NOAA Technical Memorandum NMFS-NWFSC-77

U.S. DEPARTMENT OF COMMERCE

National Oceanic and Atmospheric Administration

National Marine Fisheries Service

Quality Assurance Plan

for Analyses

of Environmental Samples

for Polycyclic Aromatic Compounds,

Persistent Organic Pollutants, Fatty Acids,

Stable Isotope Ratios, Lipid Classes, and

Metabolites of Polycyclic Aromatic Compounds

July 2006
NOAA Technical Memorandum

NMFS Series

The Northwest Fisheries Science Center of the National

Marine Fisheries Service, NOAA, uses the NOAA Technical Memorandum NMFS series to issue informal scientific 

and technical publications when complete formal review 

and editorial processing are not appropriate or feasible due 

to time constraints. Documents published in this series may 

be referenced in the scientific and technical literature.

The NMFS-NWFSC Technical Memorandum series of the 

Northwest Fisheries Science Center continues the NMFSF/NWC series established in 1970 by the Northwest & 

Alaska Fisheries Science Center, which has since been 

split into the Northwest Fisheries Science Center and the 

Alaska Fisheries Science Center. The NMFS-AFSC Technical Memorandum series is now being used by the Alaska 

Fisheries Science Center.

Reference throughout this document to trade names does 

not imply endorsement by the National Marine Fisheries 

Service, NOAA.

This document should be cited as follows:

Sloan, C.A., D.W. Brown, G.M. Ylitalo, J. Buzitis, D.P. 

Herman, D.G. Burrows, G. Yanagida, R.W. Pearce, J.L. 

Bolton, R.H. Boyer, and M.M. Krahn. 2006. Quality

assurance plan for analyses of environmental samples

for polycyclic aromatic compounds, persistent organic

pollutants, fatty acids, stable isotope ratios, lipid classes, and

metabolites of polycyclic aromatic compounds. U.S. Dept. 

Commer., NOAA Tech. Memo. NMFS-NWFSC-77, 30 p.
NOAA Technical Memorandum NMFS-NWFSC-77

U.S. DEPARTMENT OF COMMERCE

National Oceanic and Atmospheric Administration

National Marine Fisheries Service

Quality Assurance Plan

for Analyses

of Environmental Samples

for Polycyclic Aromatic Compounds,

Persistent Organic Pollutants, Fatty Acids,

Stable Isotope Ratios, Lipid Classes, and

Metabolites of Polycyclic Aromatic Compounds

Catherine A. Sloan, Donald W. Brown, Gina M. Ylitalo,

Jon Buzitis, David P. Herman, Douglas G. Burrows,

Gladys Yanagida, Ronald W. Pearce, Jennie L. Bolton,

Richard H. Boyer, and Margaret M. Krahn

Northwest Fisheries Science Center

Environmental Conservation Division

2725 Montlake Boulevard East

Seattle, Washington 98112

July 2006
Most NOAA Technical Memorandums

NMFS-NWFSC are available online at the 

Northwest Fisheries Science Center

web site (http://www.nwfsc.noaa.gov)

Copies are also available from:

National Technical Information Service

5285 Port Royal Road

Springfield, VA 22161

phone orders (1-800-553-6847)

e-mail orders (orders@ntis.fedworld.gov)

ii
Table of Contents 

List of Tables ................................................................................................................................................v

Executive Summary ....................................................................................................................................vii

Abbreviations and Acronyms ......................................................................................................................ix

1.0. Introduction...........................................................................................................................................1

2.0. Project Description................................................................................................................................2

3.0. Laboratory Organization and Responsibilities......................................................................................3

3.1. Project Leader.................................................................................................................................3

3.2. Analytical Laboratory Project Managers........................................................................................3

4.0. Sample and Data Handling ...................................................................................................................4

4.1. Intralaboratory Sample Transfer.....................................................................................................4

4.2. Sample Archival.............................................................................................................................4

4.3. Laboratory Records........................................................................................................................5

4.4. Data and Data Documentation........................................................................................................5

4.5. Chain of Custody............................................................................................................................8

5.0. Assessment of Data Quality................................................................................................................10

5.1. Precision .......................................................................................................................................10

5.2. Accuracy.......................................................................................................................................10

5.3. Representativeness .......................................................................................................................10

5.4. Comparability...............................................................................................................................11

5.5. Completeness................................................................................................................................11

5.6. Sensitivity.....................................................................................................................................11

6.0. Quality Assurance Procedures............................................................................................................12

6.1. Laboratory Operations..................................................................................................................12

6.2. Quality Assurance Documentation...............................................................................................12

6.3. Participation in Intercomparison Exercises..................................................................................13

6.4. Quantitation Range.......................................................................................................................13

6.5. Quality Assurance Criteria for the Analytical Measurements......................................................14

6.5.1. Calibration ..........................................................................................................................14

6.5.2. Continuing Calibration Verification ...................................................................................14

6.5.3. Reference Materials............................................................................................................21

6.5.4. Surrogate (Internal Standard) Recovery .............................................................................22

6.5.5. Method (Reagent) Blanks...................................................................................................22

6.5.6. Sample Replicates...............................................................................................................23

6.6. Laboratory Qualification of Data .................................................................................................23

7.0. Data Reduction....................................................................................................................................25

7.1. Reported Results...........................................................................................................................25

7.2. Data Review .................................................................................................................................26

iii
7.3. Laboratory Data Deliverables.......................................................................................................26

8.0. Corrective Action/Procedure Alteration .............................................................................................27

9.0. References...........................................................................................................................................29

iv
List of Tables 

Table 1. Polycyclic aromatic compounds determined by gas chromatography/mass spectrometry. ...........5

Table 2. Persistent organic pollutants determined by GC/MS.....................................................................6

Table 3. POPs determined by high-performance liquid chromatography/photodiode array 

detection........................................................................................................................................................6

Table 4. Fatty acids determined as methyl ethers by GC/MS......................................................................7

Table 5. Stable isotope ratios determined by elemental analyzer/isotope ratio mass spectrometry.............8

Table 6. Lipid class proportions and percent lipid determined by thin-layer chromatography/ 

flame ionization detection.............................................................................................................................8

Table 7. Metabolites of PACs determined by high-performance liquid chromatography/ 

fluorescence. .................................................................................................................................................8

Table 8. Minimum analytical quality assurance criteria: Polycyclic aromatic compounds and 

persistent organic pollutants by gas chromatography/mass spectrometry. .................................................15

Table 9. Minimum analytical quality assurance criteria: POPs by high-performance liquid 

chromatography/photodiode array..............................................................................................................16

Table 10. Minimum analytical quality assurance criteria: Fatty acids by gas chromatography/ 

mass spectrometry.......................................................................................................................................17

Table 11. Minimum analytical quality assurance criteria: Stable isotope ratios by elemental 

analyzer/isotope ratio mass spectrometry. ..................................................................................................18

Table 12. Minimum analytical quality assurance criteria: Percent lipid and lipid class proportions 

by thin-layer chromatography/flame ionization detection. .........................................................................19

Table 13. Minimum analytical quality assurance criteria: Metabolites of PACs by high-performance 

liquid chromatography/fluorescence...........................................................................................................20

v
vi
Executive Summary 

This technical memorandum serves as the Quality Assurance Plan (QAP) for analyses of 

marine biota and sediment samples by the Environmental Assessment Program (EAP) within the 

Environmental Conservation Division at the Northwest Fisheries Science Center. This QAP 

describes the EAP’s quality objectives, as well as policies implemented for achieving the 

objectives and procedures for assessing the completeness of the objectives. It also provides 

guidelines for monitoring and documenting the quality of analyses so that a desired level of 

performance can be demonstrated and maintained. These guidelines are based on protocols 

established previously for specific projects under the National Oceanic and Atmospheric 

Administration and the Environmental Protection Agency and have been adapted to new types of 

analyses and current technologies. 

