United States
Environmental Protection
Agency
                             EPA-910-R-14-003
                                May 2014
                               www.epa.gov
    R10 Data Validation and
     Review (
   Polychlorinated Dibenzo-p-
   Dioxin and Polychlorinated
   Dibenzofuran Data (PCDD/
  PCDF) Using Method 1613B,
   and SW846 Method 8290A
U.S. Environmental Protection Agency
Office of Environmental Assessment

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Region 10 Office of Environmental Assessment                                            EPA-910-R-14-003
United States Environmental Protection Agency                                                   May 2014
Seattle WA 98101                                                                     Page 1 of 88
                        Data Validation and Review Guidelines for
 Polychlorinated Dibenzo-p-Dioxin and Polychlorinated Dibenzofuran Data (PCDD/PCDF)
                     Using Method 1613B, and SW846 Method 8290A

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Region 10 Office of Environmental Assessment                                                   EPA-910-R-14-003
United States Environmental Protection Agency                                                           May 2014
Seattle WA 98101                                                                                 Page 2 of 88
                                                NOTICE
     The policies and procedures set forth here are intended as guidance to the United States Environmental
     Protection Agency Region 10 (hereafter referred to as RIO) and other governmental employees. They do
     not constitute rule making by EPA, and may not be relied upon to create a substantive or procedural right
     enforceable by any other person.  The Government may take action that is at variance with the policies and
     procedures in this manual.

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
       May 2014
     Page 3 of 88
                                    Acknowledgement


Special thanks to the following for the peer review of this document: Donald M Brown, EPA
RIO QA Chemist, Karin Feddersen, QA Officer, Washington State Department of Ecology
Laboratory, Brian Boling, Organic Laboratory Manager,  Oregon DEQ Laboratory and Peter
Kepler, HRGC/HRMS Chemist, Analytical Resources, Inc.
For Questions contact:
                          Gina Grepo-Grove, RIO QA Manager
                          US EPA Office of Environmental Assessment
                          1200 6th Ave Suite 900 MS-OEA/095
                          Seattle WA 98101
                          (206) 553-1632
                          grepo-grove.gina@ epa.gov

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Region 10 Office of Environmental Assessment                                          EPA-910-R-14-003
United States Environmental Protection Agency                                                May 2014
Seattle WA 98101                                                                   Page 4 of 88
TABLE OF CONTENTS
  1.   General Information	5
  2.   Scope/Application	5
  3.   Analytical Methods	6
  4.   Overall Implementation of Data Review	6
  5.   Elements of Data Review	8
  6.   Data Validation Procedure	8
6.1.   Data Validation Deliverables	9
6.2.   Laboratory Documentation and Deliverables	9
6.3.   Holding Time Evaluation	11
6.4.   Sample Integrity, Handling and Processing	12
6.5.   Sample Preparation and Sample Clean-Up	14
6.6.   System Performance Checks	17
6.7.   Mass Calibration and Tuning	17
6.8.   SEVI Scan Descriptor Switching Times	18
6.9.   Chromatographic Resolution	21
6.10.    Instrument Stability	22
6.11.    Initial Calibration	22
6.12.    Initial Precision & Recovery Check (TPR)	26
6.13.    On-Going Precision and Recovery Check (OPR)	27
6.14.    Continuing Calibration or Verification (VER)	27
6.15.    Blanks Analyses	30
6.16.    Performance TEST Sample/Standard Reference Material (PTs/SRMs)	32
6.17.    Laboratory Control Samples (LCS)	34
6.18.    Internal Standard (Labeled Compound) Recoveries	35
6.19.    Compound Identification	37
6.20.    Compound Quantitation	39
6.21.    Toxicity Equivalency Quotients (teqs)	40
6.22.    Laboratory Contact	40
6.23.    Overall Assessment of the Data	40
  7.   List of Validation Qualifiers	41
  Appendix A - PCDD/PCDF Validation Worksheets	42
  Appendix B- Puget Sound Sediment Reference Material: Requesting, Analyzing, Validating
  and Reporting Data Procedure	65
  Appendix C - Rules,  Calculations and Equations	78
  Definitions	85
  References	88

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Region 10 Office of Environmental Assessment                                         EPA-910-R-14-003
United States Environmental Protection Agency                                               May 2014
Seattle WA 98101                                                                  Page 5 of 88
1. GENERAL INFORMATION

This document defines the minimum requirements, responsibilities and methodology for
polychlorinated dibenzodioxin/polychlorinated dibenzofuran (PCDDs/PCDFs) data verification
and validation processes.

The objective of this document is to assist the RIO Quality Staff and other external data
reviewers in the review and validation of PCDDs and PCDFs analytical data generated by
commercial laboratories.

2. SCOPE/APPLICATION

The information contained in this document is provided by Region 10 as guidance to be used by
the data reviewers/validators and the regulated community in making judgments necessary to
determine if  the generated results meet the data  quality objectives of the program for the
intended application or use.

The  National Functional  Guidelines (NFG) for dioxin and  furan data review was not  used
entirely in  this document because the NFG's criteria  are based  on the OSWER's Contract
Laboratory Program  (CLP) contract Statement of Work  (SOW) for the  Superfund program.
Other EPA environmental programs do not have access to the CLP and instead, use the analytical
services provided by commercial laboratories that utilize the CWA Method 1613b,  or SW846
Method  8290A.  This  document is intended for  use  by  the  data  reviewers   evaluating
PCDD/PCDF analytical data generated by commercial laboratories using the EPA analytical
methods cited above and not the CLP SOW.

This document is designed to offer guidance and consistency for data reviewers and describe the
scope and contents of data validation and validation conducted on PCDD/PCDF  laboratory
analytical data packages in support of the various  environmental programs within  EPA.  The
validation procedures discussed in this SOP is based on OSWER Directive 9200.1, Guidance for
Labeling Externally Validated Laboratory Analytical  Data for Superfund Use, EPA-540-R-08-
005, January 2009 and the technical specifications and quality control (QC) requirements of the
Clean Water Act EPA Method 1613B, Tetra Through Oeta-Chlorinated Dioxins and Furans by
Isotope Dilution High  Resolution Gas  Chromatography/High resolution Mass  Spectrometry
(HRGC/HRMS),  EPA 921-B-94-005, 1994, re-issued March,  2012, and the EPA's SW846
Method  8290A,   Polychlorinated  Dibenzo-p-Dioxins  (PCDDs)   and  Polychlorinated
Dibenzofurans (PCDFs  by  High  Resolution Gas  Chromatography/High resolution Mass
Spectrometry (HRGC/HRMS), February 2007.

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Region 10 Office of Environmental Assessment                                          EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                   Page 6 of 88
The use of this  SOP is restricted to use by,  or under supervision of personnel appropriately
experienced in residue analysis of organic compounds and skilled in GC/MS or HRGC/HRMS
operations and techniques.

3. ANALYTICAL METHODS

The analytical method to be used for the analysis of PCDDs/PCDFs depends mostly on program
requirements.

To meet the Clean Water Act (CWA) and Safe Drinking Water Act (SOWA), Method 1613b is
highly recommended. In addition, Method 1613b clean-up procedures for extracts in this method
are required,  resulting in lower reporting limits and less chromatographic interferences. Strict
adherence to  the  QC  requirements  of  this  method  is necessary. This method  is highly
recommended for risk assessment.

SW846  Method 8290A is recommended for  RCRA and hazardous wastes samples for the
analysis of dioxins and furans. This is also an HRGC/HRMS method, the difference with Method
1613b is that  the analyst has the option to choose the clean-up techniques to use for the extract,
and the reporting limits are usually higher than Method 1613b.

SW846  Method 8280B -the same  sample preparation techniques  and  analytical procedures
(selected ion monitoring) are followed as the Method 8290A, the only difference, is that a low
resolution mass spectrometer is used, resulting in higher reporting limits than the Method 8290A
and chromatographic interferences are usually encountered during analysis.  This method  is
recommended for PCDD/PCDF  site characterization and clean-up but not for  the  low  level
PCDD/PCDF determination needed for risk assessments.

4. OVERALL IMPLEMENTATION OF DATA REVIEW

Data verification includes two activities:  inventory of the data package to ensure compliance
with the statement of work in terms of the required deliverables, and various checks of the data
to determine if a problem has occurred resulting in data that may need qualification. Analytical
data validation for PCDD/PCDF methods includes  a technical review of sample custody, sample
handling and preparation, holding times, instrument calibration, instrument performance, quality
control samples,  identification of target compounds, quantitation and reporting limits and the
effects of Quality Control (QC) performance and/or deficiencies on the quality of the associated
data.

There are five stages of data validation: Stage  1, Stage 2A, Stage 2B, Stage 3 and Stage 4.  The
cost  of  data  validation  depends on the  intellectual  rigor involved in the  evaluation of the

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                    Page 7 of 88
information provided by the laboratory which is dictated by the different stages of data validation
prescribed in the EPA-540-R-08-005. January 2009 document. Data Note that Stage 1 to Stage
2B  only involves the assessment of summary data reports.  Cross check with raw  data  or
instrument electronic  output is not performed. Stages 3  & 4  involve  checks for transcription
errors  and cross-checks of the  reported  results with  the instrument  raw data  output  for
consistency.

Stage 1 validation is a verification and validation based only on completeness and compliance of
sample receipt condition checks.    This  stage only involves the evaluation  of information
provided  on  the  summary  of  analytical results  (Forms   1)  and  the  chain  of  custody
documentation.  The validation report will  include assessment results for holding time, sample
integrity and reporting limits.

Stage 2A validation is a verification and  validation based on completeness and compliance
checks of sample receipt conditions  and only  sample-related QC  results.  Stage 2A validation
includes the evaluation of information provided in the summary of analytical results (Forms 1),
the  chain of custody records, and results from the analysis of the following QC samples: method
blank results, laboratory control samples (required by the CLP program), on-going precision &
recovery check (OPR required by Method  1613b) and matrix spike and matrix  spike duplicate
(not required by RIO). The validation  report  will  cover assessment of holding time, sample
integrity, analytical and  system performance through OPR results and bias  and limitation  of
reported  results  obtained from the QC sample analyses. Stage 2A validation  corresponds  to
WDOE's QA2 data review.

Stage 2B validation is a verification and  validation based on completeness and compliance
checks of sample receipt conditions and both sample-related and instrument-related QC results.
The validation report will cover assessment of holding time,  sample  integrity,  analytical and
system performance through OPR results and data bias obtained from the analysis of QC sample
plus the limitation of the data use obtained from the evaluation of calibration results.

Stage 3 validation incorporates Stage 2B requirements and also includes recalculation checks of
the  QC results. 100% calculation checks can only be conducted if the  data went through a full
electronic data review (as in the CLP program). For manual data validation, calculation checks of
the  reported  detected sample results and a minimum of 20% check of the QC samples and
standards are acceptable for Stage 3. The validation report will cover assessments listed in Stage
2B plus the calculation and transcription error checks.

Stage 4 validation incorporates Stage 3 requirements and also includes the review of the actual
instrument outputs.  Due to the complexity of the analysis, Region 10 highly recommends the

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                   Page 8 of 88
stage 4 data validation for PCDD/PCDF. This SOP will guide the user through a Stage 4
verification and validation.

5. ELEMENTS OF DATA REVIEW

To determine the quality, usability and limitations on data use of a PCDD/PCDF data package
the following QA Elements shall be evaluated by the data reviewer:

          1.  Holding Time and Preservation
          2.  Sample Integrity -Handling and Processing in the Field and in the laboratory
          3.  Sample Preparation
          4.  Sample Clean-up
          5.  System Performance
          6.  Initial Precision and Recovery Check (IPR) or Initial Demonstration of Capability
          7.  Initial Calibration
          8.  Continuing Calibration Verification
          9.  On-going Precision & Recovery Check
          10. Blanks
          11. Quality Assurance Performance Evaluation Sample or Standard reference
             Material (PE sample or SRM)
          12. Laboratory Control  Sample
          13. Instrument Recovery & Internal Standards Recovery
          14. Compound Identification
          15. Quantitation and Reporting Limits
          16. Laboratory Contact (if needed)
          17. Overall Assessment

List of validation qualifiers is at the end of this SOP. Appendix A has the PCDD/PCDF
validation worksheets. Appendix B is the RIO Sediment Reference Standard (SRM) Guidance
for Dioxin/Furan and Aroclors and Appendix C has equations used for calculations.

6. DATA VALIDATION PROCEDURE

Review the project specific DQOs, reporting limit requirements, targets goals and QC
requirements. If the data is for EPA use, the information listed above may be found in the site's
QA Project Plan (QAPP). The hierarchy of the criteria used during data validation are: (1)
criteria listed  in the QAPP (2) criteria listed in the analytical method and (3) laboratory
established acceptance/control limits.

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                  May 2014
Seattle WA 98101                                                                    Page 9 of 88
   6.1. DATA VALIDATION DELIVERABLES

Product submitted by the data reviewer/validator to RIO or other clients:

       1.  Data Validation Report
       2.  Validated Data Spreadsheet
       3.  List of Qualifiers
       4.  Other documents supporting the data validation report (optional)

   6.2. LABORATORY DOCUMENTATION AND DELIVERABLES

Each data reviewer has their own style and procedure when validating analytical data but based
on the author's professional experience, the following procedure is recommended:

Data Package Completion Check

Data deliverables,  both  hard copy and  electronic, vary  from lab to lab depending  on the
analytical methods used  and the program/project requirements that are stipulated in their contract
for analytical  services.  Generally, the laboratory send  a hard copy data, an electronic data
deliverables, usually referred to as EDDs with the summary of analytical results per analysis and
if needed, raw data.

The data review should organize the hard  copy data  and separate them per section, this will
facilitate  an organized process for cross-checking information. For a stage 4 data validation, the
following must be included  in the EDDs and the hard copy raw data submitted by the lab:

       1.  Case Narrative
       2.  Sample Traffic Reports/Chain of custody records
       3.  Sample Data
              •   Tabulated  Sample Results   Summary  with  labeled   internal  standards
                 recoveries,  mass/ions used for quantitation and the mass-ion ratios
              •   Toxicity  Equivalence  Summary using the  most  recent  WHO  toxicity
                 equivalence factor (TEFs) in the calculation. Note: Some projects require the
                 calculations of min, mid  and max TEQs. Check  the  summary form for
                 compliance
              •   Second Column Confirmation for 2, 3, 7, 8 - TCDF. If a complete separation
                 of 2,  3,  7,  8-TCDF   from other isomers is achieved, a  second  column
                 confirmatory run is not necessary.
              •   Selected  ion  current profile (SICP)  for each sample,  including dilutions and
                 re-analyses. SICPs  must  be  presented so the  two  quantitation  ions,  any

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                   Page 10 of 88
                 relevant labeled compounds, and diphenyl ether interferents are on one page.
                 The internal standards can be presented on another page.  The SICPs for the
                 lock mass ions (PFK) may be presented on another page. The SICP must show
                 the full time window scanned for each ion. Enlarge any SICP peak for any 2,
                 3, 7, 8-substituted congener present below the signal-to-noise (S/N) ratio of 10
                 or below the Required Reporting or Quantitation Limit.   Each SICP must
                 contain the following header information: sample number, date and time of
                 analysis,  absolute retention time (and scan number if available), the name of
                 identified compounds, HRGC/HRMS instrument ID, Lab file  ID and Analyst
                 ID.
              •   Complete data system report for each sample run  in  addition to the SICP-
                 usually referred to as the "raw data sheets. If manual integration was made or
                 the  data  system report  has been edited,  the  analyst must sign and date the
                 changes made and the  chromatogram displaying the  unaltered and manual
                 integration shall be included in the package.
              •   Second column confirmation run is required for all samples wherein 2, 3, 7, 8-
                 TCDF was identified at concentrations above the reporting limits or as EMPC.

       4.   Total Homologue Concentration Summary for each sample, blank and QC samples.

       5.   Calibration Data

              •   Initial Calibration
              •   Initial calibration summary for each instrument
              •   Complete initial calibration data system report  in chronological order per
                 instrument used and includes: PFK mass resolution checks and complete data
                 system reports for each standard analyzed
              •   Continuing Calibration Verification
              •   Continuing calibration summary in chronological order for each instrument
                 used
              •   Complete continuing calibration data system report in chronological order per
                 instrument  used  and includes: FIRMS  PFK  mass resolution  checks  and
                 complete data system reports for each standard analyzed; RT of isomers per
                 homologue (window defining mix); HRGC column resolution check; internal
                 standard recovery summaries, mass ion ratios, and signal-to noise ratio check
                 for each standard  analyzed. These verification checks are good for a 12 hour
                 analytical sequence.  A12-hour Analytical Sequence Summary must also be
                 submitted by the lab.

       6.  Raw Quality Control Data

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Region 10 Office of Environmental Assessment                                          EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                   Page 11 of 88
              Since the analytical method is an isotope dilution technique using labeled internal
              standard for quantitation, the analysis of matrix spike and matrix spike duplicate
              is not required. The following are the usual QC data submitted by the lab for
              dioxin/furan analyses:

                 •  Method Blank Summary
                 •  On-Going Precision and Recovery (OPR) Laboratory Control Sample
                    Summary
                 •  PE Sample or Standard Reference Material

              All QC samples analyzed for the project shall submit a tabulated summary of
              results, SICPs and a complete data system report including labeled area
              summaries

       7.  Miscellaneous Data
                 •  This is the section where a data  reviewer may find the extraction and
                    extract  clean-up bench  sheets,  instrument logs,  standard  traceability
                    certificates, standard preparation logs,  project communication logs and
                    other information that may not be submitted in the final EDD but are still
                    relevant to the project.  This is where the  data  reviewer will find hand-
                    written notations,  problems  encountered during sample receipt, sample
                    prep and  analysis and the different corrective actions taken by  the lab to
                    resolve or correct the problem. Sample clean-up and  screening data may
                    also be  found here  (like the GPC  clean-up  chromatograms,  clean-up
                    column preparations and verification checks, etc.).

       8.  Project EDD - usually submitted in a "comma-separated values" (.csv) or Excel (.xls
          or .xlsx) file format. This file contains all of the reported results. When reviewing
          data always refer and cross check the information obtained from the raw data with the
          EDD submitted by the lab.

