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APPENDIX E

COMMENCEMENT BAY DAMAGE ASSESSMENT

QUALITY ASSURANCE PLAN
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Commencement Bay

Damage Assessment

Quality Assurance Plan

Analytical Chemistry

Prepared by

NOAA/NMFS/Environmental Conservation Division

December 1995
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Table of Contents

Introduction.................................................................................................................... 3

Project Description......................................................................................................... 4

Project Organization and Responsibilities ..................................................................... 6

Sample Handling and Chain of Custody Procedures ..................................................... 8

Laboratory Operations .................................................................................................. 11

Assessment of Data Quality .......................................................................................... 13

Quality Control Procedures........................................................................................... 15

Data Reduction, Validation and Reporting ................................................................... 22

Corrective Action/Procedure Alteration ....................................................................... 26

Quality Assurance Reports to Management ................................................................. 27

References ..................................................................................................................... 27
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Introduction

The National Oceanic and Atmospheric Administration (NOAA) is acting as lead Federal Trustee for assessing damage and injury in Commencement Bay. The legal and

procedural framework for damage claims for injury or destruction of natural resources

resulting from the release of hazardous substances is provided under Superfund legislation and its amendments (Superfund Amendments and Reauthorization Act of 1986

(P.L. 99-499).

This Quality Assurance (QA) Plan is in support of laboratory testing and characterization of contaminants in environmental samples (sediments and biota)—i.e., selected

PCBs, DDTs, pesticides and other organochlorine compounds (sediments and biota),

PAHs (sediments and biota), plithalates (sediments) selected phenols (sediments), selected metals (sediments), and butyltins (sediments)—collected from the selected stations in Hylebos, Waterway (located along the southeastern shore of Commencement

Bay) and in Commencement Bay, Tacoma, Washington. This plan does not address the

collection or generation of these samples. The requirements specified in this plan are

designed to: (1) monitor the performance of the measurement systems to maintain statistical control and provide rapid feedback so that corrective measures can be taken

before data quality is compromised and (2) verify that reported data are sufficiently

complete, comparable, representative, unbiased and precise so as to be suitable for their

intended use.

This QA Plan is consistent with the intent of NRDA regulations, as provided in 43 CFR

Subtitle A, subpart C and satisfies the requirements listed in the National Contingency

Plan and relevant EPA guidance for QA/QC plans. It has been prepared in general

accordance with the “Interim Guidelines and Specifications for Preparing Quality Assurance Project Plans” (Stanley and Verner, 1983). Some of the items specified in the

above document, however, are extensively addressed in other QA or work plans prepared for this damage assessment and are only summarized or referenced herein.

Many of the requirements described in this document are based on protocols developed

by NOAA’s National Status and Trends Program, EPA’s Puget Sound Estuary Program

and EPA’s Environmental Monitoring and Assessment Program-Estuaries. All three of
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these programs are designed to measure low-level (i.e. low parts per billion) concentrations of contaminants in marine and estuarine sediments and biota, and thus serve as a

useful prototypes for this QA plan even though they are not subject to the stringent legal

requirements of a damage assessment.

This QA plan will be revised as appropriate, as changes are made to the QA program

and the damage assessment.

Section 1.0

Project Description

Samples, including sediments and fish tissues, will be analyzed for the presence and

concentrations of a variety of contaminants (Tables 1.1 and 1.2). The QA and work

plans under which these samples were generated or collected are independent documents and not included or considered herein. This QA plan describes the minimum

requirements to be taken to provide for the chemical (and associated physical normalizing parameters) analyses of the previously generated or collected samples in a technically sound and legally defensible manner.

More detailed descriptions of the procedures and protocols under which the samples

were collected, including sample custody procedures are given in the work plans for

each individual project. A brief summary of the types of samples to be analyzed under

this plan is given in Table 1.1. The list of analytes to be determined in the samples is

presented in Table 1.2. The compounds selected for analysis are representative of the

contaminants known to have been released into the area and capable of describing the

exposure of the resources, as well as indicating the magnitude and extent of the injury to

the resources.
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Table 1.1 Sample Summary

Sample Analytes Preservative

Sediment organics1 Frozen (-20°C)

metals Frozen (-20°C)

butyltins Frozen (-20°C)

Tissue

liver PCBs, DDTs, Frozen (-20°C)

pesticides, HCBD

stomach contents AHs, PCBs, Frozen (-20°C)

DDTs, pesticides,

HCBD

1AHs, PCBs (including selected congeners) DDTs, pesticides, phthalates, phenols,

other chlorinated hydrocarbons (see Table 1.2).

Table 1.2. List of Analytes

Organics (semivolatiles)

Low molecular weight AHs (sediments, stomach contents)

Naphthalene Acenaphthene

Acenaphthylene Phenanthrene

Fluorene 2-Methylnaphthalene

Anthracene

LAH [sum of low molecular weight AHs]

High molecular weight AHs (sediments, stomach contents)

Fluoranthene

Pyrene Benz(a)andu-acene

Chrysene Benzofluoranthenes (sum of b + k)

Benzo(a)pyrene Indeno(1,2,3-cd)pyrene

Dibenz(a,h)anthracene Benzo(ghi)perylene

HAH [sum of high molecular weight AHs]
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Table 1.2. List of Analytes, continued.

