United States Office of Water EPA-823-R-02-006

 Environmental Protection 4303T

 Agency Washington, DC 20460

Quality Assurance Project Plan for

Analytical Control and Assessment

Activities in the National Study of

Chemical Residues in Lake Fish Tissue

Prepared for:

U.S. Environmental Protection Agency

 Office of Water

Office of Science and Technology

Engineering and Analysis Division

Prepared by:

DynCorp Environmental

Prepared under: 

Sample Control Center Contract No. 68-C-98-139 and 

MOBIS Contract No. GS-23F-9820, Task 68-C-00-137 September 2000
Quality Assurance Project Plan

for

Analytical Control and Assessment Activities in the

National Study of Chemical Residues in Lake Fish Tissue

September 2000

Prepared for 

United States Environmental Protection Agency

Office of Water

Office of Science and Technology

Engineering and Analysis Division

Prepared by

DynCorp Environmental

Prepared under

Sample Control Center Contract No. 68-C-98-139

and MOBIS Contract No. GS-23F-9820, Task 68-C-00-137

TABLE OF CONTENTS

1.0 Project Background ............................................................ 1

2.0 Project Description ............................................................ 1

3.0 Project Organization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

3.1 EPA Staff . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

3.1.1 OST Director . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

3.1.2 OST QA Manager . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

3.1.3 OST Study Manager . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

3.1.4 OST Project Manager for Sample Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

3.1.5 OST Project Manager for Sample Collection . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

3.2 Sample Control Contractor Staff . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

3.2.1 SCC Project Manager . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

3.2.2 SCC QA Manager . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

3.2.3 SCC Study Coordinator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

3.2.4 SCC Scheduling Coordinators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

3.2.5 SCC Data Review Manager . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

3.2.6 SCC Data Reviewers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

3.2.7 SCC Database Administrator ....................................... 9

3.3 Contract Laboratories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

3.3.1 Laboratory Project Manager . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

3.3.2 Laboratory QA Manager . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

3.3.3 Sample Custodian . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

3.3.4 Laboratory Supervisors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

3.3.5 GC/MS Operators, Mass Spectral Interpretation Specialists, Purge and Trap

Specialists, Extraction Specialists, Inductively Coupled Plasma Spectroscopists,

Atomic Absorption Spectroscopists, and Sample Prep Specialists . . . . . . . . . . 10

3.3.6 Systems Manager and Programmer Analysts . . . . . . . . . . . . . . . . . . . . . . . . . . 10

3.3.7 Data Reporting and Delivery Officer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

4.0 Quality Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

4.1 Project Quality Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

4.2 Measurement Quality Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

4.2.1 Precision . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

4.2.2 Bias . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

4.2.3 Accuracy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

4.2.4 Sensitivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

4.2.5 Representativeness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

4.2.6 Completeness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

4.2.7 Comparability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

5.0 Special Training Requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

6.0 Documentation and Records . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

6.1 Sample Preparation Laboratory Records . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

6.2 Analytical Laboratory Records . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

6.3 Data Compilation, Review and Validation Records . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
7.0 Sampling Process Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

8.0 Sampling Method Requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

8.1 Target Species and Sample Type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

8.2 Sample Collection Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

8.3 Sampling Period . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

9.0 Sample Handling and Custody Requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

9.1 Field Requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

9.2 Laboratory requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

9.2.1 Sample Preparation Laboratories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

9.2.2 Analytical Laboratories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

10.0 Analytical Methods Requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

10.1 Organohalide Pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

10.2 Organophosphorus pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

10.3 Dioxins/Furans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

10.4 Polychlorinated Biphenyls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

10.5 Semi-Volatile Organics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

10.6 Total Mercury . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

10.7 Arsenic Speciation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

11.0 Quality Control Requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

12.0 Instrument/Equipment Testing, Inspection, and Maintenance Requirements . . . . . . . . . . . . . . . 29

13.0 Instrument Calibration and Frequency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

14.0 Inspection/Acceptance Requirements for Supplies and Consumables . . . . . . . . . . . . . . . . . . . . 29

15.0 Requirements for Acquisition of Non-direct Measurement Data . . . . . . . . . . . . . . . . . . . . . . . . 30

16.0 Data Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

16.1 Laboratory Data Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

16.2 SCC Data Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

17.0 Assessments and Response Actions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

17.1 Surveillance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33

17.2 Peer Review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35

17.3 Quality Systems Audit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35

17.4 Readiness Review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35

17.5 Technical Systems Audit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36

17.6 Data Quality Audits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36

17.7 Data Quality Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37

18.0 Reports to Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37

19.0 Data Review, Validation, and Verification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37

20.0 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
LIST OF FIGURES AND TABLES

Table 1. National Fish Tissue Study Target Analyses and Corresponding Analysis Methods ......... 2

Figure 1. Project organizational chart . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

Table 2. Method performance criteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

Table 3 - Assessment and Response Actions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
National Fish Study Analytical QAPP September 2000 1

This Quality Assurance Project Plan (QAPP) presents performance and acceptance criteria and

measurement quality objectives (MQOs) established for the analysis of environmental samples collected

during the National Fish Tissue Study. This QAPP also describes the methods and procedures that will

be followed to ensure these criteria and MQOs are met. This document addresses only the sample

analysis effort; performance criteria and procedures related to sample collection are described in a

separate QAPP [3]. 

This document was prepared in accordance with and contains each of the elements described in

the most recent version of EPA QA/R-5, EPA Requirements for Quality Assurance Project Plans for

Environmental data Operations [4]. To improve clarity, the order of certain elements in this QAPP has

been modified slightly from the order presented in EPA QA/R-5. For example, in this QAPP the Project

Organization section (element ìA4" in QA/R-5) follows the Project Background and Project Description

sections (elements ìA5" and ìA6" in QA/R-5).

In accordance with the instructions provided in EPA QA/R-5, this QAPP is considered to be a

dynamic document that is subject to change as sample collection and analysis progresses. All changes to

procedures described in this QAPP will be reviewed by the EPA Analytical Project Manager and the EPA

Quality Assurance Manager to determine if the changes significantly impact the technical and quality

objectives of the project. If changes are deemed to be significant, the QAPP will be revised accordingly,

and revisions will be provided to all project participants listed in the QAPP distribution list.

1.0 PROJECT BACKGROUND

In 1987, the USEPA Office of Water (OW) conducted a national screening-level investigation to

determine the prevalence of selected bioaccumulative pollutants in fish, and to correlate elevated fish

tissue contaminant levels with pollutant sources [1]. Game fish and bottom-dwelling fish were collected

from 388 locations thought to be influenced by various point and non-point sources, and fish tissue

samples were analyzed to determine levels of approximately 60 contaminants, including dioxins and

furans, PCBs, pesticides and herbicides, mercury, and several other organic compounds. Results of the

1987 study indicated that target analytes were present in fish tissue at many of the sampling sites, and

some of the contaminants occurred at levels posing potential human health risks. OW is conducting a

new four year national study of chemical residues in fish tissue, broader in scope than the 1987 study. 

The new study is statistically designed to provide screening level data on a larger set of fish tissue

contaminants and from a greater number of water bodies than were sampled in 1987.

2.0 PROJECT DESCRIPTION

The objective of the new National Study of Chemical Residues in Lake Fish Tissue (herein

referred to as the National Fish Tissue Study) is to estimate the national distribution of the mean levels of

selected persistent, bioaccumulative, and toxic chemicals (PBT) in fish tissue from lakes and reservoirs of

the continental United States. To fulfill this objective, the National Fish Tissue Study will involve the

collection of predator and bottom-dwelling fish from 500 randomly-selected lakes and reservoirs of the

conterminous United States (excluding the Great Lakes) over a period of 4 years (~125 lakes per year)

beginning in 1999. Fish samples from a given lake and sampling period will be sent to a Sample

Preparation Laboratory where they will be weighed, composited, homogenized, and sub-sampled. The

sub-samples will then be sent to analytical laboratories where they will be analyzed for the PBT

chemicals listed in Table 1. Details regarding the study design, including how lakes to be sampled were

selected, can be found in reference [2].
September 2000 National Fish Study Analysis QAPP 2

Table 1. National Fish Tissue Study Target Analyses and Corresponding Analysis

Methods

Analysis Method Analytea

Dioxins and Furans by Isotope Dilution High-resolution Gas

Chromatography/Mass Spectrometry (Method 1613, Revision

B)

2,3,7,8-TCDD 

2,3,7,8-TCDF 

1,2,3,7,8-PeCDD 

1,2,3,7,8-PeCDF 

2,3,4,7,8-PeCDF 

1,2,3,4,7,8-HxCDD 

1,2,3,6,7,8-HxCDD 

1,2,3,7,8,9-HxCDD 

1,2,3,4,7,8-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-HpCDD 

1,2,3,4,6,7,8-HpCDF 

1,2,3,4,7,8,9-HpCDF 

OCDD 

OCDF 

Total Mercury by Oxidation, Purge and Trap, and Cold

Vapor Atomic Fluorescence Spectrometry

(Method 1631, Revision B with Appendix A - Digestion

procedures for total mercury in tissue, sludge and

sediment)

Mercury

Arsenic Speciation by Arsine Generation, Chromatography,

and Atomic Absorption Spectrometry

(Method 1632, Revision A )

arsenic(III)

arsenic (V)

monomethylarsonic acid (MMA)

dimethylarsinic acid (DMA)

Polychlorinated Biphenyls by Isotope Dilution Highresolution Gas Chromatography/Mass Spectrometry 

(Method 1668, Revision A)

167 congeners, including:

3,3',4,4'-TeCB

3,4,4',5-TeCB

2,3,3',4,4'-PeCB

2,3,4,4',5-PeCB

2,3',4,4',5-PeCB

2',3,4,4',5-PeCB

3,3',4,4',5-PeCB

2,3,3',4,4',5-HxCB

2,3,3',4,4',5'-HxCB

2,3',4,4',5,5'-HxCB

3,3',4,4',5,5'-HxCB

2,3,3',4,4',5,5'-HpCB
Analysis Method Analytea

National Fish Study Analytical QAPP September 2000 3

Organo-halide Pesticides by Gas Chromatography

(Method 1656, Revision A)

4,4 -DDD (TDE)

4,4 -DDE

4,4 -DDT

Aldrin

cis and trans nonachlor

Dicofol

Dieldrin

Endosulfan sulfate

Endosulfan I

Endosulfan II

Endrin

Ethalfluralin (Sonalan)

Heptachlor

Heptachlor epoxide

Hexachlorocyclohexane

Isodrin

Kepone (Chlordecone)

Methoxychlor

Mirex

octachlorostyrene

oxychlordane 

PCB-1016

PCB-1221

PCB-1232

PCB-1242

PCB-1248

PCB-1254

PCB-1260

Pendamethalin (Prowl)

Pentachloronitrobenzene (PCNB)

cis-Permethrin

trans-Permethrin

Toxaphene

Trifluralin

" -BHC

" -Chlordane (cis-Chlordane)

$ -BHC

( -BHC (Lindane)

( -Chlordane (trans-Chlordane)

* -BHC

Pentachloroanisole

Organo-phosphorus Pesticides by Gas Chromatography

(Method 1657, Revision A)

Chloropyrifos

Diazinon

Disulfoton

Disulfoton sulfone

Disulfoton sulfoxide

Ethion

Paraoxon

Parathion (ethyl)

Terbufos

Terbufos sulfoxide

Terbufos sulfone

a

Analytes other than project target analytes (e.g., additional analytes from the method lists) may also be reported. Refer to

methods for list of other analytes.
September 2000 National Fish Study Analysis QAPP 4

Method Analytea

Semi-volatile Organic Compounds by Isotope Dilution

GC/MS

(Method 1625 , Revision C?)

1,2,4,5-Tetrachlorobenzene

1,2,4-Trichlorobenzene

1,2-Dichlorobenzene

1,3-Dichlorobenzene

1,4-Dichlorobenzene

2,4,5-Trichlorophenol

3,3'-Dichlorobenzidine 

4,4'-Methylenebis(2-chloroaniline)

4-Bromophenyl phenyl ether

4-Nonylphenol

Acenaphthene

Acenaphthylene

Anthracene 

Benzo(k)fluoranthene

Benzo[a]anthracene 

Benzo[a]pyrene 

Benzo[b]fluoranthene 

Benzo[g,h,i]perylene 

Benzo[j]fluoranthene 

Bis(2-ethylhexyl)phthalate

Butyl benzyl phthalate

Chrysene 

Dibenzo[a,h] anthrancene 

Di-n-butyl phthalate 

Diethylstilbestrol (DES)

Fluoranthene 

Fluorene

Hexachlorobenzene

Hexachlorobutadiene

Indeno[1,2,3-cd]pyrene 

Naphthalene

Nitrobenzene

Pentachlorobenzene

Pentachlorophenol 

Perylene 

Phenanthrene 

Phenol

Phenol, 2,4,6-tris(1,1-dimethylethyl)-

Pyrene 

Tetrabromobisphenol A

a

Analytes other than project target analytes (e.g., additional analytes from the method lists) may also be reported. Refer to

methods for list of other analytes.

