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United States 

Environmental Protection 

Agency 

Office of Water EPA 823-B-95-001 

(4305) April 1995 

QA/QC Guidance for Sampling 

and Analysis of Sediments, 

Water, and Tissues for Dredged 

Material Evaluations 

Chemical Evaluations 
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY 

WASHINGTON, D.C. 20460 

EPA 823-B-95-001 

APR 28 1995 OFFICE OF WATER 

Dear Colleagues: 

The U.S. Environmental Protection Agency (EPA) is pleased to 

transmit a copy of the document titled QA/QC Guidance for 

Sampling and Analysis of Sediments, Water, and Tissues for 

Dredged Material Evaluations. Chemical Evaluations. This 

document was prepared in response to regional requests for 

quality assurance/quality control (QA/QC) guidance associated 

with the testing and evaluation of proposed dredged material 

discharges into inland or ocean waters. The Workgroup that 

developed this national guidance was comprised of individuals 

from headquarters, field offices, and research laboratories of 

EPA and the U.S. Army Corps of Engineers (USACE) with experience 

related to dredged material discharge activities. 

EPA and USACE technical guidance for evaluating the 

potential for contaminant-related impacts associated with the 

discharge of dredged material into inland and ocean waters, 

respectively, is found in the documents “Evaluation of Dredged 

Material Proposed for Discharge in Waters of the U.S. Testing 

Manual (Draft)" (the Inland Testing Manual) (U.S. EPA and USACE 

1994), and “Evaluation of Dredged Material Proposed for Ocean 

Disposal--Testing Manual" (the Ocean Testing Manual) (U.S. EPA and 

USACE 1991). Results of tests conducted using the testing 

manuals are the basis of independent evaluations made by EPA and 

USACE regarding the suitability of proposed dredged material for 

aquatic disposal. 

This QA/QC guidance document serves as a companion document 

to the Inland and Ocean Testing manuals. The purpose of this 

document is as follows: 1) to provide guidance on the 

development of quality assurance project plans for ensuring the 

reliability of data gathered to evaluate dredged material 

proposed for discharge under the Clean Water Act or the Marine 

Protection Research and Sanctuaries Act, 2) to outline procedures 

that should be followed when sampling and analyzing sediments, 

water, and tissues, and 3) to provide recommended target 

detection limits for chemicals of concern. This document 

pertains largely to physical and chemical evaluations. Though it 

is directed primarily toward the evaluation of dredged material 

for aquatic disposal, it may be useful in other areas of dredged 

material assessment and management as well (e.g., disposal site 

monitoring or evaluation of alternative disposal options). The 

audience for this document is Federal and State agency personnel 

and public with an interest in the evaluation and management of 
2 

dredged material. The information provided herein is for the 

purpose of guidance only and does not constitute a regulatory 

requirement. 

Requests for copies of this document (EPA document number 

EPA 823-B-95-001) should be sent to U.S. Environmental Protection 

Agency, National Center for Environmental Publications and 

Information, 11029 Kenwood Road, Building 5, Cincinnati, Ohio 

45242. 

We appreciate your continued interest in EPA's activities 

related to impact assessment of potentially contaminated 

sediments. 

Sincerely, 

Tudor T. Davies Robert H. Wayland III 

Director Director 

Office of Science Office of Wetlands, 

and Technology Oceans and Watersheds 

Enclosure 
United States 

Environmental Protection 

Agency 

Office of Water EPA 823-B-95-001 

(4305) April 1995 

QA/QC Guidance for Sampling 

and Analysis of Sediments, 

Water, and Tissues for Dredged 

Material Evaluations 

Chemical Evaluations 
QA/QC GUIDANCE FOR SAMPLING AND ANALYSIS 

OF SEDIMENTS, WATER, AND TISSUES 

FOR DREDGED MATERIAL EVALUATIONS 

CHEMICAL EVALUATIONS 

Office of Water 

Office of Science and Technology 

Standards and Applied Science Division 

U.S. Environmental Protection Agency 

Washington, DC 20460 

April 1995 
The polices set out in this document are not final agency action, but are intended 

solely as guidance. They are not intended, nor can they be relied upon, to create any 

rights enforceable by any party in litigation with the United States. EPA officials may 

decide to follow the guidance provided in this document, or to act at variance with the 

guidance, based on an analysis of specific site circumstances. The Agency also 

reserves the right to change this guidance at any time without public notice. 

ii 
CONTENTS 

LIST OF FIGURES 

LIST OF TABLES 

ACRONYMS AND ABBREVIATIONS 

ACKNOWLEDGMENTS 

1. INTRODUCTION 

1.1 GOVERNMENT (DATA USER) PROGRAM 

1.2 CONTRACTOR (DATA GENERATOR) PROGRAM 

2. DRAFTING A QUALITY ASSURANCE PROJECT PLAN 

2.1 

2.2 

INTRODUCTORY MATERIAL 6 

QUALITY ASSURANCE ORGANIZATION AND 

RESPONSIBILITIES 7 

2.2.1 Staffing for Quality Assurance 7 

2.2.2 Statements of Work 8 

2.3 QUALITY ASSURANCE OBJECTIVES 14 

2.3.1 Program vs. Project Objectives 14 

2.3.2 Target Detection Limits for Chemicals 15 

2.4 STANDARD OPERATING PROCEDURES 16 

2.5 SAMPLING STRATEGY AND PROCEDURES 36 

2.5.1 Review of Dredging Plan 39 

2.5.2 Site Background and Existing Database 40 

2.5.3 Subdivision of Dredging Area 42 

2.5.4 Sample Location and Collection Frequency 42 

2.5.5 Sample Designation System 46 

2.5.6 Station Positioning 47 

Page 

vii 

ix 

xi 

xiii 

1 

3 

3 

6 

iii 
2.5.7 Sample Collection Methods 

2.5.8 Sample Handling, Preservation, and Storage 

2.5.9 Logistical Considerations and Safety Precautions 

2.6 SAMPLE CUSTODY 

50 

53 

59 

60 

2.6.1 Sample Custody and Documentation 

2.6.2 Storage and Disposal of Samples 

2.7 CALIBRATION PROCEDURES AND FREQUENCY 

60 

64 

64 

2.7.1 Calibration Frequency 65 

2.7.2 Number of Calibration Standards 68 

2.7.3 Calibration Acceptance Criteria 69 

2.8 ANALYTICAL PROCEDURES 70 

2.8.1 Physical Analysis of Sediment 

2.8.2 Chemical Analysis of Sediment 

2.8.3 Chemical Analysis of Water 

2.8.4 Chemical Analysis of Tissue 

2.9 DATA VALIDATION, REDUCTION, AND REPORTING 

2.9.1 Data Validation 

2.9.2 Data Reduction and Reporting 

2.10 INTERNAL QUALITY CONTROL CHECKS 

70 

71 

78 

83 

2.10.1 Priority and Frequency of Quality Control Checks 

2.10.2 Specifying Quality Control Limits 

2.10.3 Quality Control Considerations for Physical Analysis 

of Sediments 

2.10.4 Quality Control Considerations for Chemical Analysis of 

Sediments 

2.10.5 Quality Control Considerations for Chemical Analysis of 

Water 

2.10.6 Quality Control Considerations for Chemical Analysis of 

Tissue 

87 

88 

91 

91 

93 

96 

99 

99 

100 

100 

iv 
2.11 PERFORMANCE AND SYSTEM AUDITS 

2.11.1 Procedures for Pre-Award Inspections of Laboratories 

2.11.2 Interlaboratory Comparisons 

2.11.3 Routine System Audits 

2.12 FACILITIES 

2.13 PREVENTIVE MAINTENANCE 

2.14 CALCULATION OF DATA QUALITY INDICATORS 

2.15 CORRECTIVE ACTIONS 

2.16 QUALITY ASSURANCE REPORTS TO MANAGEMENT 

2.16.1 Preparing Basic Quality Assurance Reports 

2.16.2 Preparing Detailed Quality Assurance Reports 

2.17 REFERENCES 

3. REFERENCES 

4. GLOSSARY 

APPENDIX A - Example QA/QC Checklists, Forms, and Records 

APPENDIX B - Example Statement of Work for the Laboratory 

APPENDIX C - Description of Calibration, Quality Control Checks, 

and Widely Used Analytical Methods 

APPENDIX D - Standard Operating Procedures 

101 

101 

102 

104 

104 

105 

105 

107 

108 

108 

109 

110 

111 

123 

APPENDIX E - EPA Priority Pollutants and Additional Hazardous Substance 

List Compounds 

APPENDIX F - Example Quality Assurance Reports 

APPENDIX G - Analytical/Environmental Laboratory Audit 

Standard Operating Procedure 

APPENDIX H - Format for the Sediment Testing Report 

V 
LIST OF FIGURES 

Figure 1. Guidance for data assessment and screening 

for data quality 

Page 

92 

vii 
LIST OF TABLES 

Table 1. 

Table 2. 

Table 3. 

Table 4. 

Table 5. 

Table 6. 

Table 7. 

Table 8. 

Table 9. 

Table 10. 

Table 11. 

Table 12. 

Table 13. 

Table 14. 

Checklist of laboratory deliverables for the analysis 

of organic compounds 

Checklist of laboratory deliverables for the analysis 

of metals 

Routine analytical methods and target detection 

limits for sediment, water, and tissue 

Levels of data quality for historical data 

Summary of recommended procedures for sample 

collection, preservation, and storage 

Example calibration procedures 

PCDD and PCDF compounds determined by 

Method 1613 

Polychlorinated biphenyl congeners recommended 

for quantitation as potential contaminants of 

concern 

Methodology for toxicity equivalency factors 

Octanol/water partition coefficients for organic 

compound priority pollutants and 301 (h) pesticides 

Bioconcentration factors of inorganic priority 

pollutants 

Levels of data validation 

Example warning and control limits for calibration 

and quality control samples 

Sources of standard reference materials 

Page 

11 

13 

17 

41 

54 

66 

74 

76 

79 

81 

85 

90 

98 

103 

ix 
ACRONYMS AND ABBREVIATIONS 

AVS 

BCF 

CLP 

CVAA 

CWA 

EPA 

GC 

GC/ECD 

GC/MS 

GFAA 

ICP 

MPRSA 

PAH 

PCB 

PCDD 

PCDF 

QAMP 

QAPP 

QA/QC 

SRM 

TCDD 

TDL 

TEF 

TOC 

USACE 

acid volatile sulfide 

bioconcentration factor 

Contract Laboratory Program 

cold vapor atomic absorption spectrometry 

Clean Water Act 

U.S. Environmental Protection Agency 

gas chromatography 

gas chromatography/electron capture detection 

gas chromatography/mass spectrometry 

graphite furnace atomic absorption spectrometry 

inductively coupled plasma-atomic emission 

spectrometry 

Marine Pollution, Research, and Sanctuaries Act 

polycyclic aromatic hydrocarbon 

polychlorinated biphenyl 

polychlorinated dibenzo-pdioxin 

polychlorinated dibenzofuran 

quality assurance management plan 

quality assurance project plan 

quality assurance and quality control 

standard reference material 

tetrachlorodibenzo-p-dioxin 

target detection limit 

toxicity equivalency factor 

total organic carbon 

U.S. Army Corps of Engineers 
ACKNOWLEDGMENTS 

The contributions made by many individuals are gratefully acknowledged. The 

work group was comprised of individuals from headquarters, field offices, and 

research laboratories of the U.S. Environmental Protection Agency (EPA) and 

the U.S. Army Corps of Engineers (USACE) with experience related to dredged 

material discharge activities. 

Members: Jim Barron EPA/OERR (Super-fund) 

Patricia Boone EPA/Region 5 

Suzy Cantor-McKinney EPA/Region 6 

Tom Chase EPAIOWOW 

Pat Cotter EPA/Region 9 

Tom Dixon EPAIQAMS 

Bob Engler USACEMIES 

Rick Fox EPA/GLNPO 

Catherine Fox EPA/Region 4 

Bob Graves EPAIEMSL Cincinnati 

Doug Johnson EPA/Region 4 

Lloyd Kahn EPA/Region 2 

Linda Kirkland EPA/QAMS 

Mike Kravitz EPA/OST (CHAIR) 

Jim Lazorchak EPA/EMSL Cincinnati 

Alex Lechich EPA/Region 2 

John Malek EPAIRegion 10 

William Muir EPA/Region 3 

Rich Pruell EPA/ORD-N 

Norm Rubinstein EPAIORD-N 

Brian Schumacher EPA/EMSL Las Vegas 

George Schupp EPA/Region 5 

Ann Strong USACE/WES 

William Telliard EPA/OST 

Dave Tomey EPA/Region 1 

This manual also benefitted from contributions made by the following 

individuals: Robert Barrick (PTI Environmental Services), John Bourbon (EPA 

Region 2), Melissa Bowen (Tetra Tech), Alan Brenner (EPA Region 2), Peter 

Chapman (EVS Consultants), James Clausner (USACE WES), John Dorkin 

(EPA Region 5) Robert Howard (EPA Region 4), Charlie MacPherson (Tetra 

Tech), Kim Magruder (EVS Consultants), Brian Melzian (EPA ORD-N), Bob 

Runyon (EPA Region 2), Sandra Salazar (EVS Consultants), Jane Sexton (PTI 

Environmental Services), Bruce Woods (EPA Region lo), and Tom Wright 

(USACE WES). 

,.. 

XIII 
1. INTRODUCTION 

This document provides programmatic and technical guidance on quality 

assurance and quality control (QA/QC) issues related to dredged material 

evaluations. The US. Army Corps of Engineers (USACE) and U.S. 

Environmental Protection Agency (EPA) share the Federal responsibility for 

regulating the discharge of dredged material under two major acts of Congress. 

The Clean Water Act (CWA) governs discharges of dredged material into 

“waters of the United States,” including all waters landward of the baseline of 

the territorial sea. The Marine Protection, Research, and Sanctuaries Act 

(MPRSA) governs the transportation of dredged material seaward of the 

baseline (in ocean waters) for the purpose of disposal. 

EPA and USACE technical guidance for evaluating the potential for 

contaminant-related impacts associated with the discharge of dredged material 

into inland and ocean waters, respectively, is found in the documents 

“Evaluation of Dredged Material Proposed for Discharge in Waters of the 

U.S.-Testing Manual (Draft)” (the Inland Testing Manual) (U.S. EPA and 

USACE 1994), and “Evaluation of Dredged Material Proposed for Ocean 

Disposal-Testing Manual” (the Ocean Testing Manual) (U.S. EPA and USACE 

1991). Results of tests conducted using the testing manuals are the basis of 

independent evaluations made by EPA and USACE regarding the suitability of 

proposed dredged material for aquatic disposal. 

This QA/QC guidance document serves as a companion document to the 

Inland and Ocean Testing manuals. The purpose of this document is as 

follows: 1) to provide guidance on the development of quality assurance project 

plans for ensuring the reliability of data gathered to evaluate dredged material 

proposed for discharge under the CWA or the MPRSA, 2) to outline procedures 

that should be followed when sampling and analyzing sediments, water, and 

tissues, and 3) to provide recommended target detection limits (TDLs) for 

chemicals of concern. This document pertains largely to physical and chemical 

evaluations. Though it is directed primarily toward the evaluation of dredged 

material for aquatic disposal, it may be useful in other areas of dredged 

material assessment and management as well (e.g., disposal site monitoring or 

evaluation of alternative disposal options). 

QA/QC planning is necessary to ensure that the chemical and biological data 

generated during dredged material evaluations meet overall program and 

specific project needs. Establishing QA/QC procedures is fundamental to 

meeting project data quality criteria and to providing a basis for good decisionmaking. The EPA has developed a two-tiered quality management structure 
that addresses QA concerns at both the organizational level and at the 

technical/project level. QA management plans (known as QAMPs) identify the 

mission and customers of the organization, document specific roles and 

responsibilities of top management and employees, outline the structure for 

effective communications, and define how measures of effectiveness will be 

established. The quality standards, goals, performance specifications, and the 

QA/QC activities necessary to achieve them, are incorporated into projectspecific QA project plans (known as QAPPs). 

QA activities provide a formalized system for evaluating the technical adequacy 

of sample collection and laboratory analysis activities. These QA activities 

begin before samples are collected and continue after laboratory analyses are 

completed, requiring ongoing coordination and oversight. The QA program 

summarized in this document integrates management and technical practices 

into a single system to provide environmental data that are sufficient, 

appropriate, and of known and documented quality for dredged material 

evaluation. 

QA project plans (QAPPs) provide a detailed plan for the activities performed at 

each stage of the dredged material evaluation (including appropriate sampling 

and analysis procedures) and outline project-specific data quality objectives that 

should be achieved for field observations and measurements, physical 

analyses, laboratory chemical analyses, and biological tests. Data quality 

objectives should be defined prior to initiating a project and adhered to for the 

duration of the project to guarantee acquisition of reliable data. This is 

accomplished by integrating quality control (QC) into all facets of the project, 

including development of the study design, implementation of sample collection 

and analysis, and data evaluation. QC is the routine application of procedures 

for determining bias and precision. QC procedures include activities such as 

preparation of replicate samples, spiked samples, blanks: calibration and 

standardization; and sample custody and recordkeeping. Audits, reviews, and 

compilation of complete and thorough documentation are QA activities used to 

verify compliance with predefined QC procedures. Through periodic reporting, 

these QA activities provide a means for management to track project progress 

and milestones, performance of measurement systems, and data quality. 

A complete QA/QC effort for a dredged material testing program has two major 

components: a QA program implemented by the responsible governmental 

agency (the data user), and QC programs implemented by sampling and 

laboratory personnel performing the tests (the data generators). QA programs 

are also implemented by each field contractor and each laboratory. Typically, 

all field and laboratory data generators agree to adhere to the QA/QC of the 

data user for the contracted project as specified in the project QAPP. USEPA 

(1987a) provides useful guidance and may be followed on all points that are not 

in conflict with the guidance in this document. The guidance provided in this 

2 
document also incorporates information contained in U.S. EPA (1984a, 1991d) 

and U.S. EPA and USACE (1991, 1994). 

1.1 GOVERNMENT (DATA USER) PROGRAM 

Because the data generated in a dredged material evaluation are used for 

regulatory purposes, it is important to have proper QA oversight. The USACE, 

working in conjunction with the appropriate EPA Region(s), should implement a 

QA program to ensure that all program elements and testing activities (including 

field and laboratory operations) in the dredged material evaluation comply with 

the procedures in the QA project plan or with other specified guidelines for the 

production of environmental data of known quality. This QA guidance 

document was designed with the assistance of programmatic and scientific 

expertise from both EPA and USACE. Other qualified sources of QA program 

management should be contacted as appropriate. Some specific QA 

considerations in contract laboratory selection are discussed by Sturgis (1990) 

and U.S. EPA (1991d). 

The guidance in this document is intended to assist EPA and USACE dredged 

material managers in developing QA project plans to ensure that: 1) the data 

submitted with dredged material permit applications are of high quality, 

sufficient, and appropriate for determining if dredging and disposal should 

occur; and 2) the contract laboratories comply with QC specifications of the 

regulations and guidelines governing dredged material evaluations. This 

includes the development of an appropriate QA management plan. 

1.2 CONTRACTOR (DATA GENERATOR) PROGRAM 

Each office or laboratory participating in a dredged material evaluation is 

responsible for using procedures which assure that the accuracy (precision and 

bias), representativeness, comparability, and completeness of its data are 

known and documented. To ensure that this responsibility is met, each 

participating organization should have a project manager and a written QA 

management plan that describes, in specific terms, the management approach 

proposed to assure that each procedure under its direction complies with the 

criteria accepted by EPA and USACE. This plan should describe a QA policy, 

address the contents and application of specific QA project plans, specify 

training requirements, and include other elements recommended by EPA quality 

assurance management staff (e.g., management system reviews). All field 

measurements, sampling, and analytical components (physical, chemical, and 

biological) of the dredged material evaluation should be discussed. 

3 
For the completion of a dredged material testing project, the project manager of 

each participating organization should establish a well-structured QA program 

that ensures the following: 

Development, implementation, and administration of appropriate 

QA planning documents for each study 

Inclusion of routine QC procedures for assessing data quality in all 

field and laboratory standard operating procedures 

Performance of sufficiently detailed audits at intervals frequent 

enough to ensure conformance with approved QA project plans 

and standard operating procedures 

Periodic evaluation of QC procedures to improve the quality of QA 

project plans and standard operating procedures 

Implementation of appropriate corrective actions in a timely 

manner. 

The guidance provided in this document is intended to assist the data generator 

with the production of high-quality data in the field and in the laboratory (i.e., 

the right type and quality of information is provided to EPA and USACE to 

make a decision about the suitability of dredged material for aquatic disposal 

with the specified degree of confidence). 

- 

4 
2. DRAFTING A QUALITY ASSURANCE 

PROJECT PLAN 

A formal strategy should always be developed to obtain sufficient and 

appropriate data of known quality for a specific dredged material testing 

program. When the sample collection and laboratory analysis effort is small, 

this strategy may be relatively straightforward. However, when the sample 

collection and laboratory analysis effort is significant, the assurance of data 

quality may require the formulation of a formal and often quite detailed QA 

project plan. The QA project plan is a planning and an operational document. 

The QA project plan should be developed by the applicant or contractor for 

each dredged material evaluation, in accordance with this document. The QA 

project plan provides an overall plan and contains specific guidelines and 

procedures for the activities performed at each stage of the dredged material 

testing program, such as dredging site subdivision, sample collection, 

bioassessment procedures, chemical and physical analyses, data quality 

standards, data analysis, and reporting. In particular, the QA plan addresses 

required QC checks, performance and system audits, QA reports to 

management, corrective actions, and assessment of data accuracy (precision 

and bias)‘, representativeness, comparability, and completeness. The plan 

should address the quantity of data required to allow confident and justifiable 

conclusions and decisions. 

The following information should be included in each QA project plan for 

dredged material evaluation unless a more abbreviated plan can be justified 

(see U.S. EPA 1989a): 

n Introductory material, including title and signature pages, table of 

contents, and project description 

n QA organization and responsibilities (the QA organization should 

be designed to operate with a degree of independence from the 

technical project organization to ensure appropriate oversight) 

1 Historically, “accuracy” and “precision” have often been defined as separate 

and distinct terms. In particular, accuracy has often been taken to be only a 

measure of how different a value is from the true value (i.e., bias). However, data 

that have poor precision (i.e., high variability) may only have low bias on the 

average (i.e., close agreement to the true value). Therefore, recent literature (e.g., 

Kirchmer 1988) has defined accuracy as both the precision and bias of the data. 

This definition of accuracy is used throughout this guidance document, 

5 
QA objectives 

Standard Operating Procedures 

Sampling strategy and procedures 

Sample custody 

Calibration procedures and frequency 

Analytical procedures 

Data validation, reduction, and reporting 

Internal QC checks 

Performance and system audits 

Facilities 

Preventive maintenance 

Calculation of data quality indicators 

Corrective actions 

QA reports to management 

References. 

The remaining sections of this document provide more specific information on 

each of these items. 

2.1 INTRODUCTORY MATERIAL 

The following sections should be included at the beginning of every QA project 

plan: 

• Title and signature pages 

• Table of contents 

• Project description 

• Certification. 

The signature page should be signed and dated by those persons responsible 

for approving and implementing the QA project plan. The applicant’s project 

manager’s signature should be included even if other persons are primarily 

responsible for QA activities. The headings in the table of contents should 

match the headings in the QA project plan. A list of figures, list of tables, and 

list of appendices should be included in the table of contents. 

6 
The goals and objectives of the study project should be outlined in the project 

description. The project description should illustrate how the project will be 

designed to obtain the information needed to achieve those goals. Sufficient 

detail and information should be included for regulatory agency decisionmaking. 

The QA project plan should include the following certification statement signed 

by a duly authorized representative of the permit-tee: 

I certify under penalty of law that this document and all 

attachments were prepared under my direction or supervision. 

The information submitted is, to the best of my knowledge and 

belief, true, accurate, and complete. I am aware there are 

significant penalties for submitting false information, including 

the possibility of fine and imprisonment for knowing violations. 

2.2 QUALITY ASSURANCE ORGANIZATION AND 

RESPONSIBILITIES 

A clear delineation of the QA organization and line of authority is essential for 

the development, implementation, and administration of a QA program. The 

relationship of the QA personnel to the overall project team and their 

responsibilities for implementing the QA program are identified in this section. 

In addition, guidance is provided for developing statements of work that address 

the responsibilities of contract laboratories used in the project. 

2.2.1 Staffing for Quality Assurance 

Organizational charts or tables should be used in the QA project plan to 

describe the management structure, personnel responsibilities, and the 

interaction among functional units. Each QA task should be fully described and 

the responsible individual, their respective telephone number, and the 

associated organization named. Names of responsible individuals should be 

included for the sampling team, the analytical laboratory, the data evaluation, 

QA/QC effort in the laboratory, and the data analysis effort. An example of a 

QA organization flow diagram is provided in Appendix A. 

The project manager has overall responsibility for assuring the quality of data 

generated for a project. In most projects, actual QA activities are performed 

independent of the project manager. However, the project manager does 

ensure the implementation of any corrective actions that are called for during 

sampling, analysis, or data assessment. The writing of a QA project plan can 

usually be accomplished by one person with assistance as needed from 

7 
technical specialists for details of methods or QC criteria. One person should 

also have primary responsibility for coordinating the oversight of all sampling 

activities, including completion of all documentation for samples sent to the 

laboratory. Coordinating laboratory interactions before and during sample 

analysis is also best performed by one person to avoid confusion. Subsequent 

interactions that may be necessary with the laboratory during a CIA review of 

the data may involve the persons actually doing the review. 

Additional QC tasks and responsibilities during sampling and analysis are often 

assigned to technicians who collect samples, record field data, and operate and 

maintain sampling and analytical equipment. These technicians perform a 

number of essential day-to-day activities, which include calibrating and servicing 

equipment, checking field measurements and laboratory results, and 

implementing modifications to field or laboratory procedures. These individuals 

should have training to perform these functions and follow established protocols 

and guidelines for each of these tasks. 

Technical staff are responsible for the validity and integrity of the data 

produced. The QA staff should be responsible for ensuring that all personnel 

performing tasks related to data quality are appropriately qualified. Records of 

qualifications and training of personnel should be kept current for verification by 

internal QA personnel or by regulatory agency personnel. 

Technical competence and experience of all contract laboratory staff should be 

demonstrated. Staff qualifications should be documented, and training should 

be provided by the laboratory to encourage staff to attain the highest levels of 

technical competence. Staff turnover can affect the ability of a laboratory to 

perform a particular analysis. The experience of current staff with projects of 

similar scope should be assessed during the laboratory selection process. 

Technical competence and other factors such as the laboratory setup (including 

quality and capacity of the available analytical equipment), past experience 

(e.g., analysis of appropriate QC check samples and review of quarterly 

performance evaluation analyses), or an upfront demonstration of performance 

can be used to influence the project manager’s selection. The need to conduct 

a comprehensive evaluation of candidate laboratories will vary with the project 

and the familiarity with available laboratories. 

2.2.2 Statements of Work 

Statements of work are prepared for both field work and laboratory analysis. 

Data quality requirements and analytical methods need to be clearly and 

concisely communicated to either USACE personnel performing the analyses or 

to the laboratory selected by USACE’s or the permit applicant’s project 

manager. These specifications are best contained in a written laboratory 

contract. The main body of the contract should consist of general terms and 

8 
conditions common to any legal contract. A statement of work should be 

appended to the contract. The statement of work should be drafted and 

negotiated with the laboratory prior to the start of any analyses. The statement 

of work should be written in clear and concise terms, providing sufficient detail 

and references to approved protocols for each required procedure or method to 

eliminate any confusion about steps in the analysis. The statement of work 

should define all requirements for acceptable analyses, an important 

consideration even when working with a familiar laboratory, and all pertinent 

information on the price, timing, and necessary documentation of the analyses. 

All available information on the range of concentrations expected and any 

special characteristics of the samples to be analyzed should also be contained 

in the statement of work. A generic statement of work for the analysis of most 

chemicals in the most commonly analyzed sample matrices is provided in 

Appendix B, and is based on the following outline: 

w A summary of analyses to be performed, including: 

- A list of all variables to be analyzed for in each sample or 

group of samples 

- A list of all methods and target detection limits (TDLs) 

(see discussion in Section 2.3.2) for physical and 

chemical analyses and a list of test protocols for biological 

toxicity tests 

- The total number of samples provided for analysis and 

the associated laboratory QC samples, the cost of each 

analysis, and the total cost of the analytical service 

requested for each sample matrix. 

n Acceptable procedures for sample delivery and storage, including: 

- The method of delivery, schedule of delivery, and person 

responsible for notifying the laboratory of any changes in 

the schedule 

- Requirements for physical storage of samples, holding 

times (consistent with those specified in the QA project 

plan), chain-of-custody, and sample logbook procedures. 

n Methods to be followed for processing and analyzing samples. 

n QA/QC requirements, including the data quality objectives 

specified in the QA project plan and appropriate warning and 

control limits. 

n A list of products to be delivered by the laboratory, specifying the 

maximum time that may elapse between the submittal of samples 

to the laboratory and the delivery of data reports to the agency, 

-- ___- 

9 
organization, or industry requesting the analyses, Penalties for 

late delivery (and any incentives for early delivery) should be 

specified, as should any special requirements for supporting 

documentation and electronic data files. A checklist of the 

laboratory deliverables for analysis of organic compounds, 

pesticides, and polychlorinated biphenyls (PCBs) is presented in 

Table 1. A checklist of laboratory deliverables for analysis of 

metals is presented in Table 2. 

Progress notices (usually necessary only for large projects). 

Circumstances under which the laboratory should notify project 

personnel of problems, including, for example, when control limits 

or other performance criteria cannot be met, instrument 

malfunctions are suspected, or holding time limits have or will 

shortly expire. 

Written authorization for any deviations from the sampling and 

analysis plan should be obtained from EPA and USACE before the 

deviation occurs. 

Notice that scheduled and unannounced laboratory visits by the 

project manager or representative may be conducted. 

The following additional information should also be provided in the laboratory 

statement of work: 

n Requirements that each laboratory submit a QA manual for review 

and approval by the agency, organization, or industry requesting or 

funding the analysis. Each manual should contain a description of 

the laboratory organization and personnel, facilities and equipment, 

analytical methods, and procedures for sample custody, quality 

control, data handling, and results of previous laboratory audits, 

n Conditions for rejection or non-analysis of samples and reanalysis 

of samples. 

m Required storage time for records and samples prior to disposal. 

n Terms for payments to the laboratory, including a requirement that 

the quality of data must be acceptable (pending the outcome of 

the QA review) before payment is made. 

Including these elements in the statement of work helps to assure that 

responsibilities, data requirements, and expectations for performance are clear. 

A copy of the statement of work should be provided to the individual performing 

the data assessment to assist in the evaluation of data returned by the 

laboratory. 

10 
TABLE 1. CHECKLIST OF LABORATORY DELIVERABLES FOR 

THE ANALYSIS OF ORGANIC COMPOUNDS 

A cover letter discussing analytical problems (if any) and referencing or 

describing the procedures and instrumentation used. 

Cl Tabulated results, including final dilution volume of sample extracts, sample 

size, wet-to-dry ratios for solid samples (if requested), concentrations of compounds of interest (reported in units identified to two significant figures unless 

otherwise justified), and equations used to perform calculations. 

Concentration units should be lg/kg (dry weight) for sediment, and ug/L for 

water, ug/kg (wet weight) for tissue. These results should be checked for 

accuracy and the report signed by the laboratory manager or designee. 

cl Target detection limits (see discussion in Section 2.3.2 of this document), 

instrument detection limits, and detection limits achieved for the samples. 

0 Original data quantification reports for each sample. 

cl Method blanks associated with each sample, quantifying all compounds of 

interest identified in these blanks. 

cl A calibration data summary reporting the calibration range used. For the 

analysis of semivolatile organic compounds analyzed by mass spectrometry, 

this summary should include spectra and quantification reports for decafluorotriphenylphosphine (DFTPP) or an appropriate substitute standard. For 

volatile organic compounds analyzed by mass spectrometry, the summary 

should include spectra and quantification reports for bromofluorobenzene 

(BFB) or an appropriate substitute standard. 

0 Recovery assessments and replicate sample summaries. Laboratories 

should report all surrogate spike recovery data for each sample, and a 

statement of the range of recoveries should be included in reports using 

these data. 