   6.3. HOLDING TIME EVALUATION

Evaluation

Evaluate the following documents from the data package. Get the dates  and from the information
gathered, prepare a holding time summary (see Worksheet 1):
          •   Chain of custody documentation- sample collection date
          •   Sample receipt date and sample control documentation from the laboratory
          •   Sample extraction and  clean-up worksheet - write the dates

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
                                  EPA-910-R-14-003
                                         May 2014
                                      Page 12 of 88
          •   Instrument log summaries- get the sample names and date & time of injection
          •   Cross check information with the summary of reported analytical results (Form 1)
Criteria
Table 1 Holding Time Criteria - 40 CFR 136:
Method 1613b
Matrix
Aqueous
Solids & Mixed
Phase
Tissue
Tissue Solids, &
Mixed Phase
Container
Glass
Glass
Glass
Glass
Sample
Condition Upon
receipt
Cool<6°C
Cool<6°C
Cool<6°C
Cool<6°C
(somewhat frozen)
Lab Preservation /Storage conditions
Field & Lab; Cool < 6 °C
0.008% Na2S2O3;pH<9
Field: Cool <6°C
Field: Cool < 6 °C
Lab:<-10°C
Lab:^-18°C(PSEP)
Holding Time
Extraction &
Analytical
1 year
7 days
24 hours
1 year
Table 2 - Holding Time Criteria SW846 Method 8290A
Matrix
All samples, aqueous
& solids
Fish & adipose tissues
Container
Glass
Glass
Preservation
Lab: Cool < 6 ° C, store in
the dark
Lab:<-10°C
store in the dark
Extraction
Holding Time
30 days from sample
collection
30 days from sample
collection
Analytical Holding
Time
45 days of extraction
45 days of extraction
Samples stored at the Lab at Cool < 6 ° C, in the dark are good for six months.  The extraction
holding times of samples stored frozen @-10Cor-18C may be extended up to one year and
analytical holding time to additional one year (1613b). Note: Tissue samples must be extracted
within 24 hours of thawing.

Actions:

PCDDs and PCDFs are heavy and very stable in a variety of matrices. Under freezing conditions,
the holding time both extraction and analysis of extracts may be extended up to one year
(analysis). For samples not meeting the holding time criteria,  results are flagged as estimated,
"J/UJ".
   6.4. SAMPLE INTEGRITY, HANDLING AND PROCESSING

The  chain-of-custody (COC) form documents that the integrity of the  all field samples was
maintained from its origin of sample collection through sample handling, shipment, processing
and the laboratory analysis processes. The COC is used to ensure legal defensibility that proper
custody has been maintained from the time a sample is generated through its final disposition.

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Region 10 Office of Environmental Assessment                                          EPA-910-R-14-003
United States Environmental Protection Agency                                                May 2014
Seattle WA 98101                                                                  Page 13 of 88
Verification of sample documentation includes ensuring the sample is in possession  of an
authorized person as noted on the COC, the sample was secured to prevent tampering (i.e. sealed
with COC  during shipment), and/or the  sample was placed in a designated secure area while
under custody of authorized personnel.

Tissue samples:  Prior to processing tissue  samples, the laboratory must determine the exact
tissue to be analyzed. Common requests for analysis of fish tissue include whole fish-skin on,
whole fish-skin removed,  edible fish fillets (filleted in the field  or by the laboratory), specific
organs, and other portions. Once the appropriate tissue has been determined,  the sample must be
homogenized.

Homogenization: Samples  are homogenized while still frozen, where practical. Sometimes, a site
specific homogenization SOP is developed by the lab and approved by EPA for use. Refer to that
SOP if it exist when evaluating tissue sample processing. If the laboratory must dissect the whole
fish to obtain the appropriate tissue for analysis, the unused tissues may be rapidly refrozen and
stored in a  clean glass jar for subsequent use. When whole fish analysis is necessary, the entire
fish is homogenized. Homogenize the sample in a tissue homogenizer or equivalent equipment.
Cut tissue too  large to feed into the grinder into smaller pieces.  To assure homogeneity, grind
three times. Transfer the homogenized tissue to a clean jar with a fluoropolymer-lined lid. Seal
the jar and  store the tissue at the method specific temperature (<-10°C for Method 1613b/ -18C
for PSEP).  Return any tissue that was not homogenized to its original  container and store at
method  specific temperature (<-10°C for Method 1613b/ -18C for PSEP).

Evaluation: Verify and cross-check the signatures required in the chain of custody records, and
air bills. Note the conditions  of the samples upon receipt at the  lab, consistency of sample
documentation with the sample container labels, cooler and sample temperature (especially for
tissue samples). Check the sample control logs when the samples were received at the lab and
when the samples were taken in and out of the sample storage cooler or freezer for processing. In
summary, ensure that the integrity of the sample and extracts were maintained throughout the
analytical  process. Check the miscellaneous  section  for  corrective action non-conformance
memos  and communication  logs. These logs documents problems  or   potential problems
encountered during sample shipment and sample receipt at the lab.

Each sample  received by the lab shall  be  labeled  with a  Sample  Number and  will  be
accompanied by a Sample Chain of Custody Record bearing the Sample Number and descriptive
information regarding the sample. The field contractor shall complete the chain of custody record
and enter the sample name, sample location, date and time of sample collection, type of sampling
used (grab,  composite, etc) and the name or initials of the field samplers. Both the field sampler
and the laboratory designated sample custodian must sign the Chain of Custody record.

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                   Page 14 of 88
The condition of the samples upon receipt at the lab is also entered by the lab in the chain of
custody documentation and their Laboratory Information Management System (LIMS).  Look
for discrepancies  and inconsistencies between  sample documentation and the  laboratory
documentation. Tissue samples must be extracted within 24 hours of defrosting, therefore, the
tissue and shellfish samples must be frozen or partially frozen upon receipt at the lab to ensure
the maintenance of the integrity of the sample.

Tissue homogenization is documented in a separate bench sheet. The size of the fish (shellfish),
the weight and other characteristics prior to homogenization are documented in the bench sheets.
For ecological risk assessments, whole fish are used. For human health assessments, fish fillets
are used. Some projects have  varied instructions  on the parts of the specimen to be used for
analyses like: scaled vs unsealed; depurated vs not depurated; liver, blubber, right side fish fillets
compared with left side, etc. All of these  instructions are included in the QAPP. Homogenized
tissue recoveries are also documented in the bench sheets.

Actions:

If the information provided by the lab is  different from the chain of custody records and data
generated and/or other documentation problems are found, contact the lab for clarification. Note:
the PO/PM must be cc'd on all communication between the data reviewer, the field  contractors
and the lab. If other discrepancies were identified,  leading to the conclusion that the integrity of
the sample and data generated is compromised, work with the PM/PO, and the Agency's QA
Manager.  Use  professional judgment when flagging the  data due to  compromised sample
integrity.
   6.5. SAMPLE PREPARATION AND SAMPLE CLEAN-UP

Evaluation: Note the following:

   1.   Extraction procedure used for each matrix:  aqueous, solid, semi-solid or multi-phased,
       fish/tissue.

          •   Water samples:
                 o   Use Method 330.4 or 330.5 to measure residual chlorine in the sample; pH
                     must be 7-9.
                 o   Extraction for Method 1613b: Separately funnel liquid-liquid extraction-
                     Method 35 IOC; Solid phase extraction (SPE) - Method 3535A;
                     Continuous liquid-liquid extraction- Method 3520C; Soxhlet extraction
                     (SDS)-Method 3540C.
          •   Semi-solid/Solid/Soil/Sediment samples:

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                    Page 15 of 88
                 o  Ultrasonic extraction - Method 3550C; pressurized fluid extraction -
                    Method 3 545 A; microwave extraction - Method 3546; Soxhlet extraction
                    (SDS) - Method 3540C for samples containing particles, filters and/or
                    disks.
          •   Tissue samples
              o  Soxhlet extraction - Method 3540C; HC1 digestion (section 12.4.2 - method
                 1613b).

   From the extraction bench  sheets (miscellaneous data), extract the dates when  extraction
   started and ended. Note the analyst' initials. Note the amount of internal standards and clean-
   up recovery standards added to the sample. Look for hand-written notations from the analyst;
   sometimes they could provide  explanations on unexpected variations from  the  expected
   results.

   2.  Extract Clean-up Procedure: Measure clean-up  efficiency by  monitoring the clean-up
       standard recoveries - 37CU-2, 3, 7, 8-TCDD.

   Interferences  co-extracted from samples will vary considerably  from  source to source,
   depending on the diversity of the site being sampled. Interfering compounds may be present
   at concentrations  several orders of magnitude  higher  than  the  CDDs/CDFs. The most
   frequently  encountered   interferences  are  chlorinated  biphenyls,  methoxy  biphenyls,
   hydroxydiphenyl ethers, benzylphenyl ethers, polynuclear aromatics, and pesticides.

   Because very low levels of CDDs/CDFs are measured by this method,  the elimination of
   interferences is essential. Cleanup may not be necessary for relatively clean samples (e.g.,
   treated effluents, groundwater, drinking water). If particular circumstances require the use of
   a  cleanup procedure, the analyst may use any or all of the procedures below or any other
   appropriate procedure. Before using a cleanup procedure, the analyst must demonstrate that
   the requirements of the Initial Precision  and Recovery (IPR) can be met using the cleanup
   procedure. If only 2,  3, 7, 8-TCDD  and 2, 3, 7, 8-TCDF are to be determined, the cleanup
   procedures may be optimized for isolation of these two compounds.

   3.  Note that each matrix has their own specific clean-up procedures recommended  by the
       Methods.

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                  May 2014
Seattle WA 98101                                                                   Page 16 of 88
              Method 1613b Soil/sediment Extract Clean-up techniques:

       •  Gel  permeation chromatography (Section 13.2) removes high  molecular weight
          interferences that cause GC column performance to degrade. It should be used for all
          soil  and  sediment extracts and may be used for water extracts that are  expected to
          contain high molecular weight organic compounds (e.g., polymeric materials, humic
          acids).

          Verify GPC calibration every  20  samples.  In the  verification, check  the  PCP
          recovery. It must be >85%. If the calibration  was not verified  or did not meet the
          criteria,  the associated samples  must be re-extracted and  cleaned-up using the
          calibrated GPC system. Check the documentation and chromatogram, as these will
          give early indication of missed internal standards or other errors that happened during
          sample extraction.

       •  Basic silica gel  clean-up is used to remove non-polar and polar interferences. For
          extracts of samples known to contain large quantities of other organic  compounds
          (such as paper mill effluents), it may be advisable to increase the capacity of the  silica
          gel column. This may be accomplished by increasing the strengths of the acid and
          basic silica gels. The acid silica gel (Section 7.5.1.2) may be increased in strength to
          as much  as 44% w/w (7.9 g sulfuric acid added to 10 g silica gel). The basic silica gel
          (Section  7.5.1.3) may be increased in strength to as much as 33% w/w  (50  mL IN
          NaOH added to 100 g silica gel), or the potassium silicate (Section 7.5.1.4)  may be
          used.

          The use  of stronger  acid silica gel (44% w/w) may lead to  charring of  organic
          compounds in some extracts. The charred material may retain some of the analytes
          and lead  to lower recoveries of CDDs/CDFs. Increasing the strengths of the acid and
          basic silica gel may also require different volumes of hexane than those specified
          above to elute the analytes off the column. Therefore, the performance of the method
          after such modifications must be verified by the IPR procedure

       •  Activated Acid or Basic Alumina and Activated Florisil Clean-up are used to remove
          chlorodiphenyl ethers. Any of these  cleanup  techniques  may be used for sample
          extract clean-up, provided that the laboratory can meet the performance specifications
          for the recovery of labeled compounds in the IPR. The same type of alumina must be
          used for  all  samples, including those  used to  demonstrate initial precision and
          recovery and ongoing  precision and recovery.

       •  Carbon column clean-up (Carbopak CŪ & Celite 545Ū mix) is used to remove non-
          polar interferences. For PCB congeners,  the  laboratories charge extra for carbon
          column clean-up because it is an additional clean-up procedure used to determine the
          concentrations of the toxic congeners in the WHO list and the interferences caused by

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                   Page 17 of 88
          the other PCB congeners and other organic materials are removed. Therefore, if total
          PCB congener is desired, carbon column clean-up is not recommended.

       •  HPLC is used to provide specificity for the 2, 3, 7,  8-substituted and other CDD and
          CDF  isomers. HPLC  needs a column calibration verification every  20 extracts
          analyzed. In the calibration verification, CDDs/CDFs recoveries must be between 75-
          125% compared to the instrument calibration. If calibration was not verified or did
          not meet the criteria, the  associated samples must be re-extracted and  cleaned-up
          using the re-calibrated HPLC system.

          Method 1613b Tissue Extract clean-ups:

       •  Anthropogenic isolation column packed with silica gel, potassium silicate,  granular
          anhydrous sodium sulfate,  acid silica gel and granular anhydrous sodium sulfate
          (from bottom to top).
       •  Acidified silica gel batch adsorption procedure- alternate clean-up procedure for
          anthropogenic isolation column
       •  Sulfuric acid and base back-extraction are used for removal of lipids from tissue
          samples used with HC1 digested tissue extracts.


   6.6. SYSTEM PERFORMANCE CHECKS

There are four fundamental HRGC/HRMS system performance checks, i.e., mass calibration and
resolution, selected ion monitoring (SIM) scan descriptor switching times, GC resolution and
instrument stability. Use information provided in Table 3 when  assessing HRMS system
performance check.

   6.7. MASS CALIBRATION AND TUNING

Frequency of check: at the beginning and end of each 12-hour  QC period.

Criteria >10,000 resolving power of the selected ion current profile (SICP) of each target
analyte at the two exact mass/ions (m/zs) specified in Table 3 below.

Evaluation

The  analysis  time for CDDs/CDFs  may exceed the  long-term mass stability of the  mass
spectrometer. Because the instrument is operated in the high-resolution mode, mass drifts of a
few ppm (e.g., 5 ppm in mass) can  have serious adverse effects on instrument performance.
Therefore, a mass-drift correction is mandatory and a lock-mass m/z from  PFK is used for drift
correction. Using a PFK molecular leak,  the instrument must be tuned to meet the minimum
required resolving power of 10,000 (10%  valley) at m/z 304.9824 (PFK) or any other reference
signal  close to m/z 304  (from  TCDF). Tuning chromatograms will  be  submitted  by  the lab

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Region 10 Office of Environmental Assessment                                          EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                   Page 18 of 88
conducted at the beginning and at the end of each analytical sequence for each mass descriptor.
The resolution must be greater than or equal to 10,000, and the deviation between the exact m/z
and the theoretical m/z (Table 3) for each exact m/z monitored must be less than 5 ppm.

Action

In the  event that Mass  Spectrometer resolution is <10,000, there may be evidence of system
noise and false positive results may exist. It is very unusual for labs to continue the analysis with
mass tuning resolution  <10,000.  However, if only one  or two out of five  descriptors show
resolution < 10,000, the reviewer  must evaluate all  the PFK resolution checks  per instrument
submitted by the lab and look for trends. Using  professional judgment, the reviewer may
consider qualifying only associated results as estimated, "J/UJ". If system noise is apparent and
interfering with the analysis, check the initial calibration  and continuing calibration. Check the
signal  to noise  ratios,  retention times,  absolute  retention times,  mass-ion ratios,  and  GC
resolutions.  If necessary,  adjust or elevate the reporting limits to compensate for significant
baseline  noise. If the  signal to noise ratios, retention times, absolute retention times, mass-ion
ratios,  and GC resolutions in the  initial calibration and continuing calibration verifications are
acceptable, the data associated with a resolution <10,000 may only need to be flagged qualified
estimated, "J/UJ". Other QC results may be evaluated prior to rejecting the data based on mass
tuning  resolution.


   6.8. SIM SCAN DESCRIPTOR SWITCHING TIMES

In Method 1613b, the  SIM scan descriptor switching times are monitored through the analysis of
the GC retention time window defining mix solution (WDM) and isomer specificity test
standard. The analysis of this standard is used to define the beginning and ending retention times
for the dioxin and furan isomers and to demonstrate isomer specificity of the GC columns
employed for determination of 2,3,7,8-TCDD and 2,3,7,8-TCDF. It is not necessary to monitor
the window-defining compounds if only 2, 3, 7, 8-TCDD and 2, 3, 7, 8-TCDF are to be
determined.  In this case, an isomer-specificity test standard containing the most closely eluted
isomers may be used.

In Method 8290A, to check the first and last eluting dioxin and furan isomers for each
homologous series from tetra- through heptachlorinated congeners, the GC performance  check
solutions (CPS) and high -resolution concentration calibration solution (HRCC-3) are used.
These two solutions are also commercially available as a combined standard. Use Table 3 as a
guide for the mass descriptors.

Frequency of the analysis of WDM or CPS

          •   Before  initial calibration on each instrument and GC column used for analysis;

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                   Page 19 of 88
          •  Each time a new initial calibration is performed, regardless of reason;
          •  Each time adjustments or instrument maintenance activities are performed that
             may affect RTs; and
          •  At the beginning each 12-hour sample analysis period prior to the calibration
             verification.
Evaluation

    1.  Examine the WDM chromatograms to determine whether the switching times have been
       optimized properly, demonstrated by complete elution of the first and last isomers in each
       homologous series.

    2.  The ions in each of the five recommended descriptors are arranged for minimal overlap
       between  the descriptors.  The ions for  the  TCDD  and  TCDF  isomers  are  in the first
       descriptor, the ions for the PeCDD and PeCDF isomers are in the second descriptor, the
       ions for the HxCDD and HxCDF isomers  are in the third descriptor, the ions for the
       HpCDD and HpCDF isomers are in the fourth descriptor, and the ions for the  OCDD and
       OCDF isomers are in the fifth descriptor. In some cases, TCDD/DF and PeCDD/DF are
       combined in a single descriptor.

    3.  The descriptor switching times are set such that the isomers that elute from the GC during
       a given  RT window will  also be those isomers for which the ions  are monitored. If
       homologue overlaps  between descriptors occur, the laboratory may use professional
       judgment in setting the switching times.  The switching times are not to be set such that a
       change in descriptors  occurs at or near the expected RT of any 2,  3,  7, 8-substituted
       isomers. Note the RT of each first and last eluting isomer in each homologous series for
       identification  of switching times.

    4.  Each positive dioxin and furan result (tetra- through hepta-) must have an RT within the
       limits established by the WDM for the corresponding homologous series.  The 2, 3, 7, 8-
       substituted dioxins and furans must also meet the Relative Retention Time (RRT) limits
       listed in the summary Table 5 below or Table 2 Method 1613b.
Action
       If the WDM was not analyzed at the required frequency or correct adjustments in
       descriptor switching times are not evident, but the calibration standards met
       specifications for the individual 2, 3, 7, 8-substituted target analytes, results may be
       usable without qualification. Qualify total homologue results as estimated "J" or "UJ"
       since one or more CDDs/CDFs may not have been detected.