3.0 PROJECT ORGANIZATION

The Office of Science and Technology (OST) is responsible for overall management of the

National Fish Tissue Study. Day-to-day responsibility for managing various aspects of the study has been

delegated to the Standards and Applied Science Division (SASD) and the Engineering and Analysis

Division (EAD) within OST. SASD is responsible for managing all sample collection and data analysis

activities associated with this study; EAD is responsible for managing all laboratory analysis and data

verification (data review) activities. Both EAD and SASD are responsible for day-to-day interaction with

contractors and with other federal, state, and local authorities involved in the project.
National Fish Study Analytical QAPP September 2000 5

Several federal, state, tribal, local, and contractor organizations are participating in this project. 

To the extent possible, partner programs, agencies, EPA regional staff, states, and tribes will be solicited

to assist with sampling logistics for this study. In all cases, however, EPA will be responsible for

sampling coordination and quality assurance. 

EAD will contract all laboratory services needed to support this study. Due to the large and

diverse number of analyses required, it is anticipated that several contract laboratories will be used. To

minimize variability that could arise from sample handling and grinding, homogenizing, compositing, and

aliquotting, EAD intends to contract these activities to a single ìSample Preparation Laboratoryî that

will be used throughout the duration of the study. This laboratory must be capable of performing all

types of analyses required in the study (to verify the absence of contamination for each target analyte),

must have sufficient capacity to receive and process all fish collected during each study year, and must be

capable of preparing, compositing, and aliquotting all fish samples in an environment that is free from

detectable levels of all target contaminants. To further minimize analytical variability, EAD hopes to

select only one contract laboratory to perform each type of analysis (i.e., one laboratory will perform all

dioxin/furan analyses, one laboratory will perform all organohalide pesticide analyses, etc.) for the

duration of the study. It also is possible (and desirable) that one laboratory will be responsible for more

than one type of analysis (e.g., one laboratory performs all of the dioxin/furan and PCB analyses) for the

duration of the study. All ìSample Analysis Laboratoriesî will receive study samples from the Sample

Preparation Laboratory. The Sample Preparation Laboratory will receive samples from field sampling

teams or from a frozen storage repository.

Potential problems will be controlled through the use of a Sample Control Contractor (SCC) that

will be charged with facilitating effective communication among all parties involved in the shipment and

analysis of samples under this study. SCC responsibilities also will include 1) preparing and distributing

field sampling kits, 2) documenting all sample shipments, problems that arise, and resolutions to those

problems, 3) reviewing laboratory data to ensure that the measurement quality objectives (MQOs)

detailed in Section 5 of this QAPP are met, 4) working with the laboratories and EPA to correct quality

control failures, where possible, and 5) documenting the extent to which data submissions meet study

MQOs. The role of the Sample Control Contractor is critical to the timely identification and resolution of

shipping, laboratory, or data quality problems as soon as they occur.

Figure 1 illustrates the project organization and relationships between groups participating in the

major activities to be conducted under this study. Sections 3.1 through 3.3 describe the roles and

responsibilities of the individuals involved in study activities related to sample preparation and analysis. 

Details regarding roles of individuals involved in sample collection and handling can be found in

reference [3]. Section 3.1 of this QAPP describes the responsibilities of EPA staff; Section 3.2 describes

the responsibilities of the Sample Control Contractor staff, and Section 3.3 describes the responsibilities

of staff at each of the contract laboratories that will support this study.

3.1 EPA Staff

3.1.1 OST Director

The OST Director, Geoffrey Grubbs, is responsible for providing financial and staff resources

necessary to meet study objectives and implement study requirements described in this QAPP.
September 2000 National Fish Study Analysis QAPP 6

3.1.2 OST QA Manager

The OST QA Manager, William Telliard, is responsible for assisting the EPA Study Manager and

Project Managers with the development and implementation of QAPPs for this study. The QA Manager

also is responsible for ensuring that all QA procedures described in this QAPP are followed, reporting any

deviations from this QAPP to the Project Managers, and assisting the Project Managers in implementing

corrective actions necessary to resolve these deviations. The QA Manager reports directly to the OST

Director.

3.1.3 OST Study Manager

The OST Study Manager, Leanne Stahl, reports directly to the OST Director and is responsible

for providing overall direction concerning the study to the EPA Project Managers shown in Figure 1. The

OST Study Manager also is responsible for:

ï Overseeing the development and implementation of QAPP for all phases of the National Fish

Tissue Study.

ï Communicating study objectives to the EPA Project Managers shown in Figure 1.

ï Reviewing and approving all major work products associated with the study.

ï Participating in meetings with the EPA Project Managers, other EPA staff, and staff from other

organizations and contractors concerning the study.

ï Working with the OST QA Manager to identify corrective actions necessary to ensure that study

objectives are met.

ï Assisting the OST Project Manager for Sample Analysis with sample coordination activities.

3.1.4 OST Project Manager for Sample Analysis

The OST Project Manager for Sample Analysis, Cynthia Simbanin, reports directly to the OST

Director, and is responsible for:

ï Developing and implementing the QAPP describing the analytical activities of the National Fish

Tissue Study.

ï Daily oversight of EPA and contractor staff involved in activities related to analysis of samples

collected in this study.

ï Communicating project objectives to all EPA and contractor staff involved in the analysis of

samples collected in this study.

ï Reviewing and approving major deliverables related to the analysis of samples collected in this

study.

ï Participating in meetings with the OST Project Manager for Sample Collection, the OST QA

Manager, and the OST Director concerning study objectives, schedules, and concerns.

ï Providing technical assistance concerning sample analysis and data evaluation to the OST Project

Manager for Sample Collection.

ï Coordinating analytical method selection.

ï Assisting the OST Project Manager for Sample Collection with sample coordination activities,

such as sample scheduling, tracking, and kit distribution.
National Fish Study Analytical QAPP September 2000 7

3.1.5 OST Project Manager for Sample Collection

The OST Project Manager for Sample Collection, Leanne Stahl, reports directly to the OST

Director, and is responsible for:

ï Ensuring that sample collection resources are available and ready to implement the study design.

ï Technical and daily oversight of EPA and contractor staff, and staff from other institutions or

agencies involved in sample collection activities related to this study.

ï Communicating project objectives to all EPA and contractor staff involved in sample collection.

ï Reviewing and approving major deliverables related to the collection of samples associated with

this study.

ï Participating in meetings with the OST Project manager for Sample Analysis, the OST QA

Manager, the OST director concerning study objectives, schedules, and concerns.

3.2 Sample Control Contractor Staff

3.2.1 SCC Project Manager

The SCC Project Manager, Lynn Riddick, is responsible for acquiring and applying resources

needed to ensure that project deliverables are completed on time, within budget and to client satisfaction. 

The Project Manager also is responsible for developing and obtaining approval of this QAPP and for

ensuring that the practices required in this QAPP meet or exceed those outlined in Quality Management

Plan approved for use in the SCC contract. The Project Manager reports directly to the EPA Analytical

Project Manager (Cynthia Simbanin). Other responsibilities of the SCC Project Manager include:

ï Working with the EPA Analytical Project Manager to address project objectives and develop a

project schedule.

ï Communicating project objectives to the SCC Study Coordinator (see 3.2.3).

ï Monitoring performance of the SCC Study Coordinator and other SCC staff participating in this

study to ensure the quality, timeliness, and responsiveness of work performed.

ï Reviewing and approving major study deliverables for the analytical activities.

ï Participating in meetings with EPA staff concerning study objectives, schedules, and concerns.

3.2.2 SCC QA Manager

The SCC QA Manager, Marguerite Jones, is independent of the National Fish Tissue Study. Ms.

Jones is responsible for:

ï Assisting the SCC Project Manager with the development and implementation of this QAPP;

ï Ensuring that all QA procedures described in this QAPP are followed during the Study.

ï Reporting deviations from this QAPP to the Project Manager and assisting the Project Manager in

implementing corrective actions to resolve these deviations.

3.2.3 SCC Study Coordinator

The SCC Study Coordinator, Sara Conrad, reports directly to the SCC Project Manager. The

SCC Study Coordinator is responsible for:

ï Understanding and implementing the requirements described in this QAPP.

ï Reviewing all deliverables for the analytical activities prior to submission.

ï Adhering to the schedule approved for this study.
September 2000 National Fish Study Analysis QAPP 8

ï Ensuring that all necessary corrective action procedures are documented and implemented in a

timely manner.

ï Communicating study objectives and requirements to the SCC Scheduling Coordinators, the SCC

Data Review Team Leader, and the Database Administrator.

ï Supervising daily activities of the SCC Scheduling Coordinators, Data Reviewers, and Database

Administrator and assisting these individuals with the resolution of problems that arise during

study implementation.

ï Developing and implementing any SOPs necessary to meet the objectives of the National Fish

Tissue Study.

ï Day-to-day oversight of technical activities performed by SCC staff participating in the National

Fish Tissue Study.

ï Notifying the Project Manager of anticipated difficulties in meeting project schedules or other

requirements.

ï Identifying problems at the task level and resolving difficulties in consultation with the SCC

Project Manager, and the EPA Analytical Project Manager.

3.2.4 SCC Scheduling Coordinators

A primary SCC Scheduling Coordinator, Christian Maynard, will be assigned to the National Fish

Tissue Study. This coordinator will report directly to the SCC Study Coordinator and will be supported

by a back-up Scheduling Coordinator. Responsibilities of the SCC Scheduling Coordinators include:

ï Understanding and implementing all sample scheduling and tracking requirements described in

this QAPP.

ï Documenting and notifying the Study Coordinator of problems related to the scheduling,

shipment, and tracking of samples and data.

ï Working with the Study Coordinator to identify and implement corrective actions for such

problems.

ï Day-to-day communication and coordination with national field sampling coordinators, field

sampling teams, and laboratory personnel during sample shipment and laboratory analysis.

ï Preparing and submitting to the Study Coordinator reports that summarize the status of sample

analysis, data reporting, and data evaluation activities.

ï Entering information in and updating the automated sample and data tracking system in a timely

manner.

3.2.5 SCC Data Review Manager

The SCC Data Review Manager, Lisa White, reports directly to the SCC Study Coordinator and

is responsible for:

ï Understanding and communicating to SCC Data Reviewers all National Fish Tissue Study

requirements concerning data quality objectives, measurement quality objectives, data quality

audits, data quality assessments, and data management.

ï Supervising day-to-day activities of SCC Data Reviewers supporting the National Fish Tissue

Study and working with the Data Reviewers and the Study Coordinator to resolve problems and

implement corrective actions in a timely manner.
National Fish Study Analytical QAPP September 2000 9

ï Ensuring that SCC Data Reviewers adhere to all data quality audit and assessment requirements,

including documentation, corrective action, and database development procedures, described in

this QAPP.

ï Immediately notifying the Study Coordinator of technical or resource limitations that adversely

affect study schedules or requirements.

ï Performing a technical review of all SCC deliverables pertaining to data quality audits and

assessments before submission to the SCC Study Coordinator for final review.

3.2.6 SCC Data Reviewers

Several SCC chemists will be assigned to perform data quality audits and data quality

assessments as described in this QAPP. These SCC Data Reviewers will report directly to the SCC Data

Review Manager and are responsible for:

ï Understanding and implementing the data quality audit and assessment requirements described in

this QAPP.

ï Immediately notifying the SCC Data Review Manager of technical difficulties or other problems

that adversely impact study schedules.

ï Working with the analytical laboratories to implement corrective actions necessary to resolve data

quality problems in a timely manner and to maximize the amount of usable data generated in this

study.

ï Documenting all problems and corrective actions related to data quality.

ï Preparing written narratives that describe the overall quality of each laboratory data submission

and recommendations concerning data usability.

ï Updating the automated sample and data tracking system in a timely manner.

3.2.7 SCC Database Administrator

The SCC Database Administrator, Michael Walsh will report directly to the SCC Study

Coordinator and is responsible for:

ï Understanding and implementing all database development and maintenance requirements

described in this QAPP.

ï Working with SCC Data Reviewers, the SCC Data Review Manager, and the SCC Study

Coordinator to identify problems and implement corrective actions in a timely manner.

ï Notifying the SCC Study Coordinator of technical or resource constraints that may adversely

impact study schedules.

ï Documenting database problems and corrective actions in a manner that is both timely and

consistent with this QAPP.

ï Preparing written database status reports as requested by the SCC Study Coordinator.

3.3 Contract Laboratories

All sample preparation and chemical analyses in this study will be performed by contract

laboratories. Each laboratory contract will document detailed requirements for sample preparation,

storage, homogenization, compositing, shipment, and/or analysis as well as data management, QA,

confidentiality, personnel, and equipment requirements. Each contract will also stipulate that the

laboratory, and any subcontract laboratory utilized by that laboratory for the purposes of supporting this

study, maintain and adhere to an approved QAPP. Due to the size and complexity of this study, each

contract will require that a laboratory Project Manager, a Quality Assurance Manager, and certain
September 2000 National Fish Study Analysis QAPP 10

laboratory staff be available and dedicated to each project. Sections 3.3.1 through 3.3.6 below describe

the responsibilities of each of these staff members.