Cl All data qualification codes assigned by the laboratory, their description, and 

explanations for all departures from the analytical protocols. 
TABLE 1. (cont.) 

Additional Deliverables for Volatile or Semivolatile Organic Compound Analyses” 

Cl 

cl 

Cl 

0 

0 

Tentatively identified compounds (if requested) and methods of quantification, 

along with the three library spectra that best match the spectra of the 

compound of interest (see Appendix C, Figure 1 for an example of a library 

spectrum). 

Reconstructed ion chromatograms for gas chromatography/mass 

spectrometry (GUMS) analyses for each sample. 

Mass spectra of detected compounds for each sample. 

Internal standard area summary to show whether internal standard areas 

were stable. 

Gel permeation chromatography (GPC) chromatograms (for analyses of 

semivolatile compounds, if performed), recovery assessments, and replicate 

sample summaries. Laboratories should report all surrogate spike recovery 

data for each sample, and a statement of the range of recoveries should be 

included in reports using these data. 

Additional Deliverables for Pesticide and Polychlorinated Biphenyl Analyses” 

Gas chromatography/electron capture detection (GC/ECD) chromatograms for 

quantification column and confirmation columns for each sample and for all 

standards analyzed. 

0 GPC chromatograms (if GPC was performed). 

0 An evaluation summary for 4,4’-DDT/endrin breakdown. 

Cl A pesticide standard evaluation to summarize retention time shifts of internal 

standards or surrogate spike compounds. 

a Many of the terms in this table are discussed more completely in Appendix C. 

12 
TABLE 2. CHECKLIST OF LABORATORY DELIVERABLES FOR 

THE ANALYSIS OF METALS 

Cl A cover letter discussing analytical problems (if any) and referencing or 

describing the digestion procedures and instrumentation used. 

Cl Tabulated results for final dilution volumes of sample digestates, sample size, 

wet-to-dry ratios for solid samples (if requested), and concentrations of 

metals (reported in units identified to two significant figures unless otherwise 

justified). Concentration units should be p.g/kg (dry weight) for sediment, pg/L 

for water, and @kg (wet weight) for tissue.a These results should be 

checked for accuracy and the report signed by the laboratory manager or 

designee. 

cl Target detection limits (see discussion in Section 2.3.2 of this document), 

instrument detection limits, and detecticn limits achieved for the samples. 

0 Method blanks for each batch of samples. 

0 Results for all the quality control checks and initial and continuing calibration 

control checks conducted by the laboratory. 

q All data quantification codes assigned by the laboratory, their description, and 

explanations for all departures from the accepted analytical protocols. 

a Most laboratories will report metals data in mgkg for solid samples. The specification here 

of lgkg is for consistency with organic chemical analyses, which are typically reported as 

pg/kg for solid samples. If different units are used, care should be taken to ensure that results 

are not confused. 

73 
2.3 QUALITY ASSURANCE OBJECTIVES 

Data quality objectives are addressed in this section of the QA project plan. 

Data quality objectives define performance-based goals for accuracy (precision 

and bias), representativeness, comparability, and completeness, as well as the 

required sensitivity of chemical measurements (i.e., TDLs). Accuracy is defined 

in terms of bias (how close the measured value is to the true value) and 

precision (how variable the measurements are when repeated) (see footnote at 

the beginning of Section 2). Data quality objectives for the dredged material 

program are based on the intended use of the data, technical feasibility, and 

consideration of cost. Therefore, data that meet all data quality objectives 

should be acceptable for unrestricted use in the project and should enable all 

project objectives to be addressed. 

Numerical data quality objectives should be summarized in a table, with all data 

calculated and reported in units consistent with those used by other 

organizations reporting similar data, to allow comparability among databases. 

All measurements should be made so that results are representative of the 

medium (e.g., sediments, water, or tissue) being measured. Data quality 

objectives for precision and bias established for each measurement parameter 

should be based on prior knowledge of the measurement system employed, 

method validation studies, and the requirements of the specific project. 

Replicate tests should be performed for all test media (e.g., sediments, water, 

or tissue). Precision of approximately I 30-50 relative percent difference 

between measurements (the random error of measurement) and bias of 

50-150 percent of the true value (the systematic error of measurement) are 

adequate in many programs for making comparisons with regulatory limits. 

Precision may be calculated using three or more replicates to obtain the 

standard deviation and the derived confidence interval. Bias may be 

determined with standard reference material (SRM) or by spiking analyte-free 

samples. 

These data quality objectives define the acceptability of laboratory 

measurements and should also include criteria for the maximum allowable time 

that samples or organisms can be held prior to analysis by a laboratory. An 

example of a data quality objectives summary for laboratory measurements is 

provided in Appendix A. 

2.3.1 Program vs. Project Objectives 

This document provides general guidance for QA activities conducted during 

dredged material evaluations. However, specific project needs will affect the 

kinds of chemical analyses that are requested by the project manager. Special 

project needs should be identified during preparation of the QA project plan and 

should be documented in this section of the plan. For example, a preliminary 

74 
reconnaissance of a large area may only require data from simple and quick 

checks performed in the field. In contrast, a complete characterization of 

contamination in a sensitive area may require specialized laboratory methods, 

lower TDLS, and considerable documentation of results. 

Before defining the analyses that should be performed to meet the data quality 

objectives established on a project-specific basis, a thorough review of all 

historical data associated with the site (if applicable) should be performed (see 

discussions in U.S. EPA and USACE 1991, 1994). A review of the historical 

data should be conducted in response to data needs in the testing program. A 

comprehensive review of all historical data should eliminate unnecessary 

chemical analyses and assist in focusing the collection of chemical-specific data 

that are needed. A more thorough discussion of how to review and use 

historical data is provided in Section 2.5.2. 

2.3.2 Target Detection Limits for Chemicals 

Different analytical methods are capable of detecting different concentrations of 

a chemical in a sample. In general, as the sensitivity and overall accuracy of a 

technique increases, so does the cost. Recommended TDLs that are judged to 

be feasible by a variety of methods, cost effective, and to meet the 

requirements for dredged material evaluations are summarized in Table 3 (at 

the end of Section 2.4), along with example analytical methods that are capable 

of meeting the TDLs. However, any method that can achieve these TDLs is 

acceptable, provided that the appropriate documentation of the method 

performance is generated for the project. 

The TDL is a performance goal set between the lowest, technically feasible, 

detection limit for routine analytical methods and available regulatory criteria or 

guidelines for evaluating dredged material (see summaries in McDonald et al. 

[1992]; PSEP [1991]). The TDL is, therefore, equal to or greater than the 

lowest amount of a chemical that can be reliably detected based on the 

variability of the blank response of routine analytical methods (see 

Section 2.10.1 for discussion of method blank response). However, the 

reliability of a chemical measurement generally increases as the concentration 

increases. Analytical costs may also be lower at higher detection limits. For 

these reliability, feasibility, and cost reasons, the TDLs in Table 3 have been set 

at not less than IO times lower than available regional or international dredged 

material guidelines for potential biological effects associated with sediment 

chemical contamination. In many cases, lower detection limits than the TDL 

can be obtained and may be desired for some regional programs (e.g., for 

carefully documenting changes in conditions at a relatively pristine site). 

All data generated for dredged material evaluation should meet the TDLs in 

Table 3 unless a regional requirement is made or sample-specific interferences 
2.4 

occur. Any sample-specific interferences should be well documented by the 

laboratory. If significantly higher or lower TDLs are required to meet rigorously 

defined data quality objectives (e.g., for human health risk assessments) for a 

specific project, then on a project-specific basis, modification to existing 

analytical procedures may be necessary. Such modifications should be 

documented in the CIA project plan. An experienced analytical chemist should 

be consulted so the most appropriate method modifications can be assessed, 

the appropriate coordination with the analytical laboratory can be implemented, 

and the data quality objectives can be met. A more detailed discussion of 

method modifications is provided in Section 2.8.2.2. 

STANDARD OPERATlNG PROCEDURES 

Standard operating procedures are written descriptions of routine methods and 

should be provided for as many methods used during the dredged material 

evaluation as possible. A large number of field and laboratory operations can 

be standardized and presented as standard operating procedures. Once these 

procedures are specified, they can be referenced or provided in an appendix of 

the CIA project plan. Only modifications to standard operating procedures or 

non-standard procedures need to be explained in the main body of the CIA 

project plan (e.g, sampling or analytical procedures summaries discussed in 

Sections 2.5 and 2.8, respectively). 

General types of procedures that benefit from standard operating procedures 

include field measurements ancillary to sample collection (e.g., depth of 

overlying water, sampling depth, water quality measurements or mixing model 

input measurements), chain-of-custody, sample handling and shipment, and 

routine analytical methods for chemical analyses. Standard operating 

procedures ensure that all persons conducting work are following the same 

procedures and that the procedures do not change over time. All personnel 

should be thoroughly familiar with the standard operating procedures before 

work is initiated. Deviations from standard operating procedures may affect 

data quality and integrity. If it is necessary to deviate from approved standard 

operating procedures, these deviations should be documented and approved 

through an appropriate chain-of-command. Personnel responsible for ensuring 

the standard operating procedures are adhered to should be identified in the 

QA project plan. Example standard operating procedures are provided in 

Appendix D. 

16 
TABLE 3. ROUTINE ANALYTlCAL METHODS AND TARGET DETECTION LIMITS 

FOR SEDIMENT, WATER, AND TlSSUE (parts per billion, unless otherwise noted) 

Chemical 

Example Recommended 

Sediment Sediment 

Method’ TDL 

Example 

Tissue 

Method 

Recommended 

Tissue 

TDLb 

Example 

Water 

MethodRecommended 

Water 

TDLb 

lnorganlc Chemicals 

Aluminum 

Antimony 

Arsenic 

Beryllium 

Cadmium 

Chromium 

3050+%-01 OA; 

U.S. EPA (1993a) 

3050A; 

7040/7041: 

U.S. EPA (1993a); 

PSEP (1990a) 

706 1; 7060A; 

3050A; 

U.S. EPA (1993a); 

PSEP (1990a); 

EPRI (1986) 

200.8; 

7090/7091; 

U.S. EPA (1993a) 

3050A; 601 OA; 

7131AJ7130; 

U.S. EPA (1993a); 

PSEP (1990a) 

305oN7191; 

7190; 6OlOA; 

U.S. EPA (1993a); 

2,500 

5,000 

2,500d 

300 

5,ooo 

200.8; 

U.S. EPA (1993a); 

200.8; 

704wO41; 

U.S. EPA (1993a); 

200.8/7061; 

706OA; 

U.S. EPA (1993a) 

200.8; 

709017091; 

U.S. EPA (1993a) 

200.6; 7131A; 

7130; 

U.S. EPA (1993a) 

200.8/7191; 

7190; 

U.S. EPA (1993a) 

1.000 

100 

100 

100 

100 

100 

202.2; 

601 ON200.7 

7041; 204.2 

3010; 7061; 

206.2; 206.3; 

EPRI (1986) 

7091; 210.2; 

601 OA1200.7; 

200.8 

213.2; 7131A; 

3010; 

601 ON200.7; 

200.8 

7191; 200.8; 

218.2; 3010; 

601 ON200.7 

40 

3 

1 

0.2 

1 

1 

17 
TABLE 3. (cont.) 

Chemical 

Cobalt 

Copper 

Hexavalent chromium 

Iron 

Lead 

Manganese 

Mercury 

Nickel 

Selenium 

Example 

Sediment 

Method’ 

7201 

305O~V72 11; 

7210; 6OlOA; 

U.S. EPA (1993a); 

PSEP (199Oa) 

-’ 

305OAf7381; 

U.S. EPA (1993a) 

305Om421; 

7420; 601 OA; 

U.S. EPA (1993a); 

PSEP (1990a) 

305OAl746 1; 

U.S. EPA (1993a) 

7471; 

U.S. EPA (1993a) 

305OAl601 OA; 

7521; 7520; 

U.S. EPA (1993a); 

PSEP (199Oa) 

7741; 7740; 

U.S. EPA (1993a); 

EPRI (1986) 

Recommended 

Sediment 

TDL 

100 

5.000” 

50,000d 

5.ooo 

5,000” 

5,000 

1,000” 

Example 

Tissue 

Method’ 

200.8; 7201 

200.8/7211; 

7210; 

U.S. EPA (1993a) 

-’ 

200.8; 7381; 

601 OA; 

U.S. EPA (1993a) 

200.8/742 1; 

7420; 

U.S. EPA (1993a) 

200.8i7461; 

U.S. EPA (1993a) 

7471; 

U.S. EPA (1993a) 

200.8/601 OA; 

752 1; 7520; 

U.S. EPA (1993a) 

200.8/7741; 

7740; 

U.S. EPA (1993a) 

Recommended Example Recommended 

Tissue Water Water 

TDLb Method” TDLb 

100 

100 

10,000 

100 

500 

10 

100 

200 

219.2 

7211; 200.8; 

220.1; 220.2; 

3010; 

601 OIV200.7 

7197; 218.5 

6OlOA/200.7; 

3010; 7381; 

236.2 

7421; 239.2 

601 OA/200.7; 

243.2; 3010 

7471; 245.1; 

245.2 

6010A; 7521; 

249.2 

7740; 7741; 

270.2; 270.3; 

EPRI (1986) 

4 

1 

50 

10 

1 

1 

0.2 

1 

2 

18 
TABLE 3. (cont.) 

Example 

Sediment 

Method’ 

Recommended 

Sediment 

TDL 

Example 

Tissue 

Meth& 

Recommended 

Water 

TDLb 

Example 

Water 

Metho 

7761; 272.2 

Tissue 

Chemical TDLb 

Silver 30501V7761; 

7760; 

U.S. EPA (1993a); 

PSEP (1990a) 

200a 200.8l7761; 7760; 

U.S. EPA (1993a) 

100 1 

Thallium 

Tin 

Zinc 

78490841; 

U.S. EPA (1993a) 

200.8; 7840; 7841; 1 

U.S. EPA (1993a) 

200.6; 

U.S. EPA (1993a) 

200.817951; 7950; 

U.S. EPA (1993a) 

106 

100 

7840; 7841; 

279.2 

soo- 282.2 

15,000 

U.S. EPA (1993a) 

305oIv7951; 

7950; 

U.S. EPA (1993a); 

PSEP (1990a) 

E 

2,ocm 7951; 289.2; 

290.7; 3010; 

6OlOA 

10 r 0.0: 

L 

Organotin NCASI (1986); 

Uhler and Durrel 

(1989); 

Rice et al. (1987) 

NCASI (1986); 

Rice et al. 

(1987); Uhler 

and Durrel 

(1989) 

NCASI (1986); 

Rice et al. (1987); 

Uhler et al. (1989) 

10 

-~-- __- - _. ___ _. - 

19 
TABLE 3. (cont.) 

Chemical 

Example Recommended 

Sediment Sediment 

Method’ TDL 

Example 

Tissue 

Method’ 

Recommended 

Tissue 

TDLb 

Example 

Water 

Method 

Recommended 

Water 

TDLb 

Nonlonlc Organic Compounds 

LPAH Compounds 

Naphthalene 

Acenaphthylene 

Acenaphthene 

1625C; 3540A; 

355OAI8100; 

8250; 8270A; 

8310; 

NOAA (1989); 

U.S. EPA (1993a) 

1625C; 3540A; 

355OAl8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a) 

1625C; 354OA; 

355OAJ8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a) 

20 

20 

20 

1625C; 8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a) 

Sloan et al. 

(1993); 

NOAA (1989) 

1625C; 8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a); 

Sloan et al. 

(1993); 

NOAA (1989) 

1625C; 8100; 

8250; 8270A; 8310; 

U.S. EPA (1993a) 

Sloan et al. (1993); 

NOAA (1989) 

20 

20 

20 

1625C; 351 OA; 

352OAf8100; 

8250; 8270A; 

8310 

1625C; 3510A; 

352OA/8 100; 

8250; 8270A; 

8310 

1625C; 351 OA; 

352OA/8 100; 

8250; 627OA; 

8310 

10 

10 

10 

20 
TABLE 3. (cont.) 

Chemical 

Fluorene 

Phenanthrene 

Anthracene 

1 -Methylnaphthalene 

Example 

Sediment 

Method’ 

1625C; 3540A; 

355ON8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a) 

1625C; 3540A; 

355OA/8 100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a) 

1625C; 3540A; 

355ON8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a) 

162%; 3540A; 

355ON8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a) 

Recommended 

Sediment 

TDL 

20 

20 

20 

20 

Example 

Tissue 

Method” 

1625C; 8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a); 

Sloan et al. 

(1993); 

NOAA (1989) 

1625C; 8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a); 

Sloan et al. 

(1993); 

NOAA (1989) 

1625C; 8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a); 

Sloan et al. 

(1993); 

NOAA (1989) 

1625C; 8100; 

8250; 8270A; 

6310; 

U.S. EPA (1993a); 

Sloan et al. 

(1993); 

NOAA (1989) 

Recommended 

Tissue 

TDLb 

20 

20 

20 

Example 

Water 

Method” 

1625C; 351 OA; 

352ON8100; 

8250; 8270A; 

8310 

1625C; 351 OA; 

352OA18100; 

8250; 8270A; 

8310 

1625C; 351 OA; 

352OA/8100; 

8250; 8270A; 

8310 

1625C; 351 OA; 

352ON8 100; 

8250; 8270A; 

8310 

Recommended 

Water 

TDLb 

10 

l@ 

10 

10 

21 
TABLE 3. (cont.) 

Chemical 

2-Methylnaphthalene 

Example 

Sediment 

Metho& 

1625C; 3540A; 

355ON8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a) 

HPAH Compounds 

Fluoranthene 

Pyrene 

Benz[a]anthracene 

1625C; 3540A; 

355ON8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a) 

1625C; 3540A; 

355OA/8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a) 

1625C; 3540A; 

355O/V8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a) 

Recommended 

Sediment 

TDL 

20 n 

20 

20 

20 

Example Recommended 

Tissue Tissue 

Method’ TDLb 

1625C; 8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a); 

Sloan et al. (1993); 

NOAA (1989) 

16256; 8 100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a); 

Sloan et al. 

(1993); 

NOAA (1989) 

1625C; 8100; 

8250; 827OA; 8310; 

U.S. EPA (1993a); 

Sloan et al. (1993); 

NOAA (1989) 

1625C; 8100; 

8250; 8270A; 83 10; 

U.S. EPA (1993a); 

Sloan et al. (1993); 

NOAA (1989) 

Example Recommended 

Water Water 

Methoe TDL” 

16256; 351 OA; 

352OA/8100; 

8250; 8270A; 

8310 

1625C; 351 OA; 

352OAJ8100; 

8250; 8270A; 

8310 

1625C; 35 1 OA; 

352OAI8100; 

8250; 8270A; 

8310 

1625C; 35 1 OA; 

3520A/8100; 

8250; 8270A; 

8310 

10 E 

10 

10 

10 

22 
T, : 3. (cont.) 

Chrysene 

Benzo(b&k)fluoranthenes 

Denzo[a]pyrehe 

Indeno[l,2,3c,d)pyrene 

Dibenz[a,h]anthracene 

162x; 354OA 

355ON8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a) 

1625C; 354QA; 

3550Al8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a) 

1625C; 354OA; 

355QN8lOQ; 

8250; 8270A; 

8310; 

U.S. EPA (1993a) 

1825C; 354OA; 

355OA/8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a) 

1625C; 354OA; 

355ON8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a) 

20 

20 

20 

Example 

Tissue 

Method 

1625C; 8100; 

8250; 82704 8310; 

U.S. EPA (1993a); 

Sloan et al. (1993); 

NOAA (1989) 

1625C; 8100; 

8250; 8270A; 6310; 

U.S. EPA (1993a); 

Sloan et al. (1993); 

NOAA(1989) 

1625C;8100; 

0250; 8270k, 8310; 

U.S. EPA (1993a); 

Sloan et al. (1993); 

NOAA (1989) 

1625C; 8100; 

8250; 8270A; 8310; 

U.S. EPA (1993a); 

Sloan et al. (1993); 

NOAA(1989) 

1625C;8100; 

8250; 8270A; 8310; 

U.S. EPA (1993a): 

Sloan et al. (1993); 

NOAA (19891 

Recommended 

Tissue 

TDLb 

20 

20 

20 

20 

20 

Example 

Water 

Method 

1625C; 3510A; 

352ON8100; 

8250; 8270A; 

8310 

1625C;351OA; 

352OA18100; 

8250; 827OA 

8310 

1625C; 3510A; 

352ON81OO; 

8250; 8270A; 

6310 

1625C;3510A; 

352OA/8100; 

8250; 8270A; 

8310 

1625C; 3510A; 

352ON8 100; 

8250; 8270A; 

8310 

Water 

TDLb 

10 

10 

10 

10 

.__ _-- _-- _ ~- -- __-- 

23 
TABLE 3. (cont.) 

Chemical 

Example Recommended 

Sediment Sediment 

Method’ TDL 

Sento[g,h,i]perylene 1625C; 3540A; 

355OA/8100; 

8250; 8270A; 

8310; 

U.S. EPA (1993a) 

Chlorinated Benzenes 

1,3-Dichlorobenzene 

1 .CDichlorobenzene 

1 .P-Dichlorobenzene 

1,2,4-Trichlorobenzene 

Hexachlorobenzene 

1625C; 3540A; 

355OAI8 100; 

8240A; 8250; 

8260; 8270A 

16256; 3540A; 

355ON8100; 

8240A; 8250; 

8260; 8270A 

1625C; 3540A; 

355OA/8100; 

8240A; 8250; 

8260; 8270A 

16250; 3540A; 

355OAl8250; 

8260; 8270A 

1625C; 3540A; 

355OAl8250; 

8260; 8270A 

20 

20 

20 

20 

10’ 

10’ 

Example 

Tissue 

Method’ 

Recommended 

Tissue 

TDLb 

I r 

1625C; 8100; 

8250; 8270A; 8310; 

U.S. EPA (1993a); 

Sloan et al. (1993); 

NOAA (1989) 

L 

1625C; 8240A: 

8250; 8270A; 

Sloan et al. (1993) 

1625C: 8100; 

824OA; 8250; 

8270A; 

Sloan et al. (1993); 

NOAA (1989) 

1625C; 8240A: 

8250; 8270A; 

Sloan et al. (1993) 

1625C; 8250; 

8260; 8270A; 

Sloan et al. (1993) 

1625C; 8250; 

8260; 827OA; 

Sloan et al. (1993) 

20 

20 

20 

Example 

Water 

Methoe 

Recommended 

Water 

TDLb 

1625C; 351 OA; 

352OA/8100; 

8240A; 8250; 

8260; 8270A 

1625C; 3510A; 

352ON8100; 

8240A; 8250; 

8260; 8270A 

1625C; 351 OA; 

352OAf8 100; 

8240A; 8250; 

8260; 8270A 

1625C; 351 OA; 

352OAl8250; 

8260; 8270A 

1625C; 3510A; 

352OAf8250; 

8260; 8270A 

1c 

1C 

1c 

1c 

10 

24 
TABLE 3. (cont.) 

Chemical 

Example Recommended 

Sediment Sediment 

Methd TDL 

Example 

Tissue 

Method’ 

Recommended 

Tissue 

TDLb 

Example 

Water 

Method” 

Recommended 

Water 

TDLb 

Phthalate Estera 

Dirnethyl phthalate 

Diethyt phthalate 

Di-n-butyl phthalate 

Butyl benzyl phthalate 

Bis[2-ethylhexyl]phlhalate 

1625C; 354OA; 

3550A/8060; 8100; 

8250; 8270A 

1625C; 354OA; 

3550N8060; 8100; 

8250; 8270A 

1625C; 3540A; 

355OM3060; 8100; 

8250; 8270A 

1625C; 3540A; 

3550~80603 at 00; 

8250; 8270A 

1625C; 354OA, 

355OA/8060; 8100 

8250; 8270P 

50 

50 

50 

50 

SC 

1625C; 8060; 

8100; 8250; 8270A; 

Sloan et al. 

(1993); 

NOAA (1989) 

1625C; 8060; 

8 100; 8250; 8270A; 

Sloan et al. 

(1993); 

NOAA (1989) 

1625C; 8060; 

8100; 8250; 8270A; 

Sloan et al. 

(1993); 

NOAA (1989) 

16256; 8060; 

8100; 8250; 8270A; 

Sloan et al. 

(1993); 

NOAA (1989) 

16256; 8060; 

8100; 8250; 8270A; 

Sloan et al. 

(1993); 

NOAA (1989) 

20 

20 

20 

20 

20 

1625C; 3510A 

352oAr8060 

8100; 8250 

827Ok 

1625C; 3510A 

352ON8100 

8060; 8250 

82701 

1625C; 3510A 

352ON8100 

8060; 8250 

82701 

1625C: 3510A 

352ON8100; 

8060; 8250; 

8270A 

1625C; 3510A; 

352ON8100; 

8060; 8250; 

8270A 

10 

10 

10 

l( 

10 

.- ..-- 

25 
TABLE 3. (cont.) 

Example Recommended 

Water Water 

Metho@ TDLb 

Example 

Sediment 

Methob 

1625C; 354OA; 

355OA&O60; 8100; 

8250; 8270A 

Recommended 

Sediment 

TDL 

50 

Example 

Tissue 

Method’ 

1625C; 8060; 

8100; 8250; 8270A: 

Sloan et al. 

(1993); 

NOAA (1989) 

Recommended 

Tissue 

TDLb 

20 

Chemical 

10 

q 

Di-n-octyl phtbalate 16250; 3510A; 

352OA/8100; 

8060; 8250; 

6270A 

Miscellaneous Extractable Compounds 

Benzyl alcohol 1625C; 3510A; 

35201V8250; 

8270A 

50 

50 

1625C; 8250; 

8270A 

100 

100 

20 

40 

40 

50 

Benzoic acid 

Dibenzofuran 

100 1625C; 351 OA; 

352ON8250; 

8270A 

16256; 3540A; 

355oAKt250; 

8270A 

1625C; 8250; 

8270A 

50 1625C; 351 OA; 

352OAl8250; 

8270A 

1625C; 354OA; 10 

355oAl8250; 

8270A 

1625C; 354OA; 

3550N8250; 

8270A 

16256: 3540A; 

355oA&250; 

827OA 

1625C; 8100; 

8250; 8270A; 

Sloan at al. (1993); 

NOAA (1989) 

100 16256; 8250; 1625C; 3510A; 

352OA/8250; 

8270A 

Hexachloroethane 50 

Hexachlorobutadiene 20 1625C; 3510A; 50 

352OA/8250; 

8270A 

.__ ..-- ~-.- 

26 
TABLE 3. (cont.) 

Chemical 

Example Recommended Example Recommended Example Recommended 

Sediment Sediment Tissue Tissue Water Water 

Method’ TDL Meth& TDLb Method’ TDLb 

N-Nitrosodiphenylamine 

Methylethyl ketone 

Polychlorlnatsd Dlbenzofurans 

Tetrachlorinated furans 

Pentachlorinated furans 

Hexachlorinated furans 

Heptachlorinated furans 

Octachlorinated furans 

1625C; 3540A; 

355oAm250; 

8270A 

16246; 354OA; 

3550A/8250; 

824OA; 8260; 

8270A 

1613; 8290 

1813; 8290 

1813; 8290 

1813; 8290 

1613; 8290 

Polychlorlnated Dlbenzopdioxlns 

2,3,7,8-TCDD 

Other tetrachlorinated dioxins 

Pentachlorinated dioxins 

Hexachlorinated dioxins 

201 1 1625C; 8250; 

1624C; 8250; 

1 0.011 1 82901 

0.001 

0.001 El 0.0025 

0.005 

20 

20 

_. 