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
        May 2014
     Page 20 of 88
Table 3- Descriptors, Exact Mass-to-Charge (m/z), m/z Types and Common names of PCDDs/PCDFs
Descriptor
1











2









3










4









5







Exact m/z
292.9825
303.9016
305/8987
315.9419
317.9389
319.8965
321.8936
327.8847
330.9792
331.9368
333.9339
375.8364
339.8597
341.8567
351.9000
353.8970
354.9792
355.8546
357.8516
367.8949
369.8919
409.7974
373.8208
375.8178
383.8639
385.8610
389.8157
391.8127
392.9760
401.8559
403.8529
430.9729
445.7555
407.7818
409.7789
417.8253
419.8220
423.7766
425.7737
430.9729
435.8269
437.8140
479.7165
441.7428
442.9728
443.7399
457.7377
459.7348
469.7779
471.7750
513.6775
m/z Type
Lock
M
M + 2
M
M + 2
M
M + 2
M
QC
M
M + 2
M+2
M + 2
M + 4
M
M + 2
Lock
M
M + 2
M
M + 2
M+2
M + 2
M + 4
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
M+4
M + 2
Lock
M + 4
M + 2
M + 4
M + 2
M + 4
M+4
Common Name
PFK
TCDF
TCDF
13Ci2-2,3,7,8-TCDF
13Ci2-2,3,7,8-TCDF
TCDD
TCDD
37Cl4-2,3,7,8-TCDD
PFK
13Ci2-2,3,7,8-TCDD
13Ci2-2,3,7,8-TCDD
HxCDPE
PeCDF
PeCDF
13Ci2-l,2,37,8-PeCDF
13Ci2-2,3,4,7,8-PeCDF
PFK
PeCDD
PeCDD
13Ci2-l,2,37,8-PeCDD
13Ci2-l,2,37,8-PeCDD
HpCDPE
HxCDF
HxCDF
13C 12 -HxCDF
13Ci2 -HxCDF
HxCDD
HxCDD
PFK
13Ci2 -HxCDD
13Ci2- HxCDD
PFK
OCDPE
HpCDF
HpCDF
13Ci2- HpCDF
13Ci2- HpCDF
HpCDD
HpCDD
PFK
13Ci2- HpCDD
13Ci2- HpCDD
NCDPE
OCDF
PFK
OCDF
OCDD
OCDD
13Ci2-OCDD
13Ci2- OCDD
DCDPE

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Region 10 Office of Environmental Assessment                                          EPA-910-R-14-003
United States Environmental Protection Agency                                                May 2014
Seattle WA 98101                                                                  Page 21 of 88
   6.9. CHROMATOGRAPHIC RESOLUTION

The resolution criteria must be evaluated using measurements made on the SICPs for the
appropriate ions for each isomer. Technical acceptance criteria must be met before any
standards, samples, QC samples, and required blanks are analyzed.

GC resolution criteria for DB-5 (or equivalent) column: The chromatographic peak separation
between the 2, 3, 7, 8-TCDD peak and the 1, 2, 3, 8-TCDD peak shall be resolved with a valley
of <25% using the following equation:

       % valley = valley between 2. 3. 7. 8-TCDD and 1.2.3.8 - TCDD (100)
                    Peak height of 2, 3, 7, 8-TCDD
GC resolution criteria for DB-225 (or equivalent) column: The chromatographic peak separation
between the 2, 3, 7, 8-TCDF peak and the 2, 3, 4, 7-TCDF peak must be resolved with a valley
of <25% using the following equation:

       % valley = valley between 2. 3. 7. 8-TCDF and 2.3.4.7 - TCDF (100)
                    Peak height of 2, 3, 7, 8-TCDF

If the laboratory uses a GC column other than the columns specified here, the laboratory must
ensure that the isomers eluting closest to 2, 3, 7,  8-TCDD on that column are used to evaluate
GC column resolution. The chromatographic peak separation between 2, 3, 7, 8-TCDD and the
peaks representing all other TCDD isomers shall be resolved with a valley of <25%.

Analysis on a single GC column (as opposed to situations requiring second column
confirmation) is acceptable if the required separation of all of the 2, 3, 7, 8-substituted isomers is
demonstrated and the resolution criteria for both the DB-5 and DB-225 (or equivalent) columns
are met.

Action

If the GC resolution on the DB-5 (or equivalent) column does not meet the specifications for
chromatographic resolution (% valley<25%), professional judgment should be used to  evaluate
the severity of the non-compliant chromatographic resolution and qualify results as necessary.
The failed resolution criteria can be indicative of the potential for poor resolution between other
closely eluting homologues, as well as between  CDD/CDFs and interfering compounds. Qualify
all detects as estimated " J", non-detects are not qualified.

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                   Page 22 of 88
   6.10.      INSTRUMENT STABILITY

Criteria: Either CSS solution (Method 1613b) or the HRCC-2 (Method 8290A) is used to
monitor instrument stability. The CS3/HRCC-3 solution must meet the following QC criteria:

1. Absolute RT criteria: The absolute RT of the first internal standard must exceed 25.0 minutes
on the DB-5 column (or equivalent column), and 15.0 minutes on the DB-225 column (or
equivalent column).
2. Relative Retention Time (RRT) criteria: The RRTs of the native and labeled CDDs/CDFs
shall be within the limits listed in Table 5 below or Table 2 of Method 1613b.
3. Ion abundance ratio criteria: All native and labeled CDDs/CDFs in the CS3 standard must be
within their respective ion abundance ratios listed in Table 4 below.
4. Instrument sensitivity criteria: The peaks representing both native and labeled analytes in the
CS3  standard must have signal-to-noise (S/N) ratios >10:1.
5. Response criteria: The Percent Difference (%D) of the Relative Response (RR) must be within
ą25% of the mean RR of the initial calibration. The %D of the mean Relative Response Factor
(RRF) must be within ą35% of the initial calibration. Use the following equation to calculate the
       %D = Response (RRF or RR) from CCV -Mean Response (RR or RRF) ICAL (100)
                           Mean Response ICAL
Action:

The relative ion abundance, sensitivity  (S/N, RRF), and percent  difference (%D) determined
from the CS3 calibration check are all indicators of instrument  stability.  Qualify detects as
estimated "J" if any of these criteria fail. Failure of the S/N criteria (S/N ratio <10:1 in the CS3
calibration  verification standard) is especially  indicative of degraded instrument performance.
Qualify all positive results in associated samples  as estimated "J". Reporting limits may need
adjustment if the S/N ratio not met; non-detects ("UJ").When relative ion abundances are non-
compliant in the calibration check  standard, and  a trend is  evident, the  laboratory should be
contacted to repeat the analytical sequence. If no trend is observed, the  impact should be on
quantitation of detects and non-detects. % D not met the criteria,  qualify all results estimated,
"J/UJ".

   6.11.      INITIAL CALIBRATION

The objective of the initial calibration is to establish a linear range, Mean Relative Responses
(RRs) of the unlabeled native analytes and the  Mean Relative Response Factors  (RRFs) for the
labeled internal standards and cleanup standard. The initial calibration is to be used for routine
quantitation of. Subsequent calibration verifications occurring every  12 hours thereafter are not
to be used for quantitation of samples, nor is the initial midpoint (CS3) solution is to be used for
this purpose.

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Region 10 Office of Environmental Assessment                                            EPA-910-R-14-003
United States Environmental Protection Agency                                                  May 2014
Seattle WA 98101                                                                     Page 23 of 88
Criteria:

After the analyses of resolution check, and after meeting the criteria for system performance, the
initial calibration (minimum of 5 standards) must be analyzed prior to any sample analysis.

The following criteria must be met for the initial calibration to be acceptable:  GC resolution; ion
abundance ratio; retention  time (RT); relative retention time  (RRT); instrument sensitivity
[signal-to-noise (S/N)]; linearity of analyte response associated with relative response (RR) and
relative response factor (RRF); analyte concentration (ng/mL);  and calibration frequency.

Evaluation:

    1.  Verify that the PFK resolution check was performed, and system performance checks
       passed.
    2.  Verify that all analytes in all calibration solutions are present at the correct
       concentrations (see QAPP requirements).
    3.  Verify that the requirements for frequency of initial calibration were observed.
    4.  Verify that the ion abundance ratios in each calibration standard are within ą15% of the
       limits listed in the methods.
    5.  Verify that the five RRF %RSDs (internal standards) are <35%.
    6.  Verify that the five RR %RSDs (native compounds) are <20%.
    7.  Verify that the GC resolution criteria are met [Percent Valley (% Valley) <25%].
    8.  Verify that the instrument sensitivity criteria are met (S/N >10) in all Selected Ion
       Current Profiles (SICPs) from CS1 standard.
    9.  Verify that the RT criteria for each target analyte and internal standard have been met. If
       this cannot be verified in the documentation, examine the SICPs for each descriptor. All
       analytes must be present in the proper descriptor, and RRT and minimum RT criteria
       must be met. Verify that RTs are consistent between the calibration standards, and
       between the calibration and any subsequent samples.

Action:
    1.  Criteria #1 -  system  performance check. If it not met,  all  of the succeeding  analyses are
       unusable.  Initial calibration must not be analyzed at all.
    2.  Criteria #2 & 3- concentrations and frequency of analysis, CS1 must be at the reporting
       level specific for the  project, check the QAPP requirements. Frequency of analysis: check
       the most recent date of initial calibration analysis for  the same instrument.  If no initial
       calibration has been  performed, the data should not be considered definitive (reject or
       flag as screening-level only). If the prescribed calibration levels have not been used,  it
       may be necessary to modify the linear range for reporting (with approval of the data

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                  May 2014
Seattle WA 98101                                                                    Page 24 of 88
       user). If an otherwise  compliant initial calibration has been performed, but not at the
       prescribed frequency, the data may be usable with qualification as estimated.
    3.  Criteria # 4- Ion Abundance ratios. Failed ion abundance ratio criteria for any analyte is a
       cause for concern, and may indicate that the Mass Spectrometer is not tuned correctly,
       that the ion source is dirty, or that other electronic problems exist.  If there is a systemic
       problem resulting in failed ion ratios in the calibration, using professional judgment, a
       more in-depth review may be performed to minimize the qualification of data. The +15%
       expanded criteria is already included in Table 4, if the ion abundance ratios are still
       outside the acceptance  windows,  the initial calibration  is  not acceptable and  all
       subsequent analyzes are  unusable. Sometimes, the laboratory generates mass/ion ratios
       for some of the target compounds, check the case narrative (usually for heptas and octas).
    4.   Criteria #  5 & 6 -Analyte response - internal standard and native compounds.  If the
       %RSD is not within ą 20% and ą 35% for the RR and RRF, respectively, qualify detects
       and non-detects as estimated "J". The reviewer may discard either the CS1 or CSS values
       for the initial calibration and recalculate the %RSD. If discarding  either of these points
       brings  the  %RSD within the specified limits, qualify  either the low-  or high-end hits,
       based on the newly defined linear  range. It may  be necessary to request reanalysis if
       either of these scenarios  affects a majority of the data,  or project data quality objectives
       (DQOs) are negatively impacted.
    5.  Criteria #7 - GC Resolution.  Failed resolution  criteria can have an impact on closely
       eluting pairs other than the TCDD isomers subject to these  criteria. Qualify all results as
       estimated ("J/UJ").
    6.  Criteria #8 - Sensitivity.  Problems with the S/N ratio not being met usually occur in the
       CS1  standard. If this is  the case, professional judgment could be used to increase the
       reporting limit  to the  lowest calibration standard which meets criteria  (CS2 standard
       concentration),  depending on data requirements. Qualify any positive results below the
       CS2 standard as estimated.  If the S/N ratio is not met in CS2-CS5, qualify the associated
       compound unusable, "R".
    7.  Criteria #9 - Retention  Time.  If not within appropriate windows  and absolute RT of
       internal standard 13C12-1,  2, 3, 4-TCDD >25 minutes  on DB-5 (or equivalent) column,
       or >15 minutes on DB-225  (or equivalent) column, conduct a more detailed evaluation. If
       a sample-specific matrix caused cases of RTs not meeting the absolute RT  criteria, the
       RRTs of the analytes and their respective labeled compound should still be valid. In this
       case, identification can still be made, although quantitative interferences may be present
       and associated data may need to be flagged estimated, "J/UJ", or unusable "R", using
       reviewer's professional judgment.

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
        May 2014
     Page 25 of 88
Table 4 - Theoretical Ion Abundance Ratios and Quality Control Limits
Number of Chlorine
Atoms
4 - Tetra CDD & CDF2
5 -Penta CDDs & CDFs
6- Hexa CDDs
13Ci2-HxCDFs only
7 - Hepta CDD
13Ci2-HpCDF only
8 - OCDD & OCDF
Theoretical Ratio
0.77
1.55
1.24
0.51
1.05
0.44
0.89
QC Limit1
Lower Limit
0.65
1.32
1.05
0.43
0.88
0.37
0.76
Upper Limit
0.89
1.78
1.43
0.59
1.20
0.51
1.02
   ^C limit represents + 15% windows around the theoretical ion abundance ratios.
   2Does not apply to 37C14- 2, 3, 7, 8-TCDD (clean-up standard)
Table 5 - Relative Retention Times (RRT) and Quantitation Reference of the Native and
Labeled CDDs/CDFs
PCDD/PCDFs
Retention Time and Quantitation
Reference
Relative Retention Time
Compounds Using 13Ci2-l,2,3,4-TCDD as the injection internal standard
2,3,7,8-TCDF
2,3,7,8-TCDD
1,2,37,8-PeCDF
2,3,4,7,8-PeCDF
1,2,37,8-PeCDD
13Ci2 -2,3,7,8-TCDF
13Ci2- 2,3,7,8-TCDD
37Cl4-2,3,7,8-TCDD
13Ci2-l,2,37,8-PeCDF
13Ci2-2,3,4,7,8-PeCDF
13Ci2-l,2,37,8-PeCDD
13Ci2 -2,3,7,8-TCDF
13Ci2- 2,3,7,8-TCDD
13Ci2-l,2,37,8-PeCDF
13Ci2-2,3,4,7,8-PeCDF
13Ci2-l,2,37,8-PeCDD
13Ci2-l,2,3,4-TCDD
13Ci2-l,2,3,4-TCDD
13Ci2-l,2,3,4-TCDD
13Ci2-l,2,3,4-TCDD
13Ci2-l,2,3,4-TCDD
13Ci2-l,2,3,4-TCDD
0.999- .003
0.999- .002
0.999- .002
0.999- .002
0.999- .002
0.923- .103
0.976- .043
0.989- .052
1.000- .425
1.011- .526
1.000- .567
Compounds using 13Cn -1,2,3, 7,8,9-HxCDD as the injection internal standard
,2,3,4,7,8-HxCDF
,2,3,6,7,8-HxCDF
,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
,2,3,4,7,8-HxCDD
,2,3,6,7,8-HxCDD
,2,37,8,9-HxCDD1
,2,3,4,6,7,8-HpCDF
,2,3,4,7.8.9-HpCDF
,2,3,4,6,7,8-HpCDD
OCDF
OCDD
13Ci2-,2,3,4,7,8-HxCDF
13Ci2-l,2,3,6,7,8-HxCDF
13Ci2-l,2,3,7,8,9-HxCDF
13Ci2-2,3,4,6,7,8-HxCDF
13Ci2-,2,3,4,7,8-HxCDF
13Ci2-l,2,3,6,7,8-HxCDF
13Ci2-l,2,3,7,8,9-HxCDF
13Ci2-2,3,4,6,7,8-HxCDF
13Ci2-l,2,3,4,7,8-HxCDD
13Ci2-l,2,3,6,7,8-HxCDD

13Ci2-l,2,3,4,6,7,8-HpCDF
13Ci2-l,2,3,4,7.8.9-HpCDF
13Ci2-l,2,3,4,6,7,8-HpCDD
13Ci2-OCDD
13Ci2-OCDD
13Ci2 -1,2,3,7,8,9-HxCDD
13Ci2 -1,2,3,7,8,9-HxCDD
13Ci2 -1,2,3,7,8,9-HxCDD
13Ci2 -1,2,3,7,8,9-HxCDD
0.999- .001
0.997- .005
0.999- .001
0.999- .001
0.999- .001
0.998- .004
1.000- .019
0.999- .001
0.999- .001
0.999- .001
0.999- .008
0.999- .001
0.944-0.970
0.949-0.975
0.977-1.047
0.959-1.021

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Region 10 Office of Environmental Assessment                                            EPA-910-R-14-003
United States Environmental Protection Agency                                                  May 2014
Seattle WA 98101                                                                     Page 26 of 88
13Ci2-l,2,3,4,7,8-HxCDD
13Ci2-l,2,3,6,7,8-HxCDD
13Ci2-l,2,3,4,6,7,8-HpCDF
13Ci2-l,2,3,4,7.8.9-HpCDF
13Ci2-l,2,3,4,6,7,8-HpCDD
13Ci2-OCDD
13Ci2 -1,2,3,7,8,9-HxCDD
13Ci2 -1,2,3,7,8,9-HxCDD
13Ci2 -1,2,3,7,8,9-HxCDD
13Ci2 -1,2,3,7,8,9-HxCDD
13Ci2 -1,2,3,7,8,9-HxCDD
13Ci2 -1,2,3,7,8,9-HxCDD
0.977-1.000
0.981-1.003
1.043-1.085
1.057-1.151
1.086-1.110
1.032-1.311
    The retention time reference for 1,2,3,7, 8, 9-HxCDD is 13Ci2-l, 2, 3, 6, 7, 8-HxCDD. 1,2,3,7, 8, 9-HxCDD is
   quantitated using the averaged responses of 13Ci2-l,2,3,4,7,8-HxCDD and 13Ci2-l,2,3,6,7,8-HxCDD.
    6.12.      INITIAL PRECISION & RECOVERY CHECK (IPR)

The IPR check is required by Method 1613b and analyzed to establish the ability to generate
acceptable precision and recovery following the analytical method or Standard Operating
Procedure (SOP) established by the laboratory for the analysis. To the lab community, this is
also commonly referred to as the Initial Demonstration of Capability (IDOC).

For IPR, the following reference matrices are spiked with the labeled compound spiking solution
and the precision and recovery standard in sets of 4 and go through the same analytical processes
(extraction clean-up and analysis) as  real samples:

          •   Reagent water for aqueous samples
          •   Playground sand, Ottawa sand or similar material can be used for high solids
              reference matrix (soil/sediment). The reference material must be prepared by
              extraction with methylene chloride and/or baking at 450 C for a minimum of 4
              hours.
          •   Glass-fiber filter, Gelman Type A, or equivalent as paper reference matrix. The
              reference matrix paper must be cut to simulate the surface area of the paper
              sample being analyzed.
          •   Corn or other vegetable oil can be used as reference matrix for tissues. The oil
              may be prepared by extraction with methylene chloride.

Using the results from the set of four analyses, the average concentration of the  extracts (x) and
the standard  deviation (s) of the concentrations for each compound are calculated by isotope
dilution for CDDs/CDFs with a labeled analog, and by internal standard for 1,2,3,7,8,9-HxCDD,
OCDF, and the labeled compounds.  Compare  the results with the acceptance criteria listed in
Table 6. If "x" and "s" meet the acceptance criteria for  all  compounds, system performance is
acceptable and analysis of blanks and samples may begin. If the criteria were not met, the IPR
will be repeated until  it passed. Sample analyses may not proceed unless the IPR meets the
acceptance criteria.

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Region 10 Office of Environmental Assessment                                          EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                  Page 27 of 88
Action:

Not all laboratories submit the IPR results with the package. If that is the case, the validator must
contact the lab and request the IPR. The IPR and/or IDOC are required not only by the Method
1613b but also by the accreditation organizations. Sample analysis without an acceptable IPR is
unusable.