vii
viii
Abbreviations and Acronyms 

CM control material 

COC chain of custody 

CCV continuing calibration verification 

DDT dichlorodiphenyltrichloroethane

DQO data quality objectives 

EA/IRMS elemental analyzer/isotope ratio mass spectrometry 

EAP Environmental Assessment Program 

GC/MS gas chromatography/mass spectrometry 

GLP good laboratory practices 

HPLC/PDA high-performance liquid chromatography/photodiode array 

IAEA International Atomic Energy Agency 

IRM interim reference material 

LOQ limit of quantitation 

mV millivolt 

NIST National Institute of Standards and Technology 

PAC polycyclic aromatic compound 

PBDE polybrominated diphenyl ether 

PCB polychlorinated biphenyl 

POP persistent organic pollutant 

QA quality assurance 

QAP quality assurance plan 

RSD relative standard deviation 

SRM Standard Reference Material 

SOP standard operating procedure 

TLC/FID thin-layer chromatography/flame ionization detection 

ix
x
1.0. Introduction 

The Environmental Assessment Program (EAP) within the Environmental Conservation 

Division at the Northwest Fisheries Science Center has developed a Quality Assurance Plan 

(QAP) for analyses of marine biota and sediment samples. Many of the requirements described 

in the QAP, this technical memorandum, are based on protocols that were originally developed 

for programs under the National Oceanic and Atmospheric Administration (National Status and 

Trends Program and Natural Resource Damage Assessment) and the Environmental Protection 

Agency (Puget Sound Estuary Program and Environmental Monitoring and Assessment 

Program-Estuaries). These programs were designed to measure low-level (i.e., low parts per 

billion) concentrations of contaminants in marine and estuarine sediments and biota using gas 

chromatography/mass spectrometry (GC/MS) and high-performance liquid 

chromatography/photodiode array (HPLC/PDA). More recently the EAP has expanded its 

studies to include analyses of samples for fatty acids by GC/MS and for stable isotope ratios by 

elemental analyzer/isotope ratio mass spectrometry (EA/IRMS). Other analyses performed by 

the EAP include determining lipid classes in tissues using thin-layer chromatography/flame 

ionization detection (TLC/FID) and measuring relative amounts of metabolites of polycyclic 

aromatic compounds (PACs) in bile by HPLC/fluorescence. 

The requirements specified in this QAP are designed to: 

1) monitor the performance of the measurement systems to maintain quality, and 

2) document the extent to which the reported data are sufficiently complete, comparable, 

representative, unbiased, and precise to be suitable for their intended use. 

This QAP will be adapted to specific projects as needed, and will be revised as 

appropriate as changes are made to the EAP quality assurance program. 

The term “field samples” in this technical memorandum refers to samples collected from 

the environment (e.g., sediments, plant or animal tissues). The term “samples” refers to field 

samples or quality assurance (QA) samples. QA samples are analyzed concurrently with the 

field samples using the same method. The established methods used to measure the various 

groups of analytes (i.e., contaminants, fatty acids, stable isotope ratios, lipids, or metabolites) are 

documented separately and are available in the form of standard operating procedures (SOPs). 

In addition this QAP does not address the collection of samples; that will be addressed in a 

separate document (e.g., a sampling plan), when appropriate. 
2.0. Project Description 

The description of a specific project is to be provided before the analyses begin in order 

to ensure that the project requirements are known and can be met. The project description may 

include the following information: 

● the principal investigator(s), 

● the project’s objectives, questions, or issues, 

● what type, quantity, and quality of analyses are required, 

● timeframe for receipt of samples, analyses, and data delivery, 

● how the results are to be formatted and reported, 

● who will use the data, and 

● what decision(s) will be made from the information obtained. 

A project proposal that includes the information in a project description may be used for this 

purpose. 

2
3.0. Laboratory Organization and 

Responsibilities 

The analyses for the project will be performed primarily by personnel from the 

Environmental Conservation Division of the Northwest Fisheries Science Center. 

3.1. Project Leader 

Dr. Margaret (Peggy) Krahn, EAP manager, is responsible for ensuring that the analytical 

data quality objectives (DQOs) for the project are met and that staff resources are available to 

fulfill laboratory analytical requirements. Her contact information is: 

Margaret Krahn

Northwest Fisheries Science Center 

Environmental Conservation Division 

2725 Montlake Boulevard East 

Seattle, WA 98112 

Phone: (206) 860-3326 

Fax: (206) 860-3335 

E-mail: Peggy.Krahn@noaa.gov 

3.2. Analytical Laboratory Project Managers 

Donald Brown, Catherine Sloan, and Gina Ylitalo, EAP team leaders, are responsible for 

ensuring that the analytical results meet QA criteria and the stated objectives. Their mailing 

address and fax number is the same as for the project leader. Their individual contact 

information is: 

Donald Brown 

Phone: (206) 860-3300 

E-mail: Donald.W.Brown@noaa.gov 

Catherine Sloan 

Phone: (206) 860-3304 

E-mail: Catherine.A.Sloan@noaa.gov 

Gina Ylitalo 

Phone: (206) 860-3325 

E-mail: Gina.Ylitalo@noaa.gov 

3
4.0. Sample and Data Handling 

Sample handling procedures may be dependent on the matrix and the analytes of concern. 

The groups of analytes that can be determined by the EAP laboratory are presented in Tables 

1–7; the analytes within each group are measured concurrently using the specified method. 

Sampling procedures, including sample collection, preservation, storage, and documentation, are 

addressed in detail elsewhere (e.g., in a sampling and analysis plan). In general, samples and 

data are handled according to the following steps: 

1) inventory all samples received, 

2) store the samples in freezers prior to analyses, 

3) record the sample identification, information, and storage location in a sample database, 

4) schedule the batches of samples to be analyzed and prepare tracking paperwork, 

5) analyze the batches of samples for the specified analytes, 

6) process the raw sample data, 

7) review the processed and formatted data, 

8) report the reviewed data, 

9) archive all remaining sample material in freezers, and 

10) archive the raw and processed sample data. 

Chain-of-custody (COC) procedures (subsection 4.5, Chain of Custody, page 8), if required by 

the project, will be followed for all field samples throughout the sampling and analytical process. 

4.1. Intralaboratory Sample Transfer 

The laboratory analysts will maintain a laboratory sample-tracking record, similar to the 

COC record that will follow each sample through all stages of laboratory processing. The 

sample-tracking record will show the date of sample extraction or preparation and sample 

analysis, as well as the names or initials of individuals responsible for each procedure. 

4.2. Sample Archival 

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

laboratory in a manner to preserve sample integrity (e.g., at –20°C to –80°C) for at least one year 

or a specified time period after the data have been validated, as agreed upon by the project leader 

and the principal investigator(s). 

4
Table 1. Polycyclic aromatic compounds (PACs) determined by gas chromatography/mass spectrometry 

(GC/MS).* Method: Sloan et al. 2004 and 2005. 

Low molecular weight PACs High molecular weight PACs 

Naphthalene Fluoranthene 

1-Methylnaphthalene Pyrene 

2-Methylnaphthalene Benz[a]anthracene 

Biphenyl Chrysene + triphenylene 

2,6-Dimethylnaphthalene Benzo[b]fluoranthene 

Acenaphthylene Benzo[j]fluoranthene + Benzo[k]fluoranthene 

Acenaphthene Benzo[e]pyrene 

2,3,5-Trimethylnaphthalene Benzo[a]pyrene 

Fluorene Perylene 

Dibenzothiophene Indeno[1,2,3-c,d]pyrene 

Phenanthrene Dibenz[a,h]anthracene + Dibenz[a,c]anthracene 

Anthracene Benzo[ghi]perylene 

1-Methylphenanthrene HPACs (sum of high molecular weight PACs) 

Retene 

LPAC (sum of low molecular weight PACs) 

* Sums of alkylated PACs (from petroleum sources) also can be determined, when requested. 

4.3. Laboratory Records 

Laboratory log books will be maintained for each of the following: 

● sample preparation, 

● use and maintenance of the accelerated solvent extractors, 

● use and maintenance of the HPLC, 

● use and maintenance of the GC/MS, 

● use and maintenance of the EA/IRMS, and 

● use and maintenance of the TLC/FID. 

