of accurately and precisely
measuring the halogenated dioxins and halogenated dibenzofurans at the tar-
geted levels. This review will encompass all aspects of the sampling and
analysis protocols. The review will include a summary statement citing any
deficiencies in the submitted protocol as well as specifying whether the pro-
tocol can possibly meet the accuracy, precision, and sensitivity requirements
cited in 40 CFR, Part 766. During this review process EPA will take into
account the possibility that interferences may not allow quantitation to the
levels specified and, in those cases where reasonable efforts have been made
to reach the target LOQ, the Agency may agree to an analytical protocol which
results in a higher LOQ.
To facilitate the development of extraction, cleanup and analysis
procedures in these protocols, EPA has provided a guidance document titled,
“Guidelines for the Determination of Polyhalogenated Dibenzo— -dioxins and
Dibenzofurans in Commercial Products.” 2
A. General Analytical Method Consideration
The analytical method consists of several discrete steps, each fully
described or reviewed in the guidelines document. 2 Because of the difference
in matrices of the chemicals listed for testing, no one method for sample se-
lection, preparation, extraction and cleanup is prescribed.
The analytical procedures specified in these guidelines for the
quantitative measurement of 2,3,7,8-HDDs/HDFs in commercial products include:
(a) the quantitative extraction or partitioning of the analytes from the com-
mercial product; (b) separation of the 2,3,7,8-HDDs/HDFs from interferences
present in the extract; and (c) separation and quantitation of 2,3,7,8-sub-
stituted tetra-, penta-, hexa-, and hepta-RDD/HDF congeners. The analytical
guidelines describe a rigid quality assurance/quality control program that
should be followed for each matrix.
The most significant difference in the analysis of 2,3,7,8—HDDs/}IDFs
in commercial products in comparison with environmental and biological samples
will be the extraction and cleanup procedures. The physical and chemical
properties of environmental and biological matrices are typically different
from the properties of the analytes to allow relative ease of separation. In
contrast, the commercial products, in most cases, may be structurally similar
to the analytes, complicating the separation and necessitating the complete
removal of the matrix to avoid interferences in the final determination.
B. Detection Method
EPA is specifying the use of high resolution gas chromatography with
high resolution mass spectrometry (HRGC/HRMS) as the chemical analysis method
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of choice for this proposed rule. Other analytical procedures including HRGC
with electron capture detectors (ECD), low resolution mass spectrometry (MS),
chemical ionization MS, and triple quadrupole MS may be used if they can be
demonstrated to achieve the targeted limit of quantitation (LOQ) for the spe-
cific 2,3,7,8-HDDs and HDFs.
C. Method Sensitivity
The analytical method must be capable of achieving limits of quan-
titation of 0.1 ppb per 2,3,7,8-HOD congener and 1.0 ppb per 2,3,7,8-HDF con-
gener.
0. Quality Assurance/Quality Control (QA/QC) Procedures
The first QA/QC requirement is a quality assurance plan (QAP). The
QAP should include procedures for documenting the history and disposition of
samples, sampling and sample collection procedures, and extraction and instru-
mental analysis procedures. The QAP documents the laboratory’s capability to
produce data which meet the data criteria specified in 40 CFR 766.’
A detailed QAP submitted to the Agency will provide the necessary
information required for the agency to review the specific testing protocols
for a commercial product. Figure 1 provides a suggested table of contents
for a QAP as outlined in an EPA Office of Toxic Substances guide for prepa-
ration of QAPs. 3 The specific quality assurance objectives as stated in
40 CFR 766 are summarized in Table 3.
E. Analytical Standards
Since the HOD and HDF compounds of greatest concern are those sub-
stituted at the 2,3,7,8 positions, EPA is specifying that these compounds be
used as reference standards. [ sotopically labeled standards shall be used as
internal standards. This rule requires quantitation for the specific 2,3,7,8-
substituted compounds listed in Table 4.
EPA realizes that industry may have to develop analytical standards
for HDD/HDF analysis in order to achieve the analytical accuracy and preci-
sion specified in this proposed rule. EPA has identified the following spe-
cific congeners commercially available for use as reference analytical stan-
dards (Table 5).
Ill. SUBMISSION OF TESTING PROTOCOLS
All information including letters of intent to test, testing pro-
tocols, and support data, submitted to EPA under this rule must bear the ap-
plicable Code of Federal Regulations (CFR) section number (e.g., 766.30).