3.3.1 Laboratory Project Manager

This individual will be responsible for the overall technical laboratory activities under the EPA

contract or subcontract. This individual will be responsible for planning, conducting, and supervising

projects of major significance (such as the National Fish Tissue Study), and for supplying technical

advice and counsel to other professionals.

3.3.2 Laboratory QA Manager

This individual will be responsible for quality assurance (QA) of all technical efforts performed

under the contract, and will report directly to senior management. This individual will direct assistance,

review progress, evaluate results, and make changes in methods that have been approved by SCC and

EPA, design or equipment where necessary.

3.3.3 Sample Custodian

The Sample Custodian will be responsible for logging in, handling, and storing samples.

3.3.4 Laboratory Supervisors

These individuals will be responsible for all technical efforts performed within their laboratories

in support of the study. They will be responsible for supervising the laboratory staff who prepare and

analyze samples under their study contract.

3.3.5 GC/MS Operators, Mass Spectral Interpretation Specialists, Purge and Trap Specialists,

Extraction Specialists, Inductively Coupled Plasma Spectroscopists, Atomic Absorption

Spectroscopists, and Sample Prep Specialists

These individuals will be responsible for sample preparation, sample extraction, and sample

analysis on a daily basis. They also will be responsible for adhering to the analytical and QA/QC

requirements specified in the contract and for reporting to their supervisors any difficulties encountered.

3.3.6 Systems Manager and Programmer Analysts

These individuals will be responsible for developing and maintaining any automated systems

necessary to report analytical results produced under the contract and for ensuring that these systems

report data in a manner that is consistent with contract requirements.

3.3.7 Data Reporting and Delivery Officer

This individual will be responsible for the organization, packaging, copying, and delivery of data

deliverables submitted under the contract.
National Fish Study Analytical QAPP September 2000 11

Figure 1. Project organizational chart
September 2000 National Fish Study Analysis QAPP 12

4.0 QUALITY OBJECTIVES

4.1 Project Quality Objectives

The National Fish Tissue Study will allow EPA OW to report on the extent of PBTs in lake fish

tissue with known confidence. Therefore, study results should allow statements such as: 35% of the lakes

in the U.S. have PBT levels in fish that exceed the criteria of concern, with an estimated uncertainty of ±

5%. Major sources of uncertainty include: (1) sampling from a subset of lakes rather than all lakes, (2)

collecting a small number of fish (on the order of 5 to 10) from a lake relative to the total population, (3)

compositing and sub-sampling the fish samples, and (4) variability in the laboratory analysis process

itself. The first two sources of variability are addressed through the study design; measures for

controlling these sources are described in reference [2] and [3].

The combined variability introduced by compositing fish samples, sub-sampling the composites

for analysis, and laboratory analysis itself can be considered the "index" variability. Rather than

prescribing a tolerable limit to ìindexî variability, the approach for this study is to:

(1) Prescribe sample collection procedures that would minimize ìindexî variability (e.g., through

training of sampling crews and standardization of collection methods).

(2) Employ a sample compositing and sub-sampling scheme similar to that employed in EPAís

1997/1998 Cook Inlet Contamination Study. The sample compositing and sub-sampling

procedures used in that study were shown to result in low levels of variability.

(3) Select analytical methods capable of providing the best measurement performance (e.g., low bias

and acceptable and precision). 

(4) Require analytical laboratories to satisfy previously established performance criteria for these

analytical methods. The resulting index variability would then be estimated by collecting,

compositing, and analyzing duplicate samples from 10% of the sites.

As part of its project planning activities, the OST QA Manager and OST Study Manager directed

SCC to perform a review of existing methods published by EPA, other federal agencies, and in the

literature. The objective of this review was to identify methods or techniques that would best meet EPAís

needs for reliably measuring the targeted PBTs in tissue. OST considered techniques that best met EPAís

needs to be those that a) minimized method development and validation costs, b) yielded the lowest

possible detection and quantification limits, and where possible, c) avoided the use of expensive or highly

novel analysis techniques that could increase analytical costs of the study. 

The OST QA Manager and Study Manager invited a group of recognized experts in the field of

fish tissue analysis to participate in an Analytical Methods Workgroup that would assist OST in

reviewing its method selection and method development strategies. To kick off its method selection

activities, OST planned to hold a meeting with workgroup members in Chicago and provided each

member with a briefing book outlining the study goals, OSTís method selection strategy, a list of PBTs to

be targeted in the study, and several of the most promising methods identified during the literature

review. The meeting was canceled due to funding constraints, but the book was distributed to planned

meeting participants with a request that recipients contact OST regarding their input on the materials. 
National Fish Study Analytical QAPP September 2000 13

4.2 Measurement Quality Objectives

As mentioned in the previous section, ìindexî variability can be minimized by selecting

analytical methods that provide the best available measurement performance, as gauged by standard data

quality indicators (DQIs). The methods to be used in the National Fish Tissue Study reflect state-of-theart technology and include performance criteria demonstrated to be attainable in well-operated, controlled

laboratory environments. These criteria meet EPAís needs for data quality. Therefore, the general

measurement quality objective for this study is to satisfy method-specific performance criteria. The

following subsections and Section 11 of this QAPP provide details on how standard DQIs will be

monitored and controlled in this study.

4.2.1 Precision

Precision is the degree of agreement among replicate measurements of the same property, under

prescribed similar conditions [5]. It can be expressed either as a range, a standard deviation, or a

percentage of the mean of the measurements (e.g., relative range or relative standard deviation).

Ideally, precision is measured by subdividing samples in the field, preserving and numbering

each split separately, and sending the aliquots to the analysis laboratory as ëblindí duplicates. In this

study, however, samples must be homogenized, composited, and subdivided in a strictly controlled, clean

laboratory environment. Therefore, the Sample Preparation Laboratory will prepare ìduplicate composite

pairsî on 5% of the samples analyzed. These duplicate composite pairs will be sent to each analysis

laboratory as ìblind duplicatesî (e.g., labeled with separate EPA sample numbers) and used to assess

variability arising from the sample homogenization, compositing, aliquotting, shipping, and laboratory

analysis processes. The study measurement quality objective (MQO) for analytical precision is that

results from 90% of these ëduplicate composite pairsí agree within ±50% for values greater than 5x the

minimum level of quantification (ML) and that 90% of these duplicate composite pairs agree within

±100% for values less than 5x the ML.

In addition to the use of these ìduplicate composite pairsî, all laboratories will employ EPA

Office of Waterís (OWís) standard suite of laboratory QC measures (e.g., initial precision and recovery

samples, matrix spike and matrix spike duplicate samples) that provide information about the precision

associated with various components of the analytical process. These QC elements and associated

requirements are described in more detail in Section 11 (Quality Control Requirements) of this QAPP. It

should be noted that performance criteria for this study are based on overall data quality, and failure to

meet any single laboratory precision measure does not automatically imply the data are unacceptable for

use in this study. Laboratory QC measures are used to monitor and control precision in real time so that

overall precision goals are met. Details regarding the data quality assessment process governing use of

data in this study are given in Sections 16, 17, and 19.

Finally, the study design specifies that 10% of the lakes will be re-sampled. The relative percent

difference (RPD) between these replicated samples will provide information about the precision of data

within the sub-sampled lakes. This precision measure will be affected by temporal, population, sampling,

and analytical variability.

4.2.2 Bias

Bias is the systematic distortion of a measurement process that causes errors in one direction [5].

In this study, bias from the analytical process will be measured by preparing and analyzing field samples 
September 2000 National Fish Study Analysis QAPP 14

spiked with 1) the analytes of interest (i.e., matrix spike samples), 2) isotopically labeled analogs of the

target pollutants, or 3) surrogate compounds that are expected to behave in a manner similar to the target

analytes. The measurement quality objective for overall analytical accuracy in this study is for 80% of the

spiked field sample results to fall within the acceptance criteria specified for each method.

In addition to the use of spiked field samples, all laboratories will employ OWís standard suite of

laboratory QC measures (e.g., initial precision and recovery samples, instrument calibration standards,

method blanks) that provide information about the bias associated with various components of the

analytical process. These QC measures and associated requirements are described in more detail in

Section 11 (Quality Control Requirements) of this QAPP. It should be noted that performance criteria for

this study are based on overall data quality, and failure to meet any single measure of bias does not

automatically imply the data are unacceptable for use in this study. Laboratory QC measures are used to

monitor and control bias in real time so that overall precision goals are met. Details regarding the data

quality assessment process governing use of data in this study are given in Sections 16, 17, and 19.

4.2.3 Accuracy

Accuracy is a measure of the closeness of an individual measurement or the average of a number

of measurements to the true value. Accuracy includes a combination of random error (precision) and

systematic error (bias) components that result from sampling and analytical operations. Accuracy is

determined by analyzing a reference material of known pollutant concentrations or by reanalyzing a

sample spiked with a known amount of pollutant. [5]

In this study, certified reference materials (CRMs), when available, will be sent to each

laboratory annually to assess bias. CRM results will be pooled at the end of this study to determine

overall study accuracy. 

4.2.4 Sensitivity

Analytical sensitivity is defined as the minimum concentration of an analyte above which a data

user can be reasonably confident that the analyte was reliably detected and quantified. For this study, the

method detection limit (MDL) and the minimum level (ML) will be used to define the sensitivity of each

measurement process.

The MDL is defined as the minimum concentration of a substance that can be measured and

reported with 99% confidence that the analyte concentration is greater than zero. EPA procedures for

determining the MDL are given at 40 CFR 136, Appendix B. [6]

The ML is defined as the lowest concentration at which the entire analytical system must give a

recognizable signal and acceptable calibration point for an analyte. It is equivalent to the concentrations

of the lowest calibration standard analyzed by a specific analytical procedure, assuming that all the

method-specified sample weights, volumes, and processing steps have been employed. 

Ideally, analytical methods to be used in this study would have MDLs that are below all levels of

concern for the target analytes. However, due to the large number of target analytes and the lack of wellestablished analytical methods for some of these analytes, the approach for this study is to select methods

that can give the lowest MDL economically feasible. The measurement quality objective (MQO) for
National Fish Study Analytical QAPP September 2000 15

detectability is that 100% of the samples be analyzed by laboratories that have demonstrated the

capability to achieve the MDLs and MLs cited in Section 11.

4.2.5 Representativeness

Representativeness is a measure of the degree to which data accurately and precisely represent a

characteristic of a population parameter at a sampling point or for an environmental condition. It is a

qualitative term that is evaluated to determine whether data appropriately reflect the media and

phenomenon measured or studied.[5] This study was statistically designed so that the target population of

lakes is represented by a statistically valid sub-sample. Details of this design are given in reference [2].

4.2.6 Completeness

Completeness is defined in terms of the percentage of data that are collected and deemed to be

acceptable for use in the study. Three measures of completeness can be defined, as follows:

Sampling Completeness: The number of valid samples collected relative to the number of

samples planned for collection

Analytical Completeness: The number of valid sample measurements relative to the number of

valid samples collected; and

Overall Completeness: The number of valid sample measurements relative to the number of

samples planned for collection.

The analytical completeness goal in this study is that EPA obtain valid measurements from 90%

of the valid samples collected. In theory, however, a lower level of completeness can still lead to a valid

study. The effects of insufficient completeness will be evaluated during the data analysis phase of this

study. 

4.2.7 Comparability

Comparability expresses the confidence that two data sets can contribute to a common analysis

and interpolation.[5] The study will require the collection and analysis of numerous samples from various

parts of the country, and data will be generated from samples collected by many different sampling teams

and analyzed by multiple laboratories. To ensure comparability of data generated during this study, EPA

will:

ï Employ standard guidelines for sample collection

ï Use detailed analytical methods specifying each step of the laboratory process

ï Use one laboratory per method over the four year study

ï Use one method for all analyses of a given pollutant

ï Use a single laboratory to weigh, homogenize, composite, sub-sample, and distribute all samples

to each analysis laboratory throughout the study

ï Specify method detection limits and QC acceptance criteria that must be met throughout the study

ï Specify data reporting formats and units that must be used throughout the study

ï Use a standardized data quality assessment process
September 2000 National Fish Study Analysis QAPP 16

5.0 SPECIAL TRAINING REQUIREMENTS

Field sampling teams must consist of (at a minimum) one experienced fisheries biologist, one

field technician, and a quality control specialist, all of whom must have experience with the array of

fisheries sampling gear types to be used. In some cases, the senior fisheries biologist may assume

responsibility for site quality control. Species identification should be conducted only by experienced

personnel knowledgeable of the taxonomy of species in the water bodies included in National Fish Tissue

Study. Additional details on field sampling training requirements can be found in the QAPP for sample

collection [3]. 