6.13.   ON-GOING PRECISION AND RECOVERY CHECK (OPR)

The  analysis of this QC sample prior to  all blank and sample analyses is a requirement of
Method 1613b.  A reagent blank water is spiked with a precision and recovery (PAR) solution
containing  all the target CDDs and CDFs and corresponding internal standards, clean-up and
recovery standards. Native and labeled CDD/CDF recoveries are calculated and compared with
technical acceptance criteria listed in Table 6. Method 8290A does not require the analysis of
OPR. In Method 1613b, OPR and laboratory control sample (LCS) are considered the same and
used interchangeably.

Criteria, Evaluation & Action

For each CDD/CDF and labeled compound, compare the concentrations obtained for the OPR
analysis to the acceptance criteria listed in Table 6, below. If all compounds meet the acceptance
criteria, system performance is acceptable and analysis of blanks and samples may proceed.  If,
however, any individual concentration falls outside of the range given, the extraction and clean-
up processes are not being performed properly for that compound. In this event, correct the
problem, re-prepare, extract, and clean up the sample batch and repeat the ongoing precision and
recovery test. Use professional judgment when qualifying data based on OPR. In Method 1613b,
OPR and laboratory control sample (LCS) are considered the same and used interchangeably.

6.14.   CONTINUING CALIBRATION OR VERIFICATION (VER)

In Method  1613b, the calibration check is referred to as Verification standard (VER) whereas in
Method 8290A, this check  is  called  Continuing  Calibration Standard check. A Continuing
calibration  or verification check standard CV check is  used to validate the relative  responses
(RRs) and the relative response factors (RRFs) of the initial calibration on which  quantitations
are based, and to check for satisfactory performance of the instrument on a day-to-day basis.

Frequency of Analysis: A midrange (CS3/HRCC-3) standard must be successfully analyzed at
the beginning and end  of each 12 hour analysis  period.  At the start of a 12 hour sequence, the
check is analyzed after the WDM and resolution  standard(s) and before OPR check/LCS, blanks
and samples are analyzed.

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Region 10 Office of Environmental Assessment                                          EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                   Page 28 of 88
The laboratory must not proceed with sample analysis until an acceptable calibration verification
has been performed and documented according to the following criteria: ion abundance ratios;
retention times (RTs); relative retention times (RRTs); instrument sensitivity [signal-to-noise
(S/N)]; and analyte response [Percent recoveries (%R) or Difference (%D) associated with the
RR for the native compounds and RRFs for the labeled compounds].

Evaluation:

Continuing calibration  ensures that the instrument(s)  is  capable  of consistently producing
acceptable qualitative and quantitative data. A continuing calibration check must be performed
every 12-hour time period in which samples were analyzed. Different analytical methods have
different acceptance criteria listed for continuing calibration verification.

Method SW-8290A:  The measured RRs for the unlabeled standards obtained during the routine
CCV runs must be within ą20 percent of the mean  RR values established during the initial
calibration (RIO expanded criteria + 25%). The measured RFs for the labeled standards obtained
during the routine CCV runs must be within ą30% of the mean RF values established during the
initial calibration (RIO expanded criteria + 35%).

Method 1613B: The concentration of each of the unlabeled and labeled standards must be within
the limits listed in Table  6 below. Use the values  listed in  the CCV  column.  Inspect  the
continuing calibration summary data and verify agreement with the raw data (quantitation sheets
and chromatograms).

Verify that the %D (Method 8290A) or the concentration (Method 1613B) for each compound is
within the specified range, or that the complete calibration curve was used for quantitation. If
criteria for the continuing calibration were not met, qualify detected results as estimated "J" and
non-detect results undetected/estimated "UJ".

    1.  Verify the frequency of analysis of CCVs in 12 hour analytical sequence. The CCV must
       be analyzed after  the analysis of acceptable  system performance checks  and  results
       compared to  the correct initial calibration. Method 1613b requires that each 12 hour
       analytical sequence is bracketed by an opening and ending CCV analyses.
   2.  Verify from the CCV raw data that the ion abundance ratios were all met.
   3.  Verify from the raw data that the absolute RT criteria for the compound 13C12-1, 2, 3, 4-
       TCDD were met. Verify that absolute retention times are within ą15 seconds of the
       initial calibration, an excursion outside this range may mean that some homologues will
       be missed.
   4.  Verify from the raw data that  the RRT criteria for  the native and labeled CDDs/CDFs
       were met.

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                    Page 29 of 88
    5.  Verify from the raw SICP data that the S/N ratio is >10:1 for the unlabeled CDD/CDF
       ions, labeled compounds, and internal standards.
    6.  Verify from the raw data that the measured RRs and RRFs for each target analyte and
       corresponding labeled internal standards  in  the CSS  solution are within the method
       requirements specified above.

       Actions:

    1.  Use professional judgment to qualify any analyte in samples associated with a calibration
       verification not meeting the RT and/or RRT criteria.
    2.  All of the target compounds must meet the ion abundance ratios in a CCV.  Failure to
       meet  the  ion  abundance criteria  in  a standard is indicative of poor tuning,  gross
       contamination,  or system instability. Qualify positive results as estimated "J" and non-
       detects as rejected ("R") because of the possibility of false negatives.
    3.  If the S/N ratio >10:1 limit is  not met in a calibration verification,  qualify all detects as
       estimated "J" and all non-detects as unusable "R".
    4.  Method 1613b - use the acceptance criteria listed in the Table 6.
    5.  Method 8290A- Since the initial calibration is used to generate the RR and RRF values
       used for quantitation, the %D relative to the initial calibration's Mean RR (RR) or Mean
       RRF (RRF) is a crucial criterion for review. Qualify data associated with an analyte with
       a %D not within ą25% (RR) and not within ą35% (RRF) as estimated "J". Recalibrate
       the HRGS/HRMS and reanalyze the affected samples.
    6.  Situation: Front CCV passed but ending CCV failed some of the acceptance criteria. Data
       does not need qualification if (1) samples analyzed before the CCVs met the technical
       acceptance criteria and (2) no samples were analyzed after the failed CCV.

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
       May 2014
    Page 30 of 88
Table 6- IPR, OPR and CCV Acceptance Criteria for Method 1613b

CDD/CDF
2,3,7,8-TCDD
1,2,37,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,37,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
2,3,7,8-TCDF
1,2,37,8-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-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7.8.9-HpCDF
OCDF
13Ci2- 2,3,7,8-TCDD
13Ci2-l,2,37,8-PeCDD
13Ci2-l,2,3,4,7,8-HxCDD
13Ci2-l,2,3,6,7,8-HxCDD
13Ci2-l,2,3,4,6,7,8-HPCDD
13Ci2-OCDD
13Ci2 -2,3,7,8-TCDF
13Ci2-l,2,37,8-PeCDF
13Ci2-2,3,4,7,8-PeCDF
13Ci2-,2,3,4,7,8-HxCDF
13Ci2-l,2,3,6,7,8-HxCDF
13Ci2-l,2,3,7,8,9-HxCDF
13Ci2-2,3,4,6,7,8-HxCDF
13Ci2-l,2,3,4,6,7,8-HpCDF
13Ci2-l,2,3,4,7.8.9-HpCDF
37CU- 2,3,7,8-TCDD
Cone.
(Ng/ml)
10
50
50
50
50
50
100
10
50
50
50
50
50
50
50
50
100
100
100
100
100
100
200
100
100
100
100
100
100
100
100
100
10
IF
s
(Ng/ml)
2.8
7.5
9.4
7.7
11.1
7.7
19.0
2.0
7.5
8.6
8.7
6.7
6.4
7.4
6.3
8.1
27.0
37
39
41
38
35
95
35
34
38
43
35
40
37
41
40
3.6
R
X
(Ng/ml)
8.3-12.9
38-66
9.4
7.7
11.1
38-65
89-127
8.7-13.7
43-62
36-75
41-59
46-60
42-61
37-74
45-65
43-63
74-126
28-134
27-184
29-147
34-122
34-129
21-138
31-113
27-156
16-279
27-152
30-122
24-157
29-136
32-110
28-141
39-154
OPR
% recovery
67-158
70-142
70-164
76-134
64-162
70-140
78-144
75-158
80 - 134
68-160
72 -134
84 - 130
78- 130
70-156
82-122
78-138
63-170
20-175
21-227
21-193
25-163
26-166
13-199
22-152
21-192
13-328
19-202
21-159
17-205
22-176
21-158
20-186
21-191
CCV
% recovery
78-129
78-130
78-128
78-128
82 - 122
86-116
79-126
84-120
82- 120
82-122
90-114
88-112
90-114
88-112
90-110
86-116
63-159
82-121
62-160
85-117
85-118
72-138
48-207
71-140
76-130
77-130
76-131
70-143
74-135
73-137
78-129
77-129
79-127
All specifications are from final extracts assuming a 20 uL final volume; s= standard deviation of the concentration;
x is the mean concentration calculated from 4 runs.
6.15.   BLANKS ANALYSES

The criteria for evaluation of blanks apply to  any method blank associated with samples.  If
problems with a blank exist, all associated data must be carefully evaluated to determine whether
or not there is an inherent variability in the  data, or if the problem is an isolated occurrence not

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                   Page 31 of 88
affecting other data. It is recommended to handle the Total Homologues contamination in the
same way as the evaluation for OCDD/OCDF.  It should be noted that other QC samples, i.e.,
field equipment  rinsates, or laboratory solvent blanks, should also be considered in  making
decisions regarding system contamination.

Criteria and Evaluation

    1.  Verify that each sample extract has an associated method blank that meets the acceptance
       criteria specified in the method used. The methods require that a blank reference matrix
       of an equivalent initial weight or volume be prepared by the same procedures, including
       extract cleanup,  and  analyzed on each instrument  used to  analyze  the  samples. Care
       should be exercised when evaluating the method blank(s) that were prepared with a given
       sample extract. In addition, the reviewer may consider blanks analyzed in the  same
       analytical sequence and any performance evaluation sample (PES) blind blanks submitted
       with the samples. Evaluation of field and equipment blanks should be done according to
       Regional policy and the criteria established in the project Quality Assurance Project Plan
       (QAPP). The reviewer should use the highest result from  the same column to  make
       decisions about data qualification.

    2.  Verify that,  with the exception of OCDD and  OCDF  (and Total  Homologues),  the
       method  blank(s) are  free from  contamination  for  the  native  compounds.  The
       concentration of OCDD/OCDF in the method blank must be 
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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                   Page 32 of 88
                 & PCDFs detected in the sample at concentrations <5x MB are qualified non-
                 detects, "U". Sample results >5x MB are not qualified.
              •   To avoid the needed considerations for matrix, weight, volumes or dilution
                 factors, when comparing blank and sample PCDD/PCDF, compare the area of
                 the  target compound in  the blank multiplied  by 5 with  the  area of  the
                 compound detected in the sample. Use the  raw data to get those information.

   2.  There may be instances where little or no contamination was present in the associated
       blanks, but qualification of the sample is deemed appropriate. Professional judgment
       should be used in these situations. One example would be where the method blank  did
       not satisfy one of the identification criteria, either the 2.5 * S/N requirement, or the  ion
       ratio requirement to report an analyte present, but the  actual sample contained the analyte
       with an acceptable ion ratio, and/or with slightly greater than 2.5 * S/N and less than five
       times the possible blank concentration. An  explanation of the  rationale used for this
       determination should be provided in the Data Review Narrative.

   3.  If an instrument blank was not  analyzed following a sample analysis which contained an
       analyte(s) at high  concentrations, the  sample  analysis results  must be evaluated  for
       carryover. Professional  judgment should be used  to  determine  if instrument cross-
       contamination has affected any  positive compound identification(s).

   4.  Blanks or samples run after a Performance Evaluation Sample (PES), Laboratory Control
       Sample (LCS), or Calibration Verification should be carefully examined to determine the
       occurrence of instrument or syringe carry-over. Since  the efficiency of sample transfer
       can vary  dramatically  according  to apparatus and operator techniques,  professional
       judgment should be used in each case to determine whether sample or blank results  are
       attributable to carry-over.

   5.  When  there is convincing  evidence that  contamination is isolated  to  a  particular
       instrument, matrix,  or  concentration level,   professional judgment should be  used to
       determine if qualification should only  be  applied  to certain associated  samples  (as
       opposed to all of the associated  samples).


6.16.   PERFORMANCE TEST SAMPLE/STANDARD REFERENCE MATERIAL
       (PTS/SRMS)

Data for PTs are  generated to provide information on the overall  accuracy and bias of  the
analytical  method and on  laboratory performance. Results for  PTs  are evaluated  for false
negatives, false  positives, and  accuracy  of  target compound quantitation.   The Region may
provide the laboratory with PTs/SRM to be  analyzed with each sample delivery group (SDG).
These may include blind spikes and/or blind blanks. The laboratory must analyze a PTs/SRM
when provided by the  Region. For  the Dredge Material Management Program (DMMP),  the
analysis  of a sediment  reference  material  is required for  dioxins  and furans.  The RIO
dioxin/furan Sediment Reference Material (SRM) may be requested from the  DMMP Project

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
       May 2014
    Page 33 of 88
Managers and sent by a  Quality  Staff from the RIO QA team.    The Guidance for SRM
distribution and reporting for the DMMP is in Appendix B of this SOP.

If the PE sample was provided by RIO through the QA Technical Services in Las Vegas, NV.
Contact the project QA Officer for the true values.
Criteria
       QC limits for the RIO dioxin/furan sediment reference material.
Acceptance Limits
Source








ą 50 Percent








Analyte
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
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-HpCDD
OCDD
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
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
OCDF
CAS No.
1746-01-6
40321-76-4
39227-28-6
67653-85-7
19408-74-3
35822-46-9
3268-87-9
51207-31-9
57117-41-6
57117-31-4
70648-26-9
57117-44-9
60851-34-5
72918-21-9
67562-39-4
55673-89-7
39001-02-0
Avg. Cone.
(ng/kg)
1.05
1.08
1.59
3.88
3.04
90.6
811
1.11
1.23
1.07
3.02
1.09
1.83
0.511
18.7
1.63
58.4
Action Low
-50%
0.525
0.542
0.797
1.94
1.52
45.3
406
0.557
0.613
0.533
1.51
0.545
0.917
0.255
9.36
0.815
29.2
Action High
+50%
1.57
1.63
2.39
5.82
4.55
136
1217
1.67
1.84
1.60
4.53
1.64
2.75
0.77
28.1
2.44
87.6
Evaluation
    1.  If PTs are included in the SDG, verify that the results are within the action limits [99%
       (3o) confidence interval] and warning limits [95% (2o) confidence interval]. If a blind
       blank is included, verify that no target analytes are present. The results of the blind blank
       analysis should be comparable to the associated method.

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                    Page 34 of 88
   2.  If a significant number (i.e., half or more) of the analytes in the PTs fall outside of the
       95% or 99% warning or action criteria,  or  if a number of false positive results are
       reported, the reviewer must evaluate the overall impact on data quality.
   3.  Acceptance criteria had been established for the  RIO dioxin/furan  SRM based on the
       round robin participation from  8  laboratories. The concentration ranges  of the  RIO
       dioxin/furan SRM are listed in Appendix B of this SOP.

Action:

If a result is not within acceptance criteria for any congener, evaluate the other Quality Control
(QC) samples in  the SDG like laboratory control sample (LCS), calibration, labeled standard
recovery,  internal standard recovery,  and cleanup standard recovery.  Performance evaluation
samples and standard reference materials are only one indicator of technical performance of the
laboratory. In general,  for  PES/SRM  analytes not within the 95%  confidence  intervals  or
warning performance windows but within the 99%  confidence interval, qualify associated
sample detects as estimated "J" and non-detects as estimated "UJ". For data outside the 95% or
99% confidence  intervals and scored  as  "warning-high"  or "action-high", qualify associated
sample detects as  estimated "J". Non-detect results should not be qualified in this instance. If the
results are scored as "action-low", qualify the  associated  sample detects as estimated "J" and
non-detects as unusable "R" (potential for false negatives).

6.17.  LABORATORY CONTROL SAMPLES (LCS)

Some projects require the analysis of LCS.  The CLP Dioxin analysis program  requires the
analysis of LCS.  OPR is a performance standard sample required by Method 1613b  analyzed
before all  samples and QC runs and recoveries compared with the initial precision and recovery
results (just like an initial  calibration verification) whereas the LCS is a stand-alone QC sample
evaluated  using  the laboratory established  recovery control  limits  or the  project specific
acceptance limits  specified in the QAPP.

An LCS is analyzed to provide accuracy of the analytical method. An LCS must be analyzed at a
frequency of at least one per 20 field samples  of similar matrix.  LCS% Recovery should fall
within specified limits defined by the QAPP or the laboratory's SOP.

If LCS recovery results are greater than the upper acceptance limits, qualify all detects for those
analytes which fail in the LCS as  estimated "J". If the LCS  recovery is below  the primary
recovery range, but above  10%, it may indicate that there is a low bias in laboratory performance
and the associated data  should be qualified as  estimated "J" or "UJ".  If the LCS results are
<10%, qualify positive results for those analytes as estimated "J" and  non-detects  as  unusable

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                  May 2014
Seattle WA 98101                                                                    Page 35 of 88
"R"  in all associated samples.  If the laboratory failed to prepare and analyze the LCS at the
required frequency, use other QC results to determine the quality of the associated data and note
this in the Data Review Narrative.

6.18. INTERNAL STANDARD (LABELED COMPOUND) RECOVERIES

The recovery of the labeled internal standard analysis is an indicator of the performance of
laboratory extraction and analysis. This solution is added to all samples, blanks, and laboratory
QC samples prior to extraction. Internal standard performance results are critical to the overall
accuracy and precision of the analysis since target compound results for each dioxin and furan
isomer are quantitated based on the response of the corresponding labeled isomer.

There are three types of isotope- labeled compounds used for PCDD/PCDF analysis, i.e.,  the 15
labeled internal standards that are added to the samples and QC samples prior to extraction that
monitor extraction efficiency; the internal standard, 37Cl-2, 3, 7, 8 - TCDD, added prior to
extract clean-up, hence, monitors extract clean-up efficiency and the 2 injection or recovery
standards, 13Ci2-l, 2, 3, 4-TCDD and 13Ci2-l, 2, 3, 7, 8,  9-HxCDD, added prior to injection of
the extract into the instrument. The labeled clean-up standard is added to the extract prior to
clean-up. The recoveries of all these labeled standards are monitored to determine the overall
process and  system efficiency

Criteria:

For Method  SW-8290A: All internal standards  should be within the range of 40-135 percent
recovery (%R). For Method 1613B: All concentrations  of the labeled compounds should be
within the ranges given in Table 7 below. When results of the internal standards indicate
atypical method performance for samples, the samples should have been diluted or re-analyzed
to bring method performance within acceptable limits. Some laboratories established laboratory
specific acceptance criteria for internal standards used in PCDD/PCDF analysis using their
accumulated recoveries from a control chart. This is  acceptable  as the methods are performance
based. When this happens, the laboratories list their deviations in the data package's Case
Narrative.