These documents must be addressed to:
Document Control Office, TS-793
Office of Pesticides and Toxic Substances
Environmental Protection Agency
Washington, DC 20460
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TABLE OF CONTENTS
1.0 Title page
2.0 Table of contents
3.0 Project description
4.0 Project organization and management
5.0 Personnel qualifications
6.0 Facilities, equipment, consumables, and services
6.1 Facilities and equipment
6.1.1 Evaluation
6.1.2 Inspections and maintenance
6.1.3 Calibration procedures and reference materials
6.2 Consumables
6.3 Services
7.0 Data generation
7.1 Experimental design
7.2 Sample collection
7.3 Sample custody
7.4 Laboratory analysis procedures
7.5 Internal quality control checks
7.6 Performance and system audits
8.0 Data processing
8.1 Collection
8.2 Validation
8.3 Storage
8.4 Transfer
8.5 Reduction
8.6 Analysis
9.0 Data quality assessment
9.1 Precision
9.2 Accuracy
9.3 Representativeness
9.4 Comparability
9.5 Completeness
10.0 Corrective action
11.0 Documentation and reporting
11.1 Documentation
11.2 Quality assurance reports to management
12.0 References
Appendices
Figure 1. Table of contents for a QA plan as specified by the
EPA Office of Toxic Substances (Ref 3)
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Table 3. QC Procedures and Criteria for Analysis of Commercial
Products for 2,3,7,8—HOD and 2,3,7,8-HDF Congeners
Analysis event QC criteria Corrective action
Instrument mass cal-
ibration
Must demonstrate accurate mass
calibration daily versus DFTTP
or PFK.
Recalibration versus
DFTTP or PFK.
Calibration standards
Calibration standards are used
to establish the working curve,
document response factors and
mass calibration. After es-
tablishing the working curve,
the calibration standards are
analyzed to bracket sample
analyses. Response factors
should vary < 30% from the
working curve.
If RF values vary by
greater than ± 30%,
sample analyses must
be repeated follow-
ing recalibration.
Samples
Accuracy of internal standards
must meet 70-130% recovery
criteria.
Precision of duplicate analy-
ses must meet ± 10% criteria.
The limit of quantitation (LOQ)
must meet 0.1 ppb for 2,3,7,8-
HDD congeners and 1.0 ppb for
2,3,7,8-HDF congener. LOQ
10 times background signal-to-
noise. Limit of detection (LOD)
must be calculated. LOD = 3
times background signal-to-
noise.
If accuracy, preci—
s-ion, or sensitivity
requirements are not
met, the sample must
be reanalyzed.
QC samples
Method blanks analyzed with
each sample batch. Spiked
samples 70-130% recovery.
If method blank gives
any positive, re-
sponse repeat analy-
sis. If recovery re-
suits do not meet the
criteria, the sample
must be reanalyzed.
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Table 4. 2,3,7,8-Substituted Congeners of HDDs
and HDFs to be Determined Under 40 CFR 766
Chlorinated compounds
Bromi nated compounds
2,3,7,8-ICOD
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-HxCDD
1,2,3,4,6,7,8-HpCOD
2,3,7,8-TCDF
1,2,3,7,8—PeCDF
2,3,4,7,8—PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8—HxCDF
1,2,3,7,8,9—FIxCDF
2,3,4,6,7,8—FfxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
2,3,7,8-TBDD
1,2,3,7,8-PeBDO
1,2,3,4,7,8-HxBDD
1,2,3,6,7,8-NxBOD
1,2,3,7,8,9-FIxCDD
1,2,3,4,6,7,8-HpBDD
2,3,7,8-TBDF
1,2,3,7,8-PeBDF
2,3,4,7,8-PeBOF
1,2,3,4,7,8-HxBDF
1,2,3,6,7,8—RxBDF
1,2,3,7,8,9—IIxBDF
2,3,4,6,7,8—HxBDF
1,2,3,4,6,7,8-I-IpBDF
1,2,3,4,7,8,9-HpBDF
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Table 5. Currently Available Halogenated Dibenzo-2-dioxin and
Dibenzofuran Standards
Unlabeled
Di benzo-p—di oxi ns
Stable isotope labeled
2,3,7,8
1,2,3,7,8
1,2,3,7,8
1,2,3,4,7,8
1,2,3,6,7,8
1,2,3,7,8,9
1,2,3,7,8,9
1,2,3,4,7,8
1,2,3,6,7,8
1,2,3,7,8,9
1,2,3,4,6,7,8
1,2,3,4,6,7,8
2,3,7,8 (U- 13 C 12 , 99%)