The laboratory contracts employed in the study will specify minimum skills required of the

analysts performing work under those contracts. Required ìskillsî will include education and experience

in using the procedures and instruments employed in this study.

Because EADís standard data review approach will be implemented during this study (and

customized to meet study needs), all SCC staff responsible for reviewing data must be experienced in

performing data reviews, trained to review data in accordance with EADís general data review guidelines,

experienced in reviewing data generated with the instrumentation that will be used in this study, and

familiar with the performance criteria and MQOs established for this study. For example, any SCC staff

member that reviews dioxins/furans data generated during this project must have some prior experience

reviewing data generated by high-resolution gas chromatography/high-resolution mass spectrometry, and

must have been trained to review such data in accordance with EADís general data review guidelines. 

This reviewer also must have read and understood the performance criteria and MQOs applicable to this

study.

6.0 DOCUMENTATION AND RECORDS

Only documentation and records relevant to sample preparation, analysis and data review are

discussed in this section. Documentation and records related to sample collection can be found in

reference [3].

6.1 Sample Preparation Laboratory Records

Sample preparation laboratories will be asked to document information on sample preparation log

forms to be prepared by SCC. Documentation related to sample preparation includes:

ï Standard operating procedure for sample preparation, compositing, homogenization and

shipment.

ï Sample preparation records documenting the following information for each composite sample

prepared: 

< arrival time of fish samples;

< description of shipment upon arrival;

< person filleting, homogenizing, and preparing composite sample;

< information about individual fish included in samples used to prepare the composite;

< Five-digit EPA sample number (as assigned by SCC, see Section 6.3, Data Compilation,

Review, and Validation Records);

< sub-sample aliquots generated from the composite sample;

< sample preparation time;
National Fish Study Analytical QAPP September 2000 17

< shipment date and destination of samples; and 

< relevant observations made during sample preparation.

ï ìTraffic reportsî documenting shipment of samples to analytical laboratories. (Traffic reports are

standardized, EPA-generated sample tracking forms.)

6.2 Analytical Laboratory Records

All laboratories involved in this study will at a minimum be required to do the following with

respect to documentation and record keeping:

ï Submit summary reports of all analytical results. These summary reports must be provided in

both hard copy and electronic format.

ï Submit hard copies of all raw data. Raw data will include items such as quantitation reports, strip

charts, spectra, bench sheets, and laboratory notebooks showing tare and sample weights, and

sample volumes. Raw data also will include any other information that would allow an

independent reviewer to verify the calculations performed and trace the final results to the raw

data. Laboratories will be required to clearly identify each data element in their data package(s).

ï Submit a written report that details any problems encountered during analysis of the samples. 

The written report also should include comments on the performance of any part of a method.

ï Obtain pre-approval of any modifications to the analytical techniques specified and submit

detailed explanations of the changes implemented.

ï Report results consistently in the reporting units (e.g., μg/kg, ng/kg, etc) specified in their

contract.

ï Submit chain-of-custody and other sample tracking information.

6.3 Data Compilation, Review and Validation Records

SCC will create and maintain a master study file, separate files for each ìepisodeî, and data

review files. For this study, an episode number will be assigned to each state for each sampling year. 

The field sampling teams will be using a field-assigned composite sample ID number to uniquely identify

each composite. SCC will assign a unique four-digit number to each episode; this episode number will be

used by EPA, the laboratories, and SCC to reference all sampling events collected by the state during that

year. In addition, SCC will provide the Sample Preparation Laboratory with a series of five-digit EPA

sample numbers that will be assigned to each sample after compositing and aliquotting. These five-digit

EPA sample numbers will be linked to the field-assigned fish composite sample identification numbers

and used by the Sample Preparation Laboratory, the analytical laboratories, SCC, and EPA to identify

each sample analyzed during the study. SCC also will provide the Sample Preparation Laboratory with a

list of analytical laboratories and EPA ìtraffic reportsî for use in documenting and shipping samples to

the analytical laboratories.

Cumulatively, the master file, the episode files, and the data review files will contain the

following records:

ï A copy of this QAPP, the sample collection activity QAPP, and the study design document;

ï A copy of each laboratory statement of work;

ï A summary page that documents the Episode Number, the sample numbers assigned to the

Episode, the laboratories that will be analyzing each sample, the EPA contract number under

which these analyses are being performed, and the date of sample collection and shipment;
September 2000 National Fish Study Analysis QAPP 18

ï The name, address, phone number and primary contact of each laboratory preparing and

analyzing samples in the episode;

ï A copy of each traffic report prepared and sent with each sample;

ï A list that cross-references the composite sample identification number assigned to each sample

by the sample collection team against the five-digit EPA sample numbers assigned by the Sample

Preparation Laboratory after homogenization, compositing, and aliquotting;

ï A log of all verbal communication with laboratory staff, sample coordinators, sampling

personnel, and EPA staff regarding the status or problems with the study;

ï Copies of all written correspondence with laboratory staff, sampling personnel, and EPA staff

regarding the study;

ï All records submitted by the sample preparation and analytical laboratories;

ï Complete records regarding the data review process, including a final copy of any written data

review assessments and the final data submission from each laboratory; and

ï A database of final analytical results associated with each field sample.

SCC will provide copies of the final laboratory summary reports, copies of any data review

assessments, and a copy of the final database to EPA EAD after the data reviews are complete. SCC will

retain the master file, each episode file, and complete copies of each laboratory data submission. SCC

will provide copies of these materials on an as-needed basis to EPA upon request.

7.0 SAMPLING PROCESS DESIGN

Because not all lakes in the continental US can be sampled with the available resources, the

approach for this study is to select a statistically representative sample from a target population of lakes. 

Trends in fish contamination levels for all water bodies will then be inferred from data collected from the

subset of lakes and reservoirs that are visited. The target population of lakes was generated using River

Reach File Version 3 (RF3). To ensure the target population included all lakes and reservoirs with an

area greater than 5,000 hectares (ha), a list from multiple sources of such lakes was constructed. The list

was sent to USEPA Regional Offices and subsequently to each state to verify that each lake on the list

was greater than 5,000 ha and to add any lakes greater than 5,000 ha that were not on the list. The

corrected list of lakes was integrated into the RF3 list of lakes before sample selection was completed. 

Lakes in the target population were classified according to six size categories, with 1-5 ha and

>5000 ha being the smallest and largest size categories, respectively. Of the 270,761 lakes in the target

population, 172,747 belong to the 1-5 ha size category but only 241 are larger than 5000 ha. However,

lakes larger than 5000 ha comprise approximately 40% of the total lake surface area, while the smaller

lakes make up only 5%. If a simple random sample were selected from this target population, it is quite

likely that the small lakes would dominate the sample, and that little information would be obtained from

large lakes. To address this problem, lakes of different size categories were sampled with varying

inclusion probabilities, with higher probabilities or weights assigned to the larger lakes so that the

resulting random sample would have approximately the same number of lakes from each size category. A

list of 900 randomly selected lakes was generated from the target population for sampling during the

study. This represented 225 lakes per year with a total of 150 lakes in each of the six size categories of

lakes included in the stratified random sampling design. The number of sites to be sampled during the

study has been adjusted to the current target of 500 lakes to respond to resource constraints. This

represents 125 lake per year and a total of about 80 lakes in each size category. A reserve sample set also
National Fish Study Analytical QAPP September 2000 19

was generated in case an inordinate number of the lakes in the initial sample do not meet the study

definition of a lake or cannot be accessed.

Further details regarding the study design and lake selection process can be found in the study

design document [2] and sample collection activity QAPP [3].

8.0 SAMPLING METHOD REQUIREMENTS

Sampling method procedures and requirements are detailed in the QAPP for sample collection

[3]. Some of the key requirements are summarized below.

8.1 Target Species and Sample Type

A list of preferred target predator and bottom-dwelling species has been developed for this

study.[3] Following the recommendations of EPA's guidance for fish sampling in support of fish

advisories [7], the primary criteria for selecting target fish for the National Fish Tissue Study are that the

species: (1) are commonly consumed in the study area, (2) may potentially accumulate high

concentrations of chemicals, and (3) have a wide geographic distribution. Secondarily, the target species

should be: (1) easy to identify, (2) abundant, (3) easy to capture, and (4) large enough to provide adequate

tissue for analysis.

The National Fish Tissue Study will focus on two distinct ecological groups of fish as target

species: bottom-dwellers and predators. This permits monitoring of a wide variety of habitats, feeding

strategies, and physiological factors that might result in differences in bioaccumulation of contaminants. 

A list of suggested target species (adapted from [7]) are listed in the study design document [2] and

sample collection activity QAPP [3]. 

Regional, state, and tribal personnel, with their knowledge of site-specific fisheries and human

consumption patterns, will aid in determinating the availability of target fish within their states. 

Additional target species may be added to the list of preferred targets on an as-needed basis. For

example, additional Salmonid species (such as Cutthroat trout or Kokanee salmon) and Catostomid

species (such as Longnose sucker, Largescale sucker, or Bridgelip sucker) may need to be added to the

target species for lakes of the northwestern United States. The criteria listed above must be considered

when selecting target species other than those listed in the study design document [1]. Every effort will

be made to collect the desired species and number of fish; however, the outcome of field sampling efforts

will ultimately depend on the natural diversity and abundance of fish in the study lakes.

Composite samples of fish fillets (for predator species) and whole fish (for bottom-dwelling

species) will be collected from each sample lake. Ideally, at least five individuals per composite will be

collected; a larger number can be collected if needed to provide the composite sample mass to do all the

required analyses (~560 g).

Organisms used in a composite sample must:

< be of the same species;

< satisfy any legal requirements of harvestable size or weight, or at least be of consumable

size if no legal harvest requirements are in effect;

< be of similar size so that the smallest individual in a composite is no less than 75 percent

of the total length of the largest individual; and
September 2000 National Fish Study Analysis QAPP 20

< be collected at the same time (i.e., collected as close to the same time as possible but no

more than 1 week apart). Note: This assumes that a sampling crew was unable to collect

all fish needed to prepare the composite sample on the same day. If organisms used in

the same composite are collected on different days (no more than 1 week apart), they

should be frozen until all the fish to be included in the composite are delivered to the

laboratory. At that time, the composite homogenate sample may be prepared.

Individual organisms used in composite samples must be of the same species because of the

significant species-specific bioaccumulation potential. Accurate taxonomic identification is essential in

preventing the mixing of closely related species with the target species. Under no circumstance should

individuals from different species be used in a composite sample. Ideally, the target species composite

should focus on the larger individuals commonly harvested by the local population. 

8.2 Sample Collection Methods

Sampling teams dedicated to the National Fish Tissue Study will be equipped with an array of

both active and passive gears to ensure the collection of the target numbers and species of fish. For a

detailed description of sample collection methods, refer to the sample collection activity QAPP [3].

8.3 Sampling Period

The field sampling period generally will begin in August and last through November (and

possibly into December in warmer regions).
National Fish Study Analytical QAPP September 2000 21

9.0 SAMPLE HANDLING AND CUSTODY REQUIREMENTS

Chain of custody forms will be used for sample documentation and tracking from the field to the

sample preparation laboratory. Detailed sample handling and custody requirements are given in sections

9.1 and 9.2. Briefly, they are as follows:

ï Field teams will use field record forms and chain of custody forms to document information

about each set of samples collected. Field teams will assign a unique 10-digit number to each

composite. This number will be coded to reflect the state (2-characters), lake (4 digits),

composite type (P=predator or B=bottom dweller), sample type (S=standard or D=duplicate), and

year (2 digits) in which the sample was collected.

ï After scaling, filleting, and compositing samples according to documentation provided by the

field teams, the Sample Preparation Laboratory will create a new set of tracking paperwork for

each laboratory that receives composite aliquots. This paperwork will be based on the use of 5-

digit EPA sample numbers that provide no information about the sample identity. It also will

include EPA Traffic Report forms, which are carbonless, multi-copy forms to facilitate sample

tracking. The Sample Preparation Laboratory will forward a copy of this form to SCC for sample

tracking and permanent record keeping.

ï Laboratories will document the date and condition of sample at the time of receipt on their copies

of the Traffic Report, and will return one copy to SCC for sample tracking and permanent record

keeping.

ï SCC will follow up with each scheduled recipient to verify that samples are received on time in

good condition and will maintain a complete record of all sampling documentation.

Field personnel are responsible for properly identifying the samples as described below. Laboratory

personnel are responsible for processing the samples as described below. All parties involved in sample

handling and processing are responsible for using protocols designed to preclude contamination.

9.1 Field Requirements

A more comprehensive description of field sample handling requirements can be found in the

QAPP for sample collection [3]. Key requirements are summarized below.