0.001 

0.0025 E 0.005 

0.005 

0.01 

1625C; 351 OA; 

352ON8250; 

8270A 

i 

1624C; 

351 OA; 

352ON8250; 

8240A; 8260; 

6270A 

50 

50 II 

1 1613; 8290 1 1 0.0091 1 

I 1613; 8290 1 1 0.00001~ 

27 
TABLE 3. (cont.) 

Chemical 

Example Recommended 

Sediment Sediment 

Metho TDL 

Example 

Tissue 

Method 

Recommended 

Tissue 

TDLb 

Example 

Water 

Methd 

Recommended 

Water 

TDLb 

Heptachlonnated dioxins 

Octachlorinated dioxins 

PCBS 

PCB congeners 1 cl 2 El 0.01 

i__ 

Sloan et al. (1993); 

NOAA (1989); 

U.S. EPA (1993a) 

NOAA (1989); NOAA (1989) 

U.S. EPA (1993a) 

Pe8ticldes 

Atdrin 

r 

10 

10 

10 

10 

10 

608; 

35lOA; 

352OABO80 

10 0.04 

10 

10 

10 

10 

8080; 

NOAA (1985) 

8080; 

NOAA (1985) 

8080; 

NOAA (1985) 

3540A; 

355OAi8080; NOAA 

(1985) 

354OA; 

355ON8080; NOAA 

(1985) 

354OA; 

355OAl8080; NOAA 

(1985) 

Chlordane and derivatives 

Dieldrin 

608; 0.14 

3510A; 

352Oti8080 

608; 

3510A; 

3520A&o80 

0.02 

4.4’-DDD 

4.4’-DDE 

354OA; 

355OAf8080; NOAA 

(1985) 

608; 

3510A; 

352ON8080 

8080; 

NOAA (1985) 

8080; 

NOAA (1985) 

608; 

3510A; 

352OAl8080 

354OA; 0.1 

355OAl8080; NOAA 

(1985) 

L 

28 
TABLE 3. (cont.) 

Chemical 

4,4’-DDT 

Endosulfan and derivatives 

Endrin and derivatives 

Heptachlor and derivatives 

yHexachlorocyclohexane 

(lindane) 

Toxaphene 

Methoxychlor 

Chlorbenside 

Example 

Sediment 

Methd 

35404 

355oAJ8080; NOM 

(1985) 

3540A; 

355ON8080; NOM 

(1Qw 

354OA; 

355oA18080; NOAA 

OQW 

354014; 

355OABO80; NOM 

(1985) 

3540A; 

355ON8080; NOM 

(1985) 

3540A; 

3550Af8080 

3540A; 

355ON808Q 

354OA: 

355OA18080; NOM 

(1985) 

Recommended 

Sediment 

TDL 

10 

10 

5 

10 

10 

50 

10 

2 

Example 

Tissue 

MethoU 

8080; 

NOM (1985) 

8080; 

NOM (1985) 

8080; 

NOM (1985) 

8080; 

NOM (1985) 

8080; 

NOM (1985) 

8080 

8080 

8080; 

NOAA (1985) 

Reccnnmended 

Tissue 

TDLb 

10 

10 

10 

10 

10 

50 

10 

2 

Example Recommended 

Water Water 

Metid TDLb 

608; 

351 OA; 

352oABoQO 

608; 

351 DA; 

352OABO80 

608: 

3510A; 

352OAl8080 

608; 

3510A; 

352OkV8080 

608; 

3510A; 

352OA/8080 

608; 

3510A; 

352OABO80 

0.1 

0.1 

0.7 

0.1 

0.1 

0.5 

I 

I 

608; 

3510A; 

352ON8080 

608; 

3510A; 

352oAJ8080 

0.5 

c0.092 

._._ .-. - .- - -- -- 

29 
TABLE 3. (cont.) 

Recommended 

Sediment 

TDL 

Example 

Tissue 

Method’ 

Recommended 

Tissue 

TDLb 

Example 

Water 

Method’ 

608; 

-7 

35lOA; 

352OAt8080 

Recommended 

Water 

TDLb 

Example 

Sediment 

M8thob 

3!54OA; 

355OAhO80; NOAA 

(19W 

354OA; 

3550A@O80; NOAA 

(1985) 

3540A; 

355ON8141 

354OA; 

355OAJ8141 

Chemical 

Dacthal 8080; 

NOAA (1985) 

2 0.03 

20 

5 

6 

2 

20 

5 

6 

Total chlorinated pesticides 8080; 

NOM (1985) 

0.02 

Malathion 

Parathion 

8141 0.8 

35lOA; 

352OAI8141 

8141 0.8 

Volatile Organic Compounds 

Benzene 

Chloroform 

Ethylbenzene 

TOhen 

Trichloroethene 

Tetrachloroethene 

I 1624C; 8240A; 

8260 I 

10 

10 

10 

10 

10 

10 

10 

10 

10 

10 

10 

10 

I 1624C; 8240A; 

8260 I 

1624C; 8240A; 

1624C; 8240A; 

1624C; 8240A; 

8260 

1624C; 8240A; 

8260 

1624C; 8240A; 

8260 

1624C; 8240A; 

8260 

1624C; 824OA; 

8260 

16246; 8240A; 

8260 l-i 1624C; 8240A; 

8260 

16246; 824OA; 

8260 

t 

1624C; 8240A; 

8260 

30 
TABLE 3. (cont.) 

Chemical 

Total xylenes 

Example 

Sediment 

Method’ 

1624C; 8240A: 

8260 

Recommended 

Sediment 

TDL 

Example 

Tissue 

Method’ 

Recommended 

Tissue 

TDLb 

10 

I I 

1624C; 8240A; 

8260 I I 

Example 

Water 

M&Off 

Recommended 

Water 

TDLb 

10 

I I 

5 -1 

lonkable Organic Compounds 

Phenols 

Phenol 

2-Methylphenol 

4-Methylphenol 

2,4-Dimethylphenol 

Pentachlorophenol 

Resin Acids and Gualacols 

1825C; 354OA; 

35501V804OA; 

8250; 8270A; 9066 

162%; 354OA; 

3550Al8040A; 

8250; 8270A 

1625C; 3540A; 

3550N8040A; 

8250; 8270A 

1625C; 3540A; 

3550N8040A; 

8250; 827OA 

1625C; 3540A; 

3550Al8040A; 

8250; 8270A 

1625C; 3540A; 

355OA; 8250; 

8270A 

100 

50 

100 

20 

100 

10 

1625C; 804QA; 

8270A 

1625C; 8040A; 

8270A 

1625C; 8040A; 

8270A 

20 

i 

20 

20 

20 

100 

-- 

l625C; 351 OA; 

3520M3040A; 

8250; B270A 

1625C; 351 OA; 

352OM304OA; 

8250; 027OA 

1625C; 3510A; 

3520ABO40A; 

8250; 827OA 

3625C; 351OA; 

3520ABMOA; 

8250; 8270A 

1625C; 3510A; 

352OAl804OA; 

8250; 8270A 

10 

10 

10 

10 

50 

.- 

37 
TABLE 3. (cont.) 

Chemical 

Example 

Sediment 

Meth& 

Recommended 

Sediment 

TDL 

Example 

Tissue 

Methoe 

Recommended 

Tissue 

TDLb 

Example 

Water 

Method 

Recommended 

Water 

TDLb 

Other Analyses 

Ammonia 

Cyanides 

Total organic carbon 

Total petroleum hydrocarbons 

Total recoverable petroleum 

hydrocarbons 

Total phenols 

Acid-volatile sulfides 

I 350.1; 350.2; -- 30 

Plumb (1981) 

9OlOA; 9012 

PSEP (1986); 

U.S. EPA (1987a, 

1992b) 

9070; 418.1; 

418.1 

804OA 

Cutter and 

Oates (1987); 

U.S. EPA (1991 a); 

DiToro et al. (1990) 

Total sulfides 

Grain size 

9030; 

Plumb (1981) 

Plumb (1981); 

ASTM (1992) 

Total suspended solids -- 

100 350.1; 350.2; 

350.3 

2,000 I 9OlOA; 9012 1,ooO 335.2 5.000 

0.1% t 0.1% -- 9060; 415.1; 

APHA 5310D 

418.1 

-- 

8040A 

5,000 100,000 418.1 

418.1 

100 

5,000 500 -- 

1.000 10,000 420.1; 625; 

8040A 

0.1 umolelg -- 

100 -- 376.2 100 

1% __ 

Total settleable solids 

__ 160.2; APHA 

2510D 

1.0 mgk 

0.05 mt5 

-- 

-- 160.5; APHA 

25408 

32 
TABLE 3. (cont.) 

Chemical 

Total solids/dry weight 

Total volatile solids 

Specific gravity 

PH 

Total water content of test 

species 

Total lipid 

Example Recommended Example 

Sediment Sediment Tissue 

Method’ TDL Methoti 

160.3; 

Plumb (1981); 

PSEP (1986) 

160.4; 

Plumb (1981}; 

APHA 2540E; 

PSEP (1986) 

0.1% 

Plumb (1981) 

9045; 

Plumb (1981) 

0.01 mgL 

0.1 pH units 

-_ 

-- 

U.S. EPA (1986b, 

1987a) 

Bligh and Dye1 

(1959) 

Folch et al. (1957: 

Recommended Example Recommended 

Tissue Water Water 

TDLb Method’ TDLb 

1 

mm -- 

-- -- 

w- 

-- 

0.1% 

0.1% 

-- 

Plumb (1981) 

-- 

0.1 pH units 

Note: HPAH - high molecular weight polycyclic aromatic hydrocarbon 

LPAH - low molecular weight polycyclic aromatic hydrocarbon 

TCDD - tetrachlorodibenzo-p-dioxin 

TDL - The target detection limit is a performance goal set between the lowest, technically feasible, detection limit for routine analytical methods and available 

regulatory criteria or guidelines for evaluating dredged material. The target detection limit is, therefore, equal to or greater than the lowest amount of a 

chemical that can be reliably detected based on the variability ot the blank response of routine analytical methods. However, the reliability of a 

chemical measurement generally increases as the concentration increases. Analytical costs may also be lower at higher detection limits. For these 

reasons, the target detection limit has been set not less than 10 times lower than available dredged material guidelines. 

’ Numbered methods are found in references as listed on following page. 

b Determined by work group discussion; no or few effects guidelines are available for comparison. 

33 
TABLE 3. (cont.) 

NO sediment screening or adverse effects guidelines are available for comparison. 

’ Less than l/l0 of available sediment guidelines for screening concentrations or potential adverse effects, but still cost effective and feasible to attain with a range of 

routine analytical methods. 

’ TDL may restriot use of some routine analytical methods, but reflects work group consensus. 

’ Sediment TDL slightly exceeds one available s&iient guideline (Washingtoo Sediment Management Standards) at low organic carbon content (c 2 percent TOC). 

I 

-- - No1 applicable. 

- _.-.- - ____ _ - 

34 --- -~ 
Method 

US EPA 1989~ 
2.5 SAMPLING STRATEGY AND PROCEDURES 

A sampling strategy should be developed to ensure that the sampling design 

supports the planned data use. For example, a project that was planned to 

characterize a specific area would have different sampling design requirements 

than a project that was screening for a suspected problem chemical. The 

sampling strategy will strongly affect the representativeness, comparability, and 

completeness that might be expected for field measurements. In addition, the 

strategy for collecting field QC samples (e.g., replicates) will assist in the 

determination of how well the total variability of a field measurement can be 

documented. Therefore, development of the sampling strategy should be 

closely coordinated with development of CIA objectives discussed in Section 

2.3. 

Specific procedures for collecting each kind of sediment, water, tissue, or 

biological sample are described in this section of the QA project plan. The level 

of detail can range from a brief summary of sampling objectives, containers, 

special sample handling procedures (including cornpositing and subsampling 

procedures, if appropriate), and storage/sample preservation to a complete 

sampling plan that provides all details necessary to implement the field 

program. Standard operating procedures do not require elaboration in this 

section of the QA project plan (see Section 2.4). 

If complete sampling details are not provided in the QA project plan, then 

reference should be made to the sampling plan that does provide all details. 

The QA project plan may be an appendix of the sampling plan, or specific 

sampling details may be provided as an appendix of the QA project plan. For 

smaller projects, a single planning document may be created that combines a 

work plan (project rationale and schedule for each task), detailed sampling plan 

(how project tasks are implemented), and the QA project plan. For larger 

projects, the QA project plan and the detailed sampling plan may be two 

separate documents. 

This section of the document provides basic guidance for assuring sample 

quality from collection to delivery to the laboratory and guidance on items to 

consider when designing a sampling plan. A well-designed sampling plan is 

essential when evaluating the potential impact of dredged material discharge on 

the aquatic environment. The purpose of the sampling plan is to provide a 

blueprint for all fieldwork by defining in detail the appropriate sampling and data 

collection methods (in accordance with the established QA objectives; see 

Section 2.3). Before any sampling is initiated, the sampling plan should meet 

clearly defined objectives for individual dredging projects. Factors such as the 

availability and content of historical data, the degree of sediment heterogeneity, 

the volume of sediment proposed to be dredged, the areal extent of the 

dredging project, the number and geographical distribution of sample collection 

sites, potential contaminant sources, and the procedures for collection, 

36 
preservation, storage, and tracking of samples should be carefully considered 

and are necessary for adequate QA/QC of the data. The magnitude of the 

dredging project and its time and budgetary constraints should also be 

considered. 

The following kinds of information should be reviewed for assistance in 

designing the sampling plan: 

n Geochemical and hydrodynamic data-The grain size, specific 

density, water content, total organic carbon (TOC), and 

identification of sediment horizons are helpful in making 

operational decisions. Areas of high tidal currents and high wave 

energy tend to have sediments with larger grain sizes than do 

quiescent areas. Many contaminants have a greater affinity for 

clay and silt than for sand. Horizontal and vertical gradients may 

exist within the sediment. If the sediments are subject to frequent 

mixing by wave action, currents or prop wash, the sediments are 

likely to be relatively homogenous. Local groundwater quality and 

movement should be determined if groundwater is a potential 

source of contamination. 

m Quality and age of available data-Reviewing the results of 

chemical analyses performed in past studies can help in selecting 

the appropriate contaminants of concern and in focusing plans for 

additional analyses. In particular, analytical costs can be reduced 

if historical results can substitute for new analyses, Collecting 

these data is only the initial step, however. Assessing their 

usefulness to the current project should always be performed 

before substantial effort is spent on incorporating historical results 

into a project database. If it is determined that the historical data 

are of questionable use for a specific project, then the 

determination of the most appropriate chemical analyses that will 

meet the project needs, including the level of effort necessary, will 

need to be assessed. 

n Spill data-Evidence of a contaminant spill within or near the 

dredging area may be an important consideration in identifying 

locations for sampling. 

n Dredging history -Knowledge of prior dredging may dramatically 

affect sampling plans. If the area is frequently dredged (every l-2 

years) or If the area is subject to frequent ship traffic, the 

sediments are likely to be relatively homogenous. Assuming that 

there.is nomajor contaminant input, the sampling effort may be 

minimal.. :However, if there is information regarding possible 

contamination, a more extensive sampling effort may be indicated. 

New excavations of material unaffected by anthropogenic input 

may require less intensive sampling than maintenance dredging. 

37 
An acceptable sampling plan, including QNQC requirements, should be in 

place before sampling begins. Regional guidance from governmental agencies 

(Le., EPA and USACE) is required for developing these project-specific 

sampling plans. The sampling plan should be written so that a field sampling 

team unfamiliar with the site would be able to gather the necessary samples 

and field information. 

Addressing quality assurance in the sampling plan includes designating field 

samples to be collected and used for assessing the quality of sampling and 

analysis, and ensuring that quality assurance is included in standard operating 

procedures for field measurements. The quality of the information obtained 

through the testing process is impacted by the following four factors: 

n Collecting representative samples 

4 Collecting an appropriate number of samples 

n Using appropriate sampling techniques 

n Protecting or presenting the samples until they are tested. 

Ideally, the importance of each of these four factors will be fully understood and 

appropriately implemented; in practice, however, this is not always the case. 

There may be occasions when time or other resource constraints will limit the 

amount of information that should or can be gathered. When this is the case, 

the relative importance of each of these factors has to be carefully considered 

in light of the specific study purposes. 

An important component of any field sampling program is a preproject meeting 

with all concerned personnel. As with the drafting of the QA project plan, 

participation by several individuals may be necessary when developing the 

sampling plan. Personnel involved may include management, field personnel, 

laboratory personnel, data management/analysis personnel, and representatives 

of regulatory agencies, the permit applicant, and the dredging company. To 

assure sampling quality, at least one individual familiar with the study area 

should be included in the preproject meeting. The purposes of the meeting 

include: 

n Defining the objectives of the sampling program 

m Ensuring communication among participating groups 

n Ensuring agreement on methods and contingency plans. 

The more explicitly the objectives of a testing program can be stated (including 

QA objectives), the easier it will be to design an appropriate sampling plan. A 

complete sampling plan will result in a level of detail such that all sampling 

procedures and locations are clearly defined, sample volumes are clearly 

established, and all logistical concerns are fully addressed. 

38 
To ensure an adequate level of confidence in the data produced and in the 

comparability of the data to information collected by other sampling teams, the 

sampling plan should adhere to published sampling protocols and guidance. 

Descriptions of widely used sampling methods can be found in several EPA 

publications, many of which are cited in this section. 

The sampling plan should include the following specific sections: 

Summary of dredging plan, including the dimensions of the 

dredging area, the dredging depths, side-slopes, and the volume of 

sediment for disposal (including overdredged material) 

Site background and existing database for the area, including 

identification of 1) relevant data, 2) need for additional data, and 3) 

areas of potential environmental concern within the confines of the 

dredging project 

Subdivision of dredging area into project segments, if appropriate, 

based on an assessment (review of historical data and past 

assessment work) of the level of environmental concern within the 

dredging area 

Sample location and sample collection frequency, including 

selection of methods and equipment for positioning vessels at 

established stations 

Sample designation system (i.e., a description of how each 

independently collected sample will be identified) 

Sample collection methods for all test media (e.g., sediment, 

water, or tissue) 

Procedures for sample handling (including container types and 

cleaning procedures), preservation, and storage, and (if applicable) 

field or shipboard analysis 

Logistical considerations and safety precautions. 

The subsections that follow discuss each of these steps and provide general 

guidance for their conduct. 

2.51 Review of Dredging Plan 

A review of the plan for the dredging project provides a basis for determining 

the sampling strategy (see summary discussion in Section 2.3). The volume of 

material to be dredged and the method of dredging are two important factors 

that will help to determine the number of samples required. The number of 

samples required is generally a judgment that considers the cost, resolution, 

39 
and the risk of an incorrect decision regarding the volume of material to be 

dredged. Knowledge of the depth, volume, and physical characteristics of the 

material to be dredged will help to determine the kind of sampling equipment 

that is required. The boundaries of the dredging area have to be known 

(including the toe and the top of all side-slopes) to ensure that the number and 

location of samples are appropriate. Sampling should generally be to below the 

project depth plus any overdredging. 

2.5.2 Site Background and Existing Database 

As previously stated, reviewing the results of chemical analyses performed in 

past studies can help in selecting the appropriate contaminants of concern and 

in focusing plans for additional analyses. The level of data quality for historical 

data will affect the selection of station locations. Examples of four levels of 

data quality that can be assigned to historical results are summarized in Table 

4. Labeling each set of results with a data quality level is also a simple way to 

summarize the relative quality of the data set for future use. This classification 

provides a useful summary of data quality when making conclusions and writing 

up the results of the project. The example classification in Table 4 considers 

the following factors when determining the suitability of historical results for a 

particular project: 

n The analytical methods used and their associated detection limitsAnalytical methods often improve over time. For example, as late 

as the 197Os, concentrations of many organic compounds in 

sediment samples were difficult to measure routinely, accurately, 

or sensitively. However, as better preparation methods and more 

sensitive analytical techniques have been developed, the ability to 

distinguish these compounds from other substances and the 

overall sensitivity of analyses have substantially improved. 

Methods are now available that afford detection limits that are well 

within the range of documented adverse biological effects. 

n QA/QC procedures and documentation-The usefulness of data will 

depend on whether appropriate QA procedures have been used 

during analysis and if the data have been properly validated (see 

Section 2.9.1) and documented. Because more rigorous methods 

to analyze samples and document data quality have been required 

by environmental scientists over the past decade, only welldocumented data that have been produced by laboratories using 

acceptable data quality controls should be considered to have no 

limitations. Historical data produced by even the best laboratories 

often may lack complete documentation, or the documentation 

may be difficult to obtain. However, historical data with incomplete 

documentation could still be used for projects with certain 

objectives (e.g., screening-level studies). 

. -. .- 

40 
TABLE 4. LEVELS OF DATA QUALITY FOR HISTORICAL DATA 

Level 1 Data are acceptable for all project uses. 

The data are supported by appropriate documentation that 

confirms their comparability to data that will be generated in 

the current project. 

Level 2 Data are acceptable for most project uses. 

Appropriate documentation may not be available to confirm 

conclusions on data quality or to support legal defensibility. 

These data are supported by a summary of quality control 

information, and the environmental distribution of 

contamination suggested by these data is comparable to the 

distribution suggested by an independent analytical technique. The data are thus considered reliable and potentially 

comparable to data that will be produced in the project. 

Level 3 Data are acceptable for reconnaissance-level analyses. 

The data can be used to estimate the nature and extent of 

contamination. No supporting quality control information is 

available, but standard methods were used, and there is no 

reason to suspect a problem with the data based on 1) an 

inspection of the data, 2) their environmental distribution 

relative to data produced by an independent analytical 

technique, or 3) supporting technical reports. These data 

should be considered estimates and used only to provide an 

indication of the nature and possible extent of contamination, 

Lbvei 4 Data are not acceptable for use in the current project. 

The data may have been acceptable for their original use. 

However, little or no supporting information is available to 

confirm the methods used, no quality control information is 

available, or there are documented reasons in technical 

reports that suggest the data may not be comparable to 

corresponding data to be collected in the current project. 

~-- .- -- -___ 

41 
2.5.3 Subdivision of Dredging Area 

Sediment characteristics may vary substantially within the limits of the area to 

be dredged as a result of geographical and hydrological features. Many 

dredging projects can be subdivided into project segments (horizontal and/or 

vertical) that can be treated as separate management units. A project segment 

is an area expected to have relatively consistent characteristics that differ 

substantially from the characteristics of adjacent segments. Project segments 

may be sampled with various intensities as warranted by the study objectives 

and testing results. 

Any established sampling program should be sufficiently flexible to allow 

changes based on field observations. However, any deviations from 

established procedures should be documented, along with the rationale for such 

deviations. An alteration checklist form is generally appropriate to implement 

required changes. An example of such a checklist is provided in Appendix A. 

2.5.4 Sample Location and Collection Frequency 

The method of dredging, the volume of sediment to be removed, the areal 

extent of the dredging project, and the horizontal and vertical heterogeneity of 

the sediment are key to determining station locations and the number of 

samples to be collected for the total dredging project. When appropriate to 

testing objectives, samples may be cornposited prior to analysis (with attention 

to the discussion in Section 2.5.4.8). The appropriate number of samples and 

the proper use of cornpositing should be determined for each operation on a 

case-by-case basis. 

Using pertinent available information to determine station locations within the 

dredging area is both cost effective and technically efficient. If a review of 

historical data (see Section 2.5.2) identifies possible sources of contamination, 

skewing the sampling effort toward those areas may be justified to thoroughly 

characterize those areas, but can lead to an incomplete assessment of 

contamination in the whole study area. In areas of unequally distributed 

contamination, the total sampling effort should be increased to ensure 

representative, but not necessarily equal, sampling of the entire site. The 

following factors should be among those considered when selecting sampling 

stations and patterns: objectives of the testing program, bathymetry, area of 

the dredging project, accessibility, flows (currents and tides), mixing (hydrology), 

sediment heterogeneity, contaminant source locations, land use activities, 

available personnel and facilities, and other physical characteristics of the 

sampling site. A discussion of locating appropriate stations, sample collection, 

and sample handling procedures is provided in the following sections. 

42 
2.5.4.1 Station Locations 

Station locations within the dredging area should include locations downstream 

from major point sources and in quiescent areas, such as turning basins, side 

channels, and inside channel bends, where fine-grained sediments and 

associated contaminants are most likely to settle. Jnformation that should help 

to define the representativeness of stations within a dredging area includes: 

n Clearly defined distribution of sediments to be dredged (i.e., project 

depth, overdredged depth, and side slopes) 

n Clearly defined area to be sampled 

n Correctly distributed sampling locations within each dredging area. 

If sample variability is suspected within the dredging area, then multiple 

samples should be collected. When sediment variability is unknown, it may be 

necessary to conduct a preliminary survey of the dredging area to better define 

the final sampling program. 

2.5.4.2 Sample Replication 

Within a station, samples may be collected for replicate testing. Sediment 

testing is conducted on replicate samples, for which laboratory replicates 

(subsamples of a composite sample of the replicates} are generally 

recommended as opposed to field replicates (separate samples for each 

replicate). The former involves pseudo-replication but is more appropriate for 

dredged material evaluations where sediments will be homogenized by the 

dredging and discharge process. The latter involves true replication but is more 

appropriate for field investigations of the extent and degree of variability of 

sediment toxicity. 

2.5.4.3 Depth Considerations 

Sediment composition can vary vertically as well as horizontally. Samples 

should be collected over the entire dredging depth (including over-dredging), 

unless the sediments are known to be vertically homogenous or there are 

adequate data to demonstrate that contamination does not extend throughout 

the depth to be excavated. Separate analyses of defined sediment horizons or 

layers may be useful to determine the vertical distribution of contamination. 

43 
2.5.4.4 Sampling Bias 

Ideally, the composition of an area and the composition of the samples 

obtained from that area will be the same. However, in practice, there often are 

differences due to bias in the sampling program, including disproportionate 

intensity of sampling in different parts of the dredging area and equipment 

limitations. 

In some cases, to minimize bias, it may be useful to develop a sampling grid. 

The horizontal dimensions may be subdivided into grid cells of equal size, 

which are numbered sequentially. Cells are then selected for sampling either 

randomly or in a stratified random manner. It can be important to collect more 

than the minimum number of samples required, especially in areas suspected 

of having high or highly variable contamination. In some cases extra samples 

may be archived (for long time periods in the case of physical characterization 

or chemical analyses and for short time periods in the case of biological tests) 

should reexamination of particular stations be warranted. 

In other cases, a sampling grid may not be desirable. This is particularly the 

case where dredging sites are not continuous open areas, but are rather a 

series of separate humps, bumps, reaches, and pockets with varying depths 

and surface areas. In these latter cases, sample distribution is commonly 

biased with intent. 

2.5.4.5 Level of Effort 

In some cases, it may be advisable to consider varying the level of sampling 

effort. Dredging areas suspected or known to be contaminated may be 

targeted for an increased level of effort so that the boundaries and 

characteristics of the contamination can be identified. A weighting approach 

can be applied whereby specific areas are ranked in increasing order of 

concern, and level of concern can then be used as a factor when determining 

the number of samples within each area. 

2.5.4.6 Number of Samples 

In general, the number of samples that should be collected within each 

dredging area is inversely proportional to the amount of known information, and 

is proportional to the level of confidence that is desired in the results and the 

suspected level of contamination. No specific guidance can be provided, but 

the following factors should be considered: 

n The greater the number of samples collected, the better the areal 

and vertical definition 

44 
n Single measurements are inadequate to describe variability 

n The means of several measurements at each station within a 

dredging area are generally less variable than individual 

measurements at each station. 

2.5.4.7 Time and Funding Constraints 

In all cases, the ultimate objective is to obtain sufficient information to evaluate 

the environmental impact of a dredged material disposal operation. The 

realities of time and funding constraints have to be recognized, although such 

do not justify inadequate environmental evaluation. Possible responses to cost 

constraints have been discussed by Higgins (1988). If the original sampling 

design does not seem to fit time or funding constraints, several options are 

available, all of which increase the risk of an incorrect decision. For example, 

the number of segments into which the project is divided can be reduced, but 

the total number of samples remains the same. This option results in fewer 

segments and maintains the power of station-to-station comparisons. This may, 

however, provide a poor assessment of spatial variability because of reduced 

stratification. Another example would be to maintain (or even increase) the 

number of stations sampled, and composite multiple samples from within a 

segment. This option results in a lower number of analyses being performed 

per segment, but may provide a poor assessment of spatial variability within 

each segment. 

2.5.4.8 Sample Cumpositing 

The objective of obtaining an accurate representation and definition of the 

dredging area has to be satisfied when cornpositing samples. Cornpositing 

provides a way to control cost while analyzing sediments from a large number 

of stations. Cornpositing results in a less detailed description of the variability 

within the area sampled than would individual analysis at each station. However if, for example, five analyses can be performed to characterize a project 

segment, the increased coverage afforded by collecting 15 individual samples 

and combining sets of three into five composite samples for analysis may justify 

the increased time and cost of collecting the extra 10 samples. Cornpositing 

can also provide the large sample volumes required for some biological tests. 

Composite samples represent the “average” of the characteristics of the 

individual samples making up the composite and are generally appropriate for 

logistical and other reasons; however, they are not recommended where they 

could serve to “dilute” a highly toxic but localized sediment “hot spot.” Further, 

composite samples are not recommended for stations with very different grain 

size characteristics. 

-.- .--. - --.. -_ -____-- .--~~ ..~~ ..- 

45 
2.5.4.9 Sample Definition 

When a sediment sample is collected, a decision has to be made as to whether 

the entire sediment volume is to be considered as the sample or whether the 

sediment volume represents separate samples. For instance, based on 

observed stratification, the top 1 m of a core might be considered to be a 

separate sample from the remainder of the core. After the sediment to be 

considered as a sample is identified, it should be thoroughly homogenized. 

Samples may be split before cornpositing, with a portion of the original 

sediment archived for possible later analysis, and the remainder combined with 

parts of other samples. These are then thoroughly homogenized (using clean 

instruments until color and textural homogeneity are achieved), producing the 

composite sample. 

2.5.5 Sample Designation Sys tern 

Information on the procedures used to designate the sampling location and type 

of sample collected should be clearly stated in the field sampling plan. The 

sampling stations should be named according to the site and the type of 

station. Each sample should be assigned an identifier that describes the 

station, type of sample, and field replicate. An example sample designation 

format is as follows: 

The first two characters of the station name could identify the site 

(e.g., BH = Boston Harbor). 

The third character of the station name could identify the type of 

station (e.g., S = site station, P = perimeter station, or R = 

reference station). 

The fourth and fifth characters of the station name could consist of 

a sequential number (e.g., 01, 02, or 03) that would be assigned to 

distinguish between different stations of the same type. 

The sixth character of the station name could describe the type of 

sample (e.g., C = sediment for chemistry and bioassay analyses, B 

= bioaccumulation, or I = benthic infauna). 

The resulting sample identifier would be: BHSOlC. 

When field replicates are collected (i.e., for benthic samples), the replicate 

number should be appended to the sample identifier. All field replicates from 

the same station should have the same sample identifier. The sample identifier 

and replicate number should be linked by a dash to form a single identifier for 

use on sample labels. The sample date should also be recorded on the sample 

label. 

46 
2.5.6 Station Positioning 

The type of positioning system used during sample collection and detailed 

procedures for station positioning should be clearly stated in the sampling plan. 

No single positioning method will be appropriate for all sampling scenarios. 

U.S. EPA (1987b), PSEP(1990b), and USACE (1990) provide useful information 

on positioning systems and procedures. Guidance in these publications may be 

followed on all points that do not conflict with this document. 

2.5.6.1 Selection of Station Positioning System 

Available systems should be evaluated based on positioning requirements and 

project-specific constraints to select the most appropriate station positioning 

method for the project. Specific design and location factors that may affect 

station positioning include physical conditions (e.g., weather and currents) and 

topography of the study site, proposed equipment and analyses, minimum 

station separation, station reoccupation, and program-imposed constraints. 

U.S. EPA’s (1993b) locational data policy implementation guidance calls for 

positioning accuracy within 25 m. 

There are many methods available for navigating and positioning sampling 

vessels. These methods range from simple extensions of well-established 

onshore survey techniques using theodolites to highly sophisticated electronic 

positioning systems. A general discussion of a few of the station positioning 

methods available for dredged material evaluations is provided in the following 

sections. U.S. EPA (1987b), PSEP (1990b), USACE (1990), and current 

literature from the manufacturers of station positioning systems should be 

thoroughly reviewed during the selection process to choose the most 

appropriate project-specific positioning system. 

Optical Positioning Techniques 

Optical positioning requires visual sighting to determine alignment on two or 

more ranges, or the distances and angles between the vessel and shore 

targets, 

Intersecting ranges can be used when a number of established landmarks 

permit easy selection of multiple ranges that intersect at the desired sampling 

point, and accuracy is not critical. One of the more traditional optical 

positioning systems is the theodolite system. Position of the sampling vessel 

can be established using theodolites by two onshore observers who 

simultaneously measure the angle between a reference object or shore traverse 

and the vessel. Using a theodolite with an accuracy of f15 seconds for a 

single angle measurement at an intercept angle of approximately 45” and a 

47 
range of 5 km, could potentially yield a positioning error of < fl m (Ingham 

1975). Although the accuracy of this method is good under optimal conditions, 

its use in open waters has several disadvantages such as limited line-of-sight, 

limits on intersection of angles, requirement of two manned shore stations, 

simultaneous measurements, and target movement and path interferences 

(e.g., fog, heavy rain, or heat waves). 

Electronic Positioning Techniques 

Electronic positioning systems use the transmission of electromagnetic waves 

from two or more stations and a vessel transmitter to define a vessel’s location. 

Under routine sampling conditions, which may disfavor optical positioning, and 

at their respective maximum ranges, electronic positioning methods have 

greater accuracy than optical positioning methods (U.S. EPA 1987b). 

LORAN-C is one type of electronic positioning system. Based on the signal 

properties of received transmissions from land-based transmitters, the LORANC receiver can be used to locate an approximate position, with a repeatable 

accuracy that varies from 15 to 90 m (U.S. EPA 1987b), depending on the 

weather and the geometry of the receiver within the LORAN-C station network. 

Although the LORAN-C system is not limited by visibility or range restrictions 

and does not require additional personnel to monitor onshore stations (as the 

theodolite system does), the LORAN-C system does experience interferences in 

some geographic areas and is more appropriately used to reposition on a 

previously sampled station. 

Microwave positioning systems are typically effective between 25 and 100 km 

offshore, depending on antenna heights and power outputs, and have 

accuracies of 1-3 m. Microwave systems consist of two or more slave shore 

stations positioned over known locations and a master receiver on the vessel. 

By accurately measuring the travel time of the microwaves between the two 

known shore points and the vessel receiver, the position of the vessel can be 

accurately determined. The shore stations, typically tripod-mounted antennas 

powered by 12-volt batteries, are very susceptible to vandalism. 

The global positioning system (GPS) is another electronic system that can 

determine station positions by receiving digital codes from three or more 

satellite systems, computing time and distance, and then calculating an earthbased position. Two levels of positioning accuracy are achievable with the GPS 

system. The positional accuracy of standard GPS is approximately 50-100 m 

(U.S. EPA 1987b). The accuracy can be improved to between 0.54 m by 

differential GPS (U.S. EPA 1987b). In differential GPS, two receivers are used. 

The master receiver is placed on a known location. It’s location is computed 

based on satellite data, and a correction is applied to account for the errors in 

48 
position from the satellites. This correction is then sent via radio link or satellite 

to vessel-mounted receivers, 

Hybrid Positioning Techniques 

A number of hybrid positioning systems combine positional data from various 

sources to obtain fixes. Such systems usually involve the intersection of a 

visual line-of-position with an electronic line-of-position. Of particular interest to 

coastal monitoring programs are dynamic positioning systems that require only 

a single shore station and that use the simultaneous measurement of angte 

from a known direction and range to the survey vessel. These range-azimuth 

systems are characterized by their operating medium (optional, microwave, 

laser) and/or procedure (i.e. manual or automatic tracking). 

2.5.6.2 Physical Conditions at the Study Site 

The ability of a positioning method to achieve its highest projected accuracy 

depends, in part, on site-specific conditions. Weather, currents and other 

physical factors may reduce the achievable accuracy of a positioning method. 

For example, the relative drift of the sampling equipment away from the boat 

under strong currents or winds can increase with depth. Resulting positioning 

errors in sample location (as opposed to boat location) may exceed acceptable 

limits for the study if effects of site location on positioning accuracy are not 

considered during design of the sampling program. 

2.5.6.3 Quality Assurance Considerations 

Once the positioning method has been selected for the specific dredged 

material evaluation, the proper setup, calibration, and operational procedures 

must be followed to achieve the intended accuracy. At least one member of 

the field crew should be familiar with the selected positioning method. 

Recordkeeping requirements should be established to ensure that station 

locations are accurately occupied and that adequate documentation is available. 