2,3,7,8 (U- 37 C1, 96%)
2,3,7,8 (U- 14 C, 33 mCi/mmol)
2,3,7,8 (U-’ 3 C, 2 , 99%
1,2,3,7,8 (U—’ 3 C 12 , 99%)
1,2,3,7,8 (U—’ 3 C 12 , 99%)
1,2,3,6,7,8/1,2,3,7,8,9 (U- ’ 3 C 12 , 99%)
1,2,3,6,7,8/1,2,3,7,8,9 (U-’ 3 C 12 , 99%)
1,2,3,4,6,7,8 (U—’ 3 C 12 , 99%)
Di benzofurans
Tetrachloro:
Tetrabromo:
Pentachloro:
Pentabromo:
Hexachioro:
Hexabromo:
Heptachl oro:
2,3,7,8
2,3,7,8
1,2,3,7,8
2,3,4,7,8
1,2,3,7,8
1,2,3,4,7,8
1,2,3,6,7,8
1,2,3,7,8,9
2,3,4,6,7,8
1,2,3,4,7,8
1,2,3,4,7,8,9
1,2,3,4,6,7,8
2,3,7,8 (U- 13 C 12 , 99%)
2,3,7,8 (U-’ 3 C , 2 , 99%)
1,2,3,7,8 (U—’ 3 C 12 , 99%)
1,2,3,7,8 (U-’ 3 C 2 , 99%)
1,2,3,4,7,8 (U-’ C 12 , 99%)
1,2,3,4,7,8 (U-’ 3 C 2’ 99%)
1,2,3,4,6,7,8 (U_1 C 12 , 99%)
Tetrachloro: 2,3,7,8
Tetrabromo:
Pentachloro:
Pentabromo:
Hexachi oro:
Hexabromo:
Heptachloro:
Heptabromo:
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The letters of intent to test must be submitted by the manufacturers
to EPA no later than 45 days from publication of the rule in the Federal Reg-
ister. Existing test data and protocols for HDO and HDF levels in specific
chemical products must be submitted for review 90 days from publication of
the rule in the Federal Register. The proposed protocols for analysis of the
HODs and HDFs in chemical products must be submitted for review 180 days from
publication of the rule in the Federal Register.
IV. REVIEW OF THE TESTING PROTOCOLS
The testing protocols submitted to EPA for review should include
all parts of the quality assurance plan for measurement of brominated or
chlorinated dibenzofurans and dibenzodioxins, as stated in Guidelines for the
Determination of Polyhalogenated Oibenzo- -dioxins and Dibenzofurans in Com-
mercial Products. ’ EPA expects to receive specific plans for collection of
samples from the process stream, naming the point of collection, the method
of collecting the sample, and an estimate of how well the samples will repre-
sent the material to be characterized; a description of how control samples
(blanks) and HDD/HDF-fortified control samples, or isotopically labeled com-
pounds (standards) and duplicate samples will be handled; a description of
the chemical extraction and cleanup procedures to be used; how extraction ef-
ficiency and measurement efficiency will be established; and a description of
instrument hardware and operating conditions, including type and source of
columns, carrier gas and flow rate, operating temperature range, and ion
source temperature.
The review will specifically address whether the proposed protocol
can provide the necessary sensitivity for achieving the 0.1 ppb (HOD congeners)
and 1.0 ppb (HOF congeners) limit of quantitation (LOQ) requirements. This
can be assessed by determining the enrichment factor from the sample prepara-
tion procedure (initial sample size versus final volume), the anticipated in-
strumental sensitivity (mass of analyte required to yield a signal 10 times
the background signal-to-noise ratio), and estimated method recovery. Equa-
tion 1 will be used to determine the method capabilities.
LOQ (Estimated) = V x S x R Equation 1
where V = final extract volume in microliters,
S = instrumental sensitivity (nanograms per microliter injected) that
yields a signal-to-noise ratio of 10 to 1,
R = estimated method recovery, and
Fl = mass or volume of the chemical product prepared for analysis.
As an example, if the initial sample size is 10 g, final extract
volume is 50 pL, instrumental sensitivity required for a 10 to 1 signal-to—
noise is 0.1 ng/pL injected and the method recovery is 90%, the estimated LOQ
is 0.35 ng/g (ppb). This indicates that the method is capable of achieving
the required LOQ value for the 2,3,7,8-HDFs (1.0 ppb) but modifications are
necessary to reach the 0.1 ppb LOQ value for the 2,3,7,8-HDDs.