Species should be identified by experienced personnel as soon as fish are removed from the

collection device. Non-target species or specimens of target species that do not meet size requirements

will be returned to the water. Individuals of the selected target species will be rinsed in ambient water to

remove any foreign material from the external surface. Each fish within the selected target species will be

measured to determine total body length (mm). After initial processing, each fish found to be suitable for

the composite sample will be assigned a specimen number that can range from 01 to 05. This number will

identify each fish within its respective composite. A ten-character composite sample identification

number consisting of the two-character state abbreviation, two-number year abbreviation, four-digit lake

identification number, composite type (ìPî or ìBî for predator or bottom species), and sample type (ìSî

or ìDî for standard or duplicate) will be assigned by the field teams for each composite collected. The

composite sample specimen number, and information regarding the fish specimens will be recorded on

the field record forms.

Each fish selected for the composite sample will be individually wrapped in cleaned (rinsed in

methylene chloride and dried at 450°C for a minimum of one hour) extra heavy duty aluminum foil. Each

individually wrapped fish will be placed into food-grade plastic tubing and sealed on each end with 
September 2000 National Fish Study Analysis QAPP 22

a nylon cable tie. The fish sample identification label containing the specimen number, composite sample

identification number, lake, and date of collection will be attached to the outside of each sample using one

of the nylon cable ties used to seal the plastic tubing. All of the foil-wrapped and plastic tubing-sealed

specimens intended for a composite sample will be kept together when possible in a large plastic bag in

the same shipping container (ice chest) for transport. The sample preparation laboratories may not have

personnel who can distinguish between predator and bottom-dwelling species, thus the field sampling

team is responsible for indicating which samples will be filleted before homogenization. The field

sampling team will accomplish this task by using a ìPî or ìBî as the second to the last digit in the

composite number on the chain of custody form. Samples designated with a ìPî are to be filleted, while

those designated with a ìBî are to be homogenized whole.

Once packaged, samples should be placed on dry ice for shipment. The sampling personnel must

ship the samples with enough dry ice to ensure temperatures of <-20o

C during shipment. Dry ice

sublimes at a rate of approximately 1⁄2 lb per hour. Therefore, a minimum of 24 lbs of dry ice is

recommended to ensure that the fish remain frozen for a 48 hour period, in case of shipping problems. If

space, funds, and logistics permit, 36 lbs of dry ice is preferred. Samples will be shipped via Federal

Express, using priority overnight service. In addition, a member of the field staff should telephone SCC

to alert them to the anticipated delivery time of the samples. Field collection staff should avoid shipping

samples for weekend delivery to the processing laboratory unless prior plans for such a delivery have

been agreed upon with the laboratory.

Field sampling teams will ship field record forms to the sample preparation laboratory and the

sample preparation laboratory will distribute the field record forms to the sampling coordinators at

EPA/SASD, SCC, and Tetratech. After receiving shipping information from the field sampling team,

SCC will document the information in the episode file and notify the recipient laboratory of the

anticipated shipment. On the day that samples are scheduled to arrive, SCC will again contact the

laboratory to confirm that samples arrived on schedule and in good condition.

9.2 Laboratory requirements

9.2.1 Sample Preparation Laboratories

Upon receipt of the fish samples, the Sample Preparation Laboratory will record the arrival time

on the chain of custody form. Any observations regarding the shipment (e.g., torn or damaged packaging,

insufficient dry ice) also will be documented on the chain of custody form, as well as on the sample

preparation records (see Section 6.1).

The sample preparation laboratory will decontaminate any filleting instruments and surfaces as

appropriate. The Sample Preparation Laboratory will weigh the fish, rinse with distilled water, scale and

fillet as appropriate, homogenize, and composite fish samples following procedures that will detailed in

each laboratoryís contract SOW. As mentioned previously, the field sampling team should have

indicated on fish sample labels and the chain-of-custody forms which fish require filleting prior to

homogenization. All samples requiring compositing will be composited using the ìbatchî method, in

which all of the individual specimens that comprise the sample are homogenized together, regardless of

each individualís proportion to one another (as opposed to the ìindividualî method, in which equal

weights of each specimen are added together). 
National Fish Study Analytical QAPP September 2000 23

After compositing, the Sample Preparation Laboratory will prepare one 60-gram aliquot (for

semi-volatile organics), one 100-gram aliquot (for PCBs and dioxins/furans), and several 50-g aliquots

(for determination of all remaining analytes and to yield extra volume for subsequent study or if samples

are lost in transit). The exact number of aliquots to be prepared from each composite sample will be

defined in the Sample Preparation Laboratory contract. Each aliquot will be placed in an appropriately

pre-cleaned glass jar with a FEP-lined cap. The Sample Preparation Laboratory will label each sample

container with the five-digit composite sample number (assigned by SCC). The Sample Preparation

Laboratory also will document the sample number and the associated episode number (to be provided by

SCC) on the EPA traffic report. 

The Sample Preparation Laboratory will ship sample containers by Federal Express priority

overnight service to the analytical laboratories in dry ice. These containers must be packaged in such a

way as to prevent breakage and with enough dry ice to ensure temperatures are <-20°C during shipment. 

Samples also must be shipped in accordance with local, state and federal regulations. Immediately after

shipping samples, the Sample Preparation Laboratory will notify SCC of the number of samples shipped,

the package tracking number(s), the designated recipient(s), and the anticipated arrival date. The Sample

Preparation Laboratory will retain one copy of the EPA traffic report and forward one copy to SCC. The

remaining two copies will be shipped along with the samples to the analytical laboratories. After

receiving shipping information from the Sample Preparation Laboratory, SCC will document the

information in the episode file and notify the recipient laboratory of the anticipated shipment. On the day

that samples are scheduled to arrive, SCC will again contact the laboratory to confirm that samples

arrived on schedule and in good condition.

The Sample Preparation Laboratory will store any left-over composite sample in a labeled

solvent-rinsed glass jar with a foil-lined plastic cap. The sample must be maintained at -20°C until

archival in EPAís sample repository. Additional requirements related to sample preparation will be

contained in the Sample Preparation Laboratory contract.

9.2.2 Analytical Laboratories

Upon receipt of samples from the Sample Preparation Laboratory, the analytical laboratories will

sign and date the EPA traffic reports, retain one copy and return one copy to SCC to document the date

and condition of samples upon receipt. Following receipt of samples at the analytical laboratories, SCC

staff will maintain communication with laboratory personnel throughout the duration of analysis. The

purpose of this communication is to promptly identify, resolve, and document any problems that arise

during the course of analysis. In the event that samples are lost or damaged in transit, SCC will work

with the laboratories, EPA, field personnel, and/or the shipping carrier to resolve the problem. SCC will

document any such problems and resolutions in the episode file.

The analytical laboratories will be required to store all samples and sample aliquots at -20o

 C

prior to analysis. Additional sample handling requirements will be detailed in the laboratory contracts.

10.0 ANALYTICAL METHODS REQUIREMENTS

As indicated in Table 1, most of the target analytes can be measured using existing 1600-series

EPA methods adapted to the analysis of fish tissues through the application of appropriate

digestion/extraction procedures and extract clean-up techniques. Modifications of these methods to

extend their applicability to fish tissue matrices will be written before the analytical phase of this study is
September 2000 National Fish Study Analysis QAPP 24

initiated. Where possible, analytes for which no established EPA methods exist will be measured using

current literature techniques modified to include the 1600-series QA/QC elements (see Section 11.0). If

necessary, more extensive method development will be pursued after a comprehensive literature search

and consultation with experts in the specific area of interest. All method modifications will be tested

prior to use in the study, and formal validation efforts will be employed for newly developed procedures. 

Method performance criteria specific to fish tissue matrices will be obtained either from existing QC data

(such as for methods used in the Cook Inlet Study), or from single-laboratory validation studies to be

completed before the analytical phase of this study is initiated. Where feasible, method testing and/or

development of performance criteria will be performed in accordance with the procedures described for

single laboratory (Tier 1) use in OWís PBMS initiative.

Sections 10.1 through 10.8 below summarize the methodologies that EPA expects to use in the

National Fish Tissue Study.

10.1 Organohalide Pesticides

The target organohalide pesticides listed in Table 1 and total PCB aroclors will be analyzed by

Method 1656, Revision A (Organo-Halide Pesticides in Wastewater, Soil, Sludge, Sediment, and Tissue

by GC/HSD). These modifications were successfully employed by EPA during the 1997/1998 Cook Inlet

Contaminant Study. Analysis of the target pesticides in fish tissue samples by Method 1656 involves the

following steps: (1) drying a 10-g aliquot of a homogenized fish tissue sample with sodium sulfate, (2)

soxhlet extraction of the dried fish sample using 1:1 methylene chloride/hexane as the extraction solvent,

(3) drying with sodium sulfate and concentration of the extract to dryness (to measure lipid content) using

a Kuderna-Danish and nitrogen blow-down techniques, (4) re-dissolution of the extract and lipid removal

by gel-permeation chromatography and/or solid-phase extraction (SPE cartridges), (5) reconcentration of

the extract using Kuderna-Danish and nitrogen blow-down techniques, and (6) quantification of the target

analytes in the extract using a gas chromatograph equipped with dual capillary columns and electron

capture detector. Analyte identification is performed by comparing the GC retention times of each

analyte on two different columns with the respective retention times of an authentic standard. 

Quantitative analysis (e.g., determining the concentration of each analyte) is performed using an authentic

standard to produce a calibration factor or calibration curve, and using the calibration data to determine

the concentration of a pollutant in the extract. The analyte concentration in the fish tissue sample can be

calculated on a mass basis (i.e., relative to the mass of the sample extracted), or lipid basis (i.e., relative to

the lipid content of the sample extracted).

10.2 Organophosphorus pesticides

The target organophosphorus pesticides listed in Table 1 will be analyzed by EPA Method 1657,

Revision A (Organo-Phosphorus Pesticides in Water, Soil, and Tissue by GC/FPD). Analysis of the

target PCB congeners in fish tissue samples by Method 1657A involves the following steps: (1) drying a

10-g aliquot of a homogenized fish tissue sample with sodium sulfate, (2) soxhlet extraction of the dried

fish sample using 1:1 methylene chloride/hexane as the extraction solvent, (3) drying with sodium sulfate

and concentration of the extract to dryness (to measure lipid content) using a Kuderna-Danish and

nitrogen blow-down techniques, (4) re-dissolution of the extract and lipid removal by gel-permeation

chromatography and/or solid-phase extraction (SPE cartridges), (5) reconcentration of the extract using

Kuderna-Danish and nitrogen blow-down techniques, and (6) quantification of the target analytes in the

extract using a gas chromatograph equipped with dual capillary columns and flame photometric detector.
National Fish Study Analytical QAPP September 2000 25

 Analyte identification is performed by comparing the GC retention times of each analyte on two different

columns with the respective retention times of an authentic standard. Quantitative analysis (e.g.,

determining the concentration of each analyte) is performed using an authentic standard to produce a

calibration factor or calibration curve, and using the calibration data to determine the concentration of a

pollutant in the extract. The analyte concentration in the fish tissue sample can be calculated on a mass

basis (i.e., relative to the mass of the sample extracted), or lipid basis (i.e., relative to the lipid content of

the sample extracted).

10.3 Dioxins/Furans

Dioxins/furans will be analyzed by EPA Method 1613, Revision B (Tetra- through OctaChlorinated Dioxins and Furans by Isotope Dilution HRGC/HRMS), EPA821-B-94-005). The method

yields results for seventeen 2,3,7,8-substituted CDDs and CDFs. 

Determination of dioxins/furans in tissue samples by Method 1613 involves the following steps: 

(1) drying a 100-g aliquot of a homogenized fish tissue sample with sodium sulfate, (2) spiking the dried

fish sample with a labeled standard solution, (3) extraction either by soxhlet extraction using 1:1

methylene chloride/hexane as the extraction solvent, or acid digestion using hydrochloric acid and 1:1

methylene chloride/hexane (3) drying with sodium sulfate and concentration of the extract to dryness (to

measure lipid content) using a Kuderna-Danish and nitrogen blow-down techniques, (4) re-dissolution of

the extract and lipid removal by passing the extract through a layered column of silica gel, potassium

silicate, and acid silica gel, (5) further clean-up of the extract using back-extraction with a strong base,

acid and/or sodium chloride solution, gel-permeation chromatography, silica gel, alumina, or Florisil

chromatography, (6) reconcentration of the extract using Kuderna-Danish and nitrogen blow-down

techniques, and (7) quantification of the target analytes in the extract using a gas chromatograph equipped

with a high-resolution mass spectrometer. Analytes are identified by comparing retention times and ion

abundance ratios at two m/zís with authentic standards. Concentrations are calculated from selected ion

current profile areas using either an isotope dilution or internal standard technique. The efficiency of the

clean-up process is monitored by spiking the extract prior to clean-up with a labeled standard (37Cl4-

labeled 2,3,7,8-TCDD) and tracking the final recovery of this standard. The analyte concentration in the

fish tissue sample can be calculated on a mass basis (i.e., relative to the mass of the sample extracted), or

lipid basis (i.e., relative to the lipid content of the sample extracted).