Adequate information to ensure consistent positioning and to allow reoccupation 

of stations for replicate sample collection or time-series monitoring should be 

kept in a field logbook. Entries should be initialed by the person entering the 

data. Required entries into the field logbook include the following: 

n Initial Survey Description-The positioning method and 

equipment used, all changes or modifications to standard methods, 

names of persons who set up and operate the station positioning 

equipment, location of on-board equipment and the reference point 

(e.g., antennae, sighting position), the type of map used for 

_- - - _ ._ - -~ - ---~ -~ ..- - -~ -~.- .- 

49 -- 
positioning and its identification number or scale should be 

recorded in the field logbook. in addition, a complete copy of the 

survey notes (if appropriate) should be included in the field 

logbook. 

n Day Log Entries-The same information that is included in the 

initial survey description is also recorded on a daily basis in the 

day log. In addition, all problems or irregularities, any weather or 

physical conditions that may affect achievable accuracy, and all 

calibration data should be recorded in the day log. 

n Station Log Entries- Each station location should be recorded in 

the coordinates or readings of the method used for positioning in 

sufficient detail to allow reoccupation of the station in the future. 

The positioning information should be recorded at the time of 

sample collection (versus time of equipment deployment) and for 

every reoccupation of that station, even during consecutive 

replicate sampling. In addition, supplemental positioning 

information that would define the station location or help 

subsequent relocation (e.g., anchored, tied to northwest corner of 

pier, buoy) should be recorded. If photographs are to be used for 

a posferioti plotting of stations, the roll and frame numbers should 

be recorded. Depth, time (tidal height) ship heading, and wire 

angle estimation should also be recorded for each occupation of a 

station. 

Sampling reports should include the type of positioning method used during 

data collection. Any specific problems (e.g., wind, currents, waves, visibility, 

electronic interferences) that resulted in positioning problems and those stations 

affected should be identified in the sampling report. Estimates of the accuracy 

achieved for station positioning should be included. Station locations should be 

reported in appropriate units (e.g., latitude and longitude to the nearest second). 

Coordinates do not need to be reported for each replicate collected; a single set 

of coordinates for the station is sufficient. Depth corrected to mean lower low 

water should also be supplied for each station. 

2.5.7 Sample Collection Methods 

Detailed procedures for performing all sampling and equipment decontamination 

should be clearly stated in the sampling plan and can be included as standard 

operating procedures (see Appendix D). Sample collection requires an 

experienced crew, an adequate vessel equipped with navigational and 

supporting equipment appropriate to the site and the study, and 

noncontaminating sampling apparatus capable of obtaining relatively 

undisturbed and representative samples. To assure sampling quality, at least 

one individual familiar with the study area should be present during the 

50 
sampling activities. Sampling effort for a proposed dredging project is primarily 

oriented toward collection of sediment samples for physical and chemical 

characterization and for biological tests. Collection of water samples is also 

required to evaluate potential water column impact. Collection of organisms 

near the disposal site might be necessary if there is a need to characterize 

indigenous populations or to assess concentrations of contaminants in tissues. 

Organisms for use in toxicity and bioaccumuiation tests may also be fieldcollected. 

In general, a hierarchy for sample collection should be established to prevent 

contamination from the previous sample, especially when using the same 

sampling apparatus to collect samples for different analyses. Where possible, 

the known or expected least contaminated stations should be sampled first. At 

a station where water and sediment are to be collected, water samples should 

be cotlected prior to sediment samples. The vessel should ideally be positioned 

downwind or downcurrent of the sampling device. When lowering and retrieving 

sampling devices, care should be taken to avoid visible surface slicks and the 

vessel’s exhaust. The deck and sample handling area should be kept clean to 

help reduce the possibility of contamination. 

2.5.7.1 Sediment Sample Collection 

Mudroch and MacKnight (1991) provide useful reference information for 

sediment sampling techniques. Higgins and Lee (1987) provide a perspective 

on sediment collection as commonly practiced by USACE. ASTM (1991 b) and 

Burton (1991) provide guidelines for collecting sediments for toxicological 

testing. Guidance provided in these publications may be followed on all points 

that do not conflict with this document. 

Care should be taken to avoid contamination of sediment samples during 

collection and handling. A detailed procedure for handling sampting equipment 

and sample containers should be clearly stated in the sampling plan associated 

with a specific project; this may be accomplished by using standard operating 

procedures. For example, samples designated for trace metal analysis should 

not come into contact with metal surfaces (except stainless steel, unless 

specifically prohibited for a project), and samples designated for organic 

analysis should not come into contact with plastic surfaces. 

A coring device is recommended whenever sampling to depth is required. The 

choice of corer design depends on factors such as the objectives of the 

sampling program, sediment volumes required for testing, sediment 

characteristics, water depth, sediment depth, and currents or tides. A gravity 

corer may be limited to cores of l-2 m in depth, depending on sediment grain 

size, degree of sediment compaction, and velocity of the drop. For penetration 

greater than 2 m, a vibratory corer or a piston corer is generally preferable. 

These types of coring devices are generally limited to soft, unconsolidated 

sediments. A split-spoon core may be used for more compacted sediment. 

The length of core that can be collected is usually limited to 10 core diameters 

in sand substrate and 20 core diameters in clay substrate. Longer cores can 

51 
be obtained, but substantial sample disturbance results from internal friction 

between the sample and the core liner. 

Gravity corers can cause compaction of the vertical structure of sediment 

samples, if they freefall into the sediment. Therefore, if the vertical stratification 

in a core sample is of interest, a piston corer or vibra corer should be used. 

The piston corer uses both gravity and hydrostatic pressure. As the cutting 

edge penetrates the sediments, an internal piston remains at the level of the 

sediment/water interface, preventing sediment compression and overcoming 

internal friction. The vibra corer is a more complex piece of equipment but is 

capable of obtaining 3- to 7-m cores in a wide range of sediment types by 

vibrating a large diameter core barrel through the sediment column with little 

compaction. If the samples will not be sectioned prior to analysis, compaction 

is not a problem, and noncontaminating gravity (freefall) corers may be the 

simplest alternative. 

Corers are the samplers of preference in most cases because of the variation in 

contamination with depth that can occur in sediment deposits. Substantial 

variation with depth is less likely in shallow channel areas without major direct 

contaminant inputs that have frequent ship traffic and from which sediments are 

dredged at short intervals. Generally, in these situations, bottom sediments are 

frequently resuspended and mixed by ship scour and turbulence, effectively 

preventing stratification. In such cases, surface grab samples can be 

representative of the mixed sediment column, and corers should be necessary 

only if excavation of infrequently disturbed sediments below the mixed layer is 

planned. Grab samplers are also appropriate for collecting sut-ficial samples of 

reference or control sediments. 

Grab samplers and gravity corers can either be Teflon@-coated or be made of 

stainless steel to prevent potential contamination of trace metal samples. The 

sampling device should at least be rinsed with clean water between samples. 

More thorough cleaning will be required for certain analyses; for instance, 

analyses performed for chlorinated dioxins require that all equipment and 

sample containers be scrupulously cleaned with pesticide-grade solvents or 

better because of the low detection limits required for these compounds. It is 

recommended that a detailed standard operating procedure specifying all 

decontamination procedures be included in the project sampling plan. 

2.5.7.2 Water Sample Collection 

If water samples are necessary, they should be collected with either a 

noncontaminating pump or a discrete water sampler. When sampling with a 

pump, the potential for contamination can be minimized by using a peristaltic or 

a magnetically coupled impeller-design pump. These kinds of pumps provide 

barriers between the sample and the surfaces of the pump (e.g., motor or fan) 

52 
that would cause contamination. The system should be flushed with the 

equivalent of 10 times the volume of the collection tubing. Also, any 

components within several meters of the sample intake should be 

noncontaminating (i.e., sheathed in polypropylene or epoxy-coated or made of 

Teflon@). Potential sample contamination must be avoided, including vessel 

emissions and other sampling apparatus. 

A discrete water sampler should be of the close/open/close type so that only 

the target water sample comes into contact with internal sampler surfaces. 

Water samplers should be made of stainless steel or acrylic plastic. Seals 

should be Teflon’coated whenever possible. Water sampling devices should 

be acid-rinsed (1 :l nitric acid) prior to use for collection of trace-metal samples, 

and solvent-rinsed (assuming the sampler material is compatible) prior to 

collection of samples for organic analyses. 

2.5.7.3 Organism Collection 

Collection methods for benthic organisms may be species-specific and can 

include, but are not limited to, bottom trawling, grabs, or cores. If organisms 

are to be maintained alive, they should be transferred immediately to containers 

with clean, well-oxygenated water, and sediment, as appropriate. Care must be 

taken to prevent organisms from coming into contact with natural predators and 

potentially contaminated areas or fuels, oils, natural rubber, trace metals, or 

other contaminants (U.S. EPA 1990a, 1992a). 

2.5.8 Sample Handling, Preservation, and Storage 

Detailed procedures for sampling handling, preservation, and storage should be 

part of the project-specific protocols and standard operating procedures 

specified for each sampling operation and included in the sampling plan. 

Samples are subject to chemical, biological, and physical changes as soon as 

they are collected. Sample handling, preservation, and storage techniques 

have to be designed to minimize any changes in composition of the sample by 

retarding chemical and/or biological activity and by avoiding contamination. 

Collection methods, volume requirements, container specifications, preservation 

techniques, storage conditions, and holding times (from the time of sample 

collection) for sediment, water, and tissue samples are discussed below and 

summarized in Table 5. Exceedance of the holding times presented in Table 5 

would not necessarily result in qualification of the data during data validation. 

However, technical reasons justifying acceptance of data that exceed the 

holding time should be provided on a compound class basis. 
TABLE 5. SUMMARY OF RECOMMENDED PROCEDURES FOR SAMPLE 

COLLECTION, PRESERVATION, AND STORAGE 

Analyses 

Collection 

Meth& 

Sample 

Volume” Containef 

Preservation 

Technique 

Storage 

Conditions Holding Timesd 

Sediment 

ChemlcaUPhyslcal Analyses 

Metals Grab/corer Precleaned polyethylene jaf 

Organic compounds 

(e.g., PC&. pesticides, 

polycyclic erometic 

hydrocarbons) 

Particle size 

Total organic carbon 

Grab/corer 

Grab/corer 

Grab/corer 

250 g Solvent-rinsed glass 

jar with Teflon* lid@ 

1ofJg 

56 g 

Whirl-pat bag’ 

Heat treated glass 

vial with Teflon’-lined 

Ii@ 

Total solids/specific 

gravity 

Miscellaneous 

Sediment from which 

elutriate is prepared 

Blologlcal Tests 

Dredged material 

Reference sediment 

Control sediment 

Grab/corer 

Grab/corer 

Grab/corer 

Whirl-pat bag 

2 50 g Whirl-pat bag 

Depends on tests Glass with Teflor?- 

being performed lined lid 

Grab/corer 

Grab/corer 

Grab/corer 

12-15 L per 

sample 

45-50 L per test 

Plastic bag or containe? 

Plastic bag or containee 

Completely fill and 

refrigerate; sieve 

Completely fill and 

refrigerate; sieve 

21-25 L per test Plastic bag or con- Completely fill and 

Wine* refrigerate; sieve 

Dry ice’ or freezer 

storage for extended 

storages; otherwise 

refrigerate 

Dry ice’ or freezer 

storage for extended 

storage; otherwise 

refrigerate 

Refrigerate 

Dry ice* or freezer 

storage for extended 

storages; otherwise 

refrigerate 

Refrigerate 

Refrigerate 

Completely fill and 

refrigerate 

Undetermined 

14 days 

5 4°C Hg - 26 days 

Others - 6 months’ 

5 4°Cb/dark’ 14 days0 

< 4% 

5 4%. 

< 4°C 

< 4°C 

4WdarkJairtight 

Undetermined 

Undetermined 

14 days 

4WdaMairtight 14 days’ 

4WdarWairtight 14 days’ 

4WdarkIairtight 14 days’ 

- 

54 
TABLE 5. (cont.) 

Analyses 

Collection 

Method” 

Sample 

Volumeb Container” 

Preservation 

Technique 

Storage 

Conditions Holding Timesd 

Water snd Elutriate 

ChemlcaWhyslcal Analyses 

Particulate analysis 

Metals 

Total Kjeldahl nitrogen 

Chemical oxygen 

demand 

Total organic carbon 

Total inorganic carbon 

Phenolic compounds 

Soluble reactive 

phosphates 

Extractable organic 

compounds {e.g., semivolatile compounds) 

Volatile organic 

compounds 

Total phosphorus 

Discrete sampler 

or pump 

Discrete sampler 

or pump 

Discrete sampler 

or pump 

Discrete sampler 

or pump 

Discrete sampler 

or pump 

Discrete sampler 

or pump 

Discrete sampler 

or pump 

Discrete sampler 

or pump 

Discrete sampler 

or Pump 

Discrete sampler 

or pump 

Discrete sampler 

or pump 

50&2,OOO mL Plastic or glass 

1L 

100-200 mL 

200 mL 

100 mt 

100 mL 

1L 

Acid-rinsed polyethy 

lene or g\ass ja$ 

Plastic or glass’ 

Plastic or glassk 

Plastic or glassk 

Plastic or glass’ 

Glass’ 

-- 

4L 

80mL 

Plastic or glass’ 

Amber gtass bottl$ 

Glass vial’ 

Plastic or gtassh 

Lugols solution and 

refrigerate 

pH < 2 with HNO,; 

tefrigerate’ 

H,SO, to pH < 2; 

refrigerate 

H,SO, to pH < 2; 

rettigerate 

HpSO, to pH < 2; 

refrigerate 

Airtight seal; refrigeratek 

0.1-l .o g cuso,; 

H,SO, to pH < 2; 

refrigerate 

Filter; refrigerate’ 

pH < 2, 6N HCI; 

airtight seal; refrigerate 

pH < 2 with 1 :l HCL; 

refrigerate in airtight, 

completely filled container’ 

H,SO, to pH < 2; 

refrigerate 

4°C 

4°C 2°C’ 

4°C’ 

4ock 

PC’ 

4%’ 

4”Ck 

40Ck 

4%’ 

4°C’ 

40Ck 

Undetermined 

Hg - 14 days 

Others - 6 mon¶h$ 

24 h’ 

7 days’ 

<48 hours’ 

6 month$ 

24 hours’ 

24 hwrs’ 

7 days for extraction; 40 days for 

sample extract 

analyses’ 

14 days for sample 

analysis, if preserved’ 

7 daysk 

55. - 

- 
TABLE 5. (cont.) 

Analyses 

Collection Sample 

Method’ Volumeb Containef 

Preservation Storage 

Techniaue Conditions Holdina Timesd 

Total solids 

Volatile solids 

Sulfides 

Discrete sampler 

or pump 

Discrete sampler 

or pump 

Discrete sampler 

or pump 

Blologlcal Tests 

Site water Grab 

Dilution water Grab or makeup 

Tissue 

Metals Trawl/Teflonecoated grab 

PCBs and chlorinated 

pesticides 

Trawl/Teflo#- 

coated grab 

Volatile organic 

compounds 

TrawlKeflon*- 

coated grab 

Semivolatile organic 

compounds 

Trawl/Teflon*- 

coated grab 

Lipids Trawl/Teflo#- Part of organic Hexane-rinsed alumicoated grab analyses num foil 

200 mL 

200 mL 

Plastic or glass’ 

Plastic or glassk 

-_ Plastic or glassk 

Depends on tests Plastic carboy 

being performed 

Depends on tests Plastic carboy 

being pedormed 

5-log Double Ziploc@’ 

10-25 g Hexane-rinsed double 

aluminum foil and 

double Ziploc* 

l&-25 g 

lo-25 g 

Heat-cleaned aluminum foil and watertight plastic bag’ 

Hexane-rinsed double 

aluminum foil and 

double Zipkx? 

Refrigerate 

Refrigerate 

pH > 9 NaOH (ZnAc); 

refrigeratek 

Refrigerate < 4°C 14 days 

Refrigerate < 4°C 14 days 

Handle with nonmetallic forceps; plastic 

gloves; dry ice’ 

Handle with hexanerinsed stainless steel 

forceps; dry ice’ 

Covered ice chest’ 

Handle with hexanerinsed stainless steel 

forceps; dry ice’ 

Handle with hexanerinsed stainless steel 

forceps; quick freeze 

4ock 

4ock 

4ock 

7 daysk 

7 daysk 

24 hoursk 

s -20°C’ or freezer Hg - 28 days 

storage Others - 6 months” 

s -20°C’ or freezer 

storage 

14 days0 

s -20°C” or 

freezer storage 

14 days” 

5 -2O”C* or freezer 

storage 

14 day@ 

s -20°C or fn3ezer 

storage 

14 days0 

Note: This table contains only a summary of collection, preservation, and storage procedures for samples. The cited references should be consufted for a more detailed 

description of these procedures. 

56 
TABLE 5. (cont.) 

PC8 - polychlorinated biphenyl 

’ Collection method should include appropriate liners. 

b Amount Of Sample required by the laboratory to perform the analysis (wet weight or volume provided, as appropriate). Miscellaneous sample size for sediment should be 

increased if auxiliary analytes that cannot be included as part of the organic or metal analyses are added to the list. The amounts shown are not intended as firm values; 

more or fess tissue may be required depending on the anatytes, matrices, detection limits, and partiCUlar analytical laboratory. 

’ All containers should be certified as clean according to U.S. EPA (799Oc). 

d These holding times are for sediment, water, and tissue based on guidance that is sometimes administrative rather than technical in nature. 

scientifically based holding time criteria for sediments, tissues, or elutriates. 

There are no promulgated, 

References should be consulted if holding times for sample extracts are desired. Holding 

times are from the time of sample collection. 

’ NOAA (7989). 

’ Tetra Tech (1986a). 

o Sample may be held for up to 1 year if < -20°C. 

’ Polypropylene should be used if phthalate bioaccumulation is of concern. 

’ Two weeks is recommended; sediments must not be held for longer than 8 weeks prior to biological testing. 

I U.S. EPA (1987a); 40 CFA Part 136, Table Ill. 

’ Plumb (1981). 

’ If samples are not preserved to pH < 2, then aromatic compounds must be analyzed within 7 days. 

m Tetra Tech (1986b). 

I-- ___I___ ----.--. - .--- - ~- 

57 
2.5.8. I Sample Handling 

Sufficient sample volume should be collected to: 

l Perform the necessary analyses 

m Partition the samples, either in the field or as soon as possible 

after sampling, for respective storage and analytical requirements 

(e.g., freezing for trace metal analysis or refrigeration fot 

bioassays) 

m Archive portions of the sample for possible later analysis. 

n Provide sample for replicate or QA analyses, if specified. 

Sample handling is project- and analysis-specific, as well as being based on 

what is practical and possible. Generally, samples to be analyzed for trace 

metals should not come into contact with metals, and samples to be analyzed 

for organic compounds shoutd not come into contact with plastics. All sample 

containers should be scrupulously cleaned (acid-rinsed for analysis of metals, 

solvent-rinsed for analysis of organic compounds). 

For analysis of volatile compounds, samples should completely fill the storage 

container, leaving no airspace. These samples should be refrigerated but never 

frozen or the containers will crack. Samples for other kinds of chemical 

analysis are sometimes frozen. Only wide-mouth (“squat”) jars should be used 

for frozen samples; narrow-mouth jars are less resistant to cracking. If the 

sample is to be frozen, sufficient air space should be left to allow expansion to 

take place (i.e., the wide-mouth sample container should be filled to no more 

than the shoulder of the bottle [just below the neck of the bottle] and the 

container should be frozen at an angle). Container labels have to withstand 

soaking, drying, and freezing without becoming detached or illegible. The 

labeling system should be tested prior to use in the field. 

Sediment samples for biological testing should have larger (possible predatory) 

animals removed from the sediment by screening or press sieving prior to 

testing. Other matter retained on the screen with the organisms, such as shell 

fragments, gravel, and debris, should be recorded and discarded. Prior to use 

in bioassays, individual test sediments should be thoroughly homogenized with 

clean instruments {until color and textural homogeneity is achieved). 

2.5.8.2 Sample Preservation 

Preservation steps should be taken immediately upon sediment collection. 

There is no universal preservation or storage technique, although storage in the 

dark at 4°C is generally used for all samples held for any length of time prior to 

processing, and for some samples after processing. A technique for one group 

58 
of analyses may interfere with other analyses. This problem can be overcome 

by collecting sufficient sample volume to use specific preservation or storage 

techniques for specific analytes or tests. Preservation, whether by refrigeration, 

freezing, or addition of chemicals, shoutd be accomplished as soon as possible 

after collection, onboard the collecting vessel whenever possible. If final 

preservation techniques cannot be implemented in the field, the sample should 

be temporarily preserved in a manner that retains its integrity. 

Onboard refrigeration is easily accomplished with coolers and ice; however, 

samples should be segregated from melting ice and cooling water. Sediment 

samples that are to be frozen on board may be stored in an onboard freezer or 

may simply be placed in a cooler with dry ice or blue ice. Sample containers to 

be frozen (wide-mouth jars; see Section 2.5.7.1) should not be filled completely 

because expansion of the sample could cause the container to break. 

Sediment samples for biological analysis should be preserved at 4”C, never 

frozen or dried. Additional guidance on sample preservation is given in Table 5. 

2.5.8.3 Sample Storage 

The elapsed time between sample collection and analysis should be as short as 

possible. Sample holding times for chemical evaluations are analysis-specific 

(Table 5). Sediments for bioassay (toxicity and/or bioaccumulation) testing 

should be tested as soon as possible, preferably within 2 weeks of coltection. 

Sediment toxicity does change with time. Studies to date suggest that 

sediment storage time should never exceed 8 weeks (at 4”C, in the dark, 

excluding air) (Becker and Ginn 1990; Tatem et al. 1991) because toxicity may 

change with storage time. Sample storage conditions (e.g., temperature, 

location of samples) should be documented. 

2.5.9 Logistical Considerations and Safety Precautions 

A number of frustrations in sample collection and handling can be minimized by 

carefully thinking through the process and requirements before going to the 

field. Contingency plans are essential. Well-trained, qualified, and experienced 

field crews should be used. Backup equipment and sampling gear, and 

appropriate repair parts, are advisable. A surplus of sampling containers and 

field data sheets should be available. Sufficient ice and adequate ice chest 

capacity should be provided, and the necessity of replenishing ice before 

reaching the laboratory should be considered. A vessel with adequate deck 

space is safer and allows for more efficient work than an overcrowded vessel. 

Unforeseeable circumstances (e.g., weather delays) are to be expected during 

field sampling, and time to adequately accommodate the unforeseen has to be 

included in sampling schedules. 
Appropriate safety and health precautions must be observed during field 

sampling and sample processing activities. The EPA Standard Operating 

Safety Guides (U.S. EPA 1984b) should be used as a guidance document to 

prepare a site-specific health and safety plan. The health and safety plan 

should be prepared as a separate document from the CIA project plan. 

Requirements implementing the Occupational Safety and Health Act at 29 CFR 

$1910.120 (Federal Register, Vol. 54, No. 43) should be met for medical 

surveillance, personal protection, respirator fit testing (if applicable), and 

hazardous waste operations training (if applicable) by all personnel working in 

contaminated areas or working with contaminated media. 

The procedures and practices established in the site-specific health and safety 

plan should be observed by all individuals participating in the field activities. 

Safety requirements should also be met by all observers present during field 

audits and inspections. The plan should include the following information: 

4 Site location and history 

m Scope of work 

n Site control 

m Hazard assessment (chemical and physical hazards) 

m Levels of protection and required safety equipment 

B Field monitoring requirements 

n Decontamination 

n Training and medical monitoring requirements 

n Emergency planning and emergency contacts. 

2.6 SAMPLE CUSTODY 

Recordkeeping procedures are described in detail in this section of the QA 

project plan, including specific procedures to document the physical possession 

and condition of samples during their transport and storage. This section also 

describes how excess or used samples will be disposed of at the end of the 

project. 

2.6.1 Sample Custody and Documentation 

Sample custody and documentation are vital components of all dredged 

material evaluations, particularly if any of the data may be used in a court of 

law. It is important to record all events associated with a sample so that the 

validity of the resulting data may be properly interpreted. Thorough 

60 
documentation provides a means to track samples from the field through the 

laboratory and prevent sample loss. The contents and location of all 

documents related to dredged sediment samples should be specified, and 

access to the samples should be controlled. 

The possession of samples should be documented from sample collection 

through laboratory analysis. Recording basic information during sample 

handling is good scientific practice even if formal custody procedures are not 

required. Sample custody procedures, including examples of forms to be used, 

shoutd be described in the QA project plan. Minimum requirements for 

documentation of sample handling and custody on simple projects should 

include the following information: 

= Sample location, project name, and unique sample number 

n Sample collection date (and time if more than one sample may be 

collected at a location in a day) 

n Any special notations on sample characteristics or problems 

n Initials of the person collecting the sample 

n Date sample sent to the laboratory 

n Conditions under which the samples were sent to the laboratory. 

For large or sensitive projects that may result in enforcement actions or other 

litigation, a strict system for tracking sample custody should be used to assure 

that one individual has responsibility for a set of samples at all times. For these 

projects, only data that have clear documentation of custody can be accepted 

without qualification. 

A strict system of sample custody implies the following conditions: 

8 The sample is possessed by an individual and secured so that no 

one can tamper with it 

n The location and condition of the sample is known and 

documented at all times 

m Access to the sample is restricted to authorized personnel only. 

Where samples may be needed for potential litigation, chain-of-custody 

procedures should be followed. Chain-of-custody procedures are initiated 

during sample collection. Chain-of-custody forms are often used to document 

the transfer of a sample from collection to receipt by the laboratory (or between 

different facilities of one laboratory). Although not always required, these forms 

provide an easy means of recording information that may be useful weeks or 

months after sample collection. When these forms are used, they are provided 

& 
to field technicians at the beginning of a project. The completed forms 

accompany the samples to the laboratory and are signed by the relinquisher 

and receiver every time the samples change hands. After sample analysis, the 

original chain-of-custody form is returned by the laboratory. The form is filed 

and becomes part of the permanent project documentation. An example of a 

chain-of-custody form is provided in Appendix A. Additional custody 

requirements for field and laboratory operations should be described in the QA 

project plan, when appropriate. 

When in doubt about the level of documentation required for sampling and 

analysis, a strict system of documentation using standard forms should be 

used. Excess documentation can be discarded; lack of adequate 

documentation in even simple projects sometimes creates the unfortunate 

impression that otherwise reasonable data are unusable or limited. Formal 

chain-of-custody procedures are outlined briefly in the statements of work for 

laboratories conducting analyses of organic and inorganic contaminants under 

EPA’s Contract Laboratory Program (CLP) (U.S. EPA 1990d,e). 

2.6.1.1 Field Operations 

The potential for sample deterioration and/or contamination exists during 

sample collection, handling, preservation, and storage. Approved protocols and 

standard operating procedures should be followed to ensure all field sampling 

equipment is acceptably calibrated and to prevent deterioration or 

contamination. Experienced personnel should be responsible for maintaining 

the sample integrity from collection through analysis, and field operations should 

be overseen by the project manager. A complete record of all field procedures, 

an inventory log, and a tracking log should be maintained. A field tracking 

report (see example in Appendix A) should identify sample custody and 

conditions in the field prior to shipment. 

Dates and times of collection, station locations, sampling methods, and sample 

handling, preservation, and storage procedures should be documented 

immediately, legibly, and indelibly so that they are easily traceable. Any 

circumstances potentially affecting sampling procedures should be documented. 

The data recorded should be thorough enough to allow station relocation and 

sample tracking. An example of a station location log is provided in 

Appendix A. Any field preparation of samples should also be described. In 

addition, any required calibration performed for field instruments should be 

documented in the field logbook. Samples should be identified with a 

previously prepared label (see example in Appendix A) containing at least the 

following information: 

n Project title 

n Sample identification number 
2.6.1.2 

Location (station number) and depth 

Analysis or test to be performed 

Preservation and storage method 

Date and time of collection 

Special remarks if appropriate 

Initials of person collecting the sample 

Name of company performing the work. 

Laboratory Operations 

Documentation is necessary in the laboratory where chemical and biological 

analyses are performed. A strict system of sample custody for laboratory 

operations should include the following items: 

n Appointment of a sample custodian, authorized to check the 

condition of and sign for incoming field samples, obtain documents 

of shipment, and verify sample custody records 

n Separate custody procedures for sample handling, storage, and 

disbursement for analysis in the laboratory 

n A sample custody log consisting of serially numbered, standard 

laboratory tracking report sheets. 

A laboratory tracking report (Appendix A) should be prepared for each sample. 

The location of samples processed through chain-of-custody must be known at 

all times. Samples to be used in a court of law must be stored in a locked 

facility to prevent tampering or alteration. 

A procedure should be established for the retention of all field and laboratory 

records and samples as various tasks or phases are completed. Replicates, 

subsamples of analyzed samples, or extra unanalyzed samples should be kept 

in a storage bank. These samples can be used to scrutinize anomalous results 

or for supplemental analyses, if additional information is needed. All samples 

should be properly stored and inventoried. The retention and archiving 

procedure should indicate the storage requirements, location, indexing codes, 

retention time, and security requirements for samples and data. 

___ _ _ - -.- - - - - - -.-- ------ __---.---- ----.-- ___- 

63 
2.6.2 Storage and Disposal of Samples 

2.7 

In the statement of work, the laboratory should be instructed to retain all 

remaining sample material (under appropriate temperature and light conditions) 

at least until after the QA review has been completed. In addition, sample 

extracts or digestates should be appropriately stored until disposal is approved 

by the project manager. With proper notice, most laboratories are willing to 

provide storage for a reasonable time period (usually on the order of weeks) 

following analysis. However, because of limited space at the laboratory, the 

project manager may need to make arrangements for long-term storage at 

another facility. 

Samples must be properly disposed when no longer needed. Ordinary sampledisposal methods are usually acceptable, and special precautions are seldom 

appropriate. Under Federal law [40 CFR 261.5(a)], where highly contaminated 

wastes are involved, if the waste generated is less than 100 Kg per month, the 

generator is conditionally exempt as a small-quantity generator and may 

accumulate up to 1,000 Kg of waste on the property without being subject to 

the requirements of Federal hazardous waste regulations. However, State and 

local regulations may require special handling and disposal of contaminated 

samples. When samples have to be shipped, 49 CFR 100-l 77 should be 

consulted for current Department of Transportation regulations on packing and 

shipping. 

Over the last few years, there has been a growing awareness of the ecological 

and economic damage caused by introduced species. Because both east and 

west coast species are often used in bioaccumulation tests, there is a real 

potential of introducing bioaccumulation test species or associated fauna and 

flora (e.g., pathogens, algae used in transporting the worms). It is the 

responsibility of the persons conducting the bioaccumulation or toxicity tests to 

assure that no non-indigenous species are released. The general procedures 

to contain non-indigenous species are to collect and then poison all water, 

sediment, organisms and associated packing materials (e.g., algae, sediment) 

before disposal. Chlorine bleach can be used as the poison. A double 

containment system is used to keep any spillage from going down the drain. 

Guidance on procedures used in toxicity tests can be found in Appendix B of 

Dewitt et al. (1992a). Flow-through tests can generate large quantities of 

water, and researchers should plan on having sufficient storage facilities. 

CALIBRATION PROCEDURES AND FREQUENCY 

Procedures for minimizing bias and properly maintaining the precision of each 

piece of equipment to be used in the field or laboratory are detailed in this 

section of the QA project plan. Procedures are also described for obtaining, 

using, and storing chemical standards of known purity used to quantify 

64 
analytical results, and reference chemicals used as positive controls in toxicity 

tests. Instruments that require routine calibration include, for example, 

navigation devices, analytical balances, and water quality meters. 

Calibration of analytical instruments is a high priority and is always required for 

any project requiring quantitative data (even if only estimated quantities are 

necessary). Calibration is essential because it is the means by which 

instrument responses are properly translated into chemical concentrations. 

Instrument calibration is performed before sample analysis begins and is 

continued during sample analysis at intervals specified in each analytical 

method to ensure that the data quality objectives established for a project are 

met. 