PCBs (sediments, stomach contents, tissues)

PCBs, total selected PCB congeners (Nos. 18, 28, 44, 52,

66, 101, 105, 118, 128, 138, 153, 170, 180,

187, 195, 206, 209)

DDTs (sediments, stomach contents, tissues)

p,p’-DDE p,p’-DDD

p,p’-DDT

Pesticides/0ther (sediments, stomach contents, tissues)

Aldrin Dieldrin

Chlordane [sum of α and γ] Lindane

Heptachlor Hexachlorobutadiene (HCBD)

Hexachlorobenzene (HCB)

Phthalates (sediments)

Dimethylphthalate Diethylphthalate

Di-n-butylphthalate Butylbenzylphthalate

Di-n-octylphthalate bis(2-Ethylhexyl)phthalate

Phenols (sediments)

Phenol 2-Methylphenol

4-Methylphenol 2,4-Dimethylphenol

Pentachlorophenol

Chlorobenzenes (sediments)

1,3-Dichlorobenzene 1,4-Dichlorobenzene

1,2-Dichlorobenzene 1,2,4-Trichlorobenzene

Toxic metals/organometals (sediments)

Antimony Arsenic

Cadmium Chromium

Copper Lead

Mercury Nickel

Silver Zinc

Butyltins (Tetra-, tri-, di- and monobutyltins)
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Section 2.0

Project Organization and Responsibilities

2.1 Project Leaders

The Project Leaders/Principal Investigators are:

Sediments/Fish Tissues

John Stein, Ph.D.

(206) 860-3338; FAX (206) 860-3335

Sin-Lam Chan, Ph.D.

(206) 860-3330; FAX (206) 860-3335

NOAA/NMFS

2725 Montlake Blvd. E.

Seattle, WA 98112

2.2 Quality Assurance

Carol-Ann Manen is the QA Coordinator reporting directly to the Case Management

Team. Dr. Manen is responsible for the preparation and implementation of this Quality Assurance Plan. She may receive assistance in the coordination and performance

of laboratory technical audits and independent data validation from the QA Contractor (EcoChem). The QA Coordinator has the authority and responsibility to cease or

temporarily halt activities not in keeping with this QA Plan. The QA Coordinator will

work closely with laboratory representatives and the project team to assure that

project and data quality objectives are met. All instructions, requests and other communications between the laboratory representatives and the QA Contractor will go

through the QA Coordinator. These people may be reached at:

Carol-Ann Manen, Ph.D. (QA Coordinator)

(301) 713-3038 FAX 301-713-4387

NOAA Damage Assessment Center

1305 East West Highway, Rm. 10218

Silver Spring, Maryland 20910

Ann Bailey (QA Contractor)

(206) 233-9332 FAX 206-233-0114

EcoChem, Inc.

801 Second Ave, Suite 1401

Seattle, Washington 98104-1504
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2.3 Analytical Laboratories

Analytical work is provided to the Commencement Bay Damage Assessment through

contracts with the Environmental Conservation Division, Northwest Fisheries Science

Center (ECD/NWFSC). The designated Project Managers are responsible for assuring

that all analyses performed by that group meet project and data quality objectives.

These Project Managers are:

Sediments/Fish Tissues—Organic Chemistry

Margaret Krahn, Ph.D.

(206) 860-3326; FAX (206) 860-3335

Donald Brown, M.S.

(206) 860-3300; FAX (206) 860-3335

NOAA/NWS

2725 Montlake Blvd. E.

Seattle, WA 98112

Sediments-Toxic—Metals, Organotins

Cheryl Krone, Ph.D.

(206) 860-3309; FAX (206) 860-3335

NOAA/NMFS

2725 Montlake Blvd. E.

Seattle, WA 98112

3.0

Sample Handling and Chain of Custody Procedures

Chain of custody procedures will be used for all samples throughout the analytical process and for all data and data documentation, whether in hard copy or electronic format.

Sampling procedures, including sample collection and documentation, are part of the

work plans of the individual projects and as such, are not considered here. Sena Camarata,

Peggy Krahn, and Doug Burrows will have the password to the electronic data fides.

3.1 Sample Preservation

A summary of the types of samples collected for analyses is given in Table 1.1. Sample

preservation and field treatment of samples for analyses are described in relevant sampling SOPs. Briefly, sediment and tissue samples are frozen rapidly as soon after collec-
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tion as possible. Once frozen, the samples are maintained frozen, at -20°C or colder

until extracted or prepared for analysis. Because most analytes involved in this damage

assessment are known to be extremely stable, sample holding times are not an issue.

3.2 Chain of Custody

Each container is considered to be an individual sample and will be assigned a unique

ID and have a separate entry on the chain of custody record.

Chain of custody records will be completed in ink.

A sample is considered in “custody” if:

• it is in the custodian’s actual possession or view,

• it is retained in a secured place (under lock) with restricted access, or

• it is placed in a container and secured with an official seal(s) such that the sample

cannot be reached without breaking the seal(s).