Action

The labeled  analogs of the native target compounds are used for sample result quantitation and
the associated results are automatically adjusted based on the amount of labeled internal standard
(IS) recovered.  Therefore, if the labeled internal standard recovery is higher compared to the

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                  May 2014
Seattle WA 98101                                                                    Page 36 of 88
CCV, the associated sample result will possibly be low biased and likewise, if the internal
standard is lower than the CCV, the associated sample results may be high biased.

Therefore, if the labeled IS did not meet the low end acceptance limit, the compound associated
with this IS may be  biased  high and the associated detected result will  need to be flagged
estimated, "J"; the associated non-detect is not qualified. If the IS recovery is extremely low
<10%, the associated detected result may be artificially high and needs to be qualified, estimated,
"J"; the bias in the non-detects EDL/RL are unknown and qualified unusable, "R". If a labeled
internal standard has  a recovery greater than the upper control limit, the associated  detected
native compound is qualified estimated, "J", indicating low bias in the associated results;  non-
detects are also qualified estimated, "UJ". If the labeled IS recovery is extremely high^200%,
the associated detected native compound is qualified estimated, "J" and  the non-detects are
qualified unusable "R", at the RL/EDL.

Sometimes there are instances when the laboratory uses the laboratory established acceptance
limits  for labeled  internal standards recovery. In instances like this,  internal standards not
meeting the laboratory established acceptance limits are also qualified as stated above.

Clean-up recovery standards  that are not within the acceptance limits but  >10% indicates low
bias in the associated  results are flagged estimated, "J/UJ".  Extremely low recovery (<10%) or
no recovery indicate potential for false negatives; detected compounds are flagged estimated,
"J", and non-detected results are qualified unusable, "R".  Note: The cleanup standard is not
required by method SW-8290A.

Injection standards, 13Clrl, 2, 3, 4- TCDD and 13Clrl, 2, 3, 7, 8, 9-HxCDD are added to samples
after extraction and prior to analysis. These recovery standards are used  to calculate the labeled
internal standard analogs added before extraction. Recoveries for these two IS are not required to
be monitored.

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
                                                                  EPA-910-R-14-003
                                                                         May 2014
                                                                      Page 37 of 88
Table 7 - QC Limits for Labeled Compound Recoveries In Samples (Method 1613B)
Compounds
13Ci2-2,3,7,8-TCDD
13Ci2-2,3,7,8-TCDF
13Ci2-l,2,37,8-PeCDD
13Ci2-l,2,37,8-PeCDF
13Ci2-2,3,4,7,8-PeCDF
13Ci2-l,2,3,4,7,8-HxCDD
13Ci2-l,2,3,6,7,8-HxCDD
13Ci2 1-,2,3,4,7,8-HxCDF
13Ci2-l,2,3,6,7,8-HxCDF
13Ci2-l,2,3,7,8,9-HxCDF
13Ci2-2,3,4,6,7,8-HxCDF
13Ci2-l,2,3,4,6,7,8-HpCDD
13Ci2-l,2,3,4,6,7,8-HpCDF

13Ci2-l,2,3,4,7.8.9-HpCDF
13Ci2-OCDD
37CU-2,3,7,8-TCDD
Test Concentration
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
10
Labeled Compound Recovery QC Limits
Ng/ml
25-164
24-169
24-181
24-185
21-178
32-141
28-130
26-152
26-123
29-147
28-136
23-140
28-143
26-138
34-313
3.5-19.7
% recovery
25-164
24-169
24-181
24-185
21-178
32-141
28-130
26-152
26-123
29-147
28-136
23-140
28-143
26-138
17-157
35-197
6.19.
Criteria
COMPOUND IDENTIFICATION
              Signal -to-noise ratio >2.5 (S/N>2.5)
              Retention time within 2 seconds of the labeled analog or if there's no labeled
              analog, within the retention time window established during the WDM analysis.
              Ion-abundance ratio met- The ratio of the integrated areas of the two exact m/z's
              must be within the limit specified in Table 4 or within ą10% of the ratio in the
              most recent Midpoint Calibration Standard (CS3). The ion ratio criterion applies
              to all 2,  3, 7, 8-native and labeled CDDs/CDFs as well as to peaks representing
              non-2, 3, 7, 8-substituted CDDs/CDFs.
              Peak identification- the ion current response for the two quantitation ions for the
              analyte and the labeled analog in question must maximize simultaneously within
              the same 2 seconds
              Absence of polychlorinated diphenyl ether co-elution or interference.
Evaluation
    1.  Check the sample result SICP chromatograms.  SICPs must be presented so that the two
       quantitation ions,  any  relevant  labeled  compounds, and  chlorinated  diphenyl  ether

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                  Page 38 of 88
       (CDPE) interferents are all on one page. For example: for 2, 3, 7, 8-TCDF, the following
       SICP chromatograms must be presented in one page: masses: 304 (m), 306 (m+ 2), 318
       (labeled 2378-TCDF) and 375 (hexaclorodiphenyl ether).  Note that diphenyl ethers are
       only monitored in PCDFs and not PCDDs.

   2.  Signal-to-noise (S/N) ratio. Sometimes, the lab provides the  S/N calculation in the Case
       Narrative. However, data reviewers will need to check the noise against the sample result
       response.   For  PCDD/PCDF analysis, most  of the  laboratories  set their  instrument
       baseline noise threshold to 2.5 and therefore,  any peak detected within the  established
       retention time window, and area >2.5 the noise level is reported by the data system as a
       detected compound.

   3.  Using the SICP print-out (electronic or hard copy), check the retention times of the native
       (parent &daughter  masses), relevant labeled compounds and the CDPE channel. For a
       compound to be reported as  detected, the peaks/retention times for the  masses  of both
       native and labeled compounds must be aligned and elute within 2 seconds of each other.
       There should be no CDPE peak eluting at the same retention time as the masses of the
       target compound and the mass- ion abundance ratio (m/z ratio) must be met. If all the
       qualitative identification criteria are met except for the mass-ion abundance, the result is
       reported as estimated maximum potential concentration (EMPC) by the laboratory.  The
       reviewer should rely on professional judgment and organizational policy to decide how to
       qualify EMPCs.  If the compound meets the expanded m/z ratio criteria, then the result
       may be reported and flagged estimated, "J. If the m/z ratio  did not meet the expanded
       criteria, the result is reported non-detect, "U", at the level of detection.

   4.  If there are diphenyl ethers co-eluting interfering with the compound peak, even with
       additional clean-up, the  compound is flagged by the lab  (usually "X" or "E") and also
       reported as EMPC. During validation, the reviewer must check the contribution of the
       CDPE  peak to the  masses being monitored. If the interference is significant (>25%) of
       the compound peak, the sample result is flagged non-detect, "UJ" elevated at the  level of
       detection of the compound.  If the  interference  of  the CDPE is minimal (<25%),  the
       compound is reported and flagged estimated, "J", due to interferences.

   5.  Total  PCDDs/PCDFs.  The  total concentration  of peaks  commonly  found in each
       descriptor and has  S/N >2.5  are reported by the lab for total homologues. These peaks
       represent the many less toxic non-2, 3, 7,  8-substituted CDDs/CDFs.  These compounds
       do not have associated toxic equivalent quantities (TEQs), but the total quantity of CDDs
       or CDFs in each homologous series is required by certain data users.  All peaks identified
       as non-2, 3, 7, 8 CDDs/CDFs must meet the same  qualitative criteria as the 2,  3, 7, 8-

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                  May 2014
Seattle WA 98101                                                                   Page 39 of 88
       substitued target analytes, except RT.  Peaks not meeting the m/z ratio due to CDPE
       interferences are reported as EMPC. These peaks must be flagged non-detects by the data
       reviewer and concentrations deducted from the totals reported.

   6.  The PCDD/PCDF result flagged by the reviewer as non-detect must not be included in
       the TEQ calculation.

6.20.    COMPOUND QUANTITATION

Criteria

The  estimated detection limits (EDLs) and/or reporting limits reported by the laboratory must
meet the data quality goals of the project. EDLs must be less than the Reporting Limits.

Evaluation:

The  site specific or project specific data quality goals can be found in the QAPP. Compare the
reported results with the DQO goals. Concentrate on the EDLs and RLs of the non-detects and
determine if they are lower than the project screening or action level. If the EDLs or RLs did not
meet the screening or action levels specified in the QAPP,  the DQOs are not met and  there
maybe potential for data gaps.

Verify that EDLs are properly calculated.  See Appendix  C for formula. Recalculate 10% of
EDLs form raw data and compare with the reported results.

EDL must be reported for each undetected analyte, except when in it is increased due to dilution
of the extract.

An EMPC is calculated for 2, 3, 7, 8-substituted isomers that have S/N ration >2.5 for both ions,
but do not meet all the identification criteria. Verify that EMPCs are  properly calculated. See
Appendix C  for formula. Recalculate  10%  of EMPCs from raw data and compare with the
reported results.

Action:

If EDLs are  not properly calculated or reported, notify the  Project Manager (PM)  and Work
Assignment Manager (WAM) and contact the laboratory for clarification.

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                   Page 40 of 88
If EDL>RL after adjusting for dilution, notify the Project Manager (PM) and Work Assignment
Manager (WAM) for action and note this non-compliance in the validation report.

If there is a discrepancy of >10% between reviewer's calculation and the value reported, request
laboratory  clarification  through the  PM/WAM. If the discrepancy remains unresolved,  use
professional judgment to decide which  is more reliable values and if qualification of data is
warranted.

If EMPC reported is EDL,  qualify data as non-detects reported at the level the analyte
was detected. If the EMPC is >RL, check the chromatogram for interferences.  If interferences
can be minimized or removed by further extract clean-up, request additional clean-up from the
laboratory through the PM/WAM. If the peak  cannot be isolated form the interferences, flag the
result estimated with a possible high bias.

6.21.     TOXICITY EQUIVALENCY QUOTIENTS (TEQS)

TEQs are used by data users for risk assessments. For consistency, the laboratories providing
analytical services for PCDD/PCDF are requested by RIO to submit the PCDD/PCDF TEQs
using 3 scenarios: (1) ND=0; (2) ND=l/2 and (3) ND=1. These 3 calculations will reflect the
potential total toxicity min-max values in the sample. If the TEQs are derived from PCDD/PCDF
values that are flagged estimated, the total TEQ is also flagged estimated, "J". Use the most 2005
or most recent WHO Human and Mammalian Toxic Equivalency Factors (TEF) for Dioxin and
Dioxin-like Compounds in the TEQ calculations.

6.22.   LABORATORY CONTACT

If the laboratory was contacted by the reviewer to obtain more information needed to complete
the review, the contact date, point of contact and  summary of issues discussed and the name of
person who contacted the lab shall be  included  in this section of the Validation Report.
6.23.   OVERALL  ASSESSMENT OF THE DATA

In this section, the data validator shall report the following: (1) if the completion target goal has
been accomplished or not; (2) the percentage of the data points qualified unusable, if any and the
reasons for the qualification; (3) the percentage of the data points qualified estimated; (4) the
most common problem(s)/issues observed with the data is also discussed in this section and (5)
overall effect of the QC issues on the quality of the associated data.

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
                                                       EPA-910-R-14-003
                                                             May 2014
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7.  LIST OF VALIDATION QUALIFIERS
                                           Data Qualifiers
                 U
                 UJ
                 R
                 JN
The substance or analyte was analyzed for, but no quantifiable concentration
was found at or above the sample quantitation or reporting limit (numerical
value).
                         The analyte was positively identified in the sample. The associated
                         numerical result is an estimate due to failure in meeting QC acceptance
                         limits.
The analyte was analyzed for, but was not detected at or above the estimated
quantitation or reporting limits due to one or more QA/QC requirements that
were not met.
The data are unusable for all purposes due to gross deficiencies in QA/QC
results.
The analysis indicates the presence of an analyte for which there is
presumptive evidence to make a "tentative identification". The associated
numerical result is an estimate. Data qualified "JN" are for screening
purposes only and will need confirmatory analysis to further increase
usability.
Bias Qualifiers Used for Hazard Ranking System (HRS) pre-scoring for NPL Listing (Note:
These bias qualifiers must be applied to qualified results supporting a Preliminary Assessment,
Site Investigation or Expanded Site Investigation projects only. Verify project needs with the
specific/project QAPP section 4.0 Data Validation and Usability).
Bias Qualifiers




L
H
K
Q
Low Bias
High Bias
Unknown Bias
Value reported below the method or contract required
reporting/ limits (CRQLs or RLs)
quantitation

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Region 10 Office of Environmental Assessment                                          EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                   Page 42 of 88
       APPENDIX A - PCDD/PCDF VALIDATION WORKSHEETS

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
      May 2014
    Page 43 of 88
    PCDD/PCDF DATA VALIDATION WORK SHEET 1 -HOLDING TIME, SAMPLE INTEGRIT, PREPARATION &
                                       EXTRACT CLEAN-UP EVALUATION
CRITERIA/ACTION
MATRIX
AQUEOUS/WATER
SOLIDS/MIXED SOLIDS
TISSUE
SOLID/TISSUE/SEMI-SOLID
PRESERVATIVE
6°C-Na2S2O3(Cl2)
6°C
6°C
-10 TO -18 °C
EXTRACTION HT
ANALYTICAL HT
1 YEAR (40 CFR 136- METHOD 1613B)
7 DAYS (40 CFR 136- METHOD 1613B)
EXTRACTION WITHIN 24 HOURS
(40 CFR 136- METHOD 1613B)
I YEAR (METHOD 1613B & PSEP)
QUALIFIERS
DETECTS
J
J
J
J
NON-DETECTS
UJ
UJ
UJ
UJ
LIST OF SAMPLES
EPA
Sample
Number














Location/
Description














Lab
Sample
Number














DATES
Sample
Collection














Lab Sample
Receipt














Homogenization
(Tissue)














Extraction














Clean-up 1














Clean-up2














Analysis 1














Analysis 2















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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
       May 2014
    Page 44 of 88
CHAIN OF CUSTODY
Signatures:
• Field Sampler
• Shipper
• Delivery (Lab)
Cooler Temperature Check
Sample Condition
Transcription errors in
documentation
Sample receipt docs Lab
Sample Storage docs

SAMPLE PREP & CLEAN-UP
Tissue Homogenization docs
Extraction Method
Analyst signature
Initial Mass
Final Extract Volume
Clean-up Techniques
Analyst Signature



















Yes










Yes






No










No






Comments










Comments






Qualified Samples:
Print Name & Signature Data Reviewer/Validator
              Date

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
      May 2014
    Page 45 of 88
               PCDD/PCDF DATA VALIDATION WORKSHEET 2 - SYSTEM PERFORMANCE CHECK
CRITERIA/ACTION
Name of Instrument:	
Date & Time of Analysis:	       Operator:	

PFK Check at required frequency?
HR/MS MASS RESOLUTION
HR/MS Resolution failed;
No re-analysis
Low/high mass per homologue?
Frequency of Analysis of WDM
Descriptor switching times for 6 descriptors
Retention Times established by WDM
S/N for quantitation
S/N for standard
Simultaneous peak responses at M & M+2
masses?
Retention times (RTs) of each other M + M+2
GC Resolution
Ion Abundance met for all target compounds
System Stability - Absolute RT & RRT met
(CS3/HRCC3)
Criteria
Front & end
>10,000

Each descriptor
Front- sequence
Minimum overlap
between descriptor
First to last isomer per
homolog
>2.5 noise
>10 noise
Simultaneous peak
responses
within 2 seconds
%valley <25%
Table 4
Table 5
Yes



Required

Required
Required







No














If < criteria
write the number
Validation Qualifiers
Detects
Non-detects
If PFK analyzed only at the front - and other criteria met-
no qualification necessary


Missing descriptor

Overlap/co-elution
Use professional
judgment
If<2.5
If<10

RT criteria no met
Co-elution
Reported as EMPC
with calculation
m/z adjustment
Without
Use professional
judgment
No flag
R
J

J
No flag
R
UJ

UJ
Call the lab to resubmit the WDF
SICP
UJ
J
UJ
UJ
Unconfirmed detect; U
Unconfirmed detect; U
J
J
UJ

UJ
UJ
UJ


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Region 10 Office of Environmental Assessment                                            EPA-910-R-14-003
United States Environmental Protection Agency                                                   May 2014
Seattle WA 98101                                                                     Page 46 of 88
List of Samples Affected by failed System Performance check and specify reason:
Print Name & Signature Data Reviewer/Validator                                         Date

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
       EPA-910-R-14-003
             May 2014
           Page 47 of 88
                            PCDD/PCDF DATA VALIDATION WORKSHEET 3- IPR/IDOC

Method 1613B: Calibration Standard Runs: Initial and On-Going Precision & Recovery Checks (IPR and OPR); Initial
Calibration and Continuing Calibration Verification
Method 8290A: Initial Demonstration of Capability (IDOC) and/or Method Detection Limit (MDL) Determination; Initial
Calibration and Continuing Calibration Verification
Instrument:
Date and Time of Analyses:
Operator:
Criteria/Action: IPR/IDOC


Method 1613B
Evaluation



Criteria

Refer to Table 6 criteria for IPR, OPR and CCV
Check standard deviations, & mean concentrations of
PCDDs/PCDFs analyzed for IPR and OPR. Compare values
with Table 6

Failed IPR/IDOC - All associated standard, sample & QC
runs are unusable - Laboratory did not meet EPA's FEM
Policy for competency; data will not be defensible in court.
Data may only be used for screening purposes.

Validation Qualifiers in
Associated Samples
Detects



Estimated, "J"
For screening
purposes only

Non-Detects



Use
professional
judgement

Print Name & Signature Data Reviewer/Validator
                   Date

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
       May 2014
    Page 48 of 88
                      PCDD/PCDF DATA VALIDATION WORKSHEET 4- INITIAL CALIBRATION
Initial Calibration (Per Instrument)
Instrument:	
Date and Time of Analysis	
      Operator:

System Performance Check
Concentrations
Frequency of Analysis

Ion Abundance Ratios

Native compound %RSD
Labeled internal standard RSD

GC Resolution
Sensitivity
Retention Time
Relative Retention Time
Criteria Not Met
See Worksheet 1
QAPP/SOP/Method
QAPP/SOP/Method
No Initial Calibration
Table 4 (Validation SOP)
Or Case Narrative
+ 25 %RSD RR
+ 35%RSD RRF

% valley<25%
S/N>10:lforCSl
S/N>10:1 CS2-CS5
Absolute RT of 13Ci2-
1,2,3,4-TCDD>25
minutes in DBS; >15
minutes in DB225
Table 5
Action- Associated Samples

Adjust RL/EDL
Screening level data
Screening level data
Use professional judgment Lab report as
EMPC- m/z corrected; > RL
Lab report as EMPC- m/z < RL
Remove CS1 or CSS and recalculate RSD
If CS1 is making RSD fail (out)
If CSS is out- flag concentrations>CS4
Check closely eluting compounds
Adjust EDLs/RLs
Problem with Instrument sensitivity
Use professional judgment. Sample matrix
may have caused RTs to shift. Check
SICP for interferences. If compound
meets other identification criteria, no flag
is necessary. If concentrations are affected
by interferences, flag results estimated.
Use professional judgment. Sample matrix
may have caused RTs to shift. Check
SICP for interferences. If compound
Validation Qualifiers
Detects
J
J
J
J
U
J
J
J
J
J
J

Non-detects
UJ
R
R
UJ/R
UJ
UJ
UJ
No flag
UJ
R
UJ


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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
       May 2014
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RT and Quantitation Reference


Table 5; must be within 2
seconds of each pair ions

meets other identification criteria, no flag
is necessary. If concentrations are affected
by interferences, flag results estimated.
Sample matrix may have caused RTs to
shift. Check SICP for interferences. If
there are interferences, the RTs of the pair
ions and labeled analogs will also shift.
May cause false positives. Use
professional judgment.