Because there are several analytical techniques that can be used for the same 

target analyte, each of which may provide different guidance for performing 

instrument calibration, it is important to establish a minimum calibration 

procedure for any chemical analysis that will be performed. Uniform adherence 

to a minimum calibration procedure will also improve the comparability of data 

generated by multiple laboratories that may be used for a specific project or 

among projects. All requirements for performing instrument calibrations should 

be clearly stated in the QA project plan and the laboratory statement of work 

prepared for any project. 

In addition to performing instrument calibrations, the acceptability of the 

calibrations performed should be evaluated. To provide control over the 

calibration process, specific guidelines should be specified. The basic elements 

of the calibration process include the calibration frequency, number of 

calibration standards and their concentrations, and the calibration acceptance 

criteria. A summary of these elements is provided below. 

Examples of the differences in calibration procedures (specifically for the 

analysis of organic compounds) for different analytical methods are provided in 

Table 6. 

2.7.1 Calibration Frequent y 

The general process of verifying that an instrument is functioning acceptably is 

to perform initial and continuing calibrations. Initial calibration should be 

performed prior to sample analysis to determine whether the response of the 

instrument is linear across a range of target analyte concentrations (i.e., the 

working linear range). In addition to establishing the initial calibration for an 

instrument, it is critical that the stability of the instrument response be verified 

during the course of ongoing sample analyses. The verification of instrument 

stability is assessed by analyzing continuing calibration standards at regular 

intervals during the period that sample analyses are performed. Although each 

anatytical method provides guidance for the frequency at which continuing 

65 
Calibration Criteria 

SW-646 Methods for 

Organic Compounds” 

EPA CLP Methods for 

Organic Compoundsb 

Number of standards for 

initial calibration 

Concentration of lowest All target analytes near, but 

initial calibration standard above, the TDL 

Concentrations for initial 

calibration to establish the 

instrument’s working linear 

range 

1. Bracket the expected concentration range of analytes expected in samples 

Concentration of continuing calibration standards 

Frequency of calibrations 

Acceptance criteria for 

initial calibrationC 

Acceptance criteria for 

continuing calibrationC 

Minimum of five for all methods 

2. Bracket the full instrument/ 

detector linear range 

Not specified, except for GUMS 

methods 

Repeat when acceptance criteria 

not met 

Calculate analyte RRFs or RFs, 

then RSD should be 5 30 percent 

for GUMS methods and 5 20 

percent for all other methods 

Alternative: generate a least 

squares linear regression (peak 

height/area vs. concentration) 

and use equation to calculate 

sample results 

Calculate analyte RRFs or RFs, 

then difference to mean RRF or 

RF of initial calibration should be 

I 25 percent for GClMS methods 

and I 15 percent for all other 

methods 

Alternative: none 

Five for all GUMS analyses 

Three for pesticides 

One for PCBs and multicomponent pesticides 

Contractually set (e.g., 10 pg/L for 

volatile organic compounds) 

Contractually set (e.g., 10, 50, 

100, 150, and 200 l.@L for volatile 

organic compounds) 

Contractually set (e.g., 50 pg/L for 

all GCIMS analyses) 

Repeat when acceptance criteria 

not met 

Calculate analyte RRFs or RFs, 

then RSD should be I 30 percent 

for GUMS methods and I 20 

percent for pesticides 

Alternative: none 

Calculate analyte RRFs or RFs, 

then difference to mean RRF or 

RF of initial calibration should be 

I 25 percent for GUMS methods 

and I 15 percent for pesticides 

Alternative: none 

Note: CLP - Contract Laboratory Program 

GC/MS - gas chromatography/mass spectrometry 

PCB - polychlorinated biphenyl 

RF - response factor (i.e., calibration factor) 

RRF - relative response factor 

RSD - relative standard deviation 

TDL - target detection limit 

6; 
TABLE 6. (cont.) 

’ U.S. EPA (1986a). 

b U.S. EPA (199Ob). 

’ The acceptance criteria for instrument calibration (i.e., initial and continuing calibration) may not be available for all organic 

compounds listed in Table 3 (e.g., resin acids and guaiacols). The determination of acceptable instrument calibration criteria 

for organic compounds not specifically stipulated in SW-846 or EPA CLP methods should be assessed using best professional 

judgment (e.g., 5 50 percent RSD). 
calibration standards should be performed, it is recommended that at a 

minimum these standards be analyzed at the beginning of each analytical for 

table 6 sequence, after every tenth sample, and at the end of the analytical 

sequence for all organic and inorganic compound analyses performed. The 

concentration of the continuing calibration standard should be equivalent to the 

concentration of the midpoint established during initial calibration of the working 

linear range of the instrument. 

2.7.2 Number of Calibration Standards 

Specific instrument calibration procedures are provided in most analytical 

methods; however, a wide variation exists in the number of calibration 

standards specified for different analyses. To ensure that consistent and 

reliable data are generated, a minimum number of calibration standards should 

be required for all laboratories performing chemical analyses. 

Typically, as the number of calibration standards increases, the reliability of the 

results increases for concentrations detected above the TDL. The specific 

standards that are selected for calibration can have a significant impact on the 

validity of the data generated. Calibration standards should be established with 

respect to the range of standards required, the TDLs selected, and the linear 

range of the target analytes desired. Specific requirements for establishing the 

number of calibration standards, including recommendations on the 

concentrations to use, will be different for organic and inorganic analyses; 

however, some general recommended guidelines are provided below. 

The working linear range of an instrument should be established prior to 

performing sample analyses. A minimum of five calibration standards for the 

analysis of organic compounds and three calibration standards for the analysis 

of inorganic compounds should be used when establishing the working linear 

range for all target analytes of concern. Generally, the working linear range of 

an instrument for a specific analysis should bracket the expected concentrations 

of the target analyte in the samples to be analyzed. In some instances, 

however, it may not be known what analyte concentrations to expect. A 5-point 

initial caiibration sequence is recommended to establish the working linear 

range for organic chemical analyses. 

In addition to the number of standards analyzed, the difference between the 

concentration of the lowest standard and the TDL and the difference between 

each standard used to establish the initial calibration are critical. The selection 

of the lowest initial calibration standard concentration will provide more 

confidence in the documented bias of results reported as undetected at the TDL 

or any results reported at very low concentrations. The selection of this 

standard will also ensure that target analytes can be reliably detected above 

instrument background noise and potential matrix interferences. For the 

68 
dredged material program, this standard should be no lower than the TDL 

provided in Table 3. 

The decision as to which specific concentrations (i.e., calibration range) should 

be used for a multipoint calibration requires careful consideration. While 

methods established by EPA CLP protocols provide stringent requirements for 

calibration analyses, these requirements are not clearly specified for other 

analytical methods (e.g., SW-846 methods) (see Table 6). A 5-point initial 

calibration sequence is recommended for all non-CLP methods. The 

concentrations of all standards should range from the lowest concentration 

meeting the requirements suggested above to the highest standard 

concentration equivalent to the upper linear range of the instrument/detector 

configuration. The concentrations of the remaining three standards should be 

evenly distributed between these concentrations. The calibration standards 

used to establish the working linear range should encompass a factor of 20 

(i.e., 1 to 20, with the lowest concentration equal to 1 and the highest 

concentration equal to 20 times the concentration of the lowest concentration 

used). 

2.7.3 Calibration Acceptance Criteria 

Once the initial calibration has been performed, the acceptability of the 

calibration should be assessed to ensure that the bias of the data generated 

will be acceptable; this assessment should be performed by all laboratories 

prior to the analysis of any sample. In addition, the acceptability of all 

continuing calibrations should be assessed. 

Although each analytical method provides guidance for determining the 

acceptability of instrument calibrations, there are multiple options available (e.g., 

least squares linear regression, percent relative standard deviations, and 

percent differences). A specific set of acceptance criteria should be determined 

prior to sample analysis, and these criteria should be contractually binding to 

avoid unnecessary qualification or rejection of the data generated. A summary 

of the most widely used calibration acceptance criteria currently in use for 

organic analyses is provided in Table 6. Calibration acceptance criteria should 

be used to assess the acceptability of the initial calibration sequence in terms of 

the relationship between the intercept of the caJibration curve (i.e., the x-y 

intercept) and the predetermined TDLs and the overall reliability of the working 

linear range established. 

The general criteria specified by SW-846 methods are typically more stringent 

for organic analyses than the EPA CLP requirements. Acceptance criteria, as 

summarized in Table 6, should be clearly defined before sample analyses are 

performed. All specific acceptance criteria for calibrations should be stated in 

the QA project plan and the laboratory statement of work. 

69 
2.8 ANALYTICAL PROCEDURES 

The methods cited in this section may be used to meet general data quality 

objectives for dredged material evaluations. However, other methods may 

provide similar results, and the final choice of analytical procedures should be 

based on the needs of each evaluation. In all cases, proven, current methods 

should be used; EPA-approved methods, if available, are preferred. Sample 

analysis procedures are identified in this section by reference to established, 

standard methods. Any modifications to these procedures and any specialized, 

nonstandard procedures are also described in detail. When preparing a QA 

project plan, only modifications to standard operating procedures or details of 

non-standard procedures need to be described in this section of the plan. 

Any dredged material from estuarine or marine areas contains salt, which can 

interfere with the results obtained from some analytical methods. Any methods 

proposed for the analysis of sediment and water from estuarine or marine 

environments should explicitly address steps taken to control salt interference. 

The following sections provide guidance on the selection of physical and 

chemical analyses to aid in evaluating dredged material proposed for disposal, 

and on the methods used to analyze these parameters. Information on the 

chemicals on the EPA priority pollutant and hazardous substance lists is 

provided in Appendix E. 

2.8.1 Physical Analysis of Sediment 

Physical characteristics of the dredged material must be determined to help 

assess the impact of disposal on the benthic environment and the water column 

and to help determine the appropriate dredging methods. This is the first step 

in the overall process of sediment characterization, and also helps to identify 

appropriate control and reference sediments for biological tests. In addition, 

physical analyses can be helpful in evaluating the results of analyses and tests 

conducted later in the characterization process. 

The general analyses may include grain size distribution, total solids content, 

and specific gravity. Grain size analysis defines the frequency distribution of 

the size ranges of the particles that make up the sediment (e.g., Plumb 1981; 

Folk 1980). The general size classes of gravel, sand, silt, and clay are the 

most useful in describing the size distribution of particles in dredged material 

samples. Use of the Unified Soil Classification System (USCS) for physical 

characterization is recommended for the purpose of consistency with USACE 

engineering evaluations (ASTM 1992). 

Measurement of total solids is a gravimetric determination of the organic and 

inorganic material remaining in a sample after it has been dried at a specified 
temperature. The total solids values generally are used to convert 

concentrations of contaminants from a wet-weight to a dry-weight basis. 

The specific gravity of a sample is the ratio of the mass of a given volume of 

material to an equal volume of distilled water at the same temperature (Plumb 

1981). The specific gravity of a dredged material sample hetps to predict the 

behavior (i.e., dispersal and settling characteristics) of dredged material after 

disposal. 

Other physical/engineering properties (e.g., Atterburg limits, settling properties) 

may be needed to evaluate the quality of any effluent discharged from confined 

disposat facilities. QA considerations for physical analysis of sediments are 

summarized in Section 2.10.3. 

2.8.2 Chemical Analysis of Sediment 

Chemical analysis provides information about the chemicals present in the 

dredged material that, if biologically available, could cause toxicity and/or be 

bioaccumutated. This information is valuable for exposure assessment and for 

deciding which of the contaminants present in the dredged material to measure 

in tissue samples, This section discusses the selection of target analytes and 

techniques for sediment analyses. QA considerations are summarized in 

Section 2.10.4. 

2.8.2.1 Selection of Target Analytes 

If the review of data from previous studies suggests that sediment contaminants 

may be present (see Section 2.5.2), but fails to produce sufficient information to 

develop a definitive list of potential contaminants, a list of target analytes should 

be compiled. Target analytes should be selected from, but not necessarily 

limited to, those listed in Table 3. The target analyte list should also include 

other contaminants that historical information or commercial and/or agricultural 

applications suggest could be present at a specific dredging site (e.g., tributyltin 

near shipyards, berthing areas, and marinas where these compounds have 

been applied). Analysis of polycyclic aromatic hydrocarbons (PAHs) in dredged 

material should focus on those PAH compounds listed in Table 3. 

All PCB analyses should be made using congener-specific methods. The sum 

of the concentrations of specific congeners is an appropriate measure of total 

PCBs (NOAA, 1989). Congener-specific analyses also provide data that can be 

used for specialized risk assessments that reflect the widely varying toxicity of 

different PCB congeners. 

- -- 

77 
Sediments should be analyzed for TOC. This is particularly important if there 

are hydrophobic organic compounds on the target analyte list. The TOC 

content of sediment is a measure of the total amount of oxidizable organic 

material in a sample and also affects contaminant bioaccumulation by, and 

effects to, organisms (e.g., Dewitt et al. 1992b; Di Toro et at. 1991). 

Sediments in which metals are suspected to be contaminants of concern may 

also be analyzed for acid volatile sulfide (AVS) (Di Toro et al. 1990; U.S. EPA 

1991a). Although acceptable guidance on the interpretation of AVS 

measurements is not yet available, and AVS measurements are not generally 

required at this time, such measurements can provide information on the 

bioavailability of metals in anoxic sediments. 

2.8.2.2 Selection of Analytical Techniques 

Once the list of project-specific target analytes for sediments has been 

established, appropriate analytical methods should be determined (see Section 

2.3). The analytical methods selected must be able to meet the TDLs 

established to meet the requirements of the intended uses of the data. Also, 

the methods selected will, to some degree, dictate the amount of sediment 

sample required for each analysis. Examples of methods that can be used to 

meet TDLs for dredged material evaluations are provided in Table 3. General 

sample sizes are provided in Table 5, and include possible requirements for 

more than one analysis for each group of analytes. The amount of sample 

used in an analysis affects the detection limits attainable by a particular 

method. The following overview summarizes various factors to be considered 

when selecting analytical methods for physical, inorganic, and organic analyses. 

TOC analyses should be based on high-temperature combustion rather than on 

chemical oxidation, because some classes of organic compounds are not fully 

degraded by chemical/ultraviolet techniques. The volatile and nonvolatile 

organic components make up the TOC of a sample. Because inorganic carbon 

(e.g., carbonates and bicarbonates) can be a significant proportion of the total 

carbon in some sediment, the sample has to be treated with acid to remove the 

inorganic carbon prior to TOC analysis. The method of Plumb (1981) 

recommends the use of hydrochloric acid. An alternative choice might be 

sulfuric acid because it is nonvolatile, is used as the preservative, and does not 

add to the chloride burden of the sample. However, some functional groups 

(e.g., carboxylic acids) can be oxidized when inorganic carbonates are removed 

using both a non-oxidizing and an oxidizing acid. Whatever acid is used, it has 

to be demonstrated on sodium chloride blanks (for all marine samples) that 

there is no interference generated from the combined action of acid and salt in 

the sample. Acceptable methods for TOC analysis are provided in PSEP 

(1986) and U.S. EPA (1992b). 

72 
For many metals analyses in marine/estuarine areas, the concentration of salt 

may be much greater than the concentration of the analyte of interest, and can 

cause unacceptable interferences in certain analytical techniques. In such 

cases, the freshwater approach of acid digestion followed by inductively coupled 

plasma-atomic emission spectrometry (ICP) or graphite furnace atomic 

absorption spectrometry (GFAA) should be coupled with appropriate techniques 

for controlling this interference. For example, the mercury method in U.S. EPA 

(1986a; Method 7471) may be used for the analysis of mercury in sediment. 

Tributyltin may be analyzed by the methods of Rice et al. (1987) and NCASI 

(1986), and selenium and arsenic by the method of EPRI (1986). Total 

digestion of metals is not necessary for dredged material evaluations, although 

this technique is used for complete chemical characterizations in some national 

programs (e.g., NOAA Status and Trends). The standard aqua regia extraction 

yields consistent and reproducible results. The recommended method for 

analysis of semivolatile and volatile priority pollutants in sediments is described 

in Tetra Tech (1986a), and is a modified version of established EPA analytical 

methods designed to achieve lower and more reliable detection limits. Analysis 

for organic compounds should always use capillary-column gas chromatography 

(GC): gas chromatography/mass spectrometry (GCYMS) techniques for 

semivolatile and volatile priority pollutants, and dual column gas 

chromatography/electron-capture detection (GC/ECD) for pesticides and PCBs 

(NOAA 1989). Alternatively, GC/MS using selected ion monitoring can be used 

for PCB and pesticide analysis. These analytically sound techniques yield 

accurate data on the concentrations of chemicals in the sediment matrix. The 

analytical techniques for semivolatile organic compounds generally involve 

solvent extraction from the sediment matrix and subsequent analysis, after 

cleanup, using GC or GCYMS. Extensive cleanup is necessitated by the 

likelihood of 1) biological macromolecules, 2) sulfur from sediments with low or 

no oxygen, and 3) oil and/or grease in the sediment. The analysis of volatile 

organic compounds incorporates purge-and-trap techniques with analysis by 

either GC or GC/MS. If dioxin (i.e., 2,3,7,8-tetrachlorodibenzo-pdioxin [TCDD]) 

analysis is being performed, the methods of Kuehl et al. (1987), Smith et al. 

(1984), U.S. EPA (1989b; Method 8290), or U.S. EPA (1990f; Method 1613) 

should be consulted. EPA Method 1613 is the recommended procedure for 

measuring the tetra- through octa- polychlorinated dibenzo-p-dioxins (PCDDs) 

and polychlorinated dibenzofurans (PCDFs). This method has been developed 

for analysis of water, soil, sediment, sludge, and tissue. Table 7 shows the 17 

compounds determined by Method 1613. 

Techniques for analysis of chemical contaminants have some inherent 

iimitations for sediment samples. Interferences encountered as part of the 

sediment matrix, particularly in samples from heavily contaminated areas, may 

limit the ability of a method to detect or quantify some analytes. The most 

selective methods using GC/MS techniques are recommended for all 

nonchlorinated organic compounds because such analysis can often avoid 

--------__ _.- --- -. ___ _ _ - - - - - - _-----~----~-~_~ ~-- ---- __.. 

73 
TABLE 7. PCDD and PCDF Compounds Determined by Method 1613 

Native Compound’ 2,3,7,8-TCDF 

2,3,7,8-TCDD 

1,2,3,7,8-PeCDF 

2,3,4,7,8-PeCDF 

1,2,3,7,8-PeCDD 

1,2,3,4,7,8+lxCDF 

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

2,3,4,6,7,8-HxCDF 

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

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

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

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

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

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

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

OCDD 

OCDF 

’ Polychlorinated Dioxins and Furans 

TCDD = Tetrachlorodibentp-p-dioxin 

TCDF = Tetrachlorodibenzofuran 

PeCDD = Pentachlorocfibenzo-p-dioxin 

PeCDF = Pentachlorodibenzofuran 

HxCDD = Hexachlorodibenro-pdioxin 

ttxCDF = Hexachlorodibenzofuran 

HpCDD = Heptachlorodibenzo-p-dioxin 

HpCDF = Heptachlorodibenzofuran 

OCDD = Octachlorodibenro-p-dioxin 

OCDF = Octachlorodibenzofuran 

~- ---. __-- -- _____- ---_. --- - --__ 

74 
problems due to matrix interferences. GC/ECD methods are recommended by 

the EPA as the primary analytical tool for all PCB and pesticide analyses 

because GC/ECD analysis (e.g., NOAA 1989) will result in lower detection 

limits. The analysis and identification of PCBs by GCIECD methods are based 

upon relative retention times and peak shapes. Matrix interferences may result 

in the reporting of false negatives, although the congener-specific PCB analysis 

reduces this concern relative to use of the historical Aroclor@-matching 

procedure. 

For dredged material evaluations, the concentration of total PCBs should be 

determined by summing the concentrations of specific individual PCB 

congeners identified in the sample (see Table 8). The minimum number of 

PCB congeners that should be analyzed are listed in the first column of Table 7 

(i.e., “summation” column) (NOAA 1989). This summation is considered the 

most accurate representation of the PCB concentration in samples. Additional 

PCB congeners are also listed in Table 8. McFarland and Clarke (1989) 

recommend these PCB congeners for analysis based on environmental 

abundance, persistence, and biological importance. Sample preparation for 

PCB congener analysis should follow the techniques described in Tetra Tech 

(1986a) or U.S. EPA (1986a), but with instrumental analysis and quantification 

using standard capillary GC columns on individual PCB isomers according to 

the methods reported by NOAA (1989) (see also Dunn et al. 1984; Schwartz et 

al. 1984; Mullin et al. 1984; Stalling et al. 1987). 

Although the methods mentioned above are adequate for detecting and 

quantifying concentrations of those PCB congeners comprising the majority of 

total PCBs in environmental samples, they are not appropriate for separating 

and quantifying PCB congeners which may coelute with other congeners and/or 

may be present at relatively small concentrations in the total PCB mixture. 

included in this latter group of compounds, for example, are PCBs 126 and 

169, two of the more toxic nonortho-substituted PCB congeners (Table 8). In 

order to separate these (and other toxic nonortho-substituted congeners), it is 

necessary to initially utilize an enrichment step with an activated carbon column 

(Smith 1981). Various types of carbon columns have been used, ranging from 

simple gravity columns (e.g., in a Pasteur pipette) to more elaborate (and 

efficient) columns using high-pressure liquid chromatography (HPLC) systems 

(see Schwartz et al. 1993). The preferred method of separation and 

quantitation of the enriched PCB mixture has been via high resolution GC/MS 

with isotope dilution (Kuehl et al. 1991; Ankley et al. 1993; Schwartz et al. 

1993). However, recent studies have shown that if the carbon enrichment is 

done via HPLC, the nonortho-substituted PCB congeners of concern also may 

be quantifiable via more widely available GUECD systems (Schwartz et al. 

1993). 

75 
TABLE 8. POLYCHLORINATED BIPHENYL CONGENERS 

RECOMMENDED FOR QUANTITATION AS POTENTIAL 

CONTAMINANTS OF CONCERN 

PC6 CongeneP 

Congener Numbefi 

Highest Second 

SummationC Priorityd Priority’ 

2,4’-Dichlorobiphenyl 

2,2’,5-Trichlorobiphenyl 

2,4,4’-Trichlorobiphenyl 

3,4,4’-Trichlorobiphenyl 

2,2’,3,5’-Tetrachlorobiphenyl 

2,2’,4,5’-Tetrachlorobiphenyl 

2,2’,5,5’-Tetrachlorobiphenyl 

2,3’,4,4’-Tetrachlorobiphenyl 

2,3’,4’,5Tetrachlorobiphenyl 

2,4,4’,5-Tetrachlorobiphenyl 

3,3’,4,4’-Tetrachlorobiphenyl 

3,4,4’,5-Tetrachlorobiphenyl 

2,2’,3,4,5’-Pentachlorobiphenyl 

2,2’,3,4’,5Pentachlorobiphenyl 

2,2’,4,5,5’-Pentachlorobiphenyl 

2,3,3’,4,4’-Pentachlorobiphenyl 

2,3,4,4’,5-Pentachlorobiphenyt 

2,3’,4,4’,5Pentachlorobiphenyl 

2,3’,4,4’,6-Pentachlorobiphenyl 

2’,3,4,4’,5-Pentachlorobiphenyi 

3,3’,4,4’,5-Pentachlorobiphenyl 

2’,3,3’,4,4’-Hexachlorobiphenyl 

2,2’,3,4,4’,5’-Hexachlorobiphenyl 

2,2’,3,5,5’,6-Hexachlorobiphenyl 

2,2’,4,4’,5,5’-Hexachlorobiphenyl 

2,3,3’,4,4’,5Hexachlorobiphenyl 

2,3,3’,4,4’,5-Hexachlorobiphenyl 

2,3,3’,4,4’,6-Hexachlorobiphenyl 

2,3’,4,4’,5,5’-Hexachlorobiphenyl 

2,3’,4,4’,5’,6-Hexachlorobiphenyl 

0 

18 

28 

44 

52 

66 

77 77 

101 

105 

118 118 

126’ 126’ 

128 128 

138 138 

153 

a7 

49 

101 

105 

153 

156 

18 

37 

44 

99 

52 

70 

74 

81 

114 

119 

123 

151 

157 

15e 

167 

168 

76 
TABLE 8. (cont.) 

Congener Numbe? 

PCB Congener” Highest Second 

SummationC Priorityd Priority* 

3,3’,4,4’,5,5’-Hexachlorobiphenyl 169’ 169’ 

2,2’,3,3’,4,4’,5-Heptachlorobiphenyl 170 170 

2,2’,3,4,4’,5,5’-Heptachlorobiphenyl 180 180 

2,2’,3,4,4’.5’,6-Heptachlorobiphenyl 183 

2,2’,3,4,4’,6,6’-Heptachlorobiphenyl 184 

2,2’,3,4’,5,5’,6-Heptachlorobiphenyl 187 187 

2,3,3’,4,4’,5,5’ Heptachlorobiphenyl 189 

2,2’,3,3’,4,4’,5,6-Octachlorobiphenyl 195 

2,2’,3,3’,4,5,5’,6’-Octachtorobiphenyl 201 

2,2’,3,3’,4,4’,5,5’,6-Nonachlorobiphenyl 206 

2,2’,3,3’,4,4’,5,5’,6,6’-Decachlorobiphenyl 209 

Note: PCB - polychlorinated biphenyl 

’ PCB congeners recommended for quantitation, from dichlorobiphenyl through decachlorobiphenyl. 

b Congeners are identified by their fntemational Union of Pure and Applied Chemistry (IUPAC) number, 

as referenced in Ballschmiter and 2811 (1980) and Mullin et al. (1984). 

’ These congeners are Summed to determine total PC6 concentration using the approach in 

NOAA (1989). 

’ PCB congeners having highest priority for potential environmental importance based on potential for 

toxicity, frequency of occurrence in environmental samples, and relative abundance in animal tissues 

(McFarland and Clarke 1989). 

’ PCB congeners having second priority for potential environmental importance based on potential for 

toxicity, frequency of occurrence in environmental samples, and relative abundance in animal tissues 

(McFarland and Clarke 1989). 

’ To separate PC& 126 and 169, it is necessary to initially utilize an enrichment step with an activated 

carbon column (Smith 1981). 
The overall toxicity of nonortho-substituted PCBs at a site can be assessed 

based on a comparison with the toxicity of 2,3,7,8-TCDD. A similar procedure 

can be used for assessing the toxicity of a mixture of dioxins and furans. In 

this “toxicity equivalency factor” (TEF) approach, potency values of individual 

congeners (relative to TCDD) and their respective sediment concentrations are 

used to derive a summed 2,3,7,8-TCDD equivalent (U.S. EPA 19894; Table 9). 

EPA and the USACE are developing guidance on the use of this approach. 

To ensure that contaminants not included in the list of target analytes are not 

overlooked in the chemical characterization of the dredged material, the 

analytical results should also be scrutinized by trained personnel. The 

presence of persistent unknown analytes should be noted. Methods involving 

GC/MS techniques for organic compounds are recommended for the 

identification of any unknown analytes. 

2.8.3 Chemical Analysis of Water 

Analysis to determine the potential release of dissolved contaminants from the 

dredged material (standard elutriate) may be necessary to make determinations 

of water column toxicity (see U.S. EPA and USACE 1994). Elutriate tests 

involve mixing dredged material with dredging site water and allowing the 

mixture to settle. The portion of the dredged material that is considered to have 

the potential to impact the water column is the supernatant remaining after 

undisturbed settling and centrifugation. Chemical analysis of the elutriate allows 

a direct comparison, after allowance for mixing, to applicable water quality 

standards. When collecting samples for elutriate testing, consideration should 

be given to the large volumes of water and sediment required to prepare 

replicate samples for analysis. In some instances, when there is poor settling, 

the elutriate preparation has to be performed successively several times to 

accumulate enough water for testing. The following sections discuss the 

selection of target analytes and techniques for water analyses. QA 

considerations are summarized in Section 2.10.5. 

2.8.3. I Selection of Target Analyfes 

Historical water quality information from the dredging site should be evaluated 

along with data obtained from the chemical analysis of sediment samples to 

select target analytes. Chemical evaluation of the dredged material provides a 

known list of contaminants that might affect the water column. All target 

analytes identified in the sediment should initially be considered potential 

targets for water analysis. Nonpriority pollutant chemical components which are 

found in measurable concentrations in the sediments should be included as 

target analytes if review of the literature indicates that these analytes have the 

78 
TABLE 9. Methodology for Toxicity Equivalency Factors 

Because toxicity information on some dioxin and furan species is scarce, a structure-activity 

relationship has been assumed. The toxicity of each cogener is expressed as a fraction of the 

toxicity of 2,3,7,8 TCDD. 

Compound 

2,3,7,8 TCDD 

other TCDD 

2,3,7,8-PeCDDs 

other PeCDDs 

2,3,7,8-HxCDDs 

other HxCDDs 

2,3,7,&HpCDDs 

other HpCDDs 

OCDD 

2,3,7,8-TCDF 

other TCDFs 

1,2,3,7,8-PeCDF 

2,3,4,7,8-PeCDF 

other PeCDFs 

2,3,7,8-HxCDFs 

other HxCDFs 

2,3,7,8-HpCDFs 

other HpCDFs 

OCDF 

TEF 

1 

0 

0.5 

0 

0.1 

0 

0.01 

0 

0.001 

0.1 

0 

0.05 

0.5 

0 

0.1 

0 

0.01 

0 

0.001 

__ -- 

79 
potential to bioaccumulate in animals (i.e., have a high K, or bioconcentration 

factor [BCF]) and/or are of toxicological concern) (Table 10). 

2.8.3.2 Selection of Analytical Techniques 

In contrast to freshwater, there generally are no EPA-approved methods for 

analysis of saline water although widely accepted methods have existed for 

some time (e.g., Strickland and Parsons 1972; Grasshof et al. 1983; Parsons et 

al. 1984). Application of the freshwater methods to saltwater will frequently 

result in higher detection limits than are common for freshwater unless care is 

taken to control the effects of salt on the analytical signal. Modifications or 

substitute methods (e.g., additional extract concentration steps, larger sample 

sizes, or concentration of extracts to smaller volumes) might be necessary to 

properly determine analyte concentrations in saltwater or to meet the desired 

TDLs. It is extremely important to ascertain a laboratory’s ability to execute 

methods and attain acceptable TDLs in matrices containing up to 3 percent 

sodium chloride. 

Once the list of target analytes for water has been established, analytical 

methods should be determined. The water volume required for specific 

analytical methods may vary. A minimum of 1 L of elutriate should be prepared 

for metals analysis (as little as 100 mL may be analyzed). One liter of elutriate 

should be analyzed for organic compounds. Sample size should also include 

the additional volume required for the matrix spike and matrix spike duplicate 

analyses, required for analysis of both metals and organic compounds. Sample 

size is one of the limiting factors in determining detection limits for water 

analyses, but TDLs below the water quality standard should be the goal in all 

cases. Participating laboratories should routinely report detection limits 

achieved for a given anatyte. 

Detailed methods for the analysis of organic and inorganic priority pollutants in 

water are referenced in 40 CFR 136 and in U.S. EPA (1983). Additional 

approved methods include U.S. EPA (1986a,b; 1988a,b,c; 1990d,e), APHA 

(1989), ASTM (1991 a), and Tetra Tech (1985). Analysis of the semivolatile 

organic priority pollutants involves a solvent extraction of water with an optional 

sample cleanup procedure and analysis using GC or GC/MS. The volatile 

priority pollutants are determined by using purge-and-trap techniques and are 

analyzed by either GC or GC/MS. If dioxin (i.e., 2,3,7,8,-TCDD) analysis is 

necessary, Kuehl et al. (1987), Smith et al. (1984), U.S. EPA (1989b; Method 

8290), or U.S. EPA (1990f; Method 1613) should be consulted. EPA Method 

1613 is the recommended procedure for measuring the tetra- through octaPCDDs and PCDFs. 