Samples are kept in the custody of designated sampling and/or field personnel until

shipment.

3.3 Sample Shipping

Any transfer or movement of samples will use chain of custody procedures. The original signed, and dated chain of custody record accompanies the sample(s); a copy is

retained by the sample shipper. All shipments will comply with DOT regulations (49

CFR, Parts 172 and 173).

3.4 Sample Receipt

Immediately upon receipt of samples, the recipient win review the shipment for consistency with the accompanying chain of custody record and sample condition before signing

and dating the chain of custody record. Sample condition(s) will be noted on the original chain of custody sheet at this time. If there are any discrepancies between the chain

of custody record and the sample shipment, the, recipient will contact the sample shipper immediately.

3.5 Intra-Laboratory Sample Transfer

The laboratory sample custodian or designee will maintain a laboratory sampletracking record, similar to the chain of custody record, that will follow each sample
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through all stages of laboratory processing. The sample-tracking record will show the

name or initials of responsible individuals, date of sample extraction or preparation,

and sample analysis.

3.6 Inter-Laboratory Sample Transfer

Transfer of samples from one analytical laboratory to another, i.e. for grain size or TOC

analysis, will follow chain of custody, sample shipping and receipt procedures described

above.

3.7 Sample Archival

All unanalyzed samples and unutilized sample aliquots or extracts will be held by the

laboratory in a manner to preserve sample integrity at a secure location with chain of

custody procedures for one (1) year after the QA Contractor has validated the data

package for that particular set of samples. All archived materials will be accessible for

review upon request. These materials will become the responsibility of the QA Coordinator at the end of the archival period.

3.8 Data and Data Documentation

All data and data documentation, whether in hard copy or electronic format, is the responsibility of the QA Coordinator acting on behalf of Counsel to the Case Management Team. These materials will all be clearly marked with “Attorney Work Product.”

The QA Coordinator will receive from ECD/NWFSC data tables and QA documentation suitable for QA assessment. If the QA Contractor needs more information (or information in a different format than that provided by ECD/NWFSQ the QA Coordinator will contract with (hire) a “QA Specialist” who will have the responsibility for formatting ECD/NWFSC’s data into a package suitable for validation by the QA Contractor. All original data and data documentation developed by the laboratory for a given

data package will be kept by the laboratory in a secure location under chain of custody

procedures for one (1) year after the QA Contractor has validated that data package. All

archived materials will be accessible for review upon request. These materials will become the responsibility of the QA Coordinator upon termination of the archival period.
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A copy of the data will be transferred from the QA Specialist to the QA Contractor by

commercial courier. The QA Contractor will document receipt of packages and maintain a record of the method and date of data submittal with the complete data package.

The QA Contractor will maintain the copy of the data packages and related validation

documentation in a secure location for a period of one (1) year from the date of validation.

Section 4.0

Laboratory Operations

All laboratories providing analytical support for the Commencement Bay Damage Assessment must have the appropriate facilities to store and prepare samples, and appropriate instrumentation and staff to provide data of the required quality within the time

period dictated. Laboratories are expected to conduct operations using good laboratory

practices, including:

• A program of scheduled maintenance of analytical balances, laboratory equipment

and instrumentation.

• Routine checking of analytical balances using a set of standard reference weights

(ASTM class, NIST Class S-1, or equivalents).

• Recording all analytical data in logbooks; each entry signed and dated by the analyst.

Monitoring and documenting the temperatures of cold storage areas and freezer

units.Laboratory operations will be evaluated by the QA Coordinator through technical

systems audits, performance evaluation studies, and performance in the NIST-managed

intercomparison program. Personnel in any laboratory performing analyses for this damage assessment should be well versed in good laboratory practices, including standard

safety procedures. It is the responsibility of the laboratory manager and/or supervisor to

ensure that safety training is mandatory for all laboratory personnel. The laboratory is

responsible for maintaining a current safety manual in compliance with the Occupational Safety and Health Administration (OSHA) or equivalent state or local regulions.

Proper procedures for safe storage, handling and disposal of chemicals should be followed at all times; each chemical should be treated as a potential health hazard and good

laboratory practices should be implemented accordingly.
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4.1 Quality Assurance Documentation

All laboratories must have the latest revision of the Commencement Bay Damage Assessment Quality Assurance Plan (this document). In addition, the following documents

and information must be current and available to all laboratory personnel participating

in the processing of CBDA samples:

• Laboratory Standard Operating Procedures (SOPs)—Detailed instructions for performing routine laboratory procedures.

• Instrument performance study information—Information on instrument baseline noise

(instrument signal used for analyte quantification will be ≥5 times background noise),

calibration standard response, analytical precision and bias data, detection limits,

etc. This information usually is recorded in logbooks or laboratory notebooks, data

tables, folders, and electronic data bases.

• Control charts or data tables-These must be developed and maintained throughout

the project for all appropriate analyses and measurements.