Final analytical results will be generated and maintained in electronic database files with 

frequent backup and storage on permanent media. 

4.4. Data and Data Documentation 

The laboratory will provide data tables and QA documentation suitable for QA 

assessment. All original data and data documentation developed by the laboratory for a given 

data package will be kept by the laboratory for at least one year after the data have been 

validated and reported; and if requested, the data will be stored in the collection format for up to 

five years. 

5
Table 2. Persistent organic pollutants (POPs) determined by GC/MS. Method: Sloan et al. 2004 and 

2005. 

Polychlorinated biphenyl (PCB) congenersa

 

(by IUPAC number) and estimated total PCBsb Dichlorodiphenyltrichloroethanes (DDTs)

17, 18,* 28,* 31, 33, 44,* 49, 52,* 66,* 70, 74, 82, 

87, 95, 99, 101/90,* 105,* 110, 118,* 128,* 

138/163/164,* 149, 151, 153/132,* 156, 158, 

170/190,* 171, 177, 180,* 183, 187,* 191, 194, 

195,* 199, 205, 206,* 208, 209,*

2,4’-DDT, 4,4’-DDT, 2,4’-DDD, 4,4’-DDD, 

2,4’-DDE, 4,4’-DDE

Polybrominated diphenyl ether (PBDE) 

congeners (by IUPAC number) Other organochlorine pesticides:

28, 47, 49, 66, 85, 99, 100, 153, 154, 183 Aldrin

cis-Chlordane

trans-Chlordane

Dieldrin

Endosulfan I

Hepatchlor

Heptachlor epoxide

Hexachlorobenzene

alpha-Hexachlorocyclohexane

beta-Hexachlorocyclohexane

gamma-Hexachlorocyclohexane

Mirex

cis-Nonachlor

trans-Nonachlor

Nonachlor III

Oxychlordane

a For the PCBs, 46 congeners present in 40 chromatographic peaks are measured (listed with coeluting congeners). 

b Estimated total PCB concentrations: calculated as 2 × the sum of concentrations of 17 congeners noted * (NOAA 

1989) or as the sum of concentrations of all 40 congeners measured. 

Table 3. POPs determined by high-performance liquid chromatography/photodiode array detection 

(HPLC/PDA). Methods: Krahn et al. 1994 and Ylitalo et al. 2005a for tissues and Buzitis et al. in 

press for sediments. 

PCBa

 congeners (by IUPAC number) and 

estimated total PCBsb

: DDTs and other pesticides 

77, 101,* 105,* 110,* 118, 126, 128,* 138, 153,* 

156, 157,* 169, 170/194,* 180, 189, 190, 200 

2,4’-DDT, 4,4’-DDT, 2,4’-DDD, 4,4’-DDD, 

4,4’-DDE 

a The peaks represented by the analytes noted * may contain coeluting compounds. 

b Estimated total PCBs: calculated by summing the concentrations of identified PCB congeners above then adding 

the concentration of the remaining congeners, which have been calculated by summing their PDA response areas 

and applying an average response factor. 

6
Table 4. Fatty acids determined as methyl ethers by GC/MS.a

 Method: Krahn et al. 2004. 

Fatty acids 

(quantitative)b 

Tentatively identified fatty acids 

(semiquantitative)c 

C10:0 (capric acid) C14:1n9 

C11:0 4,8,12-trimethyl-C13:0 

C12:0 (lauric acid) C14:1n7 

C12:1 11-methyl-C14:0 

iso-C14:0 anteiso-C15:0 

C14:0 (myristic acid) anteiso-C16:0 

C14:1n5 2,6,10,14-tetramethyl-C15:0 

iso-C15:0 C16:1n11 (may coelute with C16:1n12) 

C15:0 C16:1n9 

C15:1n5 C16:1n5 

iso-C16:0 7-methyl-C16:1 

C16:0 (palmitic acid) C16:2n6 

C16:1n7 (palmitoleic acid) anteiso-C17:0 

iso-C17:0 7,8-dimethyl-C16:1 

C17:0 (margaric acid) C16:2n4 

C17:1n7 C16:3n6 

iso-C18:0 C16:3n4 

C18:0 (stearic acid) C17:1n8 (tentatively identified structural isomer) 

C18:1n9 (oleic acid) C16:4n3 

C18:1n7 (vaccenic acid) anteiso-C18:0 

C18:2n6 (linoleic acid) C16:4n11 

C19:0 C18:1n13 

C18:3n6 (gamma-linolenic acid) C18:1n11 (may coelute with C18:1n12) 

C18:3n3 (alpha-linolenic acid0 C18:1n5 

C18:4n3 (stearidonic acid) C18:2n7 

C20:0 (arachidic acid) C18:2n4 

C20:1n15 C18:3n4 

C20:1n9 (gadoleic acid) C18:3n1 

C20:2n6 C18:4n 

C20:3n6 C20:1n7 

C20:4n6 (arachidonic acid) C20:1n5 

C20:3n3 C20:1n11 (may coelute with C20:1n12) 

C20:5n3 C20:2n11 

C22:0 (behenic acid) C20:2n9 

C22:1n9 (erucic acid) C20:4n3 

C22:2n6 C22:1n11 (may coelute with C22:1n12) 

C22:4n6 C22:1n7 

C22:3n3 C22:1n5 

C24:0 C21:5n3 

C22:5n3 C22:4n3 

C22:6n3 

C24:1n9 (nervonic acid) 

a All analytes are the isomers in the cis configuration. 

b Quantitation uses the relative response factor of the analyte. c Quantitation uses the relative response factor of the most similar homolog for which there is a standard. 

7
Table 5. Stable isotope ratios determined by elemental analyzer/isotope ratio mass spectrometry 

(EA/IRMS). Method: Krahn et al. in prep. 

Delta (δ ) values Other ratios 

δ13C, δ15N Percent nitrogen by weight (Wt %N), percent carbon by weight 

(Wt %C), carbon/nitrogen ratio (C/N ratio) 

Table 6. Lipid class proportions and percent lipid determined by thin-layer chromatography/flame 

ionization detection (TLC/FID). Method: Krahn et al. 2001, Ylitalo et al. 2005b. 

Lipid classes Percent lipid 

Sterol/wax esters 

Triglycerides 

Free fatty acids 

Cholesterol/sterols 

Phospholipids/other polar lipids 

Percent lipid determined by summing the concentrations 

(g of lipid class/kg sample) of the five lipid classes and 

multiplying this sum by 0.1% 

Table 7. Metabolites of PACs determined by high-performance liquid chromatography 

(HPLC)/fluorescence. Method: Krahn et al. 1987. 

PAC equivalents 

Phenanthrene equivalents 

Benzo(a)pyrene equivalents 

Naphthalene equivalents 

4.5. Chain of Custody 

When COC records are required, each field sample will be assigned a unique identification 

number and will have a separate entry on the COC record. COC records will be completed with 

indelible ink. A sample is considered “in custody” if: 

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

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

● it is placed in a container and secured with an official seal such that the sample cannot be 

reached without breaking the seal. 

Samples are kept in the custody of the designated sampling or field personnel or both 

until shipment. Any transfer or movement of samples will use COC procedures. Samples will 

be properly packaged for shipment near the sampling area and dispatched to the appropriate 

party. The original signed and dated COC record will accompany the sample(s); a copy of the 

COC record is retained by the sample shipper. All shipments will comply with Department of 

Transportation regulations (49 CFR, parts 172 and 173). Immediately upon receipt of samples, 

8
the recipient will review the shipment for sample condition and consistency with the 

accompanying COC record before signing and dating the COC record. Sample condition(s) will 

be noted on the original COC sheet at this time. If there are any discrepancies between the COC 

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

9
5.0. Assessment of Data Quality 

The overall QA objectives are to ensure development of analytical data of known and 

acceptable quality. The quality of data required is specified in qualitative and quantitative 

DQOs. These objectives usually are expressed in terms of precision, accuracy, 

representativeness, completeness, comparability, and sensitivity. Data quality is assessed by 

applying the specific acceptance criteria to QA elements (section 6.0, Quality Assurance 

Procedures, page 12). 