A primary requirement for analysis of inorganic and organic priority pollutants is 

to obtain detection limits that will result in usable, quantitative data that can 

80 
TABLE 10. OCTANOLWATER PARTITION COEFFICIENTS 

FOR ORGANIC COMPOUND PRIORIW POLLUTANTS 

AND 301 (h) PESTICIDES 

Pollutant 

OctanoVWater 

Partition Coeff icier0 

wsl %a) Pollutant 

OctanoVfVater 

Partition Coefficient 

(log K?J 

Di-rwctyl phthalate 9.2 

Indeno[l,2,3-cd)pyrene 7.7 

Benzo[ghi]perytene 7.0 

PCB- 1260 6.9 

Mire9 6.9 

BentoF]fluoranthene 6.8 

Benzo[b]fluoranthene 6.6 

PCB-1248 6.1 

2,3,7,&TCDD (dioxin) 6.1 

Benzo[a]pyrene 6.0 

Chlordane 6.0 

PCB-1242 6.0 

4,4’-DDD 6.0 

Dibenz[a,h]anthracene 6.0 

PCB-1016 5.9 

4,4’-DDT 5.7 

4,4’-DDE 5.7 

Benz(a]anthracene 5.6 

Chrysene 5.6 

Endrin aldehyde 5.6 

Fluoranthene 5.5 

Hexachlorocyclopentadiene 5.5 

Dieldrin 5.5 

Heptachlor 5.4 

Heptachlor epoxide 5.4 

Hexachlorobenzene 5.2 

Di-rrbutyl phthalate 5.1 

4-Bromophenyl phenyl ether 5.1 

Pentachlorophenol 5.0 

4Chlorophenyl phenyl ether 4.9 

Pyrene 4.9 

2-Chloronaphthalene 4.7 

Endrin 4.6 

PCB-1232 4.5 

Phenanthrene 4.5 

Fluorene 4.4 

Anthracene 4.3 

Methoxychlor’ 4.3 

Hexachlorobutadiene 4.3 

1,2,GTrichlorobenzene 4.2 

Bis[2-ethylhexyl]phtalate 4.2 

Acenaphthylene 4.1 

Butyl benzyl phthalate 4.0 

PCB-1221 4.0 

Hexachloroethane 3.9 

Acenaphthene 3.9 

a-Hexachlorocyclohexane 3.8 

GHexachlorocyclohexane 3.8 

B-Hexachlorocyclohexane 3.8 

Parathion’ 3.8 

Chlorobenzene 3.8 

2,4,6-Trichlorophenol 3.7 

O-Endosulfan 3.6 

Endosulfan sulfate 3.6 

cr-Endosulfan 3.6 

Naphthalene 3.6 

Fluorotrichloromethaneb 3.5 

1,4-Dichlorobenzene 3.5 

1,3-Dichlorobenzene 3.4 

1,2-Dichlorobenzene 3.4 

Toxaphene 3.3 

Ethylbenzene 3.1 

NNitrosodiphenylamine 3.1 

P-Chloro-m cresol 3.1 

2,4-Dichlorophenol 3.1 

3,3’-Dichlorobenzene 3.0 

Aldrin 3.0 

1,2-Diphenylhydrazine 2.9 

4-Nitrophenol 2.9 

Malathion* 2.9 

Tetrachloroethene 2.9 

4,6-Dinitro-ocresol 2.8 

Tetrachloroethene 2.6 

Bis[2chloroisopropyl]ether 2.6 

l,l,l-Trichloroethane 2.5 

Trichloroethene 2.4 

2,CDimethylphenol 2.4 

1,1,2,2-Tetrachloroethane 2.4 

Bromoform 2.3 

1 ,P-Dichloropropane 2.3 

Toluene 2.2 

1,1,2-Trichloroethane 2.2 

Guthion’ 2.2 

Dichlorodiflouromethaneb 2.2 

2Chlorophenol 2.2 

Benzene 2.1 

Chlorodibromomethane 2.1 

2,4-Dinitrotoluene 2.1 

2,6-Dinitrotoluene 2.0 

&ins-1,2-Dichloropropene 2.0 

cis- 1,3-Dichloropropene 2.0 

Demeton* 1.9 

Chloroform 1.9 

Dichlorobromomethane 1.9 

Nitrobenzene 1.9 

Benzidine 1.8 

1,l -Dichloroethane 1.8 

2-Nitrophenol 1.8 

~Hexachlorocyclohexane 3.8 
TABLE 10. (cont.) 

Pollutant 

OctanoWater 

Partition Coefficient 

wl KImI Pollutant 

OctanoWater 

Partition Cc&t icient 

WI L) 

Dimethyl phthalate 1.6 

Chloroethane 1.5 

2.4-Dinitrophenol 1.5 

1 ,l -Dichlorcethytene 1.5 

Phenol 1.5 

1,2-Dichloroethane 1.4 

Diethyl phthalate 1.4 

Nnitrosodipropylamine 1.3 

Dichloromethane 1.3 

2Chloroethylvinylether 1.3 

Bis[2-chloroethoxy]methane 1.3 

Acrylonitrile 1.2 

Bis(2-chloroethyl]ether 1.1 

Bromomethane 1.0 

Acrolein 0.9 

Chloromethane 0.9 

Vinyl chloride 0.6 

Mnitrosodimethytamine 0.6 

Source: Tetra Tech (1985) 

Note: Mixtures, such as PCB Aroclors QD, cannot have discrete K, values; however, the value given is a rough estimate for 

the mean. (It is recommended that all PCB analyses use congener-specific methods. All PCB congeners have a log K, > 4 

(L. Burkhardt, EPA Duluth, pers. comm.).] 

’ 301 (h) pesticides not on the priority pollutant list. 

b No longer on priority pollutant or 301 (h) list. 

82 
subsequently be compared against applicable water quality standards or criteria, as appropriate. Analysis of saline water for metals is subject to matrix 

interferences from salts, particularly sodium and chloride ions, when the 

samples are concentrated prior to instrumental analysis. The gold 

amalgamation method using cold-vapor atomic absorption spectrometry (CVAA) 

analysis is recommended to eliminate saline water matrix interferences for 

mercury analysis. Methods using solvent extraction and atomic absorption 

spectrometry analysis may be required to reduce saline water matrix 

interferences for other target metals. Other methods appropriate for metals 

include: cadmium, copper, lead, iron, zinc, silver (Danielson et al. 1978); 

arsenic (EPRI 1986); selenium and antimony (Sturgeon et al. 1985); low levels 

of mercury (Bloom et al. 1983); and tributyltin (Rice et al. 1987). GFAA 

techniques after extraction are recommended for the analysis of metals, with 

the exception of mercury. All PCB and pesticide analyses should be performed 

using GC/ECD methods because such analysis (e.g., NOAA 1989) will result in 

lower detection limits. PCBs should be quantified as specific congeners (Mullin 

et al. 1984; Stalling et al. 1987) and as total PCBs based on the summation of 

particular congeners (NOAA 1989). 

2.8.4 Chemical Analysis of Tissue 

This section discusses the selection of target analytes and techniques for tissue 

analyses. QA considerations are summarized in Section 2.10.6. 

2.8.4.1 Selection 6f Target Analytes 

Bioaccumulation is evaluated by analyzing tissues of test organisms for 

contaminants determined to be of concern for a specific dredged material. 

Sediment contaminant data and available information on the bioaccumulation 

potential of those analytes have to be interpreted to establish target analytes. 

The n-octanol/water partition coefficient (K,) is used to estimate the BCFs of 

chemicals in organism/water systems (Chiou et al. 1977; Kenaga and Goring 

1980; Veith et al. 1980; Mackay 1982). The potential for bioaccumulation 

generally increases as K, increases, particularly for compounds with log K, 

less than approximately 6. Above this value, there is less of a tendency for 

bioaccumulation potential to increase with increasing K,. Consequently, the 

relative potential for bioaccumulation of organic compounds can be estimated 

from the K,, of the compounds. U.S. EPA (1985) recommends that compounds 

for which the log K, is greater than 3.5 be considered for further evaluation of 

bioaccumulation potential. The organic compound classes of priority pollutants 

with the greatest potential to bioaccumulate are PAHs, PCBs, pesticides, and 

some phthalate esters. Generally, the volatile organic, phenol, and 

organonitrogen priority pollutants are not readily bioaccumulated, but exceptions 

83 
include the chlorinated benzenes and the chlorinated phenols. Table 10 

provides data for organic priority pollutants based on L. Specific target 

analytes for PCBs and PAHs are discussed in Section 2.8.2. The water content 

and percent lipids in tissue should be routinely determined as a part of tissue 

analyses for organic contaminants. 

Table 11 ranks the bioaccumulation potential of the inorganic priority pollutants 

based on calculated BCFs. Dredged material contaminants with BCFs greater 

than 1,000 (log BCF > 3) should be further evaluated for bioaccumulation 

potential. 

Tables 10 and 11 should be used with caution because they are based on 

calculated bioconcentration from water. Sediment bioaccumulation tests, in 

contrast, are concerned with accumulation from a complex medium via all 

possible routes of uptake. The appropriate use of the tables is to help in 

selecting contaminants of concern for bioaccumulation‘analysis by providing a 

general indication of the relative potential for various chemicals to accumulate in 

tissues. 

The strategy for selecting contaminants for tissue analysis should include three 

considerations: 

n The target analyte is a contaminant of concern and is present in 

the sediment as determined by sediment chemical analyses 

n The target analyte has a high potential to accumulate and persist 

in tissues 

n The target analyte is of toxicological concern. 

Contaminants with a lower potential to bioaccumulate, but which are present at 

high concentrations in the sediments, should also be included in the target list 

because bioavailability can increase with concentration. Conversely, 

contaminants with a high accumulation potential and of high toxicological 

concern should be considered as target analytes, even if they are only present 

at low concentrations in the sediments. Nonpriority-pollutant contaminants that 

are found in measurable concentrations in the sediments should be included as 

targets for tissue analysis if they have the potential to bioaccumulate and 

persist in tissues, and are of toxicological concern. 

2.8.4.2 Selection of Analytical Techniques 

At present, formally approved standard methods for the analysis of priority 

pollutants and other contaminants in tissues are not available. However, 

studies conducted for EPA and other agencies have developed analytical 

84 
TABLE 11. BIOCONCENTRATION FACTORS (BCF) 

OF INORGANIC PRIORITY POLLUTANTS 

Inorganic Pollutant Log BCF 

Metals 

Methylmercury 

Phenylmercury 

Mercuric acetate 

Copper 

Zinc 

Arsenic 

Cadmium 

Lead 

Chromium IV 

Chromium III 

Mercury 

Nickel 

Thallium 

Antimony 

Silver 

Selenium 

Beryllium 

Nonmetals 

Cyanide 

Asbestos 

4.6 

4.6 

3.5 

3.1 

2.8 

2.5 

2.5 

2.2 

2.1 

2.1 

2.0 

1.7 

1.2 

ND 

ND 

ND 

ND 

ND 

ND 

Source: Tetra Tech (1986b) 

Note: ND - no data 

85 
methods capable of identifying and quantifying most organic and inorganic 

priority pollutants in tissues. The amount of tissue required for analysis is 

dependent on the analytical procedure and the tissue moisture content. 

General guidance, but not firm recommendations, for the amount of tissue 

required is provided in Table 5. The required amounts may vary depending on 

the analytes, matrices, detection limits, and particular analytical laboratory. 

Tissue moisture content should be determined for each sample to enable data 

to be converted from a wet-weight to a dry-weight basis for some data users. 

Detection limits depend on the sample size as well as the specific analytical 

procedure. Recommended TDLs for dredged material evaluations are provided 

in Section 2.3.2 (see Table 3). TDLs should be specified based on the 

intended use of the data and specific needs of each evaluation. 

The recommended methods for the analysis of semivolatile organic pollutants 

are described in NOAA (1989). The procedure involves serial extraction of 

homogenized tissue samples with methylene chloride, followed by alumina and 

gel-permeation column cleanup procedures that remove co-extracted lipids. An 

automated gel-permeation procedure described by Sloan et al. (1993) is 

recommended for rapid, efficient, reproducible sample cleanup. The extract is 

concentrated and analyzed for semivolatile organic pollutants using GC with 

capillary fused-silica columns to achieve sufficient analyte resolution. If dioxin 

(i.e., 2,3,7,8-TCDD) analysis is being performed, the methods of Mehrie et al. 

(1988), Smith et al. (1984), Kuehl et al. (1987) U.S. EPA (1989b; Method 

8290), or U.S. EPA (1990f; Method 1613) should be consulted. EPA Method 

1613 is the recommended procedure for measuring the tetra- through octaPCDDs and PCDFs. 

Chlorinated hydrocarbons (e.g., PCBs and chlorinated pesticides) should be 

analyzed by GC/ECD. PCBs should be quantified as specific congeners (Mullin 

et al. 1984; Stalling et al. 1987) and not by industrial formulations (e.g., 

Aroclors@) because the levels of PCBs in tissues result from complex 

processes, including selective accumulation and metabolism (see the discussion 

of PCBs in Section 2.8.2.2). Lower detection limits and positive identification of 

PCBs and pesticides can be obtained by using chemical ionization mass 

spectrometry. 

The same tissue extract is analyzed for other semivolatile pollutants (e.g., 

PAHs, phthalate esters, nitrosamines, phenols) using GC/MS as described by 

NOAA (1989), Battelle (1985), and Tetra Tech (1986b). These GC/MS 

methods are similar to EPA Method 8270 for solid wastes and soils (U.S. EPA 

1986a). Lowest detection limits are achieved by operating the mass spectrometer in the selective ion monitoring mode. Decisions to perform analysis of 

nonchlorinated hydrocarbons and resulting data interpretation should consider 

that many of these analytes are readily metabolized by most fish and many 

86 
invertebrates. Analytical methods for analysis of tissue samples for volatile 

priority pollutants are found in Tetra Tech (1986b). 

Tissue lipid content is of importance in the interpretation of bioaccumulation 

information. A lipid determination should be performed on all biota submitted 

for organic analysis if 1) food chain models will be used, 2) test organisms 

could spawn during the test, or 3) special circumstances occur, such as those 

requiring risk assessment. Bligh and Dyer (1959) provide an acceptable 

method, and the various available methods are evaluated by Randall et al. 

(1991). 

Analysis for priority pollutant metals involves a nitric acid or nitric acid/perchloric 

acid digestion of the tissue sample and subsequent analysis of the acid extract 

using atomic absorption spectrometry or ICP techniques. Procedures in Tetra 

Tech (1986b) are generally recommended. NOAA (1989) methods may also be 

used and are recommended when low detection levels are required. Microwave 

technology may be used for tissue digestion to reduce contamination and to 

improve recovery of metals (Nakashima et al. 1988). This methodology is 

consistent with tissue analyses performed by NOAA (1989), except for the 

microwave heating steps. Mercury analysis requires the use of CVAA methods 

(U.S. EPA 1991c). The matrix interferences encountered in analysis of metals 

in tissue may require case-specific techniques for overcoming interference 

problems. If tributyltin analysis is being performed, the methods of Rice et al. 

(1987), NCASI (1986), or Uhler et al. (1989) should be consulted. 

2.9 DATA VALIDATION, REDUCTION, AND REPORTING 

This section describes procedures for data compilation and verification prior to 

being accepted for making technical conclusions. In addition, special equations 

may be required and used to make calculations, models may be used in data 

analysis, criteria may be used to validate the integrity of data that support final 

conclusions, and methods may be used to identify and treat data that may not 

be representative of environmental conditions. 

The following specific information should be included in the QA project plan: 

w The principal criteria that will be used to validate data integrity 

during collection and reporting of data (the criteria selected will 

depend on the level of validation required to meet the data quality 

objectives) 

w The data reduction scheme planned for collected data, including all 

equations used to calculate the concentration or value of the 

measured parameter and reporting units 

87 
n The methods used to identify and treat outliers (i.e., data that fall 

outside the upper and lower limits such as &3 standard deviations 

of the mean value) and nondetectable data 

n The data flow or reporting scheme from collection of original data 

through storage of validated concentrations (a flowchart is usually 

necessary) 

n Statistical formulas and sample calculations planned for collected 

data 

n Key individuals who will handle the data in this reporting scheme. 

QC procedures designed to eliminate errors during the mathematical and/or 

statistical reduction of data should also be included in the QA project plan. QC 

in data processing may include both manual and automated review. Input data 

should be checked and verified to confirm compatibility and to flag outliers for 

confirmation (i.e., verify that data are outliers and not data for highly contaminated sediment, water, or tissue). Computerized data plots can be routinely 

used as a tool for rapid identification of outliers that can then be verified using 

standard statistical procedures. 

2.9.1 Data Validation 

Once the laboratory has completed the requested sample analyses, the 

analytical results are compiled, printed out, and submitted as a data package, 

which has been signed by the laboratory’s project manager. This package may 

include computer disks, magnetic tape, or other forms of electronically stored 

information. Data packages may range in size from a few pages to several 

cartons of documents, depending on the nature and extent of the analyses 

performed. The cost of this documentation can vary from no charge (in cases 

where only the final results of an analysis are reported) to hundreds of dollars 

over the cost of reporting only the final results of an analysis. 

The data and information collected during the dredged material evaluation 

should be carefully reviewed as to their relevancy, completeness, and quality. 

The data must be relevant to the overall objective of the project. Data quality 

should be verified by comparing reported detection limits and QC results to 

TDLs and QC limits, respectively, specified for the current dredged material 

evaluation. 

As soon as new data packages are received from the laboratory, they should 

be checked for completeness and data usability and, ideally, dated and 

duplicated. Dating is important for establishing the laboratory’s adherence to 

schedules identified in the statement of work. Duplication assures that a clean 

reference copy is always kept on file. Checking each element of the data 

88 
package for completeness of information, precision of analytical methods, and 

bias of all measurements helps to determine whether acceptable data from 

each type of analysis have been supplied by the laboratory. 

Screening for data quality requires knowledge of the sample holding times and 

conditions, the types of analyses requested, and the form in which data were to 

be delivered by the laboratory. Review of the statement of work is essential to 

determine any special conditions or requests that may have been stated at the 

onset of the analyses. Recommended lists of laboratory deliverables for different types of chemical analyses are provided in Tables 1 and 2. This initial 

screening of data can be performed by appropriate staff or the project manager. 

Data validation, or the process of assessing data quality, can begin after 

determining that the data package is complete. Analytical laboratories strive to 

produce data that conform to the requested statement of work, and they 

typically perform internal checks to assure that the data meet a standard level 

of quality. However, data validation is an independent check on laboratory 

performance and is intended to assure that quality of reported data meets the 

needs identified in the QA project plan. 

Data validation involves all procedures used to accept or reject data after 

collection and prior to use. These include screening, editing, verifying, and reviewing through external performance evaluation audits. Data validation 

procedures ensure that objectives for data precision and bias were met, that 

data were generated in accordance with the QA project plan and standard 

operating procedures, and that data are traceable and defensible. All chemical 

data should be reported with their associated analytical sensitivity, precision, 

and bias. In addition, the quantification level achieved by the laboratory should 

be compared to specific TDLs. 

The QA project plan should also specify an appropriate level of data validation 

for the intended data use. Examples of four alternative levels of validation 

effort for chemical data are summarized in Table 12. These four data validation 

levels range from complete, loo-percent review of the data package (Level 1) 

to acceptance of the data package without any evaluation (Level 4). 

The QA project plan should also specify who will perform the evaluations called 

for in Levels 1, 2, or 3. The following options should be considered for 

chemical data: 

n Perform a brief assessment and rely on specialists to resolve 

outstanding concerns. This assessment is equivalent to Level 3 

(Table 12). 

n Perform a complete review for Level 1 or 2 using qualified staff 

and technical guidelines for QA specialists (see Footnote a in 

Table 12). 

89 
TABLE 12. LEVELS OF DATA VALIDATION 

Level 1 

Level 2 

Level 3 

Level 4 

100 percent of the data (including data for laboratory quality control 

samples) are independently validated using the data quality objectives 

established for the project. Calculations and the possibility of transcription 

errors are checked. Instrument performance and original data for the 

analytical standards used to calibrate the method are evaluated to ensure 

that the values reported for detection limits and data values are 

appropriate. The bias and precision of the data are calculated and a 

summary of corrections and data quality is prepared.” 

20 percent of the sample data and 100 percent of the laboratory quality 

control samples are validated. Except for the lower level of effort in 

checking data for samples, the same checks conducted in Level 1 are 

performed. If transcription errors or other concerns (e.g., correct 

identification of chemicals in the samples) are found in the initial check on 

field samples, then data for an additional l&20 percent of the samples 

should be reviewed. If numerous errors are found, then the entire data 

package should be reviewed. 

Only the summary results of the laboratory analyses are evaluated. The 

data values are assumed to be correctly reported by the laboratory. Data 

quality is assessed by comparing summary data reported by the laboratory 

for blanks, bias, precision, and detection limits with data quality objectives 

in the QA project plan. No checks on the calibration of the method are 

performed, other than comparing the laboratory’s summary of calibrations 

with limits specified in the QA project plan. 

No additional validation of the data is performed. The internal reviews 

performed by the laboratory are judged adequate for the project. 

’ Screening checks that can be easily performed by the project manager are provided in (U.S. 

EPA 1991 d). Step-by-step procedures used by quality assurance specialists to validate data 

for analyses of organic compounds and metals can be found in EPA’s functional guidelines for 

data review (U.S. EPA 1988a,b). These guidelines were developed for analyses conducted 

according to the statements of work for EPA’s Contract Laboratory Program and are updated 

periodically. Regional interpretation of these detailed procedures is also contained in Data 

Validation Guidance Manual for Se/e&d Sediment Variables (PTI 1989b), a draft report 

released by the Washington Department of Ecology’s Sediment Management Unit in June 

1989. A simplified version of this guidance is provided in Data Quaky Evaluation for 

Proposed Dredged Material Disposal Projects (PTI 1989a), another report released by the 

Sediment Management Unit in June 1989. 

-. -- .-. -. 

--go 
n Send the data package to an outside technical specialist for 

review, specifying either Level 1, 2, or 3. 

Providing instructions for conducting a thorough technical validation of chemical 

data is beyond the scope of this document. Examples of detailed technical 

guidance of this nature can be found in a pair of publications, Laboratory Data 

Validation: Functional Guidelines for Evaiua ting lnorganics Analyses (U . S . EPA 

1988a) and Laboratoty Data Validation: Functional Guidelines for Evaluating 

Organics Analyses (U.S. EPA 1988b). Examples of simple evaluations that can 

be conducted by a project manager are also provided in U.S. EPA (1991d). 

The evaluation criteria in Figure 1 (abstracted from U.S. EPA [1991dJ) provide 

several signs that should alert a project manager to potential problems with 

data acceptability. 

2.9.2 Data Reduction and Reporting 

The QA project plan should summarize how validated data will be analyzed to 

reach conclusions, including major tools that will be used for statistical 

evaluations. In this section, a flow chart is useful to show the reduction of 

original laboratory data to final tabulated data in the project report. A summary 

should also be provided of the major kinds of data analyses that will be 

conducted (e.g., health risk assessments, mapping of chemical distributions). 

In addition, the format, content, and distribution of any data reports for the 

project should be summarized. 

2.10 INTERNAL QUALITY CONTROL CHECKS 

The various control samples that will be used internally by the laboratory or 

sample collection team to assess quality are described in this section of the QA 

project plan. For most environmental investigations, 10-30 percent of all 

samples may be analyzed specifically for purposes of quality control. In some 

special cases (e.g., when the number of samples is small and the need to 

establish the validity of analytical data is large), as many as 50 percent of all 

samples are used for this purpose. These QC samples may be used to check 

the bias and precision of the overall analytical system and to evaluate the 

performances of individual analytical instruments or the technicians that operate 

them. 

In addition to calibration procedures described in Section 2.7, this section of the 

guidance document (and Appendix C) summarizes the most widely used QC 

samples as follows: 

n Blanks 
Figure 1. Guidance for data assessment and screening for data quality. 

92 
n Matrix spike samples 

n Surrogate spike compounds 

n Check standards, including: 

- Spiked method blanks 

- Laboratory control samples 

- Reference materials 

n Matrix replicates (split in the laboratory from one field sample) 

n Field replicates (collected as separate field samples from one 

location). 

QC procedures for sediment, water, and tissue analyses are discussed in more 

detail in the following sections. Field QC results are not used to qualify data, 

but only to help support conclusions arrived at by the review of the entire data 

set. 

The government authorities for the program may require that certain samples 

be submitted on a routine basis to government laboratories for analysis, and 

EPA or USACE may participate in some studies. These activities provide an 

independent QA check on activities being performed and on data being 

generated and are discussed in Section 2.11 (Performance and System Audits). 

2.10.7 Priority and Frequency of Quality Control Checks 

Which QC samples will be used in analyses should be determined during 

project planning. The frequency of QC procedures is dependent upon the type 

of analysis and the objectives of the project (as established in Section 2.3). 

The statements of work for EPA’s CLP (U.S. EPA 1990d,e) specify the types of 

checks to be used during sample analysis. Determining the actual numbers of 

samples and how often they must be used is also a part of this process. These 

specifications, called QC sample frequencies, represent the minimum levels of 

effort for a project. Increasing the frequency of QC samples may be an 

appropriate measure when the expected concentrations of chemicals are close 

to the detection limit, when data on low chemical concentrations are needed, 

when there is a suspected problem with the laboratory, or when existing data 

indicate elevated chemical concentrations such that removal or other actions 

may be required. In such cases, the need for increased precision may justify 

the cost of extra QC samples. 

93 
The relative importance, rationale, and relative frequency of calibration and 

each kind of QC sample are discussed in Appendix C. The following priority, 

rationale, and frequency of use is recommended for each procedure: 

1. 

2. 

3. 

Method blank samples are one of the highest priority checks on 

QC, because they provide an assessment of possible laboratory 

contamination (and the means to correct results for such contamination), and are used to determine the detection limit. As a result, 

method blank analyses are always required; at least one analysis 

is usually performed for each group of samples that are processed 

by a laboratory. In contrast, the need for other kinds of blank 

samples (bottle, transport, or field equipment) is usually projectspecific and depends on the likelihood of contamination from 

solvents, reagents, and instruments used in the project; the matrix 

being analyzed; or the contaminants of concern. A bottle blank 

consists of an unopened empty sampling bottle that is prepared 

and retained in the field laboratory. A trip travel blank consists of 

deionized water and preservative (as added to the samples) that is 

prepared in the laboratory and transported to the sampling site. A 

field or decontamination blank consists of deionized water from the 

sample collection device and preservative (as added to the 

samples) that is prepared at the sampling site. 

Matrix spike samples are high-priority checks on QC and should 

always be analyzed to indicate the bias of analytical 

measurements due to interfering substances or matrix effects. 

The suggested frequency is 1 matrix spike for every 20 samples 

analyzed. If more than 1 matrix type is present (e.g., samples 

containing primarily sand and samples containing primarily of silt 

within the same group), then each matrix type should be spiked at 

the suggested frequency. Duplicate matrix spike samples 

analyzed at a frequency of 1 duplicate for every 20 samples can 

serve as an acceptable means of indicating both the bias and 

precision of measurement for a particular sample. Duplicate matrix 

spike samples may provide the only information on precision for 

contaminants that are rarely detected in samples. 

Surrogate spike compounds are high-priority checks on QC that are 

used to evaluate analytical recovery (e.g., sample extraction 

efficiency) of organic compounds of interest from individual 

samples. Surrogate spike compounds should be added to every 

sample, including blanks and matrix spike samples, prior to 

performing sample processing, to monitor extraction efficiency on a 

sample-by-sample basis. This kind of check is only used when the 

identity of the surrogate compound can be reasonably confirmed 

(e.g., by mass spectroscopy). Because a surrogate compound is 

--~. 

94 
chemically similar to the associated compound of interest and is 

added to the sample in a known amount, its known recovery is 

indicative of that of the compound of interest. 

Variations in recovery that can be seen using surrogate spike 

compounds with each sample will not necessarily be reflected in 

duplicate matrix spike analyses conducted on only a few of the 

samples. The reasons for possible differences between surrogate 

spike analyses and matrix spike analyses relate to sample 

heterogeneity and how these QC samples are prepared. For 

example, matrix spike analyses provide an indication of chemical 

recovery for the general sample matrix tested. However, this 

matrix may differ among individual samples leading to a range of 

recoveries for surrogate spike compounds among samples. In 

addition, surrogate spike compounds are often added at a lower 

concentration than matrix spike compounds. This difference in 

spiking concentration sometimes results in reasonable recovery of 

the higher-concentration matrix spike compounds but poorer 

recovery of the lower-concentration surrogate spike compounds. 

Finally, matrix spike compounds are typically identical to 

compounds of interest in the samples, while surrogate spike 

compounds are usually selected because they are not present in 

environmental samples, but still mimic the behavior of compounds 

of interest. Therefore, there can be more uncertainty in quantifying 

the recovery of matrix spike compounds (after subtracting the 

estimated concentration of the compounds of interest in the 

sample) than the recovery of surrogate spike compounds. 

4. Check standards should be used whenever available as a highpriority check on laboratory performance. Check standards include 

laboratory control samples, reference materials prepared by an 

independent testing facility, and spiked method blanks prepared by 

the laboratory. By comparing the results of check standards with 

those of sample-specific measurements (e.g., matrix spike 

samples and surrogate compound recovery), an overall 

assessment of bias and precision can be obtained. The laboratory 

should be contacted prior to analysis to determine what laboratory 

control samples can be used. Catalogues from organizations such 

as National institute for Standards and Technology and the 

National Research Council of Canada are available that list 

reference materials for different sediment, water, and tissue 

samples (see Section 2.11.2). 

Reference materials provide a standardized basis for comparison 

among laboratories or between different rounds of analysis at one 

laboratory. Therefore, reference materials should always be used 

95 
when comparison of results with other projects is an intended data 

use. At least 1 analysis of a reference material for every 20 

samples is recommended for this purpose. Similarly, spiked 

method blanks should be used as acceptable checks on laboratory 

performance whenever a new procedure is used or when 

laboratories with no established track record for a standard or 

nonstandard procedure will be performing the analysis. 

5. Analytical replicate samples should be included as a mediumpriority check on laboratory precision. Analytical replicate samples 

better indicate the precision of measurements on actual samples 

than do matrix spike duplicates because the contaminants have 

been incorporated into the sample by environmental processes 

rather than having been spiked in a laboratory setting. The 

suggested frequency is 1 replicate sample for every 20 samples 

for each matrix type analyzed. For organic analyses, analysis of 

analytical spike duplicate samples are sometimes a higher priority 

than matrix replicate samples if budgets are limited. The reason 

for this preference is because many organic compounds of interest 

may not be present in samples unless they are added as spiked 

compounds. 

6. Field replicate samples should be included if measuring sampling 

variability is a critical component of the study design. Otherwise, 

collection of field replicate samples is discretionary and a lower 

priority than the other QC samples. Field replicate samples should 

be submitted to the laboratory as blind samples. When included, 

the suggested frequency is at least 1 field replicate for every 20 

samples analyzed. One of the field replicate samples should also 

be split by the laboratory into analytical duplicates so that both 

laboratory and laboratory-plus-sampling variability can be 

determined on the same sample. By obtaining both measures on 

the same sample, the influence of sampling variability can be 

better discerned. It is possible that analytical variability can mask 

sampling variability at a location. 

2. IO.2 Specifying Quality Control Limits 

Prior to performing a chemical analysis, recognized limits on analytical performance should be established. These limits are established largely through 

the analysis of QC samples. QC limits apply to all internal QC checks for field 

measurements, physical characterizations, bioaccumulation studies, and toxicity 

tests. Many laboratories have established limits that are applicable to their own 

measurement systems. These limits should be evaluated to ensure that they 

are at least as stringent as general guidelines or that the reasons for a less 

96 
stringent limit are acceptable. Also, if a laboratory has consistently 

demonstrated better performance than indicated by general guidelines, limits 

tied to this better performance should be used to indicate when there may be a 

problem at that laboratory. For example, if surrogate recoveries for benzene in 

sediment samples have consistently been between 85 and 105 percent, a 

recovery of 70 percent indicates an analytical problem that should be 

investigated even if the general guideline for acceptable recovery is 50 percent. 

It may be useful to establish different kinds of limits when working with laboratories. For example, the following two kinds of limits are used by PSEP 

(1990~) and are similar to limits used in EPA’s CLP. 

Warning limits are values indicating that data from the analysis of QC samples 

should be qualified (e.g., that they represent estimated or questionable values) 

before they can be relied upon in a project. These limits serve to warn the 

project staff that the analytical system, instrument, or method may not be 

performing normally and that data should be qualified as “estimated” before 

using the results for technical analysis. The standard value for warning limits 

are ti times the standard deviation (US. EPA 1979). Examples of warning 

limits used by the Puget Sound Estuary Program are provided in Table 13. 

Such limits provide a means of ensuring that reported data are consistently 

qualified, an important consideration when combining data in a regional 

database. 