4.2 Laboratory Performance Audits

Prior to sample analysis, a QA performance audit will be performed to determine if the

laboratory has the capability to perform analyses in compliance with the objectives of

this Project. Additionally, at least once during the project, a formal laboratory audit will

be conducted by the QA Coordinator. The checklists used for the laboratory audits are

based on requirements outlined in “Good Laboratory Practice Standards” (40 CFR Part

792) and audit procedures of the EPA National Enforcement Investigations Center,

“NEIC Procedures Manual for the Contract Evidence Audit and Litigation Support for

EPA Enforcement Case Development” (EPA 330/9-89-002). The laboratory and Program Manager will be informed of the findings and recommendations of the audit before the auditors leave the facility. A written report discussing the audit will be submitted to the Case Management Team.
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4.3 Participation in Intercomparison Exercises

Each analytical laboratory is required to participate, whenever possible, in the

intercomparison exercises managed by NIST for NOAA and the EPA. A variety of

samples including accuracy-based solutions, sample extracts, and representative matrices (e.g., sediment or tissue samples) are utilized in these exercises, which typically

take place once a year. Laboratories are required to analyze the sample(s) and must

submit their results in a timely manner to NIST. Upon review by NIST, laboratories

which fail to achieve acceptable performance will be required to provide an explanation

to the QA Coordinator and/or undertake appropriate corrective actions.

Section 5

Assessment of Data Quality

The purpose of this QA Plan is to develop and document analytical data of known,

acceptable, and defensible quality. The quality of the data is presented as a set of statements that describe in precise quantitative terms the level of uncertainty that can be

associated with the data without compromising their intended use. These statements are

referred to as Data Quality Objectives (DQOs) and are usually expressed in terms of

precision, accuracy, completeness, and comparability. The DQOs for this damage assessment for completeness are presented in Table 5.1; those for accuracy and precision

are presented in Table 6.2.

TABLE 5.1 Summary of Data Quality Objectives

Completeness

Data Type Goal

Organic analytes 90%

Toxic metals 90%

Butyltins 90%

Percent moisture 90%

Completeness goals are the percentage of expected results to be obtained

successfully.
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The Commencement Bay Damage Assessment will make extensive use of the replicate

analysis of standard reference materials (SRM) or certified reference materials (CRM)

to demonstrate the precision, accuracy and comparability of the chemical analytical

data.

5.1 Precision

Precision is the degree of mutual agreement among individual measurements of the

same property under prescribed similar conditions, such as replicate measurements of

the same sample. Precision is concerned with the “closeness” of the results. Where

suitable reference materials are available, precision will be expressed as the relative

standard deviation (RSD) for the repeated measurements. This use of reference materials allows for the long-term measurement of precision but does not include homogenization as a source of analytical variability. Where suitable reference materials are not

available, precision will be expressed as the relative standard deviation (RSD) between

a pair of replicate data from duplicate samples. It is recognized that precision erodes as

the limit of detection is approached.

5.2 Accuracy

Accuracy is the degree of agreement of a measurement with an accepted reference value

and may be expressed as the difference between the two measured values or as a percentage of the reference value. Reference materials will be used for AHs, chlorinated

pesticides, PCBs, phenols, chlorinated benzenes, plithalates, and elements. See Table

6.2 for criteria.

5.3 Comparability

Comparability expresses the confidence with which one data set can be evaluated in

relationship to another data set. For the Commencement Bay Damage Assessment, comparability of the chemical analytical data is established through the use of:

(1) program-defined general analytical methodology, detection limits, accuracy and

precision requirements and reporting formats;
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(2) common NIST-traceable (or other) calibration and reference materials;

(3) participation in interlaboratory comparison exercises.

5.4 Completeness

Completeness is a measure of the proportion of data specified in the sampling plan

which is determined to be valid. For the analytical chemistry component of this damage

assessment, the data quality objective for completeness is 90%, i.e. no more than 10%

of the analytical data will be qualified as unreliable (see Table 7.2).

6.0

Quality Control Procedures

No official procedure has been approved by regulatory agencies for low-level (i.e.,

parts per billion) analysis of contaminants in marine sediments and biological tissue.

No particular analytical method, therefore, is specified for this project but the QA/QC

requirements will provide a common foundation for each laboratory’s protocols. This

“common foundation” includes: (1) the specification of the analytes, to be identified

and quantified and the minimum sensitivity of the analytical methods and (2) the use of

NIST or other calibration materials, whenever possible (no NIST calibration solutions

are available for phenol, plithalate, chlorinated benzene, or butyltin compounds).

In addition, prior to the analysis of samples, each laboratory must provide written protocols for the analytical methods to be used; calculate detection limits for each analyte

in each matrix of interest and establish an initial calibration curve in the appropriate

concentration range for each analyte. The laboratory must demonstrate its continued

proficiency by participation in refereed intercomparison exercises and repeated analyses of reference materials, calibration checks, laboratory method blanks.

Lastly, the laboratory may be audited once before samples are analyzed and once during the project in order to determine and document if the laboratory has the capability to

analyze the samples and is performing in compliance with the QA plan.
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6.1 Specification of Analytes

The analytes to be determined are listed in Table 1.2.