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The testing protocols will be evaluated to determine if the QA/QC
requirements (accuracy, precision, etc.) meet or exceed the criteria estab-
lished by the rule.
Appendix A presents examples of forms that can be used to report
the review of specific test protocols to EPA and the manufacturers. These
forms include a checkoff sheet for the Agency to provide a summary of the re-
view process. This form lists the general points that should be addressed in
the testing protocols and indicates which items require additional clarifi-
cation or modification. The remaining forms present a format for consistent
review of specific analytical method topic areas. The comments/recommendations
section on the forms should be used as a summary of the specific topic area.
Specifically, the reviewer should comment on items for which a negative answer
has been given. The reviewer should note specifically what the deficiency is
and whether it significantly impacts the overall protocol. The reviewer
should indicate whether additional information is needed. The specific points
from each of the six item comments/recommendations should be presented as a
synopsis on the summary report checklist. This review process can also be
established for protocols submitted to the Agency with existing data on spe-
cificchemical products.
V. REFERENCES
1. Environmental Protection Agency. 1985. Polyhalogenated dibenzo- -dioxin/
dibenzofurans testing and reporting requirement. Proposed Rule 40 CFR,
Part 766, Fed. Reg. 50(244) 51794-51823.
2. Steele OH, Stanley JS. 1985. Midwest Research Institute. Guidelines
for the determination of polyhalogenated dibenzo-2-dioxins and dibenzo-
furans in commercial products. Draft final report. Washington, DC:
Office of Toxic Substances, U.S. Environmental Protection Agency.
Contract 68-02-3938.
3. Environmental Protection Agency. September 1984. Guide to the prepara-
tion of quality assurance program plans. Washington, DC: Office of
Toxic Substances.
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APPENDXIX A
TESTING PROTOCOL SUMMARY AND REVIEW FORMS
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TESTING PROTOCOL FOR HODs AND HOEs IN COMMERCIAL PRODUCTS
SUMMARY REPORT CHECKLIST
Prepared for the Office of Pesticides and Toxic Substances
Chemical Products: _________________________
Manufacturer: ________________________________
Information Additional
Item Submitted Information Required
I. Sample Collection
II. Sample Preparation
III. Sample Analysis
IV. Instrumentation
V. Analytical/Internal Standards
VI. Quality Assurancy Plan
VII. Application of the Proposed Extraction/Cleanup/Analysis Procedure
This protocol (is/is not) capable of accurately and precisely measuring the
halogenated dioxins and halogenated dibenzofurans at the targeted levels.
The protocol is inadequate for the following reasons:
The manufacturer is requested to submit additional information regarding
the following aspects of the protocol.
This testing protocol was reviewed by:
Date:
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REVIEW OF TESTING PROTOCOL FOR ANALYSIS OF HDDs AND HDFs
Prepared for the Office of Pesticides and Toxic Substances
Chemical Product: _____________________________________
Manufacturer: ___________________________________________
Date Submitted for Review: __________________________
I. Sample Collection Reviewed by _______________ Date
Yes No Item
— — 01 Does the testing protocol provide a sampling plan?
— — 02 Does the plan specify cyclical sampling?
— — 03 Does the plan specify a sequential sampling?
— 04 Does the plan specify a minimum of seven samples?
— — 05 Does the plan specify random sampling?
— — 06 Does the plan specify documentation for sample collection
(dates, times of collection, sampling points, proces batch
or lot identification, chain of custody or traceability)?
— — 07 Does the plan specify procedures for preservation, storage,
and archival or samples?
Comments/Recommendations:
II. Sample Preparation Reviewed by: _______________ Date
Yes No Item
— — 01 Does the protocol specify extraction and cleanup procedures?
— — 02 Does the protocol specify spiking levels of stable isotope
labeled internal standards?
— — 03 Does the protocol specify initial sample size?
— — 04 Does the protocol specify final extract volume?
— — 05 Does the protocol specify the expected method accuracy!
precision?
— — 06 Are potential interferences identified?
— — 07 Are alternate procedures to minimize interferences provided?
08 Does the protocol specify QC samples to be analyzed with
samples (e.g., method blanks, spiked samples, replicates)?