If necessary to meet project goals, project managers may specify warning limits 

as more stringent contractual requirements in laboratory statements of work. 

For example, Puget Sound Estuary Program guidelines for organic compound 

analyses state that the warning limits for the minimum recovery of surrogate 

spike and matrix spike compounds are 50 percent of the amount added prior to 

sample extraction. Data that do not meet this minimum requirement would 

normally be qualified as estimates. However, the project manager could apply 

more stringent criteria and decide to reject data that do not meet warning limits, 

which would require reanalysis of the samples associated with those 

QC samples that do not meet these limits. These more stringent criteria are 

termed control limits. 

Control limits are limits placed on the acceptability of data from the analysis of 

QC samples. Exceedance of control limits informs the analyst and the project 

manager that the analytical system or instrument is performing abnormally and 

needs to be corrected. Control limits should be contractually binding on 

laboratories, and statements of work should provide the project manager or 

designee with sole discretion in enforcing the limits. Data obtained under these 

circumstances should be corrected before they are resubmitted by the 

laboratory. Data that exceed control limits are often rejected and excluded from 

a project database, although there may be special circumstances that warrant 

acceptance of the data as estimated values. The reasons for making such an 
TABLE 13. EXAMPLE WARNING AND CONTROL LIMITS FOR 

CALIBRATION AND QUALITY CONTROL SAMPLES‘ 

Analysis Type Recommended Warning Limit Recommended Control Limit 

Ongoing calibration 

Surrogate spikes 

Method blanks 

Reference materials 

Project manager decisionb > f25 percent of the average 

response measured in the 

initial calibration 

< 50 percent recovery’ Follow EPA Contract 

Laboratory Program guidelines 

Exceeds the TDL Exceeds 5 times the TDL 

95 percent confidence interval, if To be determined 

certified 

Matrix spikes 

Spiked method 

blanks 

(check standards) 

Matrix replicates 

5&l 50 percent recovery 

50-150 percent recovery 

35 percent coefficient of variation > f50 percent coefficient of 

variation (or a factor of 2 for 

duplicates) 

Field replicates Project manager decision 

To be determinedd 

To be determined 

Project manager decision 

Note: TDL - target detection limit 

’ Warning and control limits used in the Puget Sound Estuary Program for the analysis of 

organic compounds (PSEP 199Oc). 

b See U.S. EPA (1991d) for specific examples of project manager decisions for warning or 

control limits. 

’ Except when using the isotope dilution technique, 

d Zero percent spike recovery requires rejection of data. 

98 
exception should always be documented in a QA report for the data (see 

Appendix F). 

Unlike warning limits, control limits and appropriate corrective actions (such as 

instrument recalibration, elimination of sources of laboratory contamination, or 

sample reanalysis) should be clearly identified in the statement of work. The 

standard value for control limits are _+3 times the standard deviation (U.S. EPA 

1979). Examples of regional control limits used by the Puget Sound Estuary 

Program are also provided in Table 13. In those cases that require a project 

manager’s decision to determine the appropriate control limit, it is 

recommended that the associated warning limit b8 used as an control limit to 

produce data that will have broad applicability (including use in enforcement 

proceedings). Control limits should be enforced with discretion b8CaUS8 some 

environmental samples are inherently difficult to analyze. Recommended 

actions Under different circumstances are provided below. 

2.10.3 Quality Control Considerations for Physical Analysis of 

Sediments 

The procedures used for the physical analysis of sediments should include a 

QC component. QC procedures for grain size analysis and total solids/specific 

gravity determinations are necessary to ensure that the data meet acceptable 

criteria for precision and bias. To measure precision, triplicate analyses should 

be performed for every 20 samples analyzed. TOC is a special case, where all 

samples should be analyzed in triplicate, as recommended by the analytical 

method. In addition, 1 procedural blank per 20 samples should be run, and the 

results repotted for TOC analysis. Standards used for TOC determinations 

should be Verified by independent check standards to confirm the bias of the 

reSults. Quality control limits should be agreed upon for 8aCh analytical 

procedure, and should b8 consistent with the overall QA project plan. 

2.10.4 QuaMy Control Considerations for Chemical Analysis of 

Sediments 

Methods for the chemical analysis of priority pollutants in sediments should 

include detailed QC ptYX8dUr8S and requirements that should be followed 

rigorousty throughout the evaluation. General procedures include the analysis 

of a proc8dUral blank, a matrix duplicate, a matrix spike along with every 10-20 

samples processed, and surrogate spike compounds. All analytical instruments 

should be calibrated at least daily (see Section 2.7.1). All calibration data 

should be submitted to the laboratory project QA coordinator for review. The 

QA/QC program should document the ability of the selected methods to 

address the high salt content of sediments from marine and estuarine areas. 

-. .-__- 

99 
Anatytical precision can be measured by analyzing 1 sample in duplicate or 

triplicate for every 10-20 samples analyzed. If duplicates are analyzed, the 

relative percent difference should be reported; however, if triplicates are 

analyzed, the percent relative standard deviation should be reported. 

2.10.5 Quality Control Considerations for Chemical Analysis of 

Water 

Methods recommended for the chemical analysis of priority pollutants in water 

include detailed QC procedures and requirements that should be followed 

closely throughout the evaluations. General procedures should include the 

analysis of a procedural blank, a matrix duplicate, a matrix spike for every 

10-20 samples prOCeSS8d, and surrogate spike compounds (for organic 

analyses only). Analytical precision can be measured by analyzing 1 sample in 

triplicate or duplicate for every 10-20 samples analyzed. If duplicates are 

analyzed, the relative percent difference should be reported; however, if 

triplicates are analyzed, the percent relative standard deviation should be 

reported. Analytical bias can be measured by analyzing SRM, a matrix 

containing a known amount of a pure reagent. Recoveries of surrogate spikes 

and matrix spikes should be used to measure for precision and bias; results 

from these analyses should be well documented. Special quality control is 

required for ICP and GUMS analyses. Initial calibrations using three or five 

standards (varying in concentration) are required for analyses of inorganic and 

organic compounds, respectively, before analyzing samples (see Section 2.7.2). 

Subsequent calibration checks should be performed for every 10-20 samples 

analyzed. 

2.10.6 Quality Control Considerations for Chemical Analysis of 

Tissue 

Methods recommended for the chemical analysis of priority pollutants in tissue 

include detailed QC procedures and requirements that should be followed 

closely throughout the evaluations. General procedures should include the 

analysis of a procedural blank, a matrix duplicate, a matrix spike for every 

10-20 samples processed, and surrogate spike compounds (for organic 

analyses only). Analytical precision can be measured by analyzing 1 sample in 

triplicate or duplicate for every lo-20 samples analyzed. If duplicates are 

analyzed, the relative percent difference should be reported; however, if 

triplicates are analyzed, the percent relative standard deviation should be 

reported. Analytical bias can be measured with the appropriate SRMs. 

Precision and bias determinations should be performed with the same 

frequency as the blanks and matrix spikes. 

- 

100 
2.11 PERFORMANCE AND SYSTEM AUDITS 

Procedures to determine the effectiveness of the QC program and its 

implementation are summarized in this section of the QA project plan. Each 

QA project plan should describe the various audits required to monitor the 

capability and performance of all measurement systems. Audits include a 

careful evaluation of both field and laboratory QC procedures. They are an 

essential part of the field and laboratory QA program and consist of two basic 

types: performance audits and system audits. For example, analyses of 

performance evaluation samples may simply be used for comparison with the 

results of independent laboratories (a form of performance audit), or 

comprehensive audits may be conducted by the government of the entire field 

or laboratory operations (a system audit). 

Performance and system audits should be conducted by individuals not directly 

involved in the measurement process. A performance auditor independently 

collects data using performance evaluation samples, field blanks, trip blanks, 

duplicate samples, and spiked samples. Performance audits may be conducted 

soon after the measurement systems begin generating data. They may be 

repeated periodically as required by task needs, duration, and cost. U.S. EPA 

(1991 e) should be reviewed for auditing the performance of laboratories 

performing aquatic toxicity tests. 

A systems audit consists of a review of the total data production process. It 

includes onsite reviews of field and laboratory operational systems. EPA and/or 

USACE wi!l develop and conduct external system audits based on the approved 

project plan. An example of a systems audit checklist is provided in 

Appendices A and G. 

2.1 I. 1 Procedures for Pre-Award Inspections of Laboratories 

The pre-award inspection is a kind of system audit for assessing the laboratory’s overall capabilities. This assessment includes a determination that the 

laboratory personnel are appropriately qualified and that the required equipment 

is available and is adequately maintained. It establishes the groundwork 

necessary to ensure that tests will be conducted properly, provides the initial 

contact between government and laboratory staff, and emphasizes the 

importance that government places on quality work and products. 

The purpose of the pre-award inspection is to verify the following: 

N The laboratory has an independent QA/QC program 

n Written work plans are available for each test that describe the 

approach to be used in storing, handling, and analyzing samples 
n Technically sound, written standard operating procedures are 

available for all study activities 

a Qualifications and training of staff are appropriate and documented 

m All equipment is properly calibrated and maintained 

8 Approved analytical procedures are being followed. 

2.11.2 Interlaboratory Comparisons 

It is important that data collected and processed at various laboratories be 

comparable. As part of the performance audit process, laboratories may be 

required to participate in analysis of performance evaluation samples related to 

specific projects. In particular, laboratory proficiency should be demonstrated 

before a laboratory negotiates a contract and yearly thereafter. Each laboratory 

participating in a proficiency test is required to analyze samples prepared to a 

known concentration. Analyt8S used in preparation of the samples should 

originate from a recognized source of SRMs such as the National Institute for 

Standards and Technology. Proficiency testing programs already established 

by the government may be used (e.g., EPA Environmental Monitoring and 

Systems Laboratory scoring system), or a program may be designed 

specifically for dredged material evaluations. 

In addition, the performance evaluation samples prepared by EPA 

Environmental Monitoring and Systems Laboratory (Las Vegas, Nevada) for the 

CLP may be used to assess interlaboratory comparability. Analytical results are 

compared with predetermined criteria of acceptability (e.g., values that fall 

within the 95 percent confidence interval are considered acceptable). The QA 

project plan should indicate, Where applicable, scheduled participation in all 

interlaboratory calibration exercises. 

Reference materials are substances with well-characterized properties that are 

useful for assessing the bias of an analysis and auditing analytical 

performances among laboratories. SRMs are certified reference materials 

containing precise concentrations of Chemicals, accurately determined by a 

variety of technically valid procedures, and are issued by the National Institute 

of Standards and Technology. Currently, SRMs are not available for the 

physical measurements or ali pollutants in sediments; hOWeVer, where possible, 

available SRMs or other regional reference materials that have been repeatedly 

tested should b8 analyzed with every 20 samples processed. 

SRMs for most organic compounds are not currently available for seawater, but 

reference materials for many inorganic chemicals may be obtained from the 

organizations listed in Table 14. Seawater matrix spikes of target analytes 

(e.g., seawater spiked with National Institute for Standards and Technology 

-.. ~__ ___----- - - - 

102 
TABLE 14. SOURCES OF STANDARD REFERENCE MATERIALS 

PCBS 

National Research Council of Canada 

PAM 

National Research Council of Canada 

National lnstitute for Standards and 

Technology 

Metals 

National Bureau of Standards 

National Research Council of Canada 

International Atomic Energy Agency 

Marine sedimenl 

Marine sediment 

Sediment 

Estuarine sediment 

Marine sediment 

Dogfish liver 

Dogfish muscle 

Lobster hepatopancress 

Marine sediment 

Fish flesh 

Mussel tissue 

HS-1 and HS-2 

HS-3, HS-4, HS-5, HS6 

SRM W1647 and SRM Y1597 

SRM #1646 

MESS-l, BCSS-1, PACS-1 

DOLT- 1 

DORM-1 

TORT-1 

SD-N-1/2(TM) 

MA-A-P(W) 

MAL- 1 (TM) 

Standard reference materials (SRMs) may be obtained from the following organizations: 

Orgrnlc Constltwnts 

U.S. Department of Commerce 

National Institute for Standards and Technology 

Office of Standard Reference Materials 

Room 83111 Chemistry Building 

Galthersburg, Maryland 20899 

Telephone: (361) 975-6776 

Inorgsnlc Constftuents 

U.S. Department of Commerce 

National institute for Standards and Technology 

Office of Standard Reference Materfals 

Room 83111 Chemistry Building 

Gaithersburg, Maryland 20899 

Telephone: (30 1) 976-6776 

Marine Analytical Chemistry Standards Program 

National Research Council of Canada 

Atlantic Research Laboratory 

1411 Oxford Street 

Halifax, Nova Scotia, Canada B3H 321 

Telephone: (962) 426-8280 

Marine Analytical Chemistry Standards Program 

National Research Council of Canada 

Division of Chemistry 

Montreal Road 

Ottawa, Ontario, Canada KlA OR9 

Telephone: (613) 993-2359 

103 - 

--__-..-.. - -- -.~-. - 
SRM 1647 for PAH) should be used to check analytical bias. Some available 

SRMs for priority pollutant metals in seawater are National Research Council of 

Canada seawater CASS-1 and seawater NASS-2. 

SRMs for organic priority pollutants in tissues are currently not available. The 

National Institute of Standards and Technology is presently developing SRMs 

for organic analytes. Tissue matrix spikes of target analytes should be used to 

fulfill analytical accuracy requirements for organic analyses. 

Because new SRMs appear constantly, current listings of appropriate agencies 

should be consulted frequently. SRMs that are readily available and commonly 

used are included in Table 14. 

2.17.3 Routine System Audits 

Routine system audits during the technical evaluation ensure that laboratories 

are complying with the QA project plan. It is suggested that checklists be 

developed for reviewing training records, equipment specifications, QC 

procedures for analytical tasks, management organization, etc. The government 

should also establish laboratory review files for quick assessment of the laboratory’s activity on a study, and to aid in monitoring the overall quality of the 

work. Procedures for external system audits by the government are similar to 

the internal systems audits conducted by the laboratories themselves. 

2.12 FACILITIES 

The QA Project Plan should provide a complete, detailed description of the 

physical layout of the laboratory, define space for each test area, describe 

traffic-flow patterns, and document special laboratory needs. The design and 

layout of laboratory facilities are important to maintain sample integrity and 

prevent cross-contamination. The specific areas to be used for the various 

evaluations should be identified. Aspects of the dredging study that warrant 

separate facilities include the following: 

n Receiving 

m Sample storage 

n Sample preparation 

= Sample testing 

n Reagent storage 

= Data reduction and analysis. 
2.13 PREVENTIVE MAINTENANCE 

Procedures for maintaining field and laboratory equipment in a ready state are 

described in this section, including identification of critical spare parts that must 

be available to ensure that data completeness will not be jeopardized by 

equipment failure. Regular servicing must be implemented and documented. 

The QA project plan should describe how field and laboratory equipment 

essential to sample collection and analysis will be maintained in proper working 

order. Preventive maintenance may be in the form of: 1) scheduled 

maintenance activities to minimize costly downtime and ensure accuracy of 

measurement systems, and 2) available spare parts, backup systems, and 

equipment. Equipment should be subject to regular inspection and preventive 

maintenance procedures to ensure proper working order. Instruments should 

have periodic calibration and preventive maintenance performed by qualified 

technical personnel, and a permanent record should be kept of calibrations, 

problems diagnosed, and corrective actions applied. An acceptance testing 

program for key materials used in the performance of environmental 

measurements (chemical and biological materials) should be applied prior to 

their use. 

2.14 CALCULATION OF DATA QUALITY INDICATORS 

Specific equations or procedures used to assess the precision, bias, and 

completeness of the data are identified in this section. 

The calculations and equations used routinely in QA review (e.g., relative 

percent difference of duplicates) as well as the type of samples (e.g., blanks, 

replicates) analyzed to assess precision, bias, and completeness of the data 

must be presented in the QA project plan. Routine procedures for measuring 

precision and bias include the use of replicate analyses, SRMs, and matrix 

spikes. The following routine procedures can be used to measure precision 

and bias: 

1. Replicate analysis 

Precision for duplicate chemical analyses will be calculated as the relative 

percent difference: 

Relative percent difference = WD, - 41 x ,o() 

(D, + D&/2 

where: 

D, = sample value 
D, = duplicate sample value 

abs = absolute value. 

Precision for the replicate will be calculated as the relative standard 

deviation: 

Percent relative standard deviation = t x 100 

where: 

x = mean of three or more results 

o = standard deviation of three or more results. 

a = c o-o* [ 1 lP 

n-l 

2. Matrix and surrogate spikes 

Bias of these measurements will be calculated as the ratio of the measured 

value to the known spiked quantity: 

Percent recovery = 

spiked result - unspiked result x ,oo 

spike added 

3. Method blank 

Method blank results are assessed to determine the existence and 

magnitude of contamination. Guidelines for evaluating blank results and 

specific actions to be taken are identified in U.S. EPA (1988a,b). Sample 

results will not be corrected by subtracting a blank value. 

4. Laboratory control sample 

Bias of these measurements will be calculated as the ratio of the measured 

value to the referenced value: 

Percent recovery = 

measured value x ,oo 

referenced value 

5. Completeness 

Completeness will be measured for each set of data received by dividing 

the number of valid (i.e., accepted) measurements actually obtained by the 

number of measurements that were planned: 

106 
Completeness = 

valid data points obtained x ,oo 

total data points planned 

To be considered complete, the data set should also contain all QC check 

analyses that verify the accuracy (precision and bias) of the results. 

2.75 CORRECTIVE ACTIONS 

Major problems that could arise during field or laboratory operations, 

predetermined corrective actions for these problems, and the individual 

responsible for each corrective action are identified in this section. 

One purpose of any QA program is to identify nonconformance as quickly as 

possible. A nonconformance event is defined as any event that does not follow 

defined methods, procedures, or protocols, or any occurrence that may affect 

the quality of the data or study. A QA program should have a corrective action 

plan and should provide feedback to appropriate management authority defining 

how all nonconformance events were addressed and corrected. 

Corrective actions fall into two categories: 1) handling of analytical or 

equipment malfunctions, and 2) handling of nonconformance or noncompliance 

with the QA requirements that have been established. During field and 

laboratory operations, the supervisor is responsible for correcting equipment 

malfunctions. All corrective measures taken should be documented (e.g., a 

written standard operating procedure for the corrective action) and, if required, 

an alteration checklist should be completed. 

Corrective action procedures should be described for each project and include 

the following elements: 

m Procedures for corrective actions when predetermined limits for 

data acceptability are exceeded (see DQO discussion in Section 

2.3) 

n For each measurement system, the individual responsible for 

initiating the corrective action and the individual responsible for 

approving the corrective action. 

Corrective actions for field procedures should be described in a separate 

section from the corrective actions that would apply to the data or laboratory 

analysis. Corrective actions may be initiated as a result of other QA activities 

including performance audits, system audits, interlaboratory/interfield 

comparison studies, and QA program audits. An example of a corrective 

actions checklist is provided in Appendix A. 

107 
2.16 QUALITY ASSURANCE REPORTS TO MANAGEMENT 

The process of assuring data quality does not end with the data review. A 

report summarizing the sampling event (see Appendix H) and the QA review of 

the analytical data package should be prepared, samples should be properly 

stored or disposed of, and laboratory data should be archived in a storage file 

or database. Technical interpretation of the data begins after the QA review 

has been completed. Once data interpretation is complete, the results of the 

project should be carefully examined to determine how closely the original 

project goals and objectives were met. QA reviews are particularly useful for 

providing data users with a written record of data concerns and a documented 

rationale for why certain data were accepted as estimates or were rejected. 

QA project plans provide a mechanism for periodic reporting to management on 

the performance of measurement systems and data quality. At a minimum, 

these reports should include: 

m Periodic assessment of measurement data accuracy (precision and 

bias) and completeness 

w Results of performance and system audits 

n Significant QA problems and recommended solutions. 

The individuals responsible for preparing the periodic reports should be 

identified. The final report for each project should include a separate QA 

section that summarizes data quality information contained in the periodic 

reports. These reports may be prepared by the project manager if a brief 

evaluation was conducted, or by QA specialists if a detailed review was 

requested by the project manager. 

2.16.1 Pmparhg Basic Quality Assurance Repot& 

Basic QA reports should summarize all conclusions concerning data 

acceptability and should note significant QA problems that were found. The 

table of contents for a basic QA report should include the following: 

w Data summary-The data summary section should discuss the 

number of samples collected, the laboratory(s) that analyzed the 

samples, and a summary of the data that were qualified during the 

QA review. 

n Holding times-The holding time section should briefly discuss the 

holding time requirements and holding time exceedances. 

108 
n Analytical methods-The analytical methods section should briefly 

describe the methods of analysis, any departures from the 

methods, and any calibration or instrument-specific QC criteria 

exceedances. 

n Accuracy-The accuracy section should include a discussion of 

QC criteria and exceedances for 1) analytical bias (surrogate 

compound, laboratory control sample, matrix spike, and reference 

material recoveries) and 2) precision of matrix replicates (and 

matrix spike duplicates for organic compounds. 

n Method blanks-The method blank section should include a brief 

discussion of method blank QC criteria and exceedances. 

QA reviews are usually included as appendices to technical project reports. In 

any case, the QA review becomes part of the documented project file, which 

also includes the original data package and any computer files used in data 

compilation and analysis. 

2.16.2 Preparing Detailed Quality Assurance Reports 

Depending on the project objectives, a more detailed QA report may be 

desired. An example of a detailed QA review for a metals data package is 

provided in Appendix F. In addition to the sections outlined for the basic QA 

report, the detailed QA report should also include: 

Introduction-The introduction should give a brief overview of the 

purpose of data collection and brief summaries of how the samples 

were collected and processed in the field. 

Sample set description-The sample set section should describe 

the number of samples sent to each laboratory, including the 

number of field blanks, field replicates, SRMs, and interlaboratory 

split samples. 

Sample delivery group description-The sample delivery group 

section should briefly describe how the samples were sorted by 

the analytical laboratories (how many sample delivery groups were 

returned by the laboratory), and whether or not the QC criteria 

were performed at the correct frequency for each sample delivery 

group. 

Field QC summary-The field QC section should discuss the 

evaluation of the field btank and replicate results for the sample 

survey. 
l Interlaboratory comparison-The interlaboratory section, where 

applicable, should describe the evaluation of the split samples as 

compared to the corresponding samples analyzed by the contract 

laboratory. 

n Field results description- The field results section, where 

applicable, should present tabular summaries of all data with 

appropriate qualifiers. 

For organic analyses, a discussion of the results of instrument tuning (if 

applicable), instrument calibration analyses, internal standard performance (if 

applicable), and summation of any factors that could effect overall data quality 

(e.g., system degradation) should also be included in the detailed QA report. 

2. f 7 REFERENCES 

References cited in the QA project plan should be provided at the end of the 

plan. 

110 
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__-- ____- _--- 

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121 
4. GLOSSARY 

Accuracy The ability to obtain precisely a nonbiased (true) 

value. Accuracy as used in this document is the 

combined measure of precision and bias (see 

footnote at beginning of Section 2). 

Acid Volatile Sulfide The sulfides removed from sediment by cold acid 

extraction, consisting mainly of H2S and FeS. AVS 

is a possible predictive tool for divalent metal 

sediment toxicity. 

Analyte 

Bias 

Bioaccumulation 

Bioassay 

The specific component measured in a chemical 

analysis. 

Deviation of the measurement from the true value. 

Usually expressed as the percent recovery of a 

known amount of a chemical added to a sample at 

the start of a chemical analysis. Bias (along with 

precision) is a component of the overall accuracy 

of a system. 

The accumulation of contaminants in the tissue of 

organisms through any route, including respiration, 

ingestion, or direct contact with contaminated 

water, sediment, pore water, or dredged material. 

A bioassay is a test using a biological system. It 

involves exposing an organism to a test material 

and determining a response. There are two major 

types of bioassays differentiated by response: 

toxicity tests which measure an effect (e.g., acute 

toxicity, sublethal/chronic toxicity) and 

bioaccumulation tests which measure a 

phenomenon (e.g., the uptake of contaminants into 

tissues). 

Bioconcentration Factor The degree to which an organism uptakes a 

substance from water. 

123 
Blanks 

Calibration 

Chromatography 

Cleanup 

Comparability 

Completeness 

Confined Disposal 

Facility 

Contaminant 

QC samples that are processed with the samples 

but contain only reagents. They are used to obtain 

the response of an analysis in the absence of a 

sample, including assessment of contamination 

from sources external to the sample. 

The systematic determination of the relationship of 

the response of the measurement system to the 

concentration of the analyte of interest. Instrument 

calibration performed before any samples are 

analyzed is called the initial calibration. 

Subsequent checks on the instrument calibration 

performed throughout the analyses of samples are 

called continuing calibration. 

The process of selectively separating a mixture into 

its component compounds. The compounds are 

measured and presented graphically in the form of 

a chromatogram and digitally as a quantification 

report. 

The process of removing certain components from 

sample extracts, performed to improve instrument 

sensitivity 

Reflects the confidence with which one data set 

can be compared with others and the expression of 

results consistent with other organizations reporting 

similar data. Comparability of analytical 

procedures also implies using analytical 

methodologies that produce results comparable in 

terms of precision, bias, and effective range of 

calibration. 

A measure of the amount of valid data obtained vs. 

the amount of data originally intended to be 

collected. 

A diked area, either in-water or upland, used to 

contain dredged material. 

A chemical or biological substance in a form that 

can be incorporated into, onto, or be ingested by 

and that harms aquatic organisms, consumers of 

aquatic organisms, or users of the aquatic 

environment, and includes but is not limited to the 

124 
Control Limit 

Control Sediment 

Data Package 

substances on the 307(a)( 1) list of toxic pollutants 

promulgated on January 31, 1978 (43 Federal 

Register4109). 

A value for data from the analysis of QC checks 

indicating that a system or a method is not 

performing normally and that an appropriate 

corrective action should be taken. When control 

limits are exceeded, analyses should be halted; 

samples analyzed since the last QC sample may 

need reanalysis. 

A sediment used to confirm the biological 

acceptability of the test conditions and to help 

verify the health of the organisms during the test. 

Control sediment is essentially free of 

contaminants and compatible with the biological 

needs of the test organisms such that it has no 

discernable influence on the response being 

measured in the test. Test procedures are 

conducted with the control sediment in the same 

way as the reference sediment and dredged 

material. Control sediment may be the sediment 

from which the test organisms are collected or a 

laboratory sediment. Excessive mortality in the 

control sediment indicates a problem with the test 

conditions or organisms; and can invalidate the 

results of the corresponding dredged material test. 

The results of chemical analyses completed by a 

laboratory, compiled, printed out, and presented to 

the agency or individual requesting the analyses. 

The data package should include chromatograms, 

calculations, and tuning and calibration summaries, 

where appropriate. Also included in the data 

package may be computer disks, magnetic tape, or 

other forms of electronically stored data. 

Data Quality Indicators Surrogate spike recoveries, matrix spike 

recoveries, analytical values obtained for blanks, 

standard reference material, and performance 

evaluation samples for each parameter in each 

matrix. 

Data Quality Objectives Qualitative and quantitative statements of the 

(DQOs) overall uncertainty that a decision maker is willing 

to accept in results or decisions derived from 

725 
Detector 

Digestion 

Disposal Site 

Dredged Material 

Dredged Material 

Discharge 

Elutriate 

Evaluation 

Extraction 

environmental data. DQOs provide the framework 

for planning environmental data operations 

consistent with the data user’s needs. 

A device used in conjunction with an analytical 

instrument to determine the components of a 

sample. 

A process used prior to analysis that breaks down 

samples using acids (or bases). The end product 

is called a digestate. Other chemicals, called 

matrix modifiers, may be added to improve the 

final digestate. 

That portion of inland or ocean where specific 

disposal activities are permitted. It consists of a 

bottom surface area and any overlying volume of 

water. 

Material excavated or dredged from waters of the 

United States. A general discussion of the nature 

of dredged material is provided by Engler et al. 

(1991). 

Any addition of dredged material into waters of the 

United States, including: open water discharges; 

discharges from unconfined disposal operations 

(such as beach nourishment or other beneficial 

uses); discharges from confined disposal facilities 

which enter waters of the United States (such as 

effluent, surface runoff, or leachate); and overflow 

from dredge hoppers, scows, or other transport 

vessels. 

Material prepared from the sediment dilution water 

and used for chemical analyses and toxicity 

testing. 

The process of judging data in order to reach a 

decision. 

A chemical or mechanical procedure to remove 

semivolatile organic compounds from a sample 

matrix. The end product of extraction is called an 

extract. 

Interference Unwanted elements or compounds in a sample 
Ion 

Matrix 

Matrix Effects 

that have properties similar to those of the 

chemical of interest and that collectively cause 

unacceptable levels of bias in the results of a 

measurement or in sensitive measurements. 

Unless removed by an appropriate cleanup 

procedure, the interferant is carried along with the 

chemical of interest through the analytical 

procedure. 

An atom or group of atoms that carries a positive 

or negative electric charge as a result of having 

lost or gained one or more electrons. 

The sample material (e.g., water, sediment, tissue) 

in which the chemicals of interest are found. 

Matrix refers to the physical structure of a sample 

and how chemicals are bound within this structure. 

At a gross level, tissue is one kind of sample 

matrix and soil is another. At a finer level, a 

sediment sample of silty sand containing large 

amounts of calcium carbonate from the shells of 

aquatic organisms represents a different sample 

matrix than a sediment sample of clayey silt 

containing a large amount of organic carbon from 

decaying vegetation. 

Matrix effects are physical or chemical interactions 

between the sample material and the chemical of 

interest that can bias chemical measurements in 

either a negative or positive direction. Because 

matrix effects can vary from sample to sample and 

are often not well understood, they are a major 

source of variability in chemical analyses. 

Matrix Spike Samples QC check samples created by adding known 

amounts of chemicals of interest to actual samples, 

usually prior to extraction or digestion. Analysis of 

matrix spikes and matrix spike duplicates will 

provide an indication of bias due to matrix effects 

and an estimation of the precision of the results. 

Metals A group of naturally occurring elements. Certain 

metals (such as mercury, lead, nickel, zinc, and 

cadmium) can be of environmental concern when 

they are released to the environment in unnaturally 

high amounts. This group usually includes the 

metalloid arsenic, 
Organic Compounds Carbon-based substances commonly produced by 

animals or plants. Organic chemicals are 

chemical compounds based on carbon chains or 

rings and also containing hydrogen with or without 

oxygen, nitrogen, or other elements. Organic 

chemicals may be produced naturally by plants and 

animals or processed artificially using various 

chemical reactions. 

Performance Audit 

Precision 

Quality Assurance 

Quality Assurance 

Management Plan 

Quality Assurance 

Project Plan 

Quality Control 

Quality Control 

Checks 

Audit of a laboratory’s performance by testing a 

standard reference material. The test results are 

evaluated by the auditor. 

The ability to replicate a value; the degree to which 

observations or measurements of the same 

property, usually obtained under similar conditions, 

conform to themselves. Usually expressed as 

standard deviation, variance, or range. Precision, 

along with bias, is a component of the overall 

accuracy of a system. 

The total integrated program for assuring the 

reliability of data. A system for integrating the 

quality planning, quality control, quality 

assessment, and quality improvement efforts to 

meet user requirements and defined standards of 

quality with a stated level of confidence. 

A detailed document specifying guidelines and 

procedures to assure data quality at the program 

level (i.e., multiple projects). 

A detailed, project-specific document specifying 

guidelines and procedures to assure data quality 

during data collection, analysis, and reporting. 

The overall system of technical activities for 

obtaining prescribed standards of performance in 

the monitoring and measurement process to meet 

user requirements. 

Blanks, replicates, and other samples used to 

assess the overall analytical system and to 

evaluate the performances of individual analytical 

instruments or the technicians that operate them. 

-. -. - -. - -. - .- -- - ._ . - _ 

i28 
Reference Materials Materials or substances with well-characterized 

properties that are useful for assessing the 

accuracy of an analysis and comparing analytical 

performances among laboratories. 

Reference Sediment A sediment that serves as a point of comparison to 

identify potential effects of contaminants in the 

dredged material (see Inland and Ocean Testing 

manuals for further discussion). 

Replicates One of several identical samples. When two 

separate samples are taken from the same station, 

or when one sample is split into two separate 

samples and analyzed, these samples are called 

duplicates. When three identical samples are 

analyzed, these samples are called triplicates. 