5.1. Precision 

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

property under prescribed similar conditions (e.g., replicate measurements of a particular analyte 

in one sample). Laboratory precision is evaluated using laboratory replicates of field samples 

and Standard Reference Materials (SRMs) when available (subsection 6.5.6, Sample Replicates, 

page 23). The use of SRMs allows for the long-term measurement of precision, whereas 

replicates of field samples can indicate the precision for a particular group of samples. Precision 

will be expressed as the relative standard deviation (RSD) for repeated measurements. The RSD 

is an estimate of the average standard error in a measurement; this estimate generally improves 

with increasing number of replicates. Reproducibility is affected by sample collection 

procedures and matrix variations, as well as the extraction and analytical procedures used. It is 

recognized that, typically, precision erodes as the limit of detection is approached. 

5.2. Accuracy 

Accuracy is the degree of agreement of a measurement with an accepted (e.g., certified or 

published) value. Laboratory accuracy will be evaluated through the use of SRMs when 

available (subsection 6.5.3, Reference Materials, page 21). For a particular SRM, accuracy for 

an analyte will be assessed by comparing the measured value to a value accepted (i.e., certified 

or published) by the certifying agency (i.e., the National Institute of Standards and Technology 

[NIST]) (subsection 6.5.3, Reference Materials, page 21). 

5.3. Representativeness 

Representativeness expresses the degree to which data accurately and precisely represent 

a defined or particular characteristic of a population, parameter variations at a sampling point, a 

processed condition, or an environmental condition. Representativeness is a qualitative 

parameter that is dependent upon the proper design of the sampling program (as addressed in a 

sampling plan) and proper laboratory protocol. Evaluation of the data for reference materials 

and replicate field samples may provide an assessment of the representativeness of the analyte 

measurements for field samples (subsections 6.5.3, Reference Materials, page 21, and 6.5.6, 

Sample Replicates, page 23). 

10
5.4. Comparability 

Comparability is a qualitative parameter expressing the confidence with which one data 

set can be compared to another, as well as the potential for combining the data with those 

generated outside of the present project. Comparability of the analytical data is established 

through the use of the following: 

● program-defined analytical methodology, quantitation limits, reporting units, and quality 

assurance measurements, 

● NIST-traceable (or other) calibration standards and SRMs, when available, and 

● participation in interlaboratory comparison exercises (subsection 6.3, Participation in 

Intercomparison Exercises, page 13). 

5.5. Completeness 

Completeness is defined as the percentage of measured data that meet the DQOs as 

determined by the QA review process. A typical analytical completeness goal for a project is 

90% (i.e., no more than 10% of the analytical data will be qualified as unreliable; meaning it 

does not meet the DQOs). Data qualified as estimated as a result of QA criteria not being met 

will be considered usable. 

5.6. Sensitivity 

Sensitivity refers to the capability of a method to measure the analytes at low levels. For 

each method, criteria are established for the minimum concentrations that can be measured with 

known and acceptable quality (subsection 6.4, Quantitation Range, page 13). 

11
6.0. Quality Assurance Procedures 

Prior to the analysis of samples, the laboratory will specify written protocols for the 

analytical methods to be used and will identify the analytes to be quantified. If a method is 

significantly modified, the written analytical protocol will be amended. QA procedures are 

presented with each analytical method and are applied to each batch (i.e., group of field samples 

and QA samples analyzed concurrently). The laboratory also must demonstrate its continued 

proficiency by participation in refereed intercomparison exercises, as available. The QA 

procedures and criteria presented in this document may be specific to the protocols and 

instrumentation currently in use by the EAP. 

6.1. Laboratory Operations 

The laboratory will have the appropriate facilities to store and prepare samples and the 

appropriate instrumentation and staff to provide data of the required quality within the time 

period indicated. The laboratory is expected to conduct operations using good laboratory 

practices (GLP), including: 

● performing scheduled maintenance of analytical balances, laboratory equipment, and 

instrumentation, 

● validating instrument calibration standards, and 

● recording pertinent analytical data in logbooks with each entry signed and dated by the 

analyst. 

Personnel should be well versed in GLP, including standard safety procedures. It is the 

responsibility of the project manager to ensure that mandatory safety training is completed by all 

laboratory personnel. The laboratory is responsible for maintaining a current safety manual in 

compliance with the Occupational Safety and Health Administration or equivalent state or local 

regulations. Proper procedures for safe storage, handling, and disposal of chemicals should be 

followed at all times; each chemical should be treated appropriately based on its potential health 

hazard. 

6.2. Quality Assurance Documentation 

All participants in a project must have the current version of the QAP. In addition the 

following documents and information must be current and available to all laboratory personnel 

participating in the processing of samples: 

● laboratory SOPs—the detailed instructions for performing routine laboratory procedures, 

● instrument performance information—for example, information on instrument 

calibration, range of response and stability, and 

12
● QA information—QA tables will be developed and maintained throughout the project for 

all appropriate analyses and measurements. 

The SOPs used in the analyses of samples depend on the project and the analytes to be 

determined (listed in Tables 1–7). Documentation of all analytical methods will accompany the 

analytical results. 

6.3. Participation in Intercomparison Exercises 

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

intercomparison exercises managed by the NIST or the International Atomic Energy Agency 

(IAEA). A variety of samples including accuracy-based solutions, sample extracts, and 

representative matrices (e.g., sediment or tissue samples) is used in these exercises, which 

typically take place once a year. Upon review of the results, if the laboratory fails to achieve 

acceptable performance, it will be required to undertake appropriate corrective actions. This 

section applies only to analyses for PACs (Table 1) and POPs (Tables 2 and 3); it does not apply 

to analyses for fatty acids (Table 4), carbon and nitrogen stable isotope ratios (Table 5), lipid 

classes (Table 6), or metabolites of PACs (Table 7) because formal intercomparison exercises by 

the NIST or the IAEA have not been conducted for these analytes. Acceptance criteria are the 

same as those for reference materials (subsection 6.5.3, Reference Materials, page 21). 

6.4. Quantitation Range 

For each GC/MS method (for PACs, POPs, and fatty acids), the lower limit of 

quantitation (LOQ) for a given analyte in a specific sample is the concentration that would be 

calculated if that analyte had a GC/MS response area equal to its area in the lowest level 

calibration standard used in the calibration. When an analyte is not detected in a sample or it has 

a response area that is smaller than its area in the lowest level calibration standard used, the 

concentration of the analyte in that sample is reported to be less than the value of its lower LOQ. 

When a specific analyte in a particular sample has a GC/MS response area that is larger than its 

area in the highest level calibration standard used in the calibration, the analyte amount is 

calculated using the relative response factor of that analyte in the highest level calibration 

standard used; the concentration is footnoted as exceeding the calibration range and is therefore 

an estimate. 

For the HPLC/PDA method, the lower LOQ for a given analyte in a sample is the 

concentration that would be calculated if the analyte had a PDA response area equal to the 

minimum area needed to positively identify that analyte using the PDA spectral library. When 

an analyte is not detected in a sample or it has an area that is smaller than its minimum area, the 

concentration of the analyte in that sample is reported to be less than the value of its lower LOQ. 

For the EA/IRMS method, the delta (δ)

13C and δ15N values can be affected if the signals 

for the CO2 and N2 peaks are too small or too large. Sample results are not reported and the 

samples are reanalyzed if peak amplitudes exceed the following limits: for N2, the mass 28 peak 

must have an amplitude of less than 9,500 millivolts (mV) and the mass 29 peak must have an 

amplitude greater than 500 mV; for CO2, the mass 46 peak must have an amplitude of less than 

9,500 mV and the mass 44 peak must have an amplitude greater than 500 mV. If peak 

amplitudes are near their limits, the accuracy of the result is less certain. Sample results are 

13
14

footnoted to be used with caution if the peak amplitudes are as follows: for N2, the mass 28 peak 

amplitude is between 7,500 and 9,500 mV or the mass 29 peak amplitude is between 500 and 

750 mV; for CO2, the mass 46 peak amplitude is between 7,500 and 9,500 mV or the mass 44 

peak amplitude is between 500 and 750 mV. 