10.4 Polychlorinated Biphenyls

The polychlorinated biphenyl (PCB) congeners in Table 1 will be analyzed by EPA Method

1668, Revision A (Chlorinated Biphenyls Congeners in Water, Soil, Sediment, and Tissue by

HRGC/HRMS , EPA-821-R-00-002). The method yields results for 167 PCB congeners, and although

twelve congeners designated as toxic by the World Health Organization (WHO) were selected as target

analytes of interest in the National Fish Tissue Study, EPA will collect all of the data generated by the

method. 

Analysis of the target PCB congeners in fish tissue samples by Method 1668 involves the

following steps: (1) drying a 10-g aliquot of a homogenized fish tissue sample with sodium sulfate, (2)

spiking the dried fish sample with a labeled standard solution, (3) soxhlet extraction of the dried fish

sample using 1:1 methylene chloride/hexane as the extraction solvent, (3) drying with sodium sulfate and

concentration of the extract to dryness (to measure lipid content) using a Kuderna-Danish and nitrogen

blow-down techniques, (4) re-dissolution of the extract and lipid removal by passing the extract through a
September 2000 National Fish Study Analysis QAPP 26

layered column of silica gel, potassium silicate, acid silica gel, (5) further clean-up of the extract using

back-extraction with a strong base, acid and/or sodium chloride solution, gel-permeation chromatography,

silica gel, carbon, or Florisil chromatography, (6) reconcentration of the extract using Kuderna-Danish

and nitrogen blow-down techniques, and (7) quantification of the target analytes in the extract using a gas

chromatograph equipped with a high-resolution mass spectrometer. Analytes are identified by comparing

retention times and ion abundance ratios at two m/zís with authentic standards. Concentrations are

calculated from selected ion current profile areas using either an isotope dilution or internal standard

technique. The efficiency of the clean-up process is monitored by spiking the extract prior to clean-up

with labeled standards (PCBs 81 and 111) and tracking the final recovery of these standards. The analyte

concentration in the fish tissue sample can be calculated on a mass basis (i.e., relative to the mass of the

sample extracted), or lipid basis (i.e., relative to the lipid content of the sample extracted).

10.5 Semi-Volatile Organics

The remainder of the target organic pollutants will be analyzed by EPA Method 1625, Revision C

(Semi-volatile Organic Compounds by Isotope Dilution GCMS). Analysis of the target pollutants by

Method 1625 will involve 1) homogenizing and spiking isotopically labeled analogs of each target

compound into the sample, 2) extracting the sample at pH 12-13 and then at pH <2 with methylene

chloride using continuous extraction techniques, 3) drying each extract over sodium sulfate, 4)

concentrating the extract to five mL, 5) cleaning the extract with gel permeation chromatography, 6)

concentrating the extract to 0.5 mL, 7) adding internal standards to the extract, and 8) injecting a one :L

aliquot of the extract into a gas chromatograph (GC). The compounds are then separated by GC and

detected by a mass spectrometer (MS). The labeled compounds serve to correct the variability of the

analytical technique. Compound identification is performed by comparing mass spectrum and retention

time to calibration standards (for most analytes) or through reference libraries through forward search or

reverse search techniques. Quantitative analysis is performed in one of three ways using extracted ion

current profile (EICP) areas: 1) for compounds in which standards and labeled analogs are available, the

concentration is determined using isotope dilution techniques, 2) for compounds in which standards are

available but labeled analogs are not, the concentration is determined using an internal standard

technique, and 3) for compounds in which neither standards nor known response factors are available,

concentrations are determined using the sum of the EICP areas relative to the sum of the EICP areas of

the internal standard.

10.6 Total Mercury

Total mercury (Hg) will be analyzed by EPA Method 1631, Revision B (Mercury in Water by

Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence Spectrometry) and its Appendix

(Digestion Procedures for the Determination of Total Mercury in Tissues, Sludge, Sediments, and Soils).

Procedures given in the appendix were successfully employed during EPAís 1997/1998 Cook Inlet

Contaminant Study. They also were validated in a separate 1999 study conducted by EPA EAD. 

Analysis of total Hg in fish tissue samples by Method 1631 will involve the following steps: (1) a 0.5 to

1.5 gram of tissue sample is digested and refluxed with 10 mLs concentrated nitric acid, (2) the digestate

is diluted to volume (50 or 100 mL) with 0.02N BrCl to ensure complete oxidation of methyl mercury, (3)

aliquots of the diluted digestate are pipetted into pre-purged SnCl2-containing water, (4) Hg(0) is purged

from solution onto a gold trap, and (5) Hg(0) is thermally desorbed from the gold trap and transferred to a
National Fish Study Analytical QAPP September 2000 27

cold vapor atomic fluorescence spectrometer for quantification. The analyte concentration in the fish

tissue sample is calculated on a mass basis (i.e., relative to the mass of the sample extracted).

10.7 Arsenic Speciation

The National Fish Tissue Study will include the determination of arsenic (III), arsenic (V),

monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), and inorganic arsenic in fish tissue

samples. These species, along with total inorganic arsenic, will be determined by Method 1632, Revision

A (Chemical Speciation of Arsenic in Water and Tissue using Hydride Generation Quartz Furnace

Atomic Adsorption Spectrometry). (Although it is commonly found in fish, arsenobetaine will not be

targeted in the study because of its low toxicity to fish and humans.) Method 1632A reflects procedures

developed by Battelle Laboratories and used in EPA's Cook Inlet Study (8). In this technique, arsenic

(III), arsenic (V), MMA, and DMA are volatilized from solution at a specific pH after reduction to the

corresponding arsines with sodium borohydride. The volatilized arsines are then swept onto a liquid

nitrogen cooled chromatographic trap which, upon warming, allows for a separation of species based on

boiling points. The released arsines are swept by helium carrier gas into a quartz cuvette burner cell,

where they are decomposed to atomic arsenic. Arsenic concentrations are determined by atomic

absorption spectroscopy. Strictly speaking, this technique determines the valence states of arsenate (V)

and arsenite (III) rather than the species of inorganic arsenic. The actual species of inorganic arsenic are

assumed to be those predicted by a geochemical equilibrium model.

11.0 QUALITY CONTROL REQUIREMENTS

All contaminant analyses performed in this study will be performed in conjunction with the

standard QC elements described in the EPA 600 and 1600 series methods. In developing these methods,

EPA sought scientific and technical advice from many sources, including EPAís Science Advisory Board,

scientists at EPAís environmental research laboratories, scientists in industry and academia, and

scientists, managers, and legal staff at EPA Headquarters. The results of discussions held among these

groups was the standardized QA/QC approach that is an integral part of the 600- and 1600- series

methods. Over the years, these QA/QC requirements have been refined to reflect improvements in

environmental science and policy. The most current version of these QC elements include the following:

Procedural requirements:

ï Use of pure and traceable reference standards

ï Demonstration of instrument calibration and system performance.

ï Periodic calibration verification.

Sensitivity requirement:

ï Verification that the laboratory can achieve required MDLs and MLs

Precision and accuracy requirements:

ï Analysis of initial precision and recovery (IPR) samples to demonstrate the laboratory can

achieve precise and accurate results with the method prior to use on field samples. IPR samples

consist of a reference matrix spiked to a known level with the target analytes. The reference

matrix is chosen so that it matches the field samples (e.g., corn oil or powdered eggs for fish

samples). Accuracy is measured by the average recovery in the replicate IPR samples; precision

is measured by relative standard deviation (i.e., RSD = standard deviation/mean) of the measured

levels in the IPR samples. 
September 2000 National Fish Study Analysis QAPP 28

ï Analysis of ongoing precision and recovery (OPR) samples to demonstrate continued laboratory

performance with the method. OPR samples are prepared in the same manner as the IPR samples.

ï Analysis of certified reference materials (CRM), where available.

ï Recovery of surrogate or labeled compounds, where available, spiked into the sample to assess

the effect of matrix interferences on compound identification and quantitation.

ï Duplicate matrix spike analyses (MS/MSD) to assess the effect of matrix interferences in nonisotope dilution methods

ï Calculation and monitoring of accuracy and precision using results from IPR, OPR and CRM

samples.

ï Absolute and relative retention time precision (for chromatographic analyses).

ï Analysis of blanks to demonstrate freedom from contamination.

All the methods to be used in this study will contain procedures for calculating each of the

required method performance statistics. To ensure acceptable analytical performance, method

performance criteria for new or modified methods will be established through validation studies on fish

matrices. These validation studies will be completed prior to the analytical phase of the National Fish

Tissue Study such that the performance criteria will be available to the laboratories before actual field

samples need to be analyzed. Table 2 summarizes the method performance statistics and how these will

be used to control data quality for this study.
National Fish Study Analytical QAPP September 2000 29

Table 2. Method performance criteria

Statistic Description Required frequency

Method Detection Limit

(MDL) and Minimum

Level (ML)

To be obtained following

procedures described in 40 CFR

part 136 Appendix B.

All laboratories participating in the study will

be required to do one MDL study per year on a

fish tissue matrix before the analysis of actual

field samples. The resulting MDL must

support the ML stated in the method. The

lowest standard used to calibrate the instrument

must be at or below the ML. 

IPR recovery Average measured concentration

or recovery of at least 4 replicate

IPR samples

All laboratories participating in the study will

be required to do one IPR study per year on a

reference matrix suitable for fish tissue once

before the analysis of actual field samples. The

IPR recovery and RSD must be within the

acceptable range given in the method.

IPR relative standard

deviation (RSD)

Standard deviation divided by

the average measured

concentration of at least 4

replicate IPR samples.

Labeled or surrogate

compound recovery

Recovery of labeled and

surrogate compounds spiked into

all samples; only applicable to

some methods.

Labeled and surrogate standards are spiked into

every sample analyzed. Recoveries must be

within the acceptable range given in the

method.

OPR recovery Measured concentration or

recovery of an OPR sample

(prepared in the same manner as

an IPR sample).

One typically required per analytical batch

(specific frequency provided in the methods). 

Recovery must be within the acceptable range

given in the method.

Matrix spike (MS)

recovery

Matrix spike (MS)

precision

Average recovery from duplicate

spiked field samples (MS/MSD)

RPD between measured

concentration in duplicate

spiked field samples (MS/MSD)

Laboratories will be required to spike in

duplicate 10% of each batch of samples

received for analysis. Laboratories will

determine specific samples to spike. Average

MS recoveries and RPDs must be within the

acceptable range given in the method.

Analytical precision

(includes sample

homogenization,

compositing, and

aliquotting)

RPD between duplicate analyses

of a composite sample.

Laboratories will be required to analyze in

duplicate 5% of the composite samples (to be

specified by SCC). The RPD of the duplicate

measurements must be less than 50% for

values greater than 5 times the MDL, and must

be less than 100% for values less than 5 times

the MDL.

The analytical variability in actual field samples will be assessed by the analysis of blind

composite duplicates on 5% of the samples (see Section 4.2.1).
September 2000 National Fish Study Analysis QAPP 30

12.0 INSTRUMENT/EQUIPMENT TESTING, INSPECTION, AND MAINTENANCE

REQUIREMENTS

Each laboratory participating in this study will be responsible for testing and inspecting the

equipment used in this study. The laboratories also will be responsible for implementing preventative and

corrective maintenance necessary to produce precise and accurate data that meets the measurement

quality objectives listed in this QAPP. Specific requirements for maintaining the equipment at each

laboratory will be documented in the laboratory QA plans used during the course of this study. Specific

records of preventative maintenance, problems, and corrective actions will be documented by each

laboratory in instrument log-books maintained on-site in the laboratory. These logbooks will be

periodically reviewed by a laboratory manager/supervisor and will be available to an external audit team

upon request.

13.0 INSTRUMENT CALIBRATION AND FREQUENCY

All laboratories supporting this study will be required to calibrate instruments used in the study

prior to analysis of field samples and to periodically verify calibration during the course of the study. 

Calibration standards used by the laboratories will need to be certified as to purity, concentration, and

authenticity, or prepared from materials of known purity and composition. Detailed instrument

calibration procedures will be specified in each of the analytical methods or laboratory contracts.

All methods employed in this study require a multi-point calibration prior to use of the instrument

for analysis of field and QC samples. The frequency of this initial, multi-point calibration varies across

methods due to variations in instrument stability and calibration procedures. While some methods, such

as those that employ atomic absorption (AA) spectroscopy, require daily calibration of the instrument,

other methods, such as those that employ GC/MS, require the instrument to be calibrated only if the

calibration verification standard fails to meet pre-defined acceptance criteria. All methods require the

laboratory to verify instrument calibration at least once per working shift during which samples are

analyzed. Because the stability of instruments vary by instrument type, the length of an allowable

working shift varies and is specified in each method.

14.0 INSPECTION/ACCEPTANCE REQUIREMENTS FOR SUPPLIES AND CONSUMABLES

The laboratories participating in this study will not be providing supplies or consumables to EPA. 