Representativeness The degree to which sample data depict an 

existing environmental condition; a measure of the 

total variability associated with sampling and 

measuring that includes the two major error 

components: systematic error (bias) and random 

error. Sampling representativeness is 

accomplished through proper selection of sampling 

locations and sampling techniques, and collection 

of sufficient number of samples. 

Sediment 

Semivolatile 

Organic 

Compound 

Spectrometry 

Material, such as sand, silt, or clay, suspended in 

or settled on the bottom of a water body. The term 

dredged material refers to material which has been 

dredged from a water body (see definition of 

dredged material), while the term sediment refers 

to material in a water body prior to the dredging 

process. 

An organic compound with moderate vapor 

pressure that can be extracted from samples using 

organic solvents and analyzed by gas 

chromatography. 

The use of spectrographic techniques for deriving 

the physical constants of materials. Four basic 

forms of spectrometry commonly used are atomic 

absorption spectrometry (AA), inductively coupled 

plasma-atomic emission spectrometry (ICP) for 

metals, and ultraviolet spectrometry (UV) and 

129 
fluorescence emission or excitation spectrometry 

for organic compounds. 

Spiked Method 

Blanks 

Standard Operating 

Procedure 

Standard Reference 

Material 

Statement of Work 

Method blanks to which known amounts of 

surrogate compounds and analytes have been 

spiked. Such samples are useful to verify 

acceptable method performance prior to and during 

routine analysis of samples containing organic 

compounds. Also known as check standards in 

some methods; independently prepared standards 

used to check for bias and to estimate the 

precision of measurements. 

A written document which details an operation, 

analysis, or action whose mechanisms are 

thoroughly prescribed and which is commonly 

accepted as the method for performing certain 

routine or repetitive tasks. 

Standard reference materials are certified 

reference materials containing precise 

concentrations of chemicals, accurately determined 

by a variety of technically valid procedures. 

A contract addendum used as a legally binding 

agreement between the individual or organization 

requesting an analysis and the individual, 

laboratory, or organization performing the actual 

tasks. 

Surrogate Spike 

Compounds 

Compounds with characteristics similar to those of 

compounds of interest that are added to a sample 

prior to extraction. They are used to estimate the 

recovery of organic compounds in a sample. 

Target Detection Limit 

(TW 

A performance goal set by consensus between the 

lowest, technically feasible, detection limit for 

routine analytical methods and available regulatory 

criteria or guidelines for evaluating dredged 

material. The TDL is, therefore, equal to or greater 

than the lowest amount of a chemical that can be 

reliably detected based on the variability of the 

blank response of routine analytical methods. 

However, the reliability of a chemical measurement 

generally increases as the concentration increases. 

Analytical costs may also be lower at higher 

detection limits. For these reasons, a TDL is 

730 
Tests/Testing 

Toxicity Test 

Volatile Organic 

Compound 

Warning Limit 

typically set at not less than 10 times lower than 

available dredged material guidelines for potential 

biological effects associated with sediment 

chemical contamination. 

Specific procedures which generate biological, 

chemical, and/or physical data to be used in 

evaluations. The data are usually quantitative but 

may be qualitative (e.g., taste, odor, organism 

behavior). 

A bioassay which measures an effect (e.g., acute 

toxicity, sublethal/chronic toxicity). Not a 

bioaccumulatlon test (see definition of bioassay). 

An organic compound with a high vapor pressure 

that tends to evaporate readily from a sample. 

A value indicating that data from the analysis of 

QC checks are subject to qualification before they 

can be used in a project. When two or more 

sequential QC results fall outside of the warning 

limits, a systematic problem is indicated. 

Water Quality Standard A law or regulation that consists of the beneficial 

designated use or uses of a water body, the 

numeric and narrative water quality criteria that are 

necessary to protect the use or uses of that 

particular water body, and an anti-degradation 

statement. 

131 
APPENDIX A 

Example QA/QC Checklists, 

Forms, and Records 
CONTENTS 

QA PROGRAM ORGANIZATION FLOW DIAGRAM 

EXAMPLE DATA QUALITY OBJECTIVES FOR ACCURACY 

AND COMPLETENESS 

ALTERATION CHECKLIST 

CHAIN-OF-CUSTODY RECORD 

FIELD TRACKING REPORT FORM 

LABORATORY TRACKING REPORT FORM 

GENERAL SAMPLE LABEL 

STATION LOCATION LOG 

SYSTEMS AUDIT CHECKLIST 

CORRECTIVE ACTIONS CHECKLIST 

Page 

A-1 

A-2 

A-3 

A-4 

A-5 

A-5 

A-6 

A-7 

A-8 

A-9 
QA PROGRAM ORGANIZATION FLOW DIAGRAM 

A-1 
EXAMPLE DATA QUALITY OBJECTIVES FOR 

ACCURACY AND COMPLETENESS 

Variable Matrix units 

Target 

Detection 

Limit 

Bias 

(%) 

Maximum 

Precision Completeness Holding 

(%) (%) Method Reference Time 

Volatiles Sediment μg/kg 10 ±50% ±30% 99% Purge & Trap/GC-MS EPA abc/x-cc-yy(1975) 14 days 

Grain Size Sediment Percent 0.01 - ±5% 99% Sieve & Pipet Undetermined 

A-2 
Sample Program Identification: 

Material to be Sampled: 

Measurement Parameter: 

Standard Procedure for Analysis: 

ALTERATION CHECKLIST 

Reference: 

Variation from Standard Procedure: 

Revon for Variation: 

Resultant Change in Field Sampling Procedure: 

Spedal Equipmeat, Material, or Personnel Rcquircd: 

Author’s Name: Date: 

ApP& Titk: 

mte: 

A-3 

FIELD TRACKING REPORT FORM 

I W/O No. Page 

FIELD TRACKING REPORT: 

(LOC-SN) 

LABORATORY TRACKING REPORT FORM 

I 

w/o No. Page 

LABORATORY TRACKING REPORT: 

(L&N) 

I 

X PREP/ANAL RESPONSIBLE DATE DATE 

mmON CODE REQUIRED INDIVIDUAL DELIVERED COMPLETED 

I 

A-5 
(NAME OF SAMPLING ORGANIZATION) 

PROJEm 

DATE: 

SAMPLE ID NO.: 

MEDIA: 

STATION NUMBER: 

DEPTH: 

PRESERVATION: 

ANALYSES TO BE PERFORMED 

SAMPLED BY: 

LAB NO.: 

REMARKS: 

A-6 
STATION LOCATION LOG 

PROJECT: 

STATION LOCATION: 

DESCRIPTION OF SAMPLES COLLECTED: 

SPC ZONE: (NCS) EAST: 

DATE: 

NORTH: 

LOCATION: 

Bottom Depth: - WI (m) Tide: f (m) MLLW: - (fi) - ON 

LORAN c: LOP1 LOP2 

Variable Radar Range: 

Visual Fixes: (Note: Please tape any drawings to back of this sheet) 

Photos - Roll: Piaurcs: 

PID Reading (range). 

RECORDER: SIGNATURE ORG. CORE DATE: 

A-7 
SAMPLE PROGRAM IDENTIFICATION: 

SAMPLING DATES: 

MATERIAL TO BE SAMPLED: 

MEASUREMENTPSAMPLING AND MONITORING EQUIPMENT IN USE: 

AUDIT PROCEDURES AND FREQUENCY: 

FIELD CALIBRATION PROCEDURES AND FREQUENCX 

SIGNATURE OF QA COORDINATOR: 

DATE: 

A-8 
CORRECXTVE ACITONS CHECICLB’I’ 

SAMPLE PROGRAM IDENTIFICATION: 

SAMPLING DATES: 

MATERIAL TO BE SAMPLED: 

MEASUREMENTPARAh4ETER: 

ACCEPTABLE DATA RANGE: 

CORRECTIVE ACI-IONS INITIATED BY: 

TITLE: 

DATE 

PROBLEM AREAS REQUIRING CORRECTIVE ACTION: 

MEASURES TO CORRECT PROBLEMS: 

MEANS OF DEtECTING PROBLEMS (FIELD OBSERVATIONS, SYSTEh4S AUDl-I’, ETC): 

APPROVAL FOR CORREClTVE ACTIONS: 

TITLE 

SIGNATURE 

DATE 

A-Q 
APPENDIX B 

Example Statement of Work 

for the Laboratory 
PREFACE 

This appendix contains a generic statement of work for the analysis of most chemicals 

in the most commonly analyzed sample matrices. 

B-iii 
CONTENTS 

Page 

PREFACE 

STATEMENT OF WORK 

SUMMARY OF ANALYSES AND SERVICES 

SAMPLE DELIVERY AND STORAGE 

METHODS 

QUALITY ASSURANCE AND QUALITY CONTROL REQUIREMENTS 

DELIVERABLES 

Laboratory Data Reports 

TURNAROUND TIME 

PROGRESS REPORTS, PROBLEM NOTIFICATION, AND 

PROJECT AUDITS 

B-iii 

B-1 

B-1 

B-1 

B-1 

B-5 

B-6 

B-6 

B-9 

B-9 

B-v 
STATEMENT OF WORK 

The following tasks shall be performed by as extensions to work 

identified as part of Contract No. between Contractor and 

SUMMARY OF ANALYSES AND SERVICES 

The Laboratory shall perform quantitative analyses for the analytes listed in Table 1 on 

sediment, water, and tissue samples collected from in and around . The 

analyses shall be conducted according to sampling and analysis plan 

(SAP), the project work plan, and 

SAMPLE DELIVERY AND STORAGE 

Sampling will begin approximately and continue for a period of 

approximately . Contractor will provide samples to the Laboratory no 

earlier than . Table 2 summarizes the maximum number of samples 

the Laboratory could receive each month and the associated analyses. The actual number 

of samples that will be delivered to the Laboratory may vary from these estimates. 

Samples will be sent from the site to the Laboratory’s facilities via United Parcel Service 

or equivalent carrier. Contractor may choose to use the Laboratory’s courier service if 

the Laboratory provides such a service. Contractor will coordinate with the Laboratory 

for final disposition of the samples after analysis. All samples shall be maintained under 

strict chain of custody at all times, including documentation of any transfers among 

facilities. 

METHODS 

The Laboratory shall perform the analyses according to the specified 

or other Contractor-specified protocols. Table 1 provides a list of specific method 

references, holding times, and data quality objectives. 

The Laboratory shall promptly notify the Contractor Quality Assurance and Quality 

Control (QA/QC) Coordinator prior to any deviation from these methods. Further, the 

Laboratory shall immediately notify the Contractor QA/QC Coordinator as soon as it 

becomes apparent that the data quality objectives cannot be met for a set of samples. 

B-l 
TABLE B-1. SUMMARY OF ANALYSES AND DATA QUALITY OBJECTIVES 

Analyte Matrix Units 

Target 

Detection 

Limit 

Bias 

(%) 

Precision Completeness 

(%) (%) Method Reference 

Holding 

Time 

(days) 

Organic Analyses 

TCLa semivolatile 

organic compounds 

TCL volatile organic 

compounds 

TCL pesticides and 

PCBsb 

Lipids 

Metals Analyses 

Copper 

μg/kg 

μg/L 

μg/kg 

μg/kg 

μg/L 

μg/kg 

μg/kg 

μg/L μg/kg 

μg/kg 

μg/kg 

μg/L 

μg/kg 

μg/L 

μg/kg 

μg/kg 

μg/L 

μg/kg 

Mercury 

TALc metals 

Solids 

Water 

Tissue 

Solids 

Water 

Tissue 

Solids 

Water 

Tissue 

Tissue 

Solids 

Water 

Solids 

Water 

Tissue 

Solids 

Water 

Tissue 

Conventional and Nutrient-Related Analyses 

Acid-volatile sulfide Solids μmoles/g 

Total organic carbon Solids % carbon 

Water mg/L 

Dissolved organic carbon Water mg/L 

B-2 
TABLE B-1. (cont.) 

Analyte Matrix Units 

Target 

Detection 

Limit 

Bias 

VW 

Precision Completeness 

(%) W) Method Reference 

Holding 

Time 

(days) 

Physical Analyses 

Grain size 

Percent moisture 

Total suspended solids 

Solids gdryW* 

Solids % moisture 

Water mglL 

. Target compound list. 

b Polychlorinated biphenyl. 

c Target analyte list. 

--- -.--.-- --___-- 

8-3 
TABLE B-2. ESTIMATED MAXIMUM NUMBER OF SAMPLES BY MONTH AND ANALYTE TYPE 

(date) (date) (date) (date) Total 

Maximum Maximum Maximum Maximum Maximum 

Analyte Solids Water Tissue Solids Water Tissue Solids Water Tissue Solids Water Tissue Solids Water Tissue 

Organic Analyses 

TCL’ semivolatile organic compounds 

TCL volatile organic compounds 

TCL pesticides and PCBs” 

Lipids 

Metals Analyses 

Copper 

Mercury 

TALC metals 

Conventional and Nutrient-Related Analyses 

Acid-volatile sulfide 

Total inorganic carbon 

Dissolved organic carbon 

Physical Analyses 

Greln size 

Percent moisture 

Total suspended solids 

. Target compound list. 

b Polychlorinated biphenyl. 

c Target analyte list. 

B-4 
QUALITY ASSURANCE AND QUALITY CONTROL REQUIREMENTS 

The Laboratory shall implement the following procedures to assess quality during sample 

analysis: 

Calibration Verification-Initial calibration of instruments shall be performed at the start of the project and when any ongoing calibration does 

not meet control criteria. The number of points used in the initial calibration is defined in each analytical method (e.g., Contract Laboratory 

Program [CLP]). Ongoing calibration verification shall be performed as 

specified in the analytical methods to monitor instrument performance. In 

the event that an ongoing calibration is out of control, analysis of project 

samples shall be suspended until the source of the control failure is either 

eliminated or reduced to within control specifications. Any project samples 

analyzed while the instrument was out of control shall be reanalyzed at 

Laboratory’s expense. 

Surrogate Spike Compounds-The Laboratory shall spike all project 

samples to be analyzed for organic compounds with appropriate surrogate 

compounds as defined in the analytical methods (e.g., CLP). Recoveries 

determined using these surrogate compounds shall be reported by the 

Laboratory; however, the Laboratory shall not correct sample results using 

these recoveries. 

Method Blanks-The Laboratory shall not apply blank corrections to 

original data. For organic analyses, a minimum of 1 method blank shall 

be analyzed for every extraction batch, or 1 for every 20 samples, whichever is more frequent. For metals and conventional analyses, 1 method blank 

shall be analyzed for every digestion batch, or 1 for every 20 samples, 

whichever is more frequent. 

Matrix Spike Samples-For organic analyses and metals, the Laboratory 

shall analyze a minimum of 1 matrix spike for each group of samples 

extracted or digested, or 1 for every 20 samples, whichever is more 

frequent. For organic analyses, 1 matrix spike duplicate shall either be 

analyzed for each group of samples extracted or for every 20 samples, 

whichever is more frequent. 

Laboratory Control Samples-When available, the Laboratory shall use 

laboratory control samples (LCS). For metals and applicable conventional 

parameters, 1 LCS shall either be analyzed for every digestion batch or for 

every 20 samples, whichever is more frequent. The source of the LCS 

must be included in the data package. 

Laboratory Duplicates-The Laboratory shall perform duplicate analyses 

as indicators of laboratory precision. For metals analyses {except mercury) 

and conventional analyses, the Laboratory shall analyze 1 laboratory 

duplicate either for every digestion batch or for every 20 samples, whichever is more frequent. 
n Sample Container Preparation-Sample containers shall be prepared by 

the Laboratory and delivered to the project site, as required. Sampling 

personnel shall discard any containers that have visible signs of dirt or 

contamination. Documentation of the preparation of sample containers 

shaII be prepared, signed, and dated by Laboratory personnel and included 

with the sample container shipment. 

DELIVERABLES 

The Laboratory shall report results that are supported by sufficient backup data and 

quality assurance results to enable reviewers to conclusively determine the quality of the 

data. The data and supporting documents shall be provided to the Contractor QA/QC 

Coordinator. The Laboratory shall not divulge outside of Contractor any data or other 

information obtained or generated by the Laboratory with respect to the work specified 

herein. Data reporting requirements are summarized below. 

Labora tory Data Reports 

All data reports shall include the following: 

A. General 

1. 

2. 

3. 

4. 

5. 

A cover letter documenting aII sample preparation and analytica.l protocols used 

and explaining any variance from protocols contained in the appropriate EPA 

statement of work (SOW) or this SOW. 

Copies of completed chain-of-custody records and sample analysis request 

forms. 

A cross-referenced table of Contractor and Laboratory identification numbers, 

and full explanation of all data qualifier symbols in accordance with the 

appropriate EPA SOW. 

Tabulated results in units specified in the appropriate EPA SOW or this SOW. 

A table of sample preparation data, including initial weights or volumes of 

samples, final dilution volumes, and digestion or preparation reagents. Data 

must be grouped by preparation date and include the identity of all quality 

control checks associated with each preparation batch. If subsets of a large 

number of samples are prepared or digested at separate times, then each sample 

subset is defined as a batch. Data provided in this table must be sufficient to 

unequivocally match each field sample with the corresponding quality control 

check samples. 

-___~- ~- - - _. - _ __---.- --_ 

8-6 
B. Quality Control Results 

1. For the analyses of inorganic compounds, the following summary results should 

be tabulated in the format of the appropriate indicated EPA form: 

a. 

b. 

C. 

d. 

e. 

f. 

g. 

h. 

i. 

j. 

k. 

1. 

Initial and ongoing calibration verifications 

Initial and ongoing calibration blanks and preparation blanks 

Inductively coupled plasma-atomic emission spectrometry (ICP) interference checks 

Matrix spike sample recoveries 

Duplicate samples 

Laboratory control sample recoveries 

Method of standard additions, if performed 

ICP serial dilution 

Mercury holding times, if performed 

Instrument detection limits 

ICP inter-elemental correction factors 

ICP linear ranges. 

2. For all other analyses, the following tabulated summaries of all quality control 

checks for each analyte should be included: 

a. Initial and ongoing calibration verifications 

b. Initial and ongoing calibration blanks and preparation blanks 

C. Matrix spike sample recoveries 

d. Duplicate samples 

e. Independent standards. 

C. Original Data 

1. Legible photocopies of all original data, including Laboratory notebook pages, 

computer printouts, and stripcharts, with sufficient information to unequivocally 

identify the following: 

a. Calibration and ongoing calibration results 

b. Surrogate spike compound recoveries 

8-7 
C. Samples and all dilutions 

d. Results of all method blanks 

e. Results of all matrix spikes and matrix spike duplicates 

f. Results and origin of LCS analyses 

g- Results of Laboratory duplicates and triplicates 

h. Origin of all reference materials 

i. Any instrument adjustments or apparent anomalies on the measurement 

record. 

2. The following information should be shown on the first page of each set of 

original data sheets pertaining to a particular protocol (e.g., ICP computer 

printout): 

a. A statement documenting the analyte(s) and the exact protocol used 

b. The date of analysis 

C. Typed name and signature of the analyst. 

3. Copies of all sample container preparation documentation. 

D. Electronic Deliverables 

All data reported on the EPA forms must also be submitted as a diskette deliverable. The 

data should be in Format A (on an MS-DOS diskette), as defined by the SOW. 

E. Other Information 

Although not required as a deliverable for every data package, the following documentation must be available at the request of the Contractor QA/QC Coordinator as part of the 

Laboratory’s standard QA/QC procedures: 

n All original data 

m Sample receipt and storage logbooks 

m Record of sample holding time 

n Storage temperature logbooks 

n Conductivity of distilled/deionized water 

n Analytical balance annual and routine (Class S weights) calibration 

logbooks 
Standard preparation and tracking logbooks, including purity of chemicals 

used to prepare standards 

Instrument calibration protocols and service record logbooks, including 

preventive maintenance 

Evidence of spot-checking of data handling 

In-house quality control charts. 

TURNAROUND TIME 

Schedules for delivery of results may vary, but shah not exceed a turnaround time of 

- calendar days, Generally, a turnaround time of _ days will be desired. For data that 

are delivered late, the Laboratory will be subject to, at the discretion of the Contractor, 

a penalty of _ percent per calendar day for each day the data are late up to a maximum 

of - percent of the total cost of the analyses. 

PROGRESS REPORTS, PROBLEM NOTIFICATION, 

AND PROJECT AUDITS 

A verbal progress report to the Contractor QA/QC Coordinator is required each week for 

the duration of the project. Immediate notification of the Contractor QNQC Coordinator 

is required when the Laboratory identifies a problem that could prevent all QNQC 

requirements or data quality objectives, including required detection limits, to be met for 

the final data. Contractor may conduct onsite audits of the Laboratory’s facilities during 

the period of analysis to assess implementation of QA/QC requirements. The Laboratory 

shall maintain records to support an audit of the technical quality of all analyses and shall 

provide all such records to Contractor upon request. 

-- - -.- - -.- __- - - -.- --..- - -.- 

B-9 
APPENDIX C 

Description of Calibration, 

Qualify Control Checks, and 

Widely Used Analytical Methods 
CONTENTS 

Page 

DESCRIPTION OF CALIBRATION, QUALITY CONTROL SAMPLES, AND 

WIDELY USED ANALYTICAL METHODS 

INTRODUCTION 

CALIBRATION 

QUALITY CONTROL SAMPLES 

Blanks 

Matrix Spikes 

Surrogate Spikes 

Check Standards 

Laboratory Control Samples 

Spiked Method Blanks 

Reference Materials 

Replicates 

COMMON ANALYTICAL METHODS 

Gas Chromatography 

Gas Chromatography/Mass Spectrometry 

Gas Chromatography/Electron Capture Detection 

Gas Chromatography/Flame Ionization Detection 

High Pressure Liquid Chromatography 

Atomic Absorption Spectrometry 

Inductively Coupled Plasma-Atomic Emission Spectrometry 

C-1 

C-1 

C-1 

C-3 

C-3 

C-4 

C-4 

C-5 

C-5 

C-5 

C-5 

C-6 

C-7 

C-7 

C-7 

C-9 

C-9 

C-10 

C-10 

C-11 

C-iii 
DESCRIPTION OF CALIBRATION, QUALITY 

CONTROL SAMPLES, AND WIDELY USED 

ANALYTICAL METHODS 

INTRODUCTION 

The relative importance, rationale, and recommended frequency of calibration and each 

of the quality control samples are discussed in the following sections. A summary of the 

major considerations in applying these procedures is provided in the main text (see 

Section 2.7). 

The concepts of calibration and quality control samples apply to dozens of analytical 

methods that are currently used by laboratory technicians. Selection of appropriate 

methods for particular types of analyses is based on the list of chemicals for analysis and 

the required detection limits. Some of the widely used analytical methods are described 

below, along with technical issues that should be considered when choosing individual 

methods. 

CALIBRATION 

Calibration of analytical instruments is a critical element of quality control because the 

procedures used for calibration will determine both the accuracy and precision of 

analytical results. Gas chromatography/mass spectrometry, or any other analytical 

technique, measures the magnitude of an unknown concentration of an analyte relative to 

a known concentration of the analyte or a similar analyte in a standard. Such relative 

measurements are meaningless unless the responsiveness of the analytical instrument can 

be determined over a range of analyte concentrations. Through calibration, this level of 

responsiveness can be determined. The relationship between response and concentration 

is generally expressed as an analytical curve. For the analysis of organic compounds in 

samples, response factors (RFs) for analytes relative to standards at various concentrations may be established from this analytical curve. The degree with which incremental concentrations of an analyte produce constant increments of response is called 

linearity. 

Guidelines for instrument calibration must be included in the statement of work for the 

laboratory performing the analysis. Examples of these guidelines are given in Methods 

for Chemical Analysis of Water and Wastes (U.S. EPA 1983). Project managers should 

ensure that the statement of work addresses the following points: 
• Instruments should be calibrated at the beginning of the project before any 

samples are analyzed, after each major disruption in analytical procedures, 

and whenever action limits are exceeded for certain samples. This type of 

calibration is called the initial calibration of the instrument. Through 

initial calibration, an analytical curve based on the absorbance, emission 

intensity, or other measured characteristics of known standards can be 

established. Data from subsequent analyses are considered valid as long 

as the values fall within the linear range of this curve. 

• In some analytical programs, the accuracy of the initial calibration is 

verified and documented for every analyte by analyzing U.S. Environmental Protection Agency (EPA) quality control solutions immediately 

following the initial calibration. If immediate verification is not required, 

then the verification may be conducted after several samples have been 

analyzed. When a certified solution of an analyte is not available from 

EPA or any other source, analyses should be conducted on an independent 

standard at a concentration other than that used for calibration, but within 

the calibration range. When measurements for the certified components 

exceed the action limits, the analysis should be terminated, the problem 

corrected, the instrument recalibrated, and the recalibration verified. 

• The validity of the original calibration curve should be confirmed throughout the analyses of samples. This process is called continuing calibration. 

However, unless required by a specific method, the continuing calibration 

results should not be used to quantify sample results (use the average 

response from the initial calibration instead). For gas chromatography/mass 

spectrometry (GC/MS) analyses of samples containing organic compounds, 

calibration should be checked at the beginning of each work shift, at least 

once every 12 hours (or every 10-12 analyses, whichever is more frequent), and after the last sample analysis of each work shift. For gas 

chromatography/electron capture detection analyses, calibration should be 

checked at the beginning of each shift, every 6 hours (or every 6 samples, 

whichever is less frequent), and after the last sample analysis of each shift. 

• For analyses with inductively coupled argon plasma emission spectrometry 

and atomic absorption spectrometry, all work should be performed using 

continuing calibration. A procedure for conducting these calibrations is 

outlined in EPA’s Contract Laboratory Program statement of work for 

inorganic chemicals (U.S. EPA 1990e). Frequency of continuing calibration of these instruments is 10 percent of the samples or every 2 hours 

during an analysis run, whichever is more frequent. 

C-2 
QUALITY CONTROL SAMPLES 

Blanks 

Blanks are quality control samples that are processed with the samples but contain only 

reagents. They are used to obtain the response of an analysis in the absence of a sample, 

including assessment of contamination from sources external to the sample. Contamination can arise from sources such as the reagents themselves, sample or reagent containers, and equipment used for sampling, sample storage, and analysis. The types of 

analytical blanks used to identify each of these potential sources of contamination are 

described below: 

1 Method blanks (also called preparation blanks or reagent blanks) are used 

to identify any contamination that may have been contributed by laboratories during sample preparation. A method blank should be required for 

each batch of samples prepared for analysis, except in the case of volatile 

organic analyses (VOAs), in which case, method blanks should be 

analyzed at least once every 12 hours. Because method blanks are usually 

included in the cost of sample analysis, they should not place an additional 

cost burden on a project. 

D Bottle blanks are used to determine whether sample containers are sources 

of contamination. One bottle blank should be prepared for each lot of 

sample containers. Large increases in the contaminant level for the bottle 

blank coinpared with the method blank indicate a potential container 

problem. Laboratories usually provide clean containers for performing 

bottle blank analyses at no additional cost. For most sampling efforts, 

precleaned containers from a chemical supply company can be obtained at 

reasonable cost. The use of precleaned bottles may eliminate the need to 

have bottle blanks analyzed. 

n Transport blanks (also called trip blanks) are used to detect contamination 

arising during sample shipping, handling, and storage. These blanks are 

taken from clean containers filled with deionized water, transported to the 

field, and stored and shipped with the samples. One transport blank 

should be included with each shipping container. A contaminant level for 

the transport blank that greatly exceeds the contaminant level of the 

method blank indicates a potential field handling, container, or storage 

problem. Transport blanks are important only for projects involving 

analysis of volatile organic compounds, which may migrate from one 

container to another. 

n Held equipment blanks (also called decontamination checks) are used to 

detect contamination arising from field sampling equipment. At least one 

field equipment blank should be required for each medium that is sampled 

during a sampling effort. 

c-3 
Matrix Spikes 

Matrix spike samples are used to provide an indication of the bias due to matrix effects 

and an estimation of the precision of results. They can also provide indications of how 

tightly an analyte is bound to its matrix, such as soil or tissue. Matrix spike samples are 

created by adding known amounts of chemicals of interest to actual samples, prior to 

extraction and usually prior to digestion. The addition of these chemicals is commonly 

called spiking. The matrix spike is analyzed using the same analytical procedure used 

for samples. The results are then compared with the results from the analysis of a 

replicate, unspiked sample. In this way the effect of the particular sample matrix on the 

recovery of chemicals of concern can be evaluated. By spiking and analyzing the sample 

after digestion, an analyst can determine whether spike analysis results have been affected 

by matrix binding or by sample preparation procedures. This postdigestion spiking is 

only used for metals analyses. 

Matrix spike samples should include a wide range of chemical types. For example, a 

matrix spike sample for analysis of semivolatile organic compounds may include spiking 

with three neutral compounds, two organic acid compounds, and two organic base 

compounds. Ideally, samples should be spiked either at approximately 5 times the 

expected chemical concentration in a sample or at 5 times the target detection limit, 

whichever is higher. Spiking at this concentration reduces the possibility for any increase 

in random error during the matrix spike analysis and eliminates any masking of 

interferences at representative chemical concentrations. 

One matrix spike sample and one matrix spike duplicate sample should be analyzed for 

every set of twenty or fewer samples or with each sample preparation lot. If 20 or more 

samples are submitted, 1 matrix spike duplicate pair should be run for each set of 20 

samples. Analysis of matrix spikes and matrix spike duplicates is often performed to 

assess the precision and bias of one set of results. 

Sumgate Spikes 

Surrogate spike compounds can be used to estimate the recovery of organic compounds 

in a sample. Surrogates are compounds with characteristics similar to those of compounds of interest that are added to a sample before it undergoes the process of 

extraction. Surrogates should be compounds that are not expected to be present in the 

samples, but they should have characteristics similar to the compounds of concern. 

Compounds Iabeled with stable isotopes (that is, where normal carbon or hydrogen atoms 

in the molecule have been replaced with isotopes of carbon or hydrogen) are commonly 

used as surrogates. However, all surrogates need not be isotopically labeled. They need 

only be compounds that are physically and chemically similar to the chemicals of 

interest. For example, dibromooctafluorobiphenyl is used by some laboratories as a 

surrogate for polychlorinated biphenyls (PCBs), although this compound is not identical 

in structure to a PCB. 

C-4 
Because surrogate compounds are the only means of checking method performance on 

a sample by sample basis, they should be used whenever possible. A minimum of five 

surrogate spikes (three neutral and two acid compounds) should be added to each sample 

when analyzing for semivolatile organic compounds. These surrogate spikes should 

cover a wide range of compound classes. At least three surrogate compounds should be 

used for the analysis of volatile organic compounds, and at least one surrogate compound 

should be used in each extracted sample as a check on recovery of pesticides. A separate 

surrogate compound should be used in each extracted sample to check the recovery of 

PCB mixtures. 

Check Standards 

Check standards contain known amounts of analyte and are analyzed along with the 

samples. Check standard results are used to indicate bias due to sample preparation 

and/or calibration and to control precision. 

L alwratory Conttv~ Samples 

Laboratory control samples are check standards used to assess precision in the analytical 

procedures for metals. Like reference materials, these samples can be acquired from 

EPA. Often they are routinely analyzed by the laboratory at no extra cost. 

Spiked Method Blanks 

In certain organic methods, surrogate spikes are added to the check standards; these 

quality control samples are called spiked method blanks. The different compounds and 

their required amounts are specified in EPA’s guidelines for the Contract Laboratory 

Program (U.S. EPA 1990d,e) and other regional guidelines. Such analyses are useful 

to verify acceptable method performance prior to and during routine analysis of samples 

containing organic compounds. Spiked method blanks do not take into account sample 

matrix effects, but can be used to identify basic problems in procedural steps. Spiked 

method blanks can also be used to provide minimum recovery data when no suitable 

reference material is available or when sample size is insufficient for matrix spikes. A 

spiked method blank should be analyzed whenever a method is used for the first time in 

a project and each time that a method is modified. In these instances, analysis of the 

spiked method blank should take place before analysis of any samples. 

Reference Materials 

Reference materials are substances with well-characterized properties that are useful for 

assessing the bias of an analysis and auditing analytical performances among laboratories. 

SRMs are certified reference materials containing precise concentrations