For the TLC/FID method, a linear relationship between the amount of lipid spotted on a 

Chromarod and the FID response is needed for accurate lipid quantitation. Suitable ranges of the 

lipid amounts have been determined to be as follows: 0.30–7.5 microgram (μg) for sterol/wax 

esters, 0.30–7.5 μg for triglycerides, 0.25–10 μg for free fatty acids, 0.050–0.70 μg for 

cholesterol/sterols, and 0.050–1.0 μg for phospholipids/other polar lipids. In order for the 

amount of lipid to fall within the linear range of each lipid class, the volumes of the extracts are 

routinely adjusted as necessary, depending on the matrix, by diluting or concentrating the 

extracts and then reanalyzing the sample. If a lipid class is not detected in a sample (i.e., no 

signal above the baseline), a value of zero is reported for the proportion of that lipid class. 

For the semiquantitative HPLC/fluorescence method, the amplitude of each analyte peak 

must remain on scale. If a peak amplitude goes “off scale” (i.e., recognized when the top of the 

peak is flat), the bile sample is diluted and reanalyzed. If an analyte peak is not detected in a 

sample (i.e., no signal above baseline), a value of zero is reported. 

6.5. Quality Assurance Criteria for the Analytical Measurements 

QA elements (e.g., subsections 6.5.1, Calibration, below, and 6.5.5, Method [Reagent] 

Blanks, page 22) are included in the analyses of every batch of samples. Acceptance criteria and 

required minimum frequency of analysis for each QA element are summarized in Tables 8–13. 

The results for the various QA elements are reviewed by laboratory personnel immediately 

following the analysis of each sample batch. These results are then used to determine when 

acceptance criteria have not been met and which corrective actions are required before analyses 

may proceed. 

6.5.1. Calibration 

Calibration for all methods is established before or during sample analyses and 

documentation is archived with the sample data. The GC/MS and TLC/FID methods require at 

least four concentration levels of calibration standards for analyte quantitation. The HPLC/PDA 

method uses at least four concentration levels of calibration standards to demonstrate the 

linearity of the detector’s response and a single level for analyte quantitation. The EA/IRMS 

method employs at least two points for analyte ratio calibration. The HPLC/fluorescence 

method uses a single calibration point based on the average of the responses for repeated 

analyses of the calibration standard. 

6.5.2. Continuing Calibration Verification 

Continuing calibration verification (CCV) standards will be analyzed at the specified 

frequency, including at the beginning and end of every batch of samples. If CCV results do not 

meet specified criteria, then the entire batch and calibration standards must be reanalyzed. For 

the GC/MS and HPLC/PDA methods, the CCV standards’ RSD of the analyte responses relative 

to the internal standard must be less than or equal to 15% for the repetitions. For the EA/IRMS 
Table 8. Minimum analytical quality assurance criteria: Polycyclic aromatic compounds (PACs) and persistent organic pol

chromatography/mass spectrometry (GC/MS). 

Quality assurance element Minimum frequency Acceptance criteria 

Interlaboratory comparisons At least one per year In conjunction with the NIST or the IAEA

Instrument calibration Once every batch of samples or once Analyte concentrations are to be calculate

every two batches in one continuous calibration with at least four concentratio

analytical sequence standards. 

Continuing calibration At start and end of every analytical The RSD of the analyte responses relativ

sequence and every 10 or fewer field standard is to be 

≤ 15% for the repetition

samples 

Reference materials: One with every batch of 20 or fewer Concentrations of 

≥ 70% of individual an

Sediment: NIST SRM 1944, field samples 30% of either end of the 95% confidence 

NIST SRM 1941b reference values. These criteria do not apMussel tissue: NIST SRM 1974b concentrations below their lower LOQ whBlubber: NIST SRM 1945 within or greater than the 95% confidencFish tissue: NIST SRM 1946, analytes known to have coeluting compouNIST SRM 1947 

Method blank One with every batch of 20 or fewer No more than 5 analytes in a method blan

field samples lower LOQ. Samples are not corrected fo

blank. 

Sample replicates (i.e., duplicates or One with every 20 or fewer field RSDs are to be 

≤ 15% (equivalent to rela

triplicates) samples 30% for duplicates) for 

≥ 90% of the anal

concentrations 

≥ 1 ng/g. 

Internal standards/surrogates At least one internal standard/ The recoveries are to be 60–130%. 

surrogate is added to every sample 

15
Table 9. Minimum analytical quality assurance criteria: POPs by high-performance liquid chromatography/photodiode arr

Quality assurance element Minimum frequency Acceptance criteria 

Instrument calibration Continuing calibration 

Reference materials: Sediment: NIST SRM 1944, NIST SRM 1941a, matrix spikes if needed Mussel tissue: NIST SRM 1974b Blubber: NIST SRM 1945 Fish tissue: NIST SRM 1946, NIST SRM 1947 

Method blank 

Sample replicates 

Internal standards/surrogates 

Initial instrument set up 

At start and end of every analytical 

sequence (up to 14 instrument analyses)

One with every batch of 10–12 field samples 

One with every batch of 10–-12 

field samples 

One with every 20 field samples 

Every sample 

At least a four-point curve is to be used fo

calibration. Standard curve correlation r analytes. Analyte concentrations are to bresponse factors from a single calibration 

The RSDs of the analyte responses relativstandard are to be 

≤ 15% for the repetitio

response factor for each analyte in the calcurrent batch is compared to those of the the original multilevel standard curve detdifference is to be 

≤ 15% or the multileve

repeated. 

Concentrations of 

≥ 70% of individual an

35% of either end of the 95% confidence reference values. These criteria do not apconcentrations < 10 × the lower LOQ

or t

to have coeluting compounds. 

No m

ore than 4 analytes in a method blan

lower LOQ, unless analyte is not detected sample(s). Samples are not corrected for the method blank. 

RSDs are to be 

≤ 30% (equivalent to rela

60% for duplicates) for 

≥ 80% of analyte

The recoveries are to be 60–120%. 

16
Table 10. Minimum analytical quality assurance criteria: Fatty acids by gas chromatography/mass spectrometry (GC/MS). 

Quality assurance element Minimum frequency Acceptance criteria 

Instrument calibration Continuing calibration 

Reference materials: Fish tissue: NIST SRM 1946, NIST SRM 1947 Blubber: NIST 1945 Method blank 

Sample replicates (i.e., duplicates or triplicates) 

Internal standards/surrogates Interlaboratory comparisons 

Once every batch of samples or once 

every two batches in one continuous analytical sequence 

At start and end of every analytical 

sequence and every 10 or fewer field samples 

One with every batch of 24 or fewer field samples 

One with every batch of 24 or fewer 

field samples 

One with every 24 or fewer field samples 

Every sample 

Infrequent and informal 

intercomparisons are available at present 

Analyte concentrations are to be calculatecalibration with at least eight concentratiostandards. The RSD of the analyte responses relativstandard are to be ≤ 15% for the repetitio

Concentrations ≥ 70% of individual fatty 15% of either end of the 95% confidence reference values. These criteria do not apconcentrations below their lower LOQ whwithin or greater than the 95% confidenctentatively identified fatty acids, nor to thto have coeluting compounds (Table 4). No more than five analytes in a method blower LOQ. 

RSDs are to be ≤ 15% (equivalent to rela

30% for duplicates) for ≥ 90% of the anal

The recoveries are to be 60–130%. 