Contract laboratories that consume materials (e.g., chemical standards, equipment) during the course of

sample preparation and analysis will be required to adhere to the inspection and acceptance requirements

outlined in the contracts and their approved Quality Assurance Project Plans. Each contract will stipulate

that the laboratory have a comprehensive QA program in place and operating at all times during the

performance of their contract, and that in performing laboratory work for this study, they shall adhere to

the requirements in the analytical methods specified for the study, to EPA Requirements for Quality

Assurance Project Plans for Environmental Data Operations and the general laboratory procedures

specified in the Handbook for Analytical Quality Control in Water and Wastewater (EPA-600-4-79-019). 

Cumulatively, these sources provide guidelines concerning laboratory inspection and acceptance of

chemical standards.
National Fish Study Analytical QAPP September 2000 31

15.0 REQUIREMENTS FOR ACQUISITION OF NON-DIRECT MEASUREMENT DATA

The analytical phase of this study will not involve the collection of data obtained from nonmeasurement sources such as computer databases, spreadsheets and programs, and literature files.

16.0 DATA MANAGEMENT

Data management practices employed in this study will be based on standard data management

practices used by EADís Analytical Methods Staff (AMS). The data management (i.e., sample tracking,

data tracking, data inspection, data quality assessment, database development) procedures employed by

EAD are routinely used to support the development of effluent limitation guidelines and standards and

have regularly been applied to other technical studies. These procedures are being employed because

they are effective, efficient, and have successfully withstood repeated internal and external audits,

including internal review by the Quality Assurance Division, public review and comment, judicial

challenge, and the Government Accounting Office audit. These procedures, as implemented for the

National Fish Tissue Study, are summarized below.

16.1 Laboratory Data Management

Laboratory data management procedures will be detailed in individual contracts for all

laboratories selected to participate in the National Fish Tissue Study. Briefly, they will include the

following:

ï Each laboratory participating in this study will be required to maintain all records and

documentation associated with the preparation and analysis of Lake Fish Study samples for a

minimum period of five years after completion of the study.

ï To facilitate data tracking, each laboratory will be required to use EPA-assigned episode and

sample numbers when reporting results.

ï All results of sample analyses, labeled and native standards, surrogate compounds, spike

compounds, and blanks must be reported on hard copy and on electronic media.

ï All required reports and documentation, including chromatograms and mass spectra, must be

sequentially paginated and clearly labeled with the laboratory name, contract number, episode

number, and associated EPA sample numbers. Any diskettes, or other electronic media submitted

must be similarly labeled.

ï Unless otherwise approved, the laboratories will use the hard copy reporting forms and automated

data reporting formats specified in the contract when reporting data.

ï Each of the laboratories will adhere to a comprehensive data management plan that is consistent

with the principles set forth in Good Automated Laboratory Practices, EPA Office of

Administration and Resources Management, October 10, 1995. This data management plan must

be in place and in use at all times during performance of the contracts. 

16.2 SCC Data Management

Data management procedures employed by SCC will include the use of 1) an automated

scheduling and tracking system to effectively manage data review and database development activities, 2)

standardized data review guidelines to promote consistency in data quality audits across reviewers and

over time, 3) a multi-stage data review process designed to maximize the amount of useable data
September 2000 National Fish Study Analysis QAPP 32

generated in each study, and 4) a standardized database development process that facilitates rapid

development of a database with at least 99.9% accuracy.

The automated sample scheduling and tracking system will facilitate development of up-to-date

information concerning work in progress, projected delivery dates, and notice of any problems

encountered with laboratory analyses or data turnaround times. To ensure that this information is as

complete and accurate as possible, entries will be made into the tracking system at each stage of the

sample-to-data sequence.

Standardized data review guidelines will be used in this study to facilitate rapid, consistent,

accurate, and thorough data quality audits. Data review guidelines already have been developed and are

in use for a variety of analyses performed under EPA EAD programs. These guidelines detail methodspecific data review procedures for commonly used methods and more general procedures that can be

applied to less frequently used methods. Where appropriate, SCC will modify existing data review

guidelines as necessary to reflect the methods, method modifications, and data quality objectives for the

National Fish Tissue Study. Any modifications deemed to be necessary will be made in accordance with

the Quality Assurance Program Plan for the Environmental Protection Agency, Office of Water, Sample

Control Center (August 4, 1993 or subsequent updates, if applicable).

Although each guideline will be written for a specific method, technique, or group of analytes, all

guidelines will specify a general five-stage review process that will ensure data are in proper format, are

complete, are contractually compliant, and are usable. SCC chemists will use this multi-stage process to

verify the quality of each laboratory submission under the National Fish Tissue Study. If an error is

detected in any stage of the review, SCC staff will initiate corrective action procedures to obtain the

maximum amount of usable data from the study. These actions may serve to obtain missing data, correct

typographical or transcription errors on data reporting forms, or initiate reanalysis of field or QC samples

that do not meet the performance criteria for this study. 

Concurrent with the performance of data quality audits, SCC staff will begin developing a

database of combined field and analytical results. At a minimum, this database will be formatted in a

manner that is consistent with EAD effluent guidelines databases with modifications in the format

necessary to integrate field data. The database also will be compatible with STORET; data will stored on

a stand-alone PC version of STORET during the study and delivered to EPA upon study completion or at

requested intervals. Each record in the database will contain information pertaining to both a ìfield

sampleî and to an ìanalytical sampleî. At a minimum, each record should include fields containing the

following information:

ï Five-digit EPA sample number assigned by SCC;

ï 10-digit composite sample identification number assigned by field teams;

ï Sample type (indicates the type of sample, whether it was a composite, duplicate analysis of a

composite, matrix spike, etc);

ï Species;

ï Length of fish;

ï Method of collection (active or passive);

ï Sample collection date;

ï Lake from which fish samples in composite were collected;

ï Year fish samples in composite were collected (1999, 2000, 2001, 2002);
National Fish Study Analytical QAPP September 2000 33

ï Ecological group (predator or bottom-dwelling);

ï EPA sample number of associated duplicate composite, if available;

ï Analyte levels; and

ï Lipid content measurements.

The data structure listed above for the integrated field and analytical database and the field

database (Section 16.1) will allow data users and reviewers to:

(1) Look up individual fish sample data in the database for a given composite sample

number.

(2) Extract analytical data from a given lake from the database.

(3) Extract fish sample data from a given lake from the database.

(4) Extract data from duplicate composite analyses to assess analytical variability.

(5) Extract data from duplicate composites (i.e., two composites collected from a lake within

the same sampling period) to assess population and analytical variability.

As with the data quality audits, a multi-stage process of inspections and corrective actions will be

used to facilitate timely, efficient construction of databases that are least 99.9% accurate. The database

development process will begin with a completeness check to verify the laboratory has submitted a

diskette and that the diskette contains all data in an appropriate format. If deficiencies are found,

appropriate corrective action measures will be initiated. After problems have been identified and

resolved, the SCC Database Administrator will prepare a ìQC Check Reportî that displays the results

submitted by the laboratory. The SCC chemist responsible for performing the data quality audit will

review this QC Check Report to verify that the electronic data accurately reflect the hard copy

submission. Accuracy will be confirmed by spot checking at least 10% of all results that were

downloaded directly from an analytical instrument in the laboratory and by performing a 100% QC check

of data that were manually entered by the laboratory or SCC. Corrective actions will be taken as needed

to resolve deficiencies. Following completion of the data quality audit, the SCC chemist and the

Database Administrator will modify the database to reflect data usability determinations. A report,

generated to reflect the modified database, will then be reviewed by the SCC chemist to verify database

accuracy before submission to EPA.

17.0 ASSESSMENTS AND RESPONSE ACTIONS

Each laboratory contract prepared to support this study will stipulate that the laboratory have a

comprehensive QA program in place and operating at all times during the performance of their contract,

and that in performing laboratory work for this study, they shall adhere to the requirements in the

analytical methods specified for the study, to EPA Requirements for Quality Assurance Project Plans for

Environmental Data Operations, the general laboratory procedures specified in the Handbook for

Analytical Quality Control in Water and Wastewater (EPA-600-4-79-019), and the data management

principles set forth in EPA 2185- Good Automated Laboratory Practices, EPA Office of Administration

and Resources Management, August 10, 1995. Cumulatively, these sources describe assessment and

response actions that should be implemented within the laboratory (e.g., bench level review of results and

calculations, independent surveillance by a QAO, periodic in-house audits, etc.).

Sections 17.1 - 17.7 describe other types of assessment activities and corresponding response actions

identified to ensure that data gathering activities in the National Fish Tissue Study are conducted as

prescribed and that the measurement quality objectives established in this QAPP and the performance

criteria defined for the study are met. These activities are summarized in Table 3.
September 2000 National Fish Study Analysis QAPP 34

17.1 Surveillance

An SCC Sample Scheduling Coordinator will been assigned to facilitate sample scheduling and to

track the location of samples and data throughout the study. During sample collection, the Sample

Scheduling Coordinator will maintain communication with field sampling coordinators and teams to

identify and notify the recipient Sample Preparation Laboratory of any delays or anticipated changes to

the sampling plan. In the event these delays or changes impact the laboratoryís contract or EPA

schedules, the Sample Scheduling Coordinator will notify the EPA Analytical Project Manager and work

with EPA, the sampling teams, and other SCC staff to identify and implement an appropriate solution.

When samples are shipped to the Sample Preparation Laboratory or the analytical laboratories,

the Sample Scheduling Coordinator will contact designated laboratory staff to notify them of the

forthcoming shipment(s) and request that they contact SCC if the shipments do not arrive intact as

scheduled. Within 24 hours of scheduled sample receipt, the Sample Scheduling Coordinator will contact

the laboratory to verify that the samples arrived in good condition, and if problems are noted, will work

with the laboratory, the sampling team, and EPA to resolve the problem as quickly as possible to

minimize data integrity problems.

The Sample Scheduling Coordinator also will communicate periodically with laboratory staff to

monitor the progress of sample preparation, analysis, and data reporting. If technical problems are

encountered during sample preparation and analysis, the Sample Scheduling Coordinator will discuss the

situation with SCC Study Coordinator. If warranted, the Study Coordinator will identify a technical

expert within SCC to assist in resolving the problem, work with the Scheduling Coordinator, the technical

expert, laboratory staff, and EPA to identify and implement a solution to the problem. If laboratories fail

to deliver data on time, or if the laboratories notify SCC of anticipated reporting delays, the Sample

Scheduling Coordinator will notify the Study Coordinator and the EPA Analytical Project Manager of the

situation. To the extent possible, the Study Coordinator will adjust schedules and shift resources within

SCC as necessary to minimize the impact of laboratory delays on EPA schedules. The Study Coordinator

also will immediately notify the Analytical Project Manager of any laboratory delays that are anticipated

to impact EPA schedules.

Finally, the SCC Study Coordinator will monitor the progress of the data quality audits (data

reviews) and database development to ensure that each laboratory data submission is reviewed in a timely

manner. In the event that dedicated staff are not able to meet EPA schedules, the SCC Study Coordinator

will work with the SCC Project Manager to identify additional resources who are qualified and capable of

reviewing the data in a timely manner. If such resources cannot be identified, and if training new

employees is not feasible, the SCC Project Manager will meet with the EPA Analytical Project Manager

to discuss an appropriate solution.
35

Table 3 - Assessment and Response Actions

Assessment

Measure

Definition Frequency Responsible Party 

Surveillance Continual or frequent monitoring and verification of the status of

an entity and the analysis of records to ensure that specifiedrequirements are being fulfilled

Throughout sample preparation, laboratoryanalysis, and data review procedures

SCC Sample Sched. &Study Coordinators

Identify and correct analytminimize delays; and to noearly as possible

Peer Review A documented critical review of work. Conducted by qualified

individuals who are independent, but technically equivalent ofthose who performed the work.

Performed on 5% of data audits conductedby SCC data reviewers and 100% of datareview narratives prepared by SCC datareviewers

SCC data reviewers notresponsible for originaldata review

Ensure that activities are teperformed, properly documand quality requirements.

Quality SystemAudit

Qualitative assessment of a data collection operation and/ororganization to establish whether the prevailing qualitymanagement structure, policies, practices, and procedures areadequate for ensuring that the type and quality of data needed areobtained.

Not scheduled during this study Not applicable Standard EAD/SCC proce

laboratory data in this studapproved following MSRs 

Readiness Review A systematic documented review of the readiness for the start-up

or continued use of a facility, process or activity. Typicallyconducted before proceeding beyond project milestones and priorto initiation of a major phase of work.

Prior to each laboratoryís analysis of fieldsamples collected during each year of thestudy.

Lab staff and SCC datareviewers 

Verify that laboratory is caresults with the method(s) 

Technical SystemsAudit

A thorough, systematic, on-site, qualitative audit of facilities,equipment, personnel, training, procedures, record keeping, datavalidation, data management, and reporting aspects of a system.

As needed basis only. TSAs are notrequired for this study unless specificconcerns are raised through discussionswith laboratory staff or during other dataassessment activities.