Comments/Recommendations :
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REVIEW OF TESTING PROTOCOL FOR ANALYSIS OF HDDs AND HDFs
III. Sample Analysis Reviewed by ________________ Date
Yes No Item
— — 01 Does the protocol specify appropriate instrumental capa-
bilities?
— — 02 Does the protocol specify HRGC columns?
— — 03 Does the protocol specify instrument operating parameters?
— — 04 Does the protocol specify routine QC procedures (e.g.,
establishing calibration curve, daily check of response
factors, demonstrating required method sensitivity)?
— — 05 Are criteria for calibration established (initial calibra-
tion, daily verification)?
— — 06 Are samples/controls bracketed by standards (including
necessary LOD and LOQ)?
— — 07 Are specific ions designated to monitor HDDs and HDFs?
— — 08 Are qualitative criteria for identification given (accepta-
ble ion ratios, retention times, signal-to-noise ratios)?
— — 09 Does procedure require quantitation versus specific internal
standards?
— — 10 Does protocol define LOD and LOQ?
— — 11 Is the protocol capable of achieving LOQ values of 0.1 ppb
for PHDD congeners and 1.0 ppb for PHDF congeners? The
estimate of method LOQ presented in this protocol was de-
termined to be _____ ppb for PHDDs and _____ ppb for PHDFs.
The following equation was used to determine this value.
LOQ (Estimated) = V X S x R
where V = final extract volume in inicroliters,
S instrumental sensitivity (nanograms per microliter injected) that
yields a signal-to-noise ratio of 10 to 1,
R = estimated method recovery, and
M = mass or volume of the chemical product prepared for analysis.
Cornments/Recommendati ons :
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REVIEW OF TESTING PROTOCOL FOR ANALYSIS OF HDDs AND HOES
IV. Instrumentation Reviewed by _________________ Date
Yes No Item
01 Are equipment/instruments capable of achieving the necessary
sensitivity?
02 Is resolving power of mass spectrometer specified?
03 Does protocol specify proper instrument calibration?
04 Are instrument capabilities provided by analysis laboratory?
Comments/Recommendations:
V. Analytical Standards/Internal Standards
Reviewed by _________________ Date
Yes No Item
01 Are analytical standards available for chlorinated dibenzo-
2-dioxin and dibenzofuran analyses?
02 Are internal standards available for chlorinated dibenzo-2-
dioxin and dibenzofuran analyses?
03 Are analytical standards available for brominated dibenzo-2-
dioxin and dibenzofuran analysis?
— — 04 Are internal standards available for brominated dibenzo-2-
dioxin and dibenzofuran analyses?
05 Are analytical standards available for all 2,3,7,8-HOD and
2,3,7,8-HDF congeners?
06 Does protocol specify additional or alternate analytical
or internal standards?
07 Does protocol specify analytical/internal standard quanti-
tation pairs?
08 Does protocol specify the source of analytical/internal
standards?
Comments/Recommendations :
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REVEIW OF TESTING PROTOCOL FOR ANALYSIS OF HDDs AND HDFs
VI. Quality Assurance Plan (QAP) Reviewed by _______________ Date
Yes No Item
— — 01 Does QAP specify QC method criteria?
— — 02 Does QAP include calibration procedures and criteria (± 30%
variability)?
— — 03 Does QAP include accuracy of internal standards (70-130%)?
— — 04 Does QAP include precision of duplicate samples (± 10%)?
— 05 Does QAP include method blanks?
— — 06 Does QAP include spiked samples (70-130% accuracy)?
— — 07 Does QAP include limit of quantitation (0.1 ppb HDD con-
geners, 1.0 ppb HDF congener)?
— — 08 Does QAP include analytical method validation through intra-
or interlaboratory studies?
Comments/Recommendations :
VII. Application of the Proposed Extraction/Cleanup/Analysis Procedure
Reviewed by _________________ Date
Has the extraction/cleanup/chemical analysis procedure ever been actually
used for (data must be provided):
Yes No Item
— — 01 PHDDs/PHDFs in the listed chemical products?
— — 02 PHDDs/PHDFs in other chemical products?
— — 03 Other halogenated aromatic compounds in
— — 04 Other halogenated aromatic compounds in
— — 05 Other halogenated organic compounds in
— — 06 Other halogenated organic compounds in
— — 07 PHDDs/PHDFs in biological matrices?
— — 08 PHDDs/PHDFs in environmental (air/water/solid waste)
matrices?
Comments/Recommendations :
the listed products?
other products?
the listed products?
other products?
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