In conjunction with the NIST or the IAEAparticipation with government or univers

17
Table 11. Minimum analytical quality assurance criteria: Stable isotope ratios by elemental analyzer/isotope ratio mass spe

Quality assurance element Minimum frequency Acceptance criteria 

Instrument calibration Continuing calibration 

Reference material: Fish tissue: NIST SRM 1946 

Method blank Maximum a

n

d mi

nimum N2 peak 

amplitudes 

Maximum a

n

d mi

nimum C

O2 peak 

amplitudes 

Once every analytical sequence 

At start and end of every analytical 

sequence and between every 10 field samples 

Between every 20 or fewer field samples with a minimu

m of four per 

analytical sequence 

Three with every analytical sequence 

Each sample must have N2 peak 

amplitudes between limit values 

Each sample must have CO2 peak 

amplitudes between limit values 

At least a two-point line is to be used for 

and to calculate δ15N and δ13C. A standar

> 0.9900 for δ15N and δ13C. 

Working standards: δ15N values are to ha

≤ ± 0.30 per mil and δ13C values must hav

≤ ± 0.20 per mil after the outliers have becannot exceed 20% of the total number oSRM: δ15N and δ13C values are to be wit

per mil respectively of the interim value adeviation must be 

≤ 0.30 for δ15N and 

≤ 0

%

N and Wt %

C values are to be within ± 

respectively of the calculated value or Wt should not be reported. 

Nitrogen peak amplitude and carbon diox

to be < 15% of the corresponding sample out of three of the blanks. 

For N2 the mass 28 peak is to have an am

if the amplitude is between 7,500 and 9,5footnoted to be used with caution. Also thave an amplitude > 500 m

V; if the ampl

and 750 m

V, it is to be footnoted to be us

For CO2 the mass 46 peak is to have an am

m

V; if the amplitude is between 7,500 an

footnoted to be used with caution. Also thave an amplitude > 500 m

V; if the ampl

and 750 m

V, it is to be footnoted to be us

18
Table 12. Minimum analytical quality assurance criteria: Percent lipid and lipid class proportions by thin-layer chromatogr

detection (TLC/FID). 

Quality assurance element Minimum frequency Acceptance criteria 

Instrument calibration Every two weeks At least a four-point line for each lipid cl

instrument calibration. Concentrations of triglycerides, free fatty acids, cholesterol/phospholipids/other polar lipids are to be calibration. The standard curve is to have 

0.98 for each of the five lipid classes. 

Continuing calibration One standard between every three The measured values for the CCV standa

field samples the expected values. 

Reference materials: For every 20 or fewer field samples The percent lipid values of each NIST SRMussel tissue: NIST SRM 1974b Blubber: NIST SRM 1945 

with a minimu

m of four per batch of either end of the 95% confidence inter

value. 

Fish tissue: NIST SRM 1946, NIST SRM 1947 

Method blank One extraction method blank with No peak is to be detected in a method bla

every batch of 10–14 field samples and a solvent method blank between every three field samples 

Sample replicates One with every 28 or fewer field RSDs are to be 

≤ 25% (equivalent to rela

samples 50% for duplicates). 

Interlaboratory comparisons Informal and infrequent at present. As defined by the NIST or through inform

comparable government or university lab

19
20

Table 13. Minimum analytical quality assurance criteria: Metabolites of PACs by high-performance liquid chromatograph

Quality assurance element Minimum frequency Acceptance criteria 

Instrument calibration Once per analytical sequence None. Continuing calibration At least three standards at the start of The RSD of the analyte responses relativ

every analytical sequence, one every standard is to be ≤ 10% for the repetition15 field samples and at least one at the end of the analytical sequence 

Reference material: One before and after the sample batch Concentration of PAC equivalents are to ASMBC2 and lower control limits. These limits are 

minus two standard deviations of historiccontrol material. 

Method blank One HPLC method blank before and PAC equivalents in the blank are to be le

after each sample batch lowest concentration in any field sample 

Sample replicates One with every 20 or fewer field RSDs are to be ≤ 30% (equivalent to rela

samples ≤ 60% for duplicates). 
method, δ15N values of the working stands must have a standard deviation less than or equal to 

plus or minus 0.30 per mil and δ13C values of the working standards must have a standard 

deviation less than or equal to plus or minus 0.20 per mil after the statistically significant outliers 

have been removed. Outliers cannot exceed 20% of the total number of standards. For the 

TLC/FID method, the measured values for the CCV standards must be plus or minus 15% of the 

expected values. For the HPLC/fluorescence method, the RSD of the responses for the standard 

must be less than or equal to 10% for the repetitions. 

6.5.3. Reference Materials 

At least one SRM from the NIST, if available, is analyzed with every batch of field 

samples for quality assurance, except for analyses for PAC metabolites in bile, which uses an 

in-house control material (CM) (e.g., bile of Atlantic salmon exposed to 25 μg/mL of Monterey 

crude oil for 48 hours). The data resulting from the analyses of SRMs/CMs are reported in the 

same manner as field samples and are used to document the estimated accuracy of the associated 

field sample data. If the SRM results exceed the control limit criteria, then the entire batch of 

samples is to be considered suspect. The source of the error must be identified and corrected, 

and the samples may need to be reanalyzed, depending on the project requirements. 

The laboratory’s performance for PACs or POPs by the GC/MS method is considered 

acceptable if greater than or equal to 70% of reported values are within their control limits: 

• Upper control limit = [1.3 × (certified concentration + uncertainty value for 95% 

confidence)]. 

• Lower control limit = [0.7 × (certified concentration – uncertainty value for 95% 

confidence)]. 

The laboratory’s performance for fatty acids by the GC/MS method is considered 

acceptable if greater than or equal to 70% of reported values are within their control limits: 

• Upper control limit = [1.15 × (certified concentration + uncertainty value for 95% 

confidence)]. 

• Lower control limit = [0.85 × (certified concentration – uncertainty value for 95% 

confidence)]. 

For all GC/MS methods, acceptance criteria do not apply to analytes that: 

1) have a lower LOQ that is above the lower control limit, 

2) that coelute with other compounds, or 

3) do not have calibration standards available. 

The laboratory’s performance for POPs by the HPLC/PDA method is considered 

acceptable if greater than or equal to 70% of reported values are within their control limits: 

• Upper control limit = [1.35 × (certified concentration + uncertainty value for 95% 

confidence)]. 

• Lower control limit = [0.65 × (certified concentration – uncertainty value for 95% 

confidence)]. 

21
These criteria apply only to those congeners that are greater than 10 times the lower LOQ and 

those that are free from coeluting substances. 

There are no tissue SRMs certified for ratios of stable isotopes of carbon and nitrogen. 

An interim reference material (IRM) being used is a NIST SRM tissue (certified for POPs) 

which has been measured repeatedly in-house against IAEA primary standard materials. The 

laboratory’s performance for the EA/IRMS method is considered acceptable if the mean of 

reported values is within plus or minus 0.30 per mil of the reference value for δ15N, the mean of 

reported values is within plus or minus 0.20 per mil of the reference value for δ13C, the standard 

deviation for δ15N is less than or equal to 0.30 per mil and the standard deviation for δ13C is less 

than or equal to 0.20 per mil. The Wt %N and Wt %C values should be within plus or minus 

2.5% and plus or minus 5.0% respectively of the established mean IRM reference values. 

For lipids, the percent lipid of each NIST SRM should be within its control limits: 

• Upper control limit = [1.35 × (certified concentration + uncertainty value for 95% 

confidence)] 

• Lower control limit = [ 0.65 × (certified concentration – uncertainty value for 95% 

confidence)] 

There are no tissue SRMs certified for lipid classes. 

For metabolites of PACs, an in-house bile control material is used because there are no 

bile SRMs. The laboratory’s performance is considered acceptable if the reported values are 

within their control limits, defined as plus or minus two standard deviations from the mean of 

historical values for the control material. 

6.5.4. Surrogate (Internal Standard) Recovery 

All samples analyzed for PACs, POPs and fatty acids will be spiked with appropriate 

extraction surrogates (internal standards) as described in the laboratory SOPs. If a percent 

recovery does not meet the specified criteria, the sample will be reextracted and reanalyzed if 

possible (i.e., the sample is still available); otherwise the corresponding data will be qualified as 

being an estimate. For the GC/MS analyses, the measured percent recovery of the surrogates 

must be 60–130%; for the HPLC/PDA analyses, the measured percent recovery of the surrogates 

must be 60–120%. 