If TSAs are deemednecessary, they will beperformed by EPAProject Manager and/orEPA QAO, and SCCstaff

Ability of each laboratory will be assessed prior to ananalyses via other QA/QC 

Audit of DataQuality

Systematic and independent examination to determine if qualityactivities and related results comply with planned arrangementsand whether these arrangements are implemented effectively andare suitable to achieve objectives.

100% of laboratory data packagessubmitted

SCC Data Reviewers To verify that all data colle

study.

Data QualityAssessment

Statistical and scientific evaluation of the data set to determine thevalidity and performance of the data collection design andstatistical test, and to determine the adequacy of the data set forits intended use.

Upon completion of data review anddatabase development

SCC Staff and EPAData Users

Evaluate overall accuracy trends in field and QC resu
September 2000 National Fish Study Analytical QAPP 36

17.2 Peer Review

All laboratory results and calculations will be reviewed by the laboratory manager prior to data

submission. Any errors identified during this peer review will be returned to the analyst for correction

prior to submission of the data package. Following correction of the errors, the Laboratory Manager will

verify that the final package is complete and compliant with the contract, and will sign each data

submission to certify that s/he has reviewed the package and determined it to be in compliance with the

terms and conditions of the contract.

Peer reviews also will be performed within SCC to verify that the data quality audits are being

performed consistently over time and across peer reviewers, that the audit findings are technically correct,

and that the audits are being performed in accordance with this QAPP. These peer reviews of the SCC

data quality audit process will be performed on at least 5% of the data packages received in this study. 

Peer reviewers will be charged with evaluating the completeness of the original data review, the technical

accuracy of the reviewers findings, and the technical accuracy of the analytical database developed to

store results associated with the data package. The SCC Data Review Manager will be responsible for

identifying and assigning qualified peer reviewers and for selecting packages to be peer reviewed. 

Qualified peer reviewers will include any staff members that have been trained in SCC data review

procedures, that are experienced in reviewing data similar to those being reviewed, and are familiar with

the requirements of the National Fish Tissue Study and this QAPP. Data packages will be selected for

peer review in such a way as to maximize the number of data reviewers and types of data (e.g., pesticides,

dioxins, mercury, etc) that are subjected to this peer review process. To the extent possible, these peer

reviews will be performed after the primary data reviewer has drafted a written narrative describing the

results of his/her audit, but before this narrative is submitted to EPA.

To ensure the findings of each data quality audit are documented in a consistent and technically

accurate manner, SCC staff will peer review 100% of the data review summaries (narratives) prepared for

this study. Each data review summary will be subjected to at least two levels of peer review, and each

peer reviewer will be charged with evaluating the clarity, technical accuracy, and the grammatical quality

of the data review summary.

17.3 Quality Systems Audit

All data gathering procedures routinely used by EADís Analytical Methods Staff (AMS) will be

applied to the data gathering activities associated with this study. These standard AMS procedures have

been subjected to periodic Management Systems Reviews by external sources interested in assessing the

overall quality of EADís data collection operation. In every case, the external reviewers found AMSí

data gathering process to be technically sound.

Because the data gathered in the National Fish Tissue Study will be collected in accordance with

standard AMS protocols, and because these protocols have repeatedly withstood external reviews, EPA

has concluded that a formal Management Systems Review focused on the National Fish Tissue Study is

unnecessary.

17.4 Readiness Review

A readiness review of each laboratoryís capability to produce precise and accurate results with

the methods specified in this study will be performed before the laboratories are allowed to analyze field
National Fish Study Analytical QAPP September 2000 37

samples collected during the study. As part of the readiness reviews, the laboratories will submit data

demonstrating that they are capable of analyzing a known, reference matrix with the methods to be used

in this study. In most cases, laboratories will meet this requirement by performing IPR tests. IPR tests

consist of preparing four replicate aliquots that contain the target pollutants, analyzing these replicate

aliquots with the specified method, and calculating the average percent recovery and standard deviation of

the measured aliquots. If the average percent recovery and standard deviation meet pre-defined

acceptance criteria, the laboratory is considered to be qualified, or ready, to perform the analyses.

On a case by case basis, EPA and SCC may decide to accept alternate data in lieu of IPR data for

the readiness reviews. In such cases, the alternate data must provide as much information about

laboratory readiness as would the IPR samples. Examples of acceptable non-IPR data that might be used

for a readiness review include: performance evaluation (PE) sample data; ongoing QC data gathered over

a period of time, or MDL study data.

Readiness reviews will be performed by SCC data reviewers, who will document and forward

their findings to the SCC Study Coordinator. If problems are identified during these reviews, the SCC

Data Reviewer(s) and Study Coordinator will work with the laboratory, to the extent possible, to resolve

the problem. If the problem cannot be resolved within the time frame required by EPA or within the

scope of the laboratoryís existing contract, the SCC Study Coordinator will notify the EPA Analytical

Project Manager immediately.

17.5 Technical Systems Audit

All laboratory contracts will require that laboratories participating in this study be prepared for

and willing to undergo an on-site, or technical systems, audit of its facilities, equipment, staff, and sample

analysis, training, record keeping, data validation, data management, and data reporting procedures.

Audits for individual laboratories participating in this study will be conducted only if the results of the

readiness reviews, data quality audits, and surveillance suggest serious or chronic laboratory problems

that warrant on-site examinations and discussion with laboratory personnel. If such an audit is

determined to be necessary, a standardized audit checklist will be used to facilitate an audit walkthrough

and document audit findings. Audit participants will include the EPA Analytical Project Manager or the

EPA Quality Assurance Manager (or a qualified EPA staff member designated by the EPA QAM) and an

SCC staff member experienced in conducting laboratory audits. One audit team member will be

responsible for leading the audit and conducting a post-audit debriefing to convey significant findings to

laboratory staff at the conclusion of the audit. The other audit team member will be responsible for

gathering pre-audit documentation of problems that necessitated the audit, customizing the audit checklist

as necessary to ensure that those problems are addressed during the audit, documenting audit findings on

the audit checklist during the audit, and drafting a formal report of audit findings for review by EPA.

17.6 Data Quality Audits

Every laboratory data package submitted under this study will be subjected to a data quality audit. 

These data quality audits will be performed by qualified SCC data review staff who have been trained in

procedures for performing data quality audits and who are familiar with the laboratory methods used to

prepare the data packages. These data quality audits will be performed using a multi-stage review process

designed to identify and correct data deficiencies as early as possible in order to maximize the amount of

usable data generated during this study. 
September 2000 National Fish Study Analytical QAPP 38

17.7 Data Quality Assessment

Upon completion of each data quality audit, the SCC Data Reviewer will work with SCCís

database development staff to create an analytical database that contains all field sample results from the

National Fish Tissue Study (see Section 16.3).

At selected intervals and upon completion of the study, SCCís database development staff will

perform statistical analyses to verify the accuracy of the database. The statistical procedures will be

directed at evaluating the overall quality of the database against data quality objectives established for the

study, and in identifying trends in field and QC results obtained during the study. SCC staff will

document their findings and recommendations concerning this data quality assessment in a written report

to EPA.

18.0 REPORTS TO MANAGEMENT

Following completion of each data quality audit and assessment, SCC chemists will prepare and

submit written reports, in narrative format, that describe data quality limitations and SCC

recommendations concerning data use.

To facilitate sample and data tracking during the course of the National Fish Tissue Study, SCC

also will prepare a monthly status report that provides a complete listing of the Episodes scheduled, the

analyses required under each Episode, the laboratory associated with each analysis type, the date of

sample receipt at the laboratory, the date of data receipt at SCC, the SCC data review completion date,

and the SCC database completion date. This report will enable the Analytical Project Manager to quickly

determine the status of individual National Fish Tissue Study components. This monthly status report

also will be used by the EPA Analytical Project Manager and other EPA staff to facilitate decisions

regarding the study and to inform senior EPA managers of the project status.

Upon request, SCC also will provide a weekly report that describes the status of all current

sampling, analysis, and data review activities, and periodic database status reports that provide up-to-date

information concerning database developments that occurred since distribution of previous reports.

19.0 DATA REVIEW, VALIDATION, AND VERIFICATION

Criteria for acceptance:

A multi-stage data review process, as summarized in Section 16 and detailed below, will be used

to evaluate the quality of all data submitted in the National Fish Tissue Study. Acceptance criteria against

which data will be evaluated will include 1) study performance criteria and MQOs detailed in this and

affiliated QAPPs, 2) applicable QC acceptance criteria outlined in the methods, and 3) best professional

judgement (BPJ) of SCC chemists responsible for performing data quality assessments. The goal of this

data review process will be to maximize the amount of useable data gathered in the study. This will be

accomplished by 1) performing data reviews promptly so that corrective actions may be taken wherever

possible, and 2) considering data quality failures in light of the entire analytical sequence rather than as

isolated events.
National Fish Study Analytical QAPP September 2000 39

Process:

In the first stage of the data review process, SCC chemists will perform a ìData Completeness

Checkî in which all elements in each laboratory submission will be evaluated to verify that results for all

specified samples are provided, that data are reported in the correct format, and that all relevant

information, such as preparation and analysis logs, are included in the data package. Corrective action

procedures will be initiated if deficiencies are noted.

The second stage of the data review process will focus on an ìInstrument Performance Checkî in

which the SCC chemists will verify that calibrations, calibration verifications, standards, and calibration

blanks were analyzed at the appropriate frequency and met method or study performance specifications. 

If errors are noted at this stage, corrective action procedures will be initiated immediately.

Stage three of the data review process will focus on a ìLaboratory Performance Checkî in which

SCC staff will verify that the laboratory correctly performed the required analytical procedures and was

able to demonstrate a high level of precision and accuracy. This stage includes evaluation of QC

elements such as the IPR and OPR tests, preparation and laboratory blanks, and reference standards. 

Corrective action procedures will be initiated with the laboratories to resolve any deficiencies identified.

In stage four of the data review process, the SCC chemist will perform a ìMethod/Matrix

Performance Checkî to discern whether any QC failures are a result of laboratory performance or

difficulties with the method or sample matrix. Data evaluated in this stage will include matrix spike,

matrix spike duplicate, duplicate sample, labeled compound, and surrogate spike results. The SCC

chemist also will verify that proper sample dilutions were performed and that necessary sample cleanup

steps were taken. If problems are encountered, the SCC chemist will immediately implement corrective

actions.

Reconciliation with user requirements:

Finally, SCC will perform a ìData Quality and Usability Assessmentî in which the overall

quality of data is evaluated against the performance criteria and MQOs detailed in this QAPP. As noted

above, this assessment will strive to maximize use of data gathered in this study based on performance

criteria established for this study. This will be accomplished by evaluating the overall quality of a

particular data set rather than focusing on individual QC failures. Results of this assessment will be

documented in written data review narratives that SCC will submit to EPA. To expedite the process,

these narratives will follow a standardized format and, wherever possible, utilize standardized language to

communicate data limitations and SCC recommendations concerning data quality.

The EPA Study Manager, EPA QA officer, and other appropriate EPA representatives will utilize

the SCC-generated data review narratives to make final data usability determinations regarding each set

of sample results.

20.0 REFERENCES

(1) U.S. Environmental Protection Agency (USEPA). 1992. National Study of Chemical Residues in

Fish. U.S. Environmental Protection Agency, Office of Science and Technology, Washington,

D.C. EPA 823-R-92-008.

(2) U.S. Environmental Protection Agency (USEPA). Study design document. undated.
September 2000 National Fish Study Analytical QAPP 40

(3) U.S. Environmental Protection Agency (USEPA). QAPP for Sample Collection Activities for a

National Study of Chemical Residues in Lake Fish Tissue. May 2000.

(4) EPA Requirements for Quality Assurance Project Plans for Environmental Data Operations,

EPA QA/R-5, EPA Quality Assurance Division, Interim Final, November 1999. 

(5) EPA Guidance for Quality Assurance Project Plans, EPA QA/G-5, EPA Office of Research and

Development, Washington, D.C. 20460. EPA/600/R-98/018. February 1998.

(6) Appendix B, 40 CFR part 136

(7) U.S. Environmental Protection Agency (USEPA). 1997. Guidance for Assessing Chemical

Contaminant Data for Use in Fish Advisories. Volume 1: Fish Sampling and Analysis. Second

Edition. U.S. Environmental Protection Agency, Office of Water, Washington, D.C. EPA

823-B-97-009.

(8) Crecelius, E.A., N.S. Bloom, C.E. Cowan, and E.A. Jenne. 1986. ìSpeciation of Selenium and

Arsenic in Natural Waters and Sediments, Volume 2: Arsenic Speciation.î Final Report prepared

for Electric Power Research Institute, Palo Alto, California by Battelle Pacific Northwest

Laboratories, Richland, Washington.

(9) Guide to Method Flexibility and Approval of EPA Water Methods, EPA Office of Water,

Engineering and Analysis Division (4303), Washington DC 20460. EPA-821-D-96-004. 

December 1996.