Associated Samples:
Print Name & Signature Data Reviewer/Validator
              Date

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
      May 2014
    Page 50 of 88
         PCDD/PCDF DATA VALIDATION WORKSHEET 5- CONTINUING CALIBRATION VERIFICATION
Continuing Calibration Verification Check (Per Instrument)
Instrument:	
Date and Time of Analysis	                       Operator:	

System Performance Check
IPR/IDOC
Initial calibration
Concentrations
Frequency of Analysis

Native compound %D
Labeled internal standard
Native compound
Labeled internal standard


Ion Abundance Ratios

GC Resolution
Sensitivity
Criteria Not Met
See Worksheet 1
See Worksheet 3
See Worksheet 4
QAPP/SOP/Method (CS3/HRC3)
QAPP/SOP/Method (every 12
hours; front & back end - method
1613B sequence)
CCV from initial calibration
+ 25RR
+ 35RRF
Table 6 of the validation SOP


Table 4 (Validation SOP)
Or Case Narrative
% valley<25%
S/N>10:lforCSl
S/N>10:1 CS2-CS5
Action- Associated Samples



Adjust RL/EDL
No CCV -Initial calibration used;
estimated results
Only front end CCV - OK- 1C AL
RR/RRF used in calculation;
Failed Back end CCV - OK as
long as no samples analyzed after
the failed CCV
OK; sate in validation report
Method 8290A criteria
Method 1613B criteria


Lab report as EMPC- m/z
corrected; > RL
Lab report as EMPC- m/z < RL
Check closely eluting compounds
Adjust EDLs/RLs
Problem with Instrument
Validation Qualifiers
Detects



J
None
J
J
J
Non-detects



R
None
UJ
UJ
UJ
See internal std section


J
U
J
J


UJ/R
UJ
UJ
R

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
                                              EPA-910-R-14-003
                                                     May 2014
                                                  Page 51 of 88
                                                                 sensitivity
Retention Time
Absolute RT of 13Ci2-l,2,3,4-
TCDD >25 minutes in DBS; >15
minutes in DB225
Use professional judgment.
Sample matrix may have caused
RTs to shift. Check SICP for
interferences. If compound meets
other identification criteria, no flag
is necessary. If concentrations are
affected by interferences, flag
results estimated.
Relative Retention Time
Table 5
Use professional judgment.
Sample matrix may have caused
RTs to shift. Check SICP for
interferences. If compound meets
other identification criteria, no flag
is necessary. If concentrations are
affected by interferences, flag
results estimated.
RT and Quantitation
Reference
Table 5; must be within 2 seconds
of each pair ions
Sample matrix may have caused
RTs to shift. Check SICP for
interferences. If there are
interferences, the RTs of the pair
ions and labeled analogs will also
shift. May cause false positives.
Use professional judgment.	

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Region 10 Office of Environmental Assessment                                             EPA-910-R-14-003
United States Environmental Protection Agency                                                    May 2014
Seattle WA 98101                                                                        Page 52 of 88
Samples Associated with the CCV:
Print Name & Signature Data Reviewer/Validator                                          Date

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
      May 2014
    Page 53 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 6- ON-GOING PRECISION AND RECOVERY (OPR)
OPR Check (Per Bath of Samples Extracted & Analyzed)
Instrument:	
Date of Extraction:
Date and Time of Analysis
      Operator:

System Performance Check
IPR/IDOC
Initial calibration
Continuing Calibration
Frequency of Analysis-OPR
Recoveries
Criteria
See Worksheet 1
See Worksheet 3
See Worksheet 4
See Worksheet 5
One per sample batch or one
per 20 samples
Table 6 of Validation SOP
Action- Associated Samples




Method 1613B only/ sometime
LCS analyzed instead of OPR
Use professional judgment for
qualifying associated data by
considering CCV results and
other QC runs (LCS)
Validation Qualifiers






Samples Associated with the OPR:
Print Name & Signature Data Reviewer/Validator
            Date

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
      May 2014
    Page 54 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 7 - BLANKS ANALYSIS
Instrument:	
Date of Extraction:
Date and Time of Analysis
      Operator:

System Performance Check
IPR/IDOC
Initial calibration
Continuing Calibration
OPR
Frequency of Analysis- MB
Contamination




Criteria
See Worksheet 1
See Worksheet 3
See Worksheet 4
See Worksheet 5
See Worksheet 6
One blank reference matrix per
sample batch/ one per 20
samples
5xMB
>5x RL OCDD/OCDF
Check cause of EMPCs in MB and
in associated samples (could be m/z
or CDPE)
IfCDPE
If m/z failed, check for correction
Validation Qualifiers
Detects





U
U
No flag
No flag
U
Corrected J
Uncorrected- U
Non-detects





U
U
U
U
U
UJ
UJ
List of Associated Samples:
Print Name & Signature Data Reviewer/Validator
             Date

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
      May 2014
    Page 55 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 8 - PE SAMPLE/REFERENCE MATERIAL ANALYSIS
Instrument:	
Date of Extraction:
Date and Time of Analysis
      Operator:

System Performance Check
IPR/IDOC
Initial calibration
Continuing Calibration
OPR
Blanks
Frequency of Analysis

Criteria
See Worksheet 1
See Worksheet 3
See Worksheet 4
See Worksheet 5
See Worksheet 6
See Worksheet 7
Regional/Program-Specific

Action- Associated Samples






See Appendix A- SRM
Guidance - Acceptance limits
only Advisory for data users
use only; do not flag associated
sample results

Validation Qualifiers






See Appendix A- SRM
Guidance - Acceptance limits
only Advisory for data users
use only; do not flag associated
sample results

List of Associated Samples:
Print Name & Signature Data Reviewer/Validator
            Date

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
      May 2014
    Page 56 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 9 - LABORATORY CONTROL SAMPLE (LCS) ANALYSIS
Instrument:	
Date of Extraction:
Date and Time of Analysis
      Operator:

System Performance Check
IPR/IDOC
Initial calibration
Continuing Calibration
OPR
Method Blanks
PE/SRM Analysis
Frequency of Analysis -LCS


Criteria
See Worksheet 1
See Worksheet 3
See Worksheet 4
See Worksheet 5
See Worksheet 6
See Worksheet 7
See Worksheet 8
One LCS per sample batch/ one
per 20 samples


Action- Associated Samples







QAPP or Lab specific control
limits
Within QC limits
 10%
<10%
>Upper limit
Validation Qualifiers
Detects






Non-Detects







No flag
J
J
J
UJ
R
None
List of Associated Samples:
Print Name & Signature Data Reviewer/Validator
             Date

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
                                                                          EPA-910-R-14-003
                                                                                 May 2014
                                                                              Page 57 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 10A - LABELED STANDARD RECOVERIES
Instrument:	
                                                                                Operator:
CCV Date and Time of Analysis

15 Labeled Standard Analog




Clean-up standard


Criteria Method 1613B
Table 7 of validation SOP




Table 7 of validation SOP


Action- Associated
Samples

Upper Limit
>200% or 400% for
i3Ci2-OCDD
Upper Limit
<10%
Validation Qualifiers
Detects *
J (biased high)
J (artificially high)
J (biased low)
J (extremely biased low)
J (biased low)
J (biased high )
J Extremely low biased
Non-Detects
None
UJ
UJ
R (potential
false negative)
UJ
None
R (potential
false negative)
       *See Narrative - Validation SOP
List Affected Samples
Print Name & Signature Data Reviewer/Validator
                                                                                       Date

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
                                                                         EPA-910-R-14-003
                                                                               May 2014
                                                                            Page 58 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 10B - LABELED STANDARD RECOVERIES
Instrument:	
                                                                               Operator:
CCV Date and Time of Analysis


15 All Labeled Internal
Standards Including Clean-up
standard



Criteria Method 8290A

40 - 135%



Action- Associated
Samples

Upper Limit
>200%
Validation Qualifiers
Detects
J (biased high)
J (artificially high)
J (biased low)
J (extremely biased low)
Non-Detects
None
UJ
UJ
R (potential false
negative)
List Affected Samples
Print Name & Signature Data Reviewer/Validator
                                                                                     Date

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
      May 2014
    Page 59 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 11 - COMPOUND IDENTIFICATION
Sample Number:	
Instrument:	
Date of Extraction:
Date and Time of Analysis
      Operator:

Compound Identification
(Individual CDD/CDF)
Total Homologues

Criteria
Signal to Noise Ratio
(S/N>2.5)
Mass-ion Abundance Ratio
Retention time
Peak ID - simultaneous peaks-
partner m/z
CDPE co-elution

Peaks must meet all criteria for
CDD/CDF identification
including m/z abundance ratio

Action- Associated Samples
Yes
No
Yes
No

Yes
No
Yes
No
Check SICP per descriptor &
compare with the non-2, 3, 7,
8-peak summary list. If
S/N>2.5 but m/z not met.
Check CDPE channel. Make
sure the peak does not co-elute
with a CDPE.
Re-calculate the total
homologue concentration
removing the peaks that were
flagged "U".
Validation Qualifiers
Detected
No
Detected
EMPCs
See worksheet
5 on EMPCs

Detected
-
J/U
Detect
Flag U. Then

No
Confirmed
ND
No
U

-
Non-detect
UJ
U



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Region 10 Office of Environmental Assessment                                          EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                   Page 60 of 88
See Narrative for more details
Summary of detected results per sample:
Summary of non-2, 3, 7, 8- peaks not meeting compound identification and were flagged "U" in the Totals.
Print Name & Signature Data Reviewer/Validator                                        Date

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
                                           EPA-910-R-14-003
                                                 May 2014
                                              Page 61 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 12 - COMPOUND QUANTITATION
Sample Number:	
Instrument:	
Date of Extraction:
Date and Time of Analysis
                                                Operator:
Check the calculation of detected results; 10% EDLS; 10%; 10% EMPCs of RLs using the equations provided in Appendix C.
List CDD/CDFs not meeting the project specific RL/EDL requirements/goals (refer to QAPP)
EDLs
Not properly calculated
Contact lab for resubmission
                                                                                         Qualificatioi
EMPCs
Incorrect calculation
                              EMPC>EDL RL
Contact lab for resubmission
                          Check Chromatogram for
                          interferences
                                  UJ- elevated at level of
                                  detection
                         1.  Check Chromatogram for
                            interferences
                            Request the lab for additional
                            extract clean-up to remove
                            interferences through PM/WAM
                            Still not corrected, flag data J
                                                                                         Estimated value- "J"
Print Name & Signature Data Reviewer/Validator
                                                       Date

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Region 10 Office of Environmental Assessment                                         EPA-910-R-14-003
United States Environmental Protection Agency                                                May 2014
Seattle WA 98101                                                                Page 62 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 13 -TEQ Calculation
Sample Number:	
Instrument:	
Date of Extraction:
Date and Time of Analysis	                      Operator:
Calculate TEQs using the 2005 or most recent WHO Human and Mammalian Toxic Equivalency Factors (TEF) for Dioxin and
Dioxin-like Compounds.  Calculate using 3 scenarios (1) ND=0; (2) ND=l/2 and (3) ND=1. If the project goals require the use of
EDLs, use the EDLs in the calculations. If there are EMPCs reported, the EMPC values are used for the TEQ calculation for the
particular CDD/CDF.  Totals are not used in the CDD/CDF TEQ calculations. If the concentrations used in the calculation  are flagged
estimated (even 1 PCDD/PCDF), the TEQ is also flagged estimated. The TEQ unit is the same as the unit reported by the lab for the
CDD/CDF (ng/L or ng/Kg).
If TEQs are already calculated by the lab using ND-0; ND-1/2 and ND=1, check the calculations. Also, if any of the 2, 3, 7, 8-
CDD/CDF was flagged "U" during data validation, recalculate the TEQ and remove the flagged CDD/CDF in the TEQ calculation.
See Summary table below.

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
       May 2014
    Page 63 of 88
Sample Number:
Instrument:
Date of Extraction:
Date and Time of Analysis

Chlorinated dibenzo-p-dioxins
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
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-HpCDD
OCDD
Chlorinated Dibenzofurans
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-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
Totals
Reported
Results




















2005 WHO TEF

1
1
0.1
0.1
0.1
0.01
0.0003

0.1
0.03
0.3
0.1
0.1
0.1
0.1
0.01
0.01
0.0003

ND=0




















Qualifier




















ND=l/2




















Qualifier




















ND= 1




















Qualifier





















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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
      May 2014
    Page 64 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 14 - OVERALL ASSESSMENT
Total Number of Data Points:

Holding Time/Preservation
Sample Integrity
Sample Prep
Sample Clean-up
System Performance
IPR/IDOC
Initial Calibration
Continuing Calibration
OPR
Blanks
PE Sample/ SRM
Laboratory Control Sample
Labeled Standard Recovery
Compound Identification
Compound Quantitation
TEQ

Total percentage
Percent Completion
Number of Data
Points - Estimated



















Number of Data
Points Rej ected



















Print Name & Signature Data Reviewer/Validator
             Date

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Region 10 Office of Environmental Assessment                                   EPA-910-R-14-003
United States Environmental Protection Agency                                         May 2014
Seattle WA 98101                                                        Page 65 of 88
APPENDIX B- PUGET SOUND SEDIMENT REFERENCE MATERIAL: REQUESTING,
ANALYZING, VALIDATING AND REPORTING DATA PROCEDURE

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Region 10 Office of Environmental Assessment                                          EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                  Page 66 of 88
   The Puget Sound Sediment Reference Material (SRM) has been developed to help assess/evaluate measurement accuracy and
   monitor laboratory performance when analyzing for chlorinated dioxin, furans, and biphenyl compounds in sediment samples
   collected from the Puget Sound area. The SRM is currently available free of charge, though recipients must pay shipping costs.
   This document provides instructions for obtaining, analyzing, and reporting on the SRM. The guidance and procedures are
   intended to ensure that SRM users:

       •   Report methods used for analysis
       •   Report QA/QC procedures used to verify and validate results, and
       •   Report results that can be included in periodic recalculations of acceptance limits

   The Puget Sound SRM has been established for chlorinated dibenzo-p-dioxins / chlorinated dibenzofurans (CDD/CDF) and/or
   chlorinated biphenyl (CB) congener analysis using high resolution gas chromatography / high resolution mass spectrometry
   (HRGC/HRMS) methods.  This SRM is also suitable for Aroclor analysis using gas chromatography/electron capture detection
   (GC/ECD) methods.

REQUEST PROCEDURE

The Seattle District Corps of Engineers, Washington Department of Ecology, and US EPA Region 10 have assigned staff to distribute
the Puget Sound SRM in support of agency missions, including regulatory programs. The request procedure is as follows:

       •   Obtain the electronic Puget Sound SRM Request Form from the appropriate agency involved with the project (see agency
          contact list below), or from the DMMO website.
       •   Return completed form to agency contact.
       •   Agency contact reviews and certifies/signs the bottom of the form as an "authorized agency requester", and then forwards
          the signed form to the EPA Region 10 SRM Manager (Donald Brown) for processing.

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Region 10 Office of Environmental Assessment                                         EPA-910-R-14-003
United States Environmental Protection Agency                                               May 2014
Seattle WA 98101                                                                Page 67 of 88


       •  Request is processed, typically within a week.

   Examples of how the request process works:

       1. CWA 404 permit applicants would request from and submit the completed form to the Corps of Engineers DMMO contact.

       2. A CERCLA PRP would submit the request form via EPA.

       3. The State of Washington's ambient monitoring program would submit the form via Ecology.

   The authorized agency contacts are  available to help with any questions about the Request Form. Submission of incomplete forms
   may delay the request processing.

AUTHORIZED AGENCY CONTACTS:

   Seattle District Corps of Engineers - Dredged Material Management Office (DMMO):
       David Fox (206) 764-6083, david.f.fox@usace.army.mil
       Lauran Warner (206) 764-6550, lauran.c.warner@usace.army.mil
       Kelsey van der Elst (206) 764-6945, kelsey.vanderelst@usace.army.mil
   Washington Department of Ecology:
       Laura Inouye (306) 407-6165, Iino461 @ecy.wa.gov
       Tom Gries (360) 407-6327, tgri461@ecv.wa.gov
   US Environmental Protection Agency Region 10:
       Justine Barton (206) 553-6051, barton.iustine@epa.gov
       Erika Hoffman (360) 753-9540, hoffman.erika@epa.gov
       Donald Brown (206) 553-0717,  brown.donaldm@epa.gov

SHIPPING

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Region 10 Office of Environmental Assessment                                         EPA-910-R-14-003
United States Environmental Protection Agency                                               May 2014
Seattle WA 98101                                                                 Page 68 of 88


   The Puget Sound SRM is stored at EPA's national Quality Assurance Technical Services (QATS) contractor located in Las Vegas,
   Nevada. Lab contacts listed on the Request Form should be prepared to confirm shipping details (including UPS or FedEx account
   number) if contacted by the EPA QATS contractor. The QATS contractor will generally ship the SRM within 24 hours of
   receiving the completed Request Form from the EPA Region 10 SRM Manager. The SRM will arrive with specific instructions on
   handling and storage requirements, data reporting requirements, as well as chain of custody paperwork.

   When the SRM has been shipped, the EPA QATS contractor will provide a notification email to the EPA Region 10 SRM
   Manager, the authorized agency contact (as indicated on the Request Form), and the destination laboratory. The email will include
   the project name as indicated on the Request Form.

SRM Storage Requirements
   Each amber glass bottle contains approximately 30 grams of the Puget Sound SRM.

   The SRM contains compounds that are light sensitive and should be protected from light during storage. Store the SRM at 4°C ą
   2°C until SRM preparation and analysis.

SRM Analysis  Requirements
   The SRM is to be analyzed as described in the appropriate methods employed for the analysis of CDD/CDF and/or CB congener
   analytes using  HRGC/HRMS instrumentation and/or Aroclors using GC/ECD instrumentation.