6.5.5. Method (Reagent) Blanks 

Method blanks are laboratory-derived samples that are subjected to the same analytical 

protocols as are the field samples. Failure to meet acceptance criteria requires definitive 

corrective action to identify and eliminate the source(s) of contamination before the subsequent 

reextraction or reanalysis of the batch of samples or both. 

For the GC/MS methods, no more than five analytes in a method blank may exceed two 

times the value of the lower LOQ. For the HPLC/PDA method, no more than four analytes in a 

method blank may exceed four times the value of the lower LOQ, unless the analyte is not 

detected in any of the field samples in the batch. 

22
For the EA/IRMS analyses, the method blanks are tin cups with no sample added, which 

are analyzed in the same manner as the environmental samples, but are not a measure of 

contamination that occurred during sample processing. These blanks are used to correct the δ15N 

and δ13C sample values for traces of nitrogen or carbon materials in the tin cups. The nitrogen 

and carbon dioxide peak amplitudes must be less than 15% of the corresponding sample peak 

amplitude for two out of three of the blanks or the samples must be reanalyzed after the problem 

has been corrected. 

For the TLC/FID method, no peaks may be detected in a method blank. For the 

HPLC/fluorescence method, PAC equivalents in the blank must be less than 10% of the lowest 

concentration in any field sample in the analytical sample batch. 

6.5.6. Sample Replicates 

Field samples will be analyzed in replicate at the specified frequency to help ascertain 

whether samples are analytically homogeneous and to indicate whether other problems with 

reproducibility occurred during analysis. The reproducibility of the SRM results can indicate the 

precision for all analyses in the project. 

For GC/MS analyses, replicate (i.e., duplicate or triplicate) samples are analyzed with 

approximately every 20 field samples, as sample amounts allow. RSDs are to be less than or 

equal to 15% (equivalent to relative percent difference ≤ 30% for duplicates) for greater than or 

equal to 90% of the analytes. For PACs and POPs, this applies only to those analytes that have 

concentrations greater than or equal to 1 ng/g. 

For HPLC/PDA and HPLC/fluorescence analyses, duplicate samples will be analyzed 

approximately every 20 field samples. The RSDs are to be less than or equal to 30% (relative 

percent difference ≤ 60% for duplicates) for greater than or equal to 80% of analytes detected. 

For EA/IRMS analyses, replicate samples of the SRM are analyzed every 20 or fewer 

field samples, with a minimum of four per analytical sequence, to show the reproducibility of the 

IRMS instrument. The standard deviations must be less than or equal to 0.30 for δ15N and less 

than or equal to 0.20 for δ13C. Duplicate or triplicate field samples are suggested for 

approximately every 10 field samples, but are not used for QA. There are no acceptance criteria 

for replicate field samples because many explanations exist for widely varying values (e.g., 

problems with the sample processing or the homogeneity of the starting sample) that are often 

outside the control of the analytical laboratory. However, within-sample variability of the results 

for replicate field samples may be useful to the researcher. 

For lipid classes by TLC/FID, duplicate samples will be analyzed at every 28 or fewer 

field samples. The RSDs are to be less than or equal to 25% (relative percent difference ≤ 50% 

for duplicates). 

6.6. Laboratory Qualification of Data 

Sample results that did not meet the quality assurance acceptance criteria or that 

presented analytical difficulties are footnoted by the laboratory so that the data user is aware of 

23
the potential limitations of the data. These footnotes are summarized and presented in text (e.g., 

a report or case narrative) accompanying the data. 

24
7.0. Data Reduction 

Data reduction is the process whereby raw data (analytical measurements) are converted 

or reduced to usable results that are reported in the format specified for the project, including QA 

data. Primary data reduction is the responsibility of the analyst(s) conducting the analytical 

measurements, and is subject to further review by laboratory staff, the project leader, and the 

project manager(s). 

Primary data reduction requires accounting for specific sample preparations, sample 

volume or weight analyzed, and any concentrations or dilutions required. All data reduction 

procedures are described in the laboratory’s SOPs. 

7.1. Reported Results 

In general, results are reported as follows: 

● To two (or, if requested, three) significant figures for PACs, POPs and PAC metabolites, 

and to three significant figures for fatty acids; to two figures following the decimal point 

for δ15N and δ13C values; and to one figure following the decimal point for Wt %N, Wt 

%C, C/N ratios, lipid classes, and percent lipid (by TLC/FID). 

● For GC/MS and HPLC/PDA analyses, the analyte concentrations are calculated based on 

the surrogate compounds spiked into the sample prior to extraction. 

● For GC/MS and HPLC/PDA analyses, percent recovery of surrogate standards are 

reported. 

● For GC/MS and HPLC/PDA analyses for PACs and POPs, analytes in sediments are 

reported as ng/g dry weight and in tissues as ng/g wet weight. Percent dry weights of 

samples are determined for tissue analyses if requested. 

● For GC/MS analyses for fatty acids, analytes are reported in units of fatty acid methyl 

esters as mass fraction (%) on a wet-mass basis. 

● Results for analytes in method blanks are reported on the same basis as those for the 

samples being analyzed. The average of the sample weights for the field samples 

comprising a batch, as well as the average of the percent dry weights for sediments, is 

used in the calculations for the method blank. 

● For PACs, POPs, and fatty acids, the lower LOQ is reported instead of a concentration 

when an analyte is below the quantitation range. 

● If a lipid class is not detected in a sample, a value of zero is reported for the proportion of 

that lipid class. 

● If a PAC metabolite peak is not detected by fluorescence in a sample, a value of zero is 

reported for that PAC equivalent. 

25
● Data generated from the analysis of blank samples are not used for correction of analyte 

concentrations in samples, except for the EA/IRMS analyses. 

● Replicate sample data is summarized as the mean plus or minus RSD. 

7.2. Data Review 

Data review is an internal process during which the data are reviewed and evaluated by 

laboratory personnel. This review is undertaken by analysts who are responsible for ensuring 

that the analytical data are correct and complete, the appropriate SOPs have been followed, and 

the QA results meet the acceptance criteria. It is the project manager’s responsibility to ensure 

that all analyses performed by the laboratory are correct, complete, and meet project DQOs. The 

project leader has final review authority. 

7.3. Laboratory Data Deliverables 

The laboratory reports any difficulties encountered during sample preparation and 

analysis, as well as any limitations to the use of the data. In addition, the following specific 

information will be provided as requested: 

● COC/sample receipt checklist, 

● procedure modifications, 

● calibration summaries (initial calibration data, correlation coefficients for HPLC/PDA 

method, continuing calibration data), 

● data tables for field samples, 

● QA data (surrogate recoveries, method blanks, SRMs, replicate field samples), as 

applicable, and 

● corrective actions that were necessary. 

26
8.0. Corrective Action/Procedure Alteration 

The laboratory is required to adhere to the SOPs specified for the project unless 

procedure alterations are necessary to correct unforeseen analytical problems. Laboratory 

personnel are alerted that corrective action is necessary when QA data do not meet the 

acceptance criteria. 

Because most of the corrective actions are handled at the laboratory level, it is the 

immediate responsibility of the analyst to identify and correct the situation before continuing 

with sample analysis. If the problem persists or cannot be identified, the matter is referred to the 

project leader or project manager for further investigation. Once resolved, a narrative describing 

1) the problem, 2) the steps taken to identify and correct the problem, and 3) the action taken to 

remedy the problem in the relevant sample batches, must be prepared and submitted with the 

relevant data package. If the action involves a change from the accepted SOP, the SOP must be 

revised as appropriate. 

27
28
9.0. References 

Buzitis, J., G. M. Ylitalo, and M. M. Krahn. In press. Rapid method for determination of dioxin-like 

PCBs and other congeners in marine sediments using sonic extraction and photodiode array 

detection. Arch. Environ. Contam. Toxicol. 

Krahn, M. M., D. G. Burrows, W. D. MacLeod, Jr., and D. C. Malins. 1987. Determination of individual 

metabolites of aromatic compounds in hydrolyzed bile of English sole (Parophrys vetulus) from 

polluted sites in Puget Sound, Washington. Arch. Environ. Contam. Toxicol. 16:511–522. 