6.2 General Analytical Methodology

Considerable retention time data, which can be used for comparison, exist for PCBs and

DDTs and certain other organic analytes as determined on fused silica capillary columns with a 95% dimethyl, 5% diphenyl polysiloxane coating (DB-5). For this reason,

a DB-5 column 30-meters or more in length will be the primary column used in quantitating the organic analytes and butyltins listed in Table 1.2.

Approximately 10% of all samples analyzed by GC/ECD for organic analytes will also

be analyzed by Mass Spectroscopy/Selected Ion Monitoring (MS/SIM) for independent

confirmation of compound identification. Samples for GUMS confirmation will be those

previously analyzed with the DB-5 column and will be selected for GC/MS confirmation on the basis of the concentration of analyte present and the representativeness of

the sample. These data will not be used for quantitation.

6.3 Initial Demonstration of Proficiency

Accuracy-based, sediment and tissue samples provided by NIST/NRCC (or others) are

to be analyzed (or have recently been analyzed) by the laboratory proposing to perform

analytical work for this damage assessment. Results from the analysis of these samples

are used to evaluate laboratory performance prior to selection of laboratories for field

sample analyses. The laboratory’s performance is considered acceptable if a majority of

reported values (that are > 10 x detection limit) are within ±50% of the reference value,

and the relative standard deviation of replicate results does not exceed 30% for the

majority of results. No accuracy based materials are available for phenols, plithalates,

chlorinated benzenes and butyltins in sediments. However, the SRM 1941 contains most

of the phenol, chlorobenzene, and phthalate analytes at concentrations; ≥ 10 ng/g. Our

recent analyses of this material gave precise results (n=5) and the results for matrix

spike samples analyzed with the series of SRMs showed acceptable recoveries; therefore, the SRM may be used for QA for phenols, plithalates, and chlorobenzenes in

sediment in place of matrix spikes.
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6.4 Standard Operating Procedures for Analytical Methods

Prior to the analysis of field samples, each laboratory is required to submit written Standard Operating Procedures (SOPs) detailing the procedures used in sample preparation

and analysis and data reduction and reporting. Copies of the SOPs from each analytical

laboratory are archived with this plan as part of the QA documentation.

6.5 Determination of Method Detection Limit (MDL)

The analytical laboratory will establish and report a method detection limit for each

analyte of interest in each matrix. The target MDLs for this project are specified in

Table 6.1. The target MDLs will be validated by following the method in 40CFR, part

136 (based on precision) and by analyzing an SRM that has values in the range of the

MDLs. Application of the 40CFR method to a highly precise determination such as

tissue analysis can result in artificially low MDLs; therefore, we have revised the QA

evaluation criteria for method blanks (tissue sets) so that 5 analytes can exceed 3x the

MDL (Table 6.2 of the QAP).

Data for organic analyte concentrations will be reported based on instrument responses

that are within the range of the calibration standards. A quantitation limit for each analyte

in a sample will be based on the smallest analyte peak measured in the lowest concentration multilevel standard, the sample weight, and appropriate response factors using

the formula below or the multilevel calibration curve for CHs.

conc (ng/g) = ng surrogate std x smallest analyte area x Rrf

 area surrogate std

 sample weight (g, dry)

R

rf

 = ng/μL of analyte in cal std x area surrogate in cal std

 area analyte in cal std ng/μL surrogate in cal std

If the analyte is not detected in a sample, the quantitation limit (as calculated above) will

be reported, preceeded by a “less than” sign (<). Reported analyte concentrations in

certain samples may be lower than the target MDL.
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Table 6.1 Target Method Detection Limits

Semivolatile Organics

Sediment (ng/g, dry weight)

AHs, phenols, phthalates, chlorinated benzenes 4

Pesticides, PCB congeners 4

Tissue (ng/g, wet weight)

AHs 4

Pesticides, PCB congeners 4

Toxic Metals (μg/g, dry weight)(Graphite furnace AA, GFAA;

Inductively coupled plasma optical emission spectroscopy, ICP,

Cold vapor AA, CVAA; Flame AA spectroscopy, FAAS)

Antimony (GFAA) 1.2

Arsenic (GFAA, ICP) 0.14,13

Cadmium (GFAA) 0.005

Chromium (GFAA, FAAS) 1.0,1.8

Copper (GFAA, FAAS) 2.3,0.6

Lead (GFAA) 0.5

Mercury (CVAA) 0.02

Nickel (GFAA) 0.2

Silver (GFAA) 0.02

Zinc (1CP, FAAS) 1.9, 16

Buty1tins (ng/g, dry weight, as tin)

Sediment, mono-, di-, tri-, tetrabutyltin 10

6.6 Quality Control Criteria for the Analytical Measurements

The results for the various QC samples will be reviewed by laboratory personnel immediately following the analysis of each sample batch. These results will then be used to

determine when control limits (numerical data criteria) have been exceeded and corrective actions are required before the analyses may proceed. Control limits and required

minimum frequency of analysis for each QC element or sample type are summarized in

Table 6.2.
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6.6.1 Initial Calibration

Acceptable calibration (initial and continuing) must be established and documented

before sample analyses may begin. NIST/NRCC-provided (or other) calibration materials must be used, whenever possible, in establishing calibration. Initial calibration will

be established with a multipoint standard calibration curve (for certain analyses, as indicated in Table 6.2). The correlation coefficient (r) for the curve will be greater than

0.9900. Failure to generate acceptable standard curves weekly (at a minimum) for >

90% of the analytes will require recalibration. Data corresponding to a calibration that

does not meet the criteria will be qualified or not reported. A specific requirement for

this project was to use methodology (and tune instrumentation) for low detection limits,

therefore, samples with analytes above the calibration range will be diluted and reanalyzed or qualified based on agreement with the QA Coordinator (e.g., where only a few

analytes exceed the calibraton range, it may not be necessary to reanalyze the sample).