   The following  analytical methods  may be used in the analysis of the SRM:

       •   SW-846 Method 8082A (or current revision), "Polychlorinated Biphenyls (PCBs) by Gas Chromatography"
       •   SW-846 Method 8290A (or current revision), " Polychlorinated Dibenzo-^-Dioxins (PCDDs) and Polychlorinated
          Dibenzofurans (PCDFs) by High-Resolution Gas Chromatography/High-Resolution Mass Spectrometry (HRGC/HRMS)"
       •   Method 1613B (or current revision), "Tetra- through Octa-Chlorinated Dioxins and Furans by Isotope Dilution
          HRGC/HRMS"

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                   Page 69 of 88


       •  Method 1668C (or current revision), "Chlorinated Biphenyl Congeners in Water, Soil, Sediment, Biosolids, and Tissue by
          HRGC/HRMS"

Data Verification/Validation
    SRM users may be held to different data validation requirements, depending on their program and project circumstances. Data
    must be validated to EPA Stage 2B but it is strongly recommended that Stage 3 or better validation be conducted. For example, the
    interagency Dredged Material Management Program (DMMP) strongly recommends third-party Stage 4 validation for all TCDD/F
    data. Any validation narrative must indicate the validation stage used. Data validation stages are described in EPA-540-R-08-005
    (see References).

Data Reporting
    Individual laboratories typically provide all project data and validation reports to their clients. The client/project proponent is
    responsible for ensuring that all information relative to the SRM,  including associated QA data, is sent to the original agency
    requester. For DMMP projects, submittal of the complete validated data package to the DMMO contact fulfills this requirement.

    For SRM data meeting established QA requirements, the agency contact will submit the validated electronic data deliverable/data
    summary sheets (or the equivalent) and validation reports relevant to the SRM to the EPA Region 10 SRM Manager. Changes
    made by the data validator (e.g. modification of data qualifiers) must be clearly indicated on the data sheets.  SRM data not
    meeting established QA requirements will not be forwarded to EPA's QATS contractor; however, the QATS contractor will be
    notified of the QA failure for their records.

    The following are the minimum required deliverables for Puget Sound SRM data submissions.  Also included below are optional
    deliverables that may or may not be needed depending on the available deliverables.

REQUIRED DELIVERABLES

    1.  Data Validation Report - report that documents the analytical quality of the data.  In regards to the Puget Sound SRM, this
       report serves two functions. First, it confirms that data validation was completed, as the guidance requires data validation to at

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Region 10 Office of Environmental Assessment                                          EPA-910-R-14-003
United States Environmental Protection Agency                                                 May 2014
Seattle WA 98101                                                                  Page 70 of 88

       least  EPA Stage IIB.  Second, the report documents the reasons for any failure to meet method, procedural, or contractual
       requirements, as well as provides an evaluation of the impact of such failure on the overall data set.

   2.  Electronic Data Deliverable (EDD) - an electronic, tabular format for sharing, manipulating, and using data. EDDs should
       be submitted in a comma- or tab-delimited file or as a Microsoft Excel spreadsheet. If in doubt about what to request from the
       lab, ask for an EDD in EIM format.

   3.  SRM Sample Data Summary Report - similar to a Form 1 from the Contract Laboratory Program, this report should provide
       a summary of the analytical parameters, analytical results, reporting limits, and laboratory/validation qualifiers. At a
       minimum, the sample data summary report should include the following:

       •   Identification and quantitation of target analytes including dilution and reanalysis
       •   CAS numbers
       •   Laboratory name
       •   Project number
       •   Project name
       •   Sample ID number (SRM bottle bar code)
       •   Agency sample number (if applicable)
       •   Laboratory sample number
       •   Date SRM received by the lab
       •   Date and time of analysis
       •   For Aroclor data, laboratory reporting limits and method detection limits
       •   For Chlorinated Biphenyl Congener and Dioxin/Furan data, reporting limits and estimated detection limits
       •   Laboratory qualifiers and definitions
       •   Validation qualifiers

OPTIONAL DELIVERABLES

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Region 10 Office of Environmental Assessment                                           EPA-910-R-14-003
United States Environmental Protection Agency                                                  May 2014
Seattle WA 98101                                                                    Page 71 of 88


    1.   Laboratory Case Narrative - laboratory report that describes the analytical process used by the lab to analyze the samples
        and any problems encountered in processing the samples, along with corrective action taken and problem resolution.  The
        case narrative should only be submitted with the SRM data if there were significant problems during sample analysis that
        affected the SRM or if there are other observations relevant to the SRM.

    2.   Raw Data - laboratory worksheets, records, notes, or instrument printouts that are the result of original observations and
        activities.  The chromatograms and integration reports associated with the SRM should be submitted with the SRM Sample
        Data Summary Report, if possible.

    3.   Data Package - the entire laboratory package including all narratives, sample summary reports, QC reports, calibrations, and
        raw data. The full data package should only be submitted if there were significant QC failures that affect the SRM result or if
        the data did not go through the data validation process.

    Storage and use of previously opened  SRM is not recommended. However, it is requested that any additional data results derived
    from use of the SRM be submitted to the EPA Region 10 SRM Manager.

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
      May 2014
    Page 72 of 88
Performance / Acceptance Limits
   The acceptance limits presented below are guidance values based on the original laboratory
   round-robin associated with the development of the SRM.  The implications associated with
   not meeting these acceptance limits will be determined by  data reviewers on a case-by-case
   basis, based on the goals of their program/project. For now, the DMMP will review results on
   a case-by-case basis and will consider the values advisory.

   PCS Aroclors: A twelve-lab round-robin testing of the SRM (including commercial and
   CLP labs) was used to calculate an acceptance limit for Aroclor 1260. The average Aroclor
   1260 concentration found during the round robin was 108 ug/kg. The acceptance limit is set
   at the 95% confidence interval.
       •  Aroclor 1260:
                    Warning low:  41 ug/kg
                    Warning high:  180 ug/kg
   CDD/CDF: A ten-lab round-robin testing of the SRM (including commercial and CLP labs)
   was used to calculate an acceptance limit of ą50% action low and action high for each
   congener as follows:
Acceptance
Limits Source
ą 50 Percent
Analyte
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
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-HpCDD
OCDD
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
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
OCDF
CAS No.
1746-01-6
40321-76-4
39227-28-6
67653-85-7
19408-74-3
35822-46-9
3268-87-9
51207-31-9
57117-41-6
57117-31-4
70648-26-9
57117-44-9
60851-34-5
72918-21-9
67562-39-4
55673-89-7
39001-02-0
Avg. Cone.
(ng/kg)
1.05
1.08
1.59
3.88
3.04
90.6
811
1.11
1.23
1.07
3.02
1.09
1.83
0.511
18.7
1.63
58.4
Action Low
-50%
0.525
0.542
0.797
1.94
1.52
45.3
406
0.557
0.613
0.533
1.51
0.545
0.917
0.255
9.36
0.815
29.2
Action High
+50%
1.57
1.63
2.39
5.82
4.55
136
1217
1.67
1.84
1.60
4.53
1.64
2.75
0.77
28.1
2.44
87.6

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
       May 2014
    Page 73 of 88
    CB Congeners:  A ten-lab round-robin testing of the SRM (including commercial and CLP
    labs) was used to calculate an acceptance limit of ą50% action low and action high for each
    congener as follows:
  Individually eluting congeners table
Congener #
1
3
4
6
7
8
9
11
15
16
17
19
22
25
27
31
32
35
37
42
46
48
52
56
60
63
64
66
67
68
72
77
82
84
92
94
96
103
Target Analyte
2-Chlorobiphenyl
4-Chlorobiphenyl
2,2'-Dichlorobiphenyl
2,3'-Dichlorobiphenyl
2,4-Dichlorobiphenyl
2,4'-Dichlorobiphenyl
2,5-Dichlorobiphenyl
3,3'-Dichlorobiphenyl
4,4'-Dichlorobiphenyl
2,2',3-Trichlorobiphenyl
2,2',4-Trichlorobiphenyl
2,2',6-Trichlorobiphenyl
2,3,4'-Trichlorobiphenyl
2,3',4-Trichlorobiphenyl
2,3',6-Trichlorobiphenyl
2,4',5-Trichlorobiphenyl
2,4',6-Trichlorobiphenyl
3,3',4-Trichlorobiphenyl
3,4,4'-Trichlorobiphenyl
2,2',3,4'-Tetrachlorobiphenyl
2,2',3,6'-Tetrachlorobiphenyl
2,2',4,5-Tetrachlorobiphenyl
2,2',5,5'-Tetrachlorobiphenyl
2,3,3',4'-Tetrachlorobiphenyl
2,3,4,4'-Tetrachlorobiphenyl
2,3,4',5-Tetrachlorobiphenyl
2,3,4',6-Tetrachlorobiphenyl
2,3',4,4'-Tetrachlorobiphenyl
2,3',4,5-Tetrachlorobiphenyl
2,3',4,5'-Tetrachlorobiphenyl
2,3',5,5'-Tetrachlorobiphenyl
3,3',4,4'-Tetrachlorobiphenyl
2,2',3,3',4-Pentachlorobiphenyl
2,2',3,3',6-Pentachlorobiphenyl
2,2',3,5,5'-Pentachlorobiphenyl
2,2',3,5,6'-Pentachlorobiphenyl
2,2',3,6,6'-Pentachlorobiphenyl
2,2',4,5',6-Pentachlorobiphenyl
Cl Level*
1
1
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
Avg
SD
Acceptance Low
(-50%)
Acceptance High
(+150%)
ng/kg dry weight
23
25
114
169
17
366
20
74
308
212
363
68
385
245
81
1132
237
26
355
413
75
246
3743
651
253
59
659
1654
56
22
37
135
486
1327
1180
20
29
57
2.6
8.4
16.5
30.4
3.3
65.5
4.0
10.5
36.5
21.3
31.7
9.7
47.8
34.8
6.5
113.8
30.9
4.3
44.7
55.9
11.8
44.4
447.6
139.8
124.4
11.4
81.3
301.0
10.2
4.9
7.5
19.3
33.3
31.5
72.1
1.6
2.0
3.5
12
13
57
85
8
183
10
37
154
106
182
34
192
122
40
566
118
13
178
206
37
123
1871
326
126
30
329
827
28
11
19
68
243
664
590
10
14
28
35
38
171
254
25
548
29
110
462
318
545
102
577
367
121
1697
355
39
533
619
112
369
5614
977
379
89
988
2481
84
34
56
203
729
1991
1770
30
43
85

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
        May 2014
     Page 74 of 88
   Individually eluting congeners table, continued
Congener
#
114
118
120
122
123
130
131
132
133
136
137
141
144
146
158
159
164
167
170
172
174
175
176
177
178
179
187
189
190
191
194
195
196
201
202
203
205
206
207
208
209
Target Analyte
2,3,4,4',5-Pentachlorobiphenyl
2,3',4,4',5-Pentachlorobiphenyl
2,3',4,5,5'-Pentachlorobiphenyl
2,3,3',4',5'-Pentachlorobiphenyl
2,3',4,4',5'-Pentachlorobiphenyl
2,2',3,3',4,5'-Hexachlorobiphenyl
2,2',3,3',4,6-Hexachlorobiphenyl
2,2',3,3',4,6'-Hexachlorobiphenyl
2,2',3,3',5,5'-Hexachlorobiphenyl
2,2',3,3',6,6'-Hexachlorobiphenyl
2,2',3,4,4',5-Hexachlorobiphenyl
2,2',3,4,5,5'-Hexachlorobiphenyl
2,2',3,4,5',6-Hexachlorobiphenyl
2,2',3,4',5,5'-Hexachlorobiphenyl
2,3,3',4,4',6-Hexachlorobiphenyl
2,3,3',4,5,5'-Hexachlorobiphenyl
2,3,3',4',5',6-Hexachlorobiphenyl
2,3',4,4',5,5'-Hexachlorobiphenyl
2,2',3,3',4,4',5-Heptachlorobiphenyl
2,2',3,3',4,5,5'-Heptachlorobiphenyl
2,2',3,3',4,5,6'-Heptachlorobiphenyl
2,2',3,3',4,5',6-Heptachlorobiphenyl
2,2',3,3',4,6,6'-Heptachlorobiphenyl
2,2',3,3',4,5',6'-Heptachlorobiphenyl
2,2',3,3',5,5',6-Heptachlorobiphenyl
2,2',3,3',5,6,6'-Heptachlorobiphenyl
2,2',3,4',5,5',6-Heptachlorobiphenyl
2,3,3',4,4',5,5'-Heptachlorobiphenyl
2,3,3',4,4',5,6-Heptachlorobiphenyl
2,3,3',4,4',5',6-Heptachlorobiphenyl
2,2',3,3',4,4',5,5'-Octachlorobiphenyl
2,2',3,3',4,4',5,6-Octachlorobiphenyl
2,2',3,3',4,4',5,6'-Octachlorobiphenyl
2,2',3,3',4,5',6,6'-Octachlorobiphenyl
2,2',3,3',5,5',6,6'-Octachlorobiphenyl
2,2',3,4,4',5,5',6-Octachlorobiphenyl
2,3,3',4,4',5,5',6-Octachlorobiphenyl
2,2',3,3',4,4',5,5',6-
Nonachlorobiphenyl
2,2', 3,3',4,4', 5,6,6'-
Nonachlorobiphenyl
2,2',3,3',4,5,5',6,6'-
Nonachlorobiphenyl
Decachlorobiphenyl
Cl Level*
5
5
5
5
5
6
6
6
6
6
6
6
6
6
6
6
6
6
7
7
7
7
7
7
7
7
7
7
7
7
8
8
8
8
8
8
8
9
9
9
10
Avg
SD
Congener #
Target Analyte
ng/kg dry weight
68
4021
19
44
54
591
116
4569
179
2141
223
3657
862
2029
1257
239
1068
367
5251
903
6604
249
806
3630
1237
2719
7316
185
1077
217
2624
1169
1579
373
487
1829
143
575
91
124
97
8.2
764.9
2.3
10.0
6.1
50.9
14.0
582.7
15.8
280.2
29.6
395.7
57.7
303.2
132.4
81.5
118.1
14.4
715.7
206.0
1100.6
29.0
95.6
471.6
194.2
293.5
1289.5
11.1
200.7
40.6
391.8
163.2
183.8
65.6
51.9
354.3
9.2
39.2
18.6
7.5
4.4
34
2011
9
22
27
296
58
2284
90
1071
112
1829
431
1014
628
119
534
184
2626
452
3302
125
403
1815
619
1359
3658
93
539
108
1312
585
789
187
243
914
71
288
46
62
48
102
6032
28
66
81
887
174
6853
269
3212
335
5486
1293
3043
1885
358
1602
551
7877
1355
9906
374
1209
5445
1856
4078
10974
278
1616
325
3936
1754
2368
560
730
2743
214
863
137
186
145
                number of chlorine substituents

-------
Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
        May 2014
     Page 75 of 88
Co-eluting congeners table
Congener
#
12
13
18
30
20
28
21
23
26
29
40
41
71
44
47
65
45
51
49
69
50
53
59
62
75
61
70
74
76
83
99
85
116
117
86
87
97
108
119
125
88
91
Co-eluting Pairs
3,4-Dichlorobiphenyl
3,4'-Dichlorobiphenyl
2,2',5-Trichlorobiphenyl
2,4,6-Trichlorobiphenyl
2,3,3'-Trichlorobiphenyl
2,4,4'-Trichlorobiphenyl
2,3,4-Trichlorobiphenyl
2,3,5-Trichlorobiphenyl
2,3',5-Trichlorobiphenyl
2,4,5-Trichlorobiphenyl
2,2',3,3'-Tetrachlorobiphenyl
2,2',3,4-Tetrachlorobiphenyl
2,3',4',6-Tetrachlorobiphenyl
2,2',3,5'-Tetrachlorobiphenyl
2,2',4,4'-Tetrachlorobiphenyl
2,3,5,6-Tetrachlorobiphenyl
2,2',3,6-Tetrachlorobiphenyl
2,2',4,6'-Tetrachlorobiphenyl
2,2',4,5'-Tetrachlorobiphenyl
2,3',4,6-Tetrachlorobiphenyl
2,2',4,6-Tetrachlorobiphenyl
2,2',5,6'-Tetrachlorobiphenyl
2,3,3', 6-Tetrachlorobiphenyl
2,3,4,6-Tetrachlorobiphenyl
2, 4,4', 6-Tetrachlorobiphenyl
2,3,4,5-Tetrachlorobiphenyl
2,3',4',5-Tetrachlorobiphenyl
2,4,4',5-Tetrachlorobiphenyl
2,3',4',5'-Tetrachlorobiphenyl
2,2',3,3',5-Pentachlorobiphenyl
2,2',4,4',5-Pentachlorobiphenyl
2,2',3,4,4'-Pentachlorobiphenyl
2,3,4,5,6-Pentachlorobiphenyl
2,3,4', 5,6-Pentachlorobiphenyl
2,2',3,4,5-Pentachlorobiphenyl
2,2',3,4,5'-Pentachlorobiphenyl
2,2',3,4',5'-Pentachlorobiphenyl
2,3,3', 4,5'-Pentachlorobiphenyl
2,3',4,4',6-Pentachlorobiphenyl
2,3',4',5',6-Pentachlorobiphenyl
2,2',3,4,6-Pentachlorobiphenyl
2,2',3,4',6-Pentachlorobiphenyl
Cl
Level*
2
2
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
Avg
70
615
1436
545
506
717
2026
224
1550
242
142
3251
2548
737
3337
674
SD
r
9.3
78.3
149.8
49.8
47.9
125.8
194.2
37.0
185.4
35.5
22.5
513.3
373.6
29.5
142.6
49.9
Acceptance
Low (-50%)
g/kg dry weight
35
307
718
273
253
359
1013
112
775
121
71
1626
1274
368
1668
337
Acceptance
High
(+150%)
105
922
2154
818
759
1076
3039
336
2325
363
213
4877
3821
1105
5005
1011
Co-eluting Sets
12/13
18/30
20/28
21/23
26/29
40/41/71
44/47/65
45/51
49/69
50/53
59/62/75
61/70/74/76
83/99
85/116/117
86/87/97/108/119/125
88/91