Krahn, M. M., G. M. Ylitalo, J. Buzitis, C. A. Sloan, D. T. Boyd, S. L. Chan, and U. Varanasi. 1994. 

Screening for planar chlorobiphenyls in tissues of marine biota by high-performance liquid 

chromatography with photodiode array detection. Chemosphere 29:117–139. 

Krahn, M. M., G. M. Ylitalo, D. G. Burrows, J. Calambokidis, S. E. Moore, M. Gosho, P. Gearin, P. D. 

Plesha, R. L. Brownell, S. A. Blokhin, K. L. Tilbury, T. Rowles, and J. E. Stein. 2001. 

Organochlorine contaminant concentrations and lipid profiles in eastern North Pacific gray 

whales (Eschrichtius robustus). J. Cetacean Res. Manag. 3:19–29. 

Krahn, M. M., D. P. Herman, G. M. Ylitalo, C. A. Sloan, D. G. Burrows, R. C. Hobbs, B. A. Mahoney, 

G. K. Yanagida, J. Calambokidis, and S. E. Moore. 2004. Stratification of lipids, fatty acids and 

organochlorine contaminants in blubber of white whales and killer whales. J. Cetacean Res. 

Manag. 64:175-189. 

Krahn, M. M., D. P. Herman, C. O. Matkin, J. W. Durban, L. Barrett-Lennard, D. G. Burrows, M. E. 

Dahlheim, N. Black, R. G. LeDuc, and P. R. Wade. In prep. Use of chemical profiles in 

assessing the feeding ecology of eastern North Pacific killer whales. (Available from Margaret 

Krahn, Northwest Fisheries Science Center, Environmental Conservation Division, 2725 

Montlake Blvd. E., Seattle, WA 98112.) 

NOAA (National Oceanic and Atmospheric Administration). 1989. National Status and Trends Program: 

A summary of data on tissue contamination from the first three years (1986–1988) of the Mussel 

Watch Project. NOAA Technical Memorandum NOS OMA 49. NOAA, NOS Office of 

Oceanography and Marine Assessment, Rockville, MD. 

Sloan, C. A., D. W. Brown, R. W. Pearce, R. H. Boyer, J. L. Bolton, D. G. Burrows, D. P. Herman, and 

M. M. Krahn. 2004. Extraction, cleanup and gas chromatography/mass spectrometry analysis of 

sediments and tissues for organic contaminants. U.S. Dept. Commer., NOAA Tech. Memo. 

NMFS-NWFSC-59. 

Sloan, C. A., D. W. Brown, R. W. Pearce, R. H. Boyer, J. L. Bolton, D. G. Burrows, D. P. Herman, and 

M. M. Krahn. 2005. Determining aromatic hydrocarbons and chlorinated hydrocarbons in 

sediments and tissues using accelerated solvent extraction and gas chromatography/mass 

spectrometry. In G.K. Ostrander (ed.), Techniques in Aquatic Toxicology, Volume 2, 

p. 631–651. CRC Press, Boca Raton, FL. 

29
Ylitalo, G. M., J. Buzitis, D. T. Boyd, D. P. Herman, K. L. Tilbury, and M. M. Krahn. 2005a. 

Improvements to high-performance liquid chromatography/photodiode array detection 

(HPLC/PDA) method that measures dioxin-like polychlorinated biphenyls and other selected 

organochlorines in marine biota. In G. K. Ostrander (ed.), Techniques in Aquatic Toxicology, 

Volume 2, p. 449–464. CRC Press, Boca Raton, FL. 

Ylitalo, G. M., G. K. Yanagida, L. C. Hufnagle Jr., and M. M. Krahn. 2005b. Determination of lipid 

classes and lipid content in tissues of aquatic organisms using a thin layer chromatography/flame 

ionization detection (TLC/FID) microlipid method. In G. K. Ostrander (ed.), Techniques in 

aquatic toxicology, Volume 2, p. 227–237. CRC Press, Boca Raton, FL. 

30
Most NOAA Technical Memorandums NMFS-NWFSC are available online at the

Northwest Fisheries Science Center web site (http://www.nwfsc.noaa.gov).

NOAA Technical Memorandum NMFS-NWFSC76 Gustafson R.G., J. Drake, M.J. Ford, J.M. Myers, E.E. Holmes, and R.S. Waples. 2006. Status review 

of Cherry Point Pacific herring (Clupea pallasii) and updated status review of the Georgia Basin Pacific 

herring distinct population segment under the Endangered Species Act. U.S. Dept. Commer., NOAA Tech. 

Memo. NMFS-NWFSC-76, 182 p. NTIS number pending.

75 Keller, A.A., B.H. Horness, V.J. Tuttle, J.R. Wallace, V.H. Simon, E.L. Fruh, K.L. Bosley, and D.J.

 Kamikawa. 2006. The 2002 U.S. West Coast upper continental slope trawl survey of groundfish resources

 off Washington, Oregon, and California: Estimates of distribution, abundance, and length composition. 

U.S. Dept. Commer., NOAA Tech. Memo. NMFS-NWFSC-75, 189 p. NTIS PB2006-111432.

74 Pool, S.S., and R.D. Brodeur. 2006. Neustonic mesozooplankton abundance and distribution in the northern California Current, 2000 and 2002. U.S. Dept. Commer., NOAA Tech. Memo. NMFS-NWFSC-74,

 76 p. NTIS PB2006-109275.

73 Myers, J., C. Busack, D. Rawding, A. Marshall, D. Teel, D.M. Van Doornik, and M.T. Maher. 2006.

 Historical population structure of Pacific salmonids in the Willamette River and lower Columbia River

 basins. U.S. Dept. Commer., NOAA Tech. Memo. NMFS-NWFSC-73, 311 p. NTIS PB2006-109278.

72 Keller, A.A., E.L. Fruh, K.L. Bosley, D.J. Kamikawa, J.R. Wallace, B.H. Horness, V.H. Simon, and 

V.J. Tuttle. 2006. The 2001 U.S. West Coast upper continental slope trawl survey of groundfish resources 

off Washington, Oregon, and California: Estimates of distribution, abundance, and length composition. U.S.

 Dept. Commer., NOAA Tech. Memo. NMFS-NWFSC-72, 175 p. NTIS PB2006-109277

71 Nash, C.E., P.R. Burbridge, and J.K. Volkman (editors). 2005. Guidelines for ecological risk assessment of marine fish aquaculture. U.S. Dept. Commer., NOAA Tech. Memo. NMFS-NWFSC-71, 90 p. 

NTIS PB2006-109287.

70 Keller A.A., T.L. Wick, E.L. Fruh, K.L. Bosley, D.J. Kamikawa, J.R. Wallace, and B.H. Horness.

 2005. The 2000 U.S. West Coast upper continental slope trawl survey of groundfish resources off

 Washington, Oregon, and California: Estimates of distribution, abundance, and length composition. U.S.

 Dept. Commer., NOAA Tech. Memo. NMFS-NWFSC-70, 163 p. NTIS PB2006-109276.

69 Fresh, K.L., E. Casillas, L.L. Johnson, and D.L. Bottom. 2005. Role of the estuary in the recovery of

 Columbia River basin salmon and steelhead: An evaluation of the effects of selected factors on salmonid

 population viability. U.S. Dept. Commer., NOAA Tech. Memo. NMFS-NWFSC-69, 105 p. NTIS PB2005-

 106685

68 Bottom, D.L., C.A. Simenstad, J. Burke, A.M. Baptista, D.A. Jay, K.K. Jones, E. Casillas, and M.H.

 Schiewe. 2005. Salmon at riverʼs end: The role of the estuary in the decline and recovery of Columbia

 River salmon. U.S. Dept. Commer., NOAA Tech. Memo. NMFS-NWFSC-68, 246 p. NTIS PB2006-

 101123.

Recent NOAA Technical Memorandums

published by the

Northwest Fisheries Science Center