The lower limit of the calibration range will be the lower limit of quantitation. HCBD

will be quantitated in tissue samples and stomach content samples based on an adjusted

response factor for HCB (because HCBD was added to the list of analytes to be determined after the multilevel standards had been prepared and thus is not in our calibration

solution). At the beginning of the project, the response curves for HCBD and HCB will

be determined from a calibration solution containing these analytes and the GC standard. For sample analysis, a corrected response curve for HCB will be used for calculating the concentration of HCBD.

6.6.2 Continuing Calibration Verification (CCV). Continuing calibration verification (CCV) standards will bracket every 10 field sample analyses at a standard curve

midpoint concentration. If CCV results do not meet specified criteria (Table 6.2), then

all samples analyzed since the last acceptable CCV must be reanalyzed after recalibration.

6.6.3 Reference Materials

Reference materials (either certified or uncertified) of an appropriate matrix will be

analyzed with every 10 field samples throughout the analytical program. The data resulting from the analysis of these samples will be reported in the same manner as that

for field samples. These data will be the prime materials used to determine and document the accuracy and precision of the associated field sample data.
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Table 6.3 Standard Reference Materials (SRMs) Used in the CBDA

NIST SRM 1941, 1941a Organics in Marine Sediment (certified)

NIST SRM 1974a Organics in Mussel Tissue (Mytilus edulis, being certified)

NRCC MESS-1, Metals in Marine/Estuarine Sediment (certified)

NRCC BCSS-1, Metals in Marine/Estuarine Sediment (certified)

NRCC PACS-1, Metals in Marine/Estuarine Sediment (certified)

Duwamish III, Butyltins in Estuarine Sediment (noncertified)

SQI, Butyltins in Marine Sediment (noncertified)

Only selected analytes may be certified in “certified” materials.

It is recognized that accuracy is usually best assessed using certified values (or advisory

values for those analytes that are not certified), hence the term relative accuracy. Relative accuracy is computed by comparing the laboratory’s value for each analyte against

either end of the range of values (i.e., 95% confidence limits) reported by the certifying

agency. The laboratory’s value must be within 35% of either the upper or lower 95%

confidence interval value for ≥70% of the analytes. Non-certified results can be compared but with less rigorous criteria. Accuracy control limit criteria (Table 6.2) will

apply only for those analytes having concentrations in the SRMs greater than 10 times

the laboratory’s target MDL.

Each laboratory will record the results for analytes in the SRM on control charts or

tables. If the values exceed the control limits, then the entire batch of samples is to be

considered suspect. The source of the error must be identified and corrected and the

samples reanalyzed (depending on agreement with the QA Coordinator). In the case of

analytes for which no concentration information is available, the laboratory will establish upper and lower control limits, based on three standard deviations of the mean.

These control limits will be evaluated on a monthly basis.

6.6.4 Surrogate (Internal Standard) Recovery

All samples, where applicable in the analytical scheme, will be spiked with extraction

surrogates (internal standards) as described in the laboratory SOPs. No surrogates will

be used for metals.
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6.6.5 Method (Reagent) Blanks

Method blanks are laboratory derived samples which have been subjected to the same

preparation or extraction procedures and analytical protocols as project samples. A

method blank will be analyzed at least with every 20 field samples analyzed. Acceptance criteria are provided in Table 6.2. Failure to meet acceptance criteria requires

definitive corrective action to identify and eliminate the source(s) of contamination before the subsequent re-extraction and reanalysis of the blank and affected samples. Sample

results will not be blank corrected.

6.6.6 Sample Duplicates

A sample duplicate will be analyzed at least with every 20 field samples. Acceptance

criteria are provided in Table 6.2.

6.7 Quality Control Criteria Percent Moisture

Duplicates must be analyzed at least with every 20 field samples. The relative

standard deviation will be less than or equal to 25%, or the batch must be reanalyzed.

6.8 Laboratory Qualification of Data

Sample results which presented analytical difficulties are qualified by the laboratory so

that the data user is aware of the potential limitations of the data. Laboratory qualifiers

are:

G Result is an estimate in concentration because analytical interference

caused difficulty with quantitation.

K Analyte was detected and quantified but actual concentration is greater

than the value shown because the analyte area exceeded that for the

corresponding highest level standard, i.e., it was out of the calibration

range. Because the methods are optimized for low detection limits, there

will be some occasions when an analyte exceeds the calibration range

and it is not reasonable to reanalyze the sample.

U Analyte was not detected. The reported value is the method detection

limit (MDL).

& Surrogate recovery is outside acceptable limits (50%-125%).
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TS Result was not corrected for recovery because surrogate recovery was

outside acceptable limits (50%-125%). Result was quantitated based on

the relative response of the injection internal standard (GC standard).

SC Surrogate was diluted out of range. Result was corrected for the surrogate recovery in the undiluted analysis of the same sample extract.

NR Result not reported for that analyte for some reason, the most common

of which may be that in a reanalysis of a diluted extract, the analyte

concentration was reported from a previous analysis.

NCA Analyte identified could not be confirmed because of coelution or analytical interference.

Section 7.0

Data Reduction, Validation and Reporting

7.1 Data Reduction

Data reduction is the process whereby raw data (analytical measurements) are converted or reduced into meaningful results (analyte concentrations). This process may be

either manual or electronic. Primary data reduction requires accounting for specific

sample preparations, sample volume (or weight) analyzed and any concentrations or

dilutions required. In addition, the concentrations of the analytes will be calculated based

on the recovery obtained for the surrogate compounds spiked into the sample prior to

extraction (for those analyses in which surrogate standards are used) in order to best

reflect the concentration of the compound in the original sample.

Primary data reduction is the responsibility of the analyst conducting the analytical

measurement and is subject to further review by laboratory staff, the Project Manager

and finally, independent reviewers. All data reduction procedures will be described in

the laboratory’s SOPs.

Concentrations greater than 10 will be reported as if 3 figures were significant and

those less than 10 will be reported as if 2 figures were significant. In addition:

Organic analytes in sediments will be reported in ng/g, dry weight, corrected for

surrogate recovery. Metals will be reported in μg/g, dry weight.
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Organic analytes in tissues will be reported in ng/g, wet weight, corrected for

surrogate recovery.

Results for analytes in method blanks will be reported as concentrations on the

same basis as for the samples being analyzed, i.e., the average of the weights of

the samples in the corresponding set are used in the calculations for the method

blank.

Data generated from the analysis of blank samples will not be utilized for correction of analyte data.

For sernivolatile organic compounds and butyltins, surrogate compounds will be

evaluated as percent recovery (%R). Recovery rates will be utilized to correct for

method efficiency by calculating all analyte concentrations using the appropriate

surrogate response factor.

Reference materials will be reported in units indicated on the certificate of analysis.

Continuing calibration factors will be presented as mean and relative standard

deviation (RSD).

Duplicate sample results will be expressed as the mean and standard deviation

(SD).

Total PCBs are calculated by summing the concentrations of PCB congeners 18,

28, 44, 52, 66, 101, 105, 118, 128, 138, 153, 170, 180, 187, 195, 206 and 209 and

multiplying by 2 (NOAA 1989). If a result is reported as non-detected, then zero

will be used in the summation.

7.2 Data Review and Validation

Data review is an internal review process where data are reviewed and evaluated by

personnel within the laboratory. Data validation is an independent review process conducted by personnel not associated with data collection and generation activities.

Data review is initiated at the bench level by the analyst, who is responsible for ensuring

that the analytical data are correct and complete, the appropriate SOPs have been followed and the QC results are within the acceptable limits. The Project Manager has

final review authority. It is the Project Manager’s responsibility to ensure that all analy-
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ses performed by that laboratory are correct, complete and meet project data quality

objectives.

External and independent data validation will be performed for all samples by the QA

Contractor using a data package (Table 7.1) containing sufficient information to allow

the independent validation of the sample identity and integrity, the laboratory measurement system, and resulting quantitative and qualitative data.

The original data packages will be archived by the laboratories for a maximum of one

year after generation and then returned to project management. A copy of each package

will be sent to the QA Contractor as soon as possible after development, for data validation. The QA Contractor will archive these copies for one (1) year after validation and

then return these to project management.

Two levels of data validation will be performed: full or cursory validation. Full validation will consist of a review of the entire data package for compliance with documentation and quality control criteria for all the following items and cursory validation for the

starred (*) items:

- Package completeness*

- Holding times from extraction to analysis*

- Instrument calibration, initial and continuing

- Blank results*

- Instrument performance

- Surrogate recovery (semivolatile organics and butyltins only)*

- Standard reference material results*

- Laboratory duplicate results

- Reported detection limits*

- Compound quantitation

Table 7.1 Laboratory Data Deliverables Per Sample Batch

Chain-of-Custody/Sample Receipt Checklist

Sample Data: Result summaries: including surrogate recoveries, % total solids,

dilutions, etc.

Standards Data:

Target MDL data based on the method in 40 CFR, 136, or data from analyses
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of SRM which has analytes at low concentrations (submitted once each year

for each laboratory/matrix).

Calibration summaries: initial calibration data, standard curve equation, correlation coefficient, continuing calibration as RSD.

Quality Control Data (Method Blanks, SRMs):

Results summaries including surrogate recoveries, plus % recovery and

%RSD, as applicable.

Case Narrative:

Special handling or analysis conditions.

Any circumstance that requires special explanation such as an exception to

QA/QC conditions or control criteria, dilutions, reanalysis, etc.

Corrective actions/procedure alterations

As the project proceeds and the quality of the data is verified and documented, the level

of validation will decrease such that 50% of the data packages will receive full review.

Cursory validation will be performed on the remaining packages, i.e. only the starred

items will be reviewed.

Qualifiers (Table 7.2) may be assigned to individual data points by the QA Contractor.

These validation qualifiers will not replace qualifiers or footnotes provided by the laboratory, but will be added to the data summary tables to inform the data user whether or

not the data met all project quality objectives. Both sets of qualifiers will be maintained

in the database.

Table 7.2 Data Validation Qualifier Codes

U Analyte concentration is not significantly above the associated blank result.

The result is judged to be the detection limit.

R Unreliable result. Data should not be used.
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J Reported concentration may not be accurate or precise, as judged by associated calibration and/or reference material results.

UJ Not detected. Detection limit may be inaccurate or imprecise, as judged by the

associated quality control results.

All discrepancies and requests for additional corrected data will be discussed with the

laboratory prior to issuing the formal data validation report. Review procedures and

findings during data validation will be documented on worksheets. A validation report

will be. prepared for each data group/data package summarizing OC results, qualifiers,

and possible data limitations. Only validated data with appropriate qualifiers will be

released for general use.

Data are not considered final until QA Coordinator has performed assessment. Data

will be subjected to validation at a later date.

Section 8.0

Corrective Action/Procedure Alteration

The analytical laboratories are required to adhere to the SOPs submitted by them to the

QA Coordinator for this project. When the data from the analyses of any quality control

sample exceeds the project specified control limits (Table 6.2) or indicates that the analytical method is drifting out of control, it is the immediate responsibility of the analyst

to identify and correct the situation before continuing with sample analysis.

A narrative describing the problem noted, the steps taken to identify and correct the

problem and the treatment of the relevant sample batches must be prepared and submitted with the relevant data package. If the action is a change from the accepted SOP, the

SOP must be revised and re-submitted within 30 working days after problem was noted.

Section 9.0

Quality Assurance Reports to Management

Quality Assurance/Quality Control (QA/QC) reports will be submitted periodically to

the Case Management Team by the QA Coordinator. These reports may be either formal or informal in response to the Case Management Team’s request. Upon termination
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of the analytical work for this damage assessment, a formal QA report will be submitted. This report will include:

• General compliance with QA objectives

• Summary of technical and performance evaluation audits

• Summary of data validation reports

• Summary of laboratory control charts

Section 10.0

References

Stanley, T. W. and S. S. Verner. 1983. Interim Guidelines and Specifications for Preparing Quality Assurance Project Plans. EPA/600/4-83/004. U. S. Environmental Protection Agency, Washington, D.C.
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List of Abbreviations

ACs aromatic compounds

MM aryl hydrocarbon hydroxylase

ANCOVA analysis of covaniance

ANOVA analysis of variance

BaP benzo[a]pyrene

BDL below detection limits

CB chlorinated biphenyl

CHs chlorinated hydrocarbons

CYPIA cytochrome P4501A

DAC Damage Assessment Center

DDTs dichlorodiphenyltrichloroethanes

DNA deoxyribonucleic acid

ECD Environmental Conservation Division

FACs fluorescent aromatic compounds

FACs

BAP

biliary FACs measured at benzo[a]pyrene wavelengths

FACs

NPH

biliary FACs measured at naphthalene wavelengths

FACs

PHN

biliary FACs, measured at phenanthrene wavelengths

FCA foci of cellular alteration

GSI gonadosomatic index

GS/ECD gas chromatography/electron capture detection
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GC/MS gas chromatography/mass spectometry

HACs high molecular weight aromatic compounds

HCB hexachlorobenzene

HCBD hexachlorobutadiene

HPLC/PDA high-performance liquid chromatography with photodiode array

detection

HSI hepatosomatic index

HydVac hydropic vacuolation of biliary epithelial cells

LACs low molecular weight aromatic compounds

NMFS National Marine Fisheries Service

NOAA National Oceanic and Atmospheric Administration

NWFSC Northwest Fisheries Science Center

NPH naphthalene

PCBs polychlorinated biphenyls

PAHs polycyclic aromatic hydrocarbons

PHN phenanthrene

pmol. mg-1min-1 picomoles/milligram/minute

ppb parts per billion

Prolif proliferation (in liver of fish)

PSAMP Puget Sound Ambient Monitoring Program

QA Commencment Bay Quality Assurance Plan (Appendix E)

QAP Commencment Bay Quality Assurance Plan (Appendix E)
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QA Plan Commencment Bay Quality Assurance Plan (Appendix E)

RReestimated relative risk

SAP Sampling and Analysis Plan (Appendix A)

SDN specific degeneration/necrosis (in liver of fish)

SE standard

SRM Standard Reference Materials. These materials are available from the

U.S. National Institute of Standards and Technology, Gaithersburg, MD

20899

TCDD 2,3,7,8 - tetrachlorodibenzo-p-dioxin

TEQs toxic equivalents

TEFS toxic equivalent factors

Tox toxicopathic