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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
        May 2014
     Page 76 of 88
   Co-eluting congeners table, continued
Congener
#
90
101
113
93
95
98
100
102
107
124
110
115
128
166
129
138
160
163
134
143
135
151
154
139
140
147
149
153
168
156
157
171
173
180
193
183
185
197
200
198
199
Co-eluting Pairs
2,2',3,4',5-Pentachlorobiphenyl
2,2',4,5,5'-Pentachlorobiphenyl
2,3,3',5',6-Pentachlorobiphenyl
2,2',3,5,6-Pentachlorobiphenyl
2,2',3,5',6-Pentachlorobiphenyl
2,2',3,4',6'-Pentachlorobiphenyl
2,2',4,4',6-Pentachlorobiphenyl
2,2',4,5,6'-Pentachlorobiphenyl
2,3,3',4',5-Pentachlorobiphenyl
2,3',4',5,5'-Pentachlorobiphenyl
2,3,3',4',6-Pentachlorobiphenyl
2,3,4,4', 6-Pentachlorobiphenyl
2,2',3,3',4,4'-Hexachlorobiphenyl
2,3,4,4', 5,6-Hexachlorobiphenyl
2,2',3,3',4,5-Hexachlorobiphenyl
2,2',3,4,4',5'-Hexachlorobiphenyl
2,3,3', 4,5,6-Hexachlorobiphenyl
2,3,3', 4, 5,6-Hexachlorobiphenyl
2,2', 3,3', 5,6-Hexachlorobiphenyl
2,2',3,4,5,6'-Hexachlorobiphenyl
2,2',3,3',5,6'-Hexachlorobiphenyl
2,2',3,5,5',6-Hexachlorobiphenyl
2,2',4,4',5,6'-Hexachlorobiphenyl
2,2',3,4,4',6-Hexachlorobiphenyl
2,2',3,4,4',6'-Hexachlorobiphenyl
2,2', 3,4, 5,6-Hexachlorobiphenyl
2,2',3,4',5',6-Hexachlorobiphenyl
2,2',4,4',5,5'-Hexachlorobiphenyl
2,3',4,4',5',6-Hexachlorobiphenyl
2,3,3',4,4',5-Hexachlorobiphenyl
2,3,3',4,4',5'-Hexachlorobiphenyl
2,2',3,3',4,4',6-Heptachlorobiphenyl
2,2',3,3',4,5,6-Heptachlorobiphenyl
2,2',3,4,4',5,5'-Heptachlorobiphenyl
2,3,3',4',5,5',6-Heptachlorobiphenyl
2,2',3,4,4',5',6-Heptachlorobiphenyl
2,2', 3,4,5,5', 6-Heptachlorobiphenyl
2,2',3,3',4,4',6,6'-Octachlorobiphenyl
2,2',3,3',4,5,6,6'-Octachlorobiphenyl
2,2', 3,3', 4,5,5', 6-Octachlorobiphenyl
2,2',3,3',4,5,5',6'-Octachlorobiphenyl
Cl
Level*
5
5
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
7
7
7
7
7
7
8
8
8
8
Avg
SD
Acceptance
Low (-50%)
Acceptance
High
(+150%)
ng/kg dry weight
6957
5608
249
6488
1354
14189
657
6326
115
14314
13913
891
1794
12396
4184
496
3260
787.6
516.7
105.2
384.7
167.1
1183.2
45.0
374.1
18.7
1582.6
1343.2
52.1
202.8
1530.7
665.7
106.0
626.4
3478
2804
124
3244
677
7094
329
3163
58
7157
6956
446
897
6198
2092
248
1630
10435
8412
373
9733
2031
21283
986
9488
173
21471
20869
1337
2691
18594
6277
744
4890
Co-eluting Sets
90/101/113
93/95/98/100/102
107/124
110/115
128/166
129/138/160/163
134/143
135/151/154
139/140
147/149
153/168
156/157
171/173
180/193
183/185
197/200
198/199
              * number of chlorine substituents

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Validation and Review of Dioxin/Furan Data                                     Revision: 1.0
OEAQASOP-007                                                Effective Date: April 2014
                                                                      Page 77 of 88

Recalculation of Acceptance Limits
   The national EPA QATS contractor will store the SRM, conduct stability testing, and
   maintain the SRM database used to recalculate acceptance limits. Timing for any acceptance
   limit recalculations will depend on the quantity of high quality data received. It is anticipated
   that the next recalculation will occur after 30 new data points have been received.

References
   Revised Supplemental Information on Polychlorinated Dioxins and Furans (PCDD/F) for
   Use in Preparing a Quality Assurance Project Plan (QAPP), dated November 8, 2010.

   Guidance for Labeling Externally Validated Laboratory Analytical Data for Superfund Use,
   dated January 13, 2009 (EPA-540-R-08-005).

Attachments
   SRM Request Form (this form may be requested and returned in an electronic-fillable form
   from/to agency contacts listed above). This form is also available on the Seattle District
   DMMO website.

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Validation and Review of Dioxin/Furan Data                                 Revision: 1.0
OEAQASOP-007                                          Effective Date: April 2014
                                                               Page 78 of 88
APPENDIX C - RULES, CALCULATIONS AND EQUATIONS

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Validation and Review of Dioxin/Furan Data                                     Revision: 1.0
OEAQASOP-007                                               Effective Date: April 2014
                                                                     Page 79 of 88


                    Appendix C - Rules, Calculations and Equations


1. In a series of calculations, carry the extra digits through to the final result, then round off.


2. If the digit to be removed is less than 5, the preceding digit stays the same. If the digit to be
removed is equal to or greater than 5, the preceding digit is increased by 1.


Equation  1: Chromatographic Peak Separation


                                 %Valley = - x 100
                                             y


x =    Measurement from the baseline to the deepest part of the valley between 2, 3, 7, 8-TCDD
       and 1, 2, 3, 8-TCDD
y =    Peak height of 2, 3,  7, 8-TCDD



Equation  2: Percent Difference of the Relative Response
                              Responsever — Responseint
                       %D = - - - — - - - — x 100
                                      Responseint


Responsever = Response (RR or RRF) observed during calibration verification

Responseint = Mean response (RR or RRF) established during initial calibration according to
             DLM02.2


Equation 3: Relative Percent Difference


                                       \R1-R2\
                                RPD             x 100
                                        ^(Rl,R2)
Rl =   Result 1
R2 =   Result 2


Equation 4: Internal Standard Percent Recovery
                                         c     -y- c
                              %R = - iĢ — -Ģ!Ģ - x 100
                                    Qis x Ars x RFn

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Validation and Review of Dioxin/Furan Data                                     Revision: 1.0
OEAQASOP-007                                               Effective Date: April 2014
                                                                      Page 80 of 88
Ais =  Sum of the integrated ion abundances of the quantitation ions (Table 6 of method) for the
       labeled internal standard
Ars =  Sum of the integrated ion abundances of the quantitation ions (Table 6 of method) for the
       labeled recovery standard
Qis =  Quantity, in pg, of the internal standard added to the sample before extraction
Qrs =  Quantity, in pg, of the recovery standard added to the cleaned-up sample residue before
       HRGC/HRMS analysis
RFm = Calculated mean relative response factor for the labeled internal standard relative to the
appropriate recovery standard.

Equation 5: Relative Response for Isotope Dilution Calibration (Method 1613B)

                                       (Aln+A2n)C1
                                 RR =
                                        (All+A2l)C2
Aln =  Area of the primary m/z for the PCDD/PCDF
A2n =  Area of the secondary m/z for the PCDD/PCDF
All =  Area of the primary m/z for the labeled compound
A2i =  Area of the secondary m/z for the labeled compound
Ci =    Concentration of the labeled compound in the calibration standard
C2 =   Concentration of the native compound in the calibration standard

Equation 6: Concentration of unlabeled PCDD/PCDF congeners (SW 846)

                                          A  v D-
                                     _    ns -\ yls
                                   x ~ Ais X W X REn

Cx =   concentration of unlabeled PCDD/PCDF congeners (or group of co-eluting isomers
       within an homologous series) in pg/g
Ax =   sum of the integrated ion abundances of the quantitation ions (Table 6 of method) for
       unlabeled PCDDs/PCDFs
Ais =  sum of the integrated ion abundances of the quantitation ions (Table 6 of method) for the
       labeled internal standards
Qis =  quantity, in pg, of the internal standard added to the sample before extraction
W =    weight, in g, of the sample (solid or organic liquid), or volume in mL of an aqueous
       sample
RFm = calculated mean relative response factor for the analyte

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Validation and Review of Dioxin/Furan Data                                   Revision: 1.0
OEAQASOP-007                                              Effective Date: April 2014
                                                                    Page 81 of 88

Equation 7: Concentration of PCDD/PCDF in extract (Method 1613B)
                                Cex    (All+A2l}RR

Cex =  Concentration of the PCDD/PCDF in the extract (ng/nL)
Aln =  Area of the primary m/z for the PCDD/PCDF
A2n =  Area of the secondary m/z for the PCDD/PCDF
All =  Area of the primary m/z for the labeled compound
A2i =  Area of the secondary m/z for the labeled compound
Ci =   Concentration of the labeled compound in the calibration standard
RR =  Relative response

Equation 8: Compound Quantitation: All Matrices Other Than Aqueous

                        Solids  ng/kg =

CL     = Concentration of the labeled standard added to the extract (includes any
        amount added during dilution procedures)
Axi    = Areas of the signals for both quantitation ions of the CDD/CDF
AX2    = Areas of the signals for both quantitation ions of the CDD/CDF
An    = Areas of labeled standard ions
AL2    = Areas of labeled standard ions
Vex    = Effective volume of the extract
W     = Sample weight
RR    = Mean Relative Response for the isomer of interest from the initial calibration

Equation 9: Compound Quantitation: Aqueous

                                           CLx(Als+A2s)Vex
                      Aqueous (pg/L} =
                                         Vs x (Al-i + A2J x RR
CL     = Quantity (pg) of appropriate labeled standard added to the extract (includes
         any amount added during dilution procedures)
Als    = Areas of the signals for both quantitation ions of the CDD/CDF
A2S    = Areas of the signals for both quantitation ions of the CDD/CDF
Vex    = Effective final volume of the extract
Vi     = Sample volume extracted in liters
RR    = Mean Relative Response for the isomer of interest from the initial calibration

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Validation and Review of Dioxin/Furan Data                                  Revision: 1.0
OEAQASOP-007                                             Effective Date: April 2014
                                                                  Page 82 of 88
Equation 10:  Compound Quantitation:  Concentration of the Labeled Compound

                                          (Al5+A2s)CI5
                          Cex (ng/ml} =
                                        (A1IS + A2ls)RRF
CEX   = Concentration of the labeled compound in the extract
Cis   = Concentration of the internal standard
RRF  = Mean Relative Response Factor determined from the initial calibration
data.

Equation 11:  Compound Quantitation:  Aqueous Adjusted CRQL


                   Adjusted CRQL = Contract CRQL x
VT    = Volume of the concentrated extract (jiL)
Vo    = Actual sample volume used (mL)
Vx    = Contract sample volume (1000 mL)
Vc    = Contract concentrated extract volume (jiL)

Equation 12:  Compound Quantitation:  Soil/Sediment Adjusted CRQL

                  Adjusted  CRQL = Contract CRQL x
VT    = Volume of the concentrated extract (jiL)
Ws   = Actual mass extracted (g)
Wx   = Contract sample weight (lOg)
Vc    = Contract concentrated extract volume (jiL)

Equation 13:  Compound Quantitation:  Extract Concentrations by Relative Response
CEX = Concentration of the native compound in the extract
CL = Concentration of the internal standard
A!N = Area of the primary m/z for the PCDD/PCDF
A2N = Area of the secondary m/z for the PCDD/PCDF
A!L= Area of the primary m/z for the labeled compound

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A2L =  Areas of the secondary m/z for the labeled compound
RR =  Relative response

Equation 14: Estimated Detection Limit (EDL)
ALL MATRICES OTHER THAN AQUEOUS:

                   c r*   m, f    n  ^   2.5 x QL x (Hxl + HX2) x D
                   Solids EDL (nq kq] = 	=—
                              ^  ai  a)      w x (HL1 + HL2) x flfl

EDL   =Estimated Detection Limit for 2, 3, 7, 8-substituted CDDs/CDFs
QL    =Quantity (pg) of appropriate labeled standard added prior to sample extraction
Hxi    =Peak heights of the noise for both quantitation ions of the CDD/CDF
HX2    =Peak heights of the noise for both quantitation ions of the CDD/CDF
HLI    =Peak heights of the labeled standard ions
HL2    = Peak heights of the labeled standard ions
D      =Dilution factor
W     =Weight extracted in grams
RR    =Mean Relative Response for the isomer of interest from the initial calibration

Aqueous:
                                          2.5  x QL x (Hxl + HX2) x D
                  Aqueous EDL (pg/L) =
                                            V X (HL1 + HL2) X RR
EDL   =Estimated Detection Limit for 2, 3, 7, 8-substituted CDDs/CDFs
QL    =Quantity (pg) of appropriate labeled standard added prior to sample extraction
Hxi    =Peak heights of the noise for both quantitation ions of the CDD/CDF
HX2    =Peak heights of the noise for both quantitation ions of the CDD/CDF
HLI    =Peak heights of the labeled standard ions
HL2    = Peak heights of the labeled standard ions
D      =Dilution factor
V      =Volume extracted in liters
RR    =Mean Relative Response for the isomer of interest from the initial calibration

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OEAQASOP-007                                              Effective Date: April 2014
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Equation 15: Estimated Maximum Possible Concentration (EMPC)

All Matrices Other than Aqueous:
                              EMPC (nglkg)  =
D      =Dilution factor
Ws    =Sample dry weight in kg
CEX    =Quantity of the native compound in the extract in nanograms (ng/|iL *
        extract volume in jiL)

Aqueous:

                                               /"„„ v n
                              EMPC (pg/L) =
                                                  Vs

D      =Dilution factor
Vs     =Sample volume in liters
CEX    =Quantity of the native compound in the extract in picograms (pg/|iL *  extract volume
in jiL)

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DEFINITIONS

Acronyms
CLP - Contract Laboratory Program
COC-Chain of Custody
DQO - Data Quality Objective
EMPC - Estimated Maximum Possible Concentration
EPA - Environmental Protection Agency
GC - Gas Chromatography
LCS - Laboratory Control Sample
LCSD - Laboratory Control Sample Duplicate
MS/MSD - Matrix Spike/Matrix Spike Duplicate
PCDD - Polychlorinated Dibenzodioxin
PCDF - Polychlorinated Dibenzofuran
PCDPE - Polychlorinated Diphenyl Ether
PFK - Perfluorokerosene
PQL - Practical Quantitation Limit
QA - Quality Assurance
QC - Quality Control
RF - Response Factor
RL - Reporting Limit
RPD - Relative Percent Difference
RSD - Relative Standard Deviation
SDG - Sample Delivery Group
SOW - Statement of Work

ANALYTICAL DATA VALIDATION - Analytical data validation is a systematic process,
performed external from the data generator, which applies a defined set of performance-based
criteria to a body of data that may result in physical qualification of the data. Data validation
occurs prior to drawing a conclusion from the body of data.

ANALYTICAL DATA VERIFICATION - Analytical data verification is a systematic process of
evaluating the completeness, correctness, consistency, and compliance of a set of facts against a
standard or contract, which is performed by either the data generator or by an entity external to
the data generator.

CASE - A finite, usually predetermined number of samples collected  over a given time period
from a particular site. A case consists of one or more sample delivery groups.

CHAIN-OF-CUSTODY - The history of the transfer of samples from the time of sample
acquisition through archival and disposal of samples. Chain-of-Custody documentation is
required as evidence of sample integrity.

CONTRACT REQUIRED QUANTITATION LIMIT (CRQL) - The CRQL is the minimum
level of detection acceptable under the current CLP contract.

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DATA QUALITY OBJECTIVES - DQOs are qualitative and quantitative statements derived
from the outputs of each step of the DQO process, which specify the study objectives, domain,
limitations, most appropriate type of data to collect, and the levels of decision error that will be
acceptable for the decision.

HOLDING TIME - Holding time, as described in this procedure, is defined as the period of time
between sample collection and sample extraction.

LABORATORY CONTROL SAMPLE (LCS) - The LCS is a control sample of known
composition. Aqueous and solid laboratory control samples are analyzed using the same
preparation, reagents, and method employed for field samples.

LABORATORY DUPLICATE - The laboratory duplicate is a randomly chosen split of an
analytical sample into two aliquots prior to sample preparation. The purpose of a laboratory
duplicate is to monitor the precision of the analytical method.

MATRIX SPIKE - The matrix spike is a split of a field-originating analytical sample in which
one half of the split is spiked with a known amount of radionuclide of interest prior to sample
preparation. The purpose of a matrix spike is to measure the effect of interferences from the
sample matrix that will preclude accurate quantitation by the instrumentation.

METHOD BLANK - The method blank is a laboratory-generated sample of the same matrix as
the analytical samples, but in absence of the analyte of interest. The purpose of a method blank is
to monitor the presence of contamination of the analyte of interest in the sample preparation and
analysis processes.

RELATIVE PERCENT DIFFERENCE - RPD is the measure of precision between two values,
defined as the absolute value of the difference between two values divided by the mean of the
two values.

RELATIVE RESPONSE FACTOR (RRF) - RRF represents the response of a compound to an
analytical instrument relative to the response of an associated standard.

RELATIVE STANDARD DEVIATION (RSD) - RSD is the measure of precision between
multiple values, defined as the standard deviation of multiple values divided by the mean of the
values.

SAMPLE DELIVERY GROUP (SDG) - An SDG is defined by one of the following, whichever
occurs first: 1) Case of field samples; 2) Each 20 field samples within a case; 3) Each 14-day
calendar period during which field samples in  a case are received, beginning with receipt of the
first sample in the SDG.

SAMPLE RESULT - A sample result, as described in this procedure, is a numeric denotation of
the concentration, amount, or activity of a specific analytical parameter uniquely associated with
an aliquot of environmental media.

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STANDARD REFERENCE MATERIAL (SRM) - A SRM is a material or substance of which
one or more properties of which are sufficiently well established to be used for the calibration of
an apparatus, the assessment of a measurement method, or for assigning values to materials. The
SRM is characterized by the U.S. National Institute of Standards and Technology (NIST) or
other certified testing authority, and issued with a certificate providing the results of the
characterization.

TRACEABLE REFERENCE MATERIAL (TRM) - A TRM is a NIST prepared standard
reference material  or a sample of known activity or concentration prepared from a NIST standard
reference material  (derived standard material).

VALIDATION QUALIFIER - A qualifier is an alphabetic character physically or electronically
associated with a discrete sample result during validation due to a data quality deficiency, which
provides guidance in data usability.

WELL CHARACTERIZED REFERENCE MATERIAL (WCRM) - The WCRM may be
derived from a field sample which has been well characterized through multiple analyses,
providing a high level of confidence of the concentration in the sample. The WCRM may be
submitted to NIST for characterization and classification as a TRM.

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REFERENCES

USEPA Contract Laboratory Program (CLP) National Functional Guidelines for Chlorinated
Dibenzo-p-Dioxins (CDDs) and Chlorinated Dibenzofurans (CDFs) Data Review, OSWER
9240.1-53, EPA-540-R-11-016, September 2011.

USEPA Guidance for Labeling Externally Validated Laboratory Analytical Data for Superfund
Use, OSWER 9200.1-85, EPA 540-R-08-005, January 2009.

USEPA Analytical Services Branch Statement of Work for the Analysis of Chlorinated Dibenzo-
p-Dioxins (CDDs) and Chlorinated Dibenzofurans (CDFs), Multi-Media, Multi-Concentration,
DLM02.2, December 2009.

USEPA Method 1613B: Tetra- through Octa-Chlorinated Dioxins and Furans by Isotope
Dilution HRGC/HRMS, Revision B, October 1994.

USEPA SW-846 Method 8290A: Polychlorinated Dibenzo-p-Dioxins (PCDDs) and
Polychlorinated Dibenzofurans (PCDFs) by High-Resolution Gas Chromatography/High-
Resolution Mass Spectrometry (HRGC/HRMS), Revision 1, February 2007.

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United States
Environmental Protection
Agency
Region 10
1200 Sixth Avenue, Suite 900
Seattle, WA 98101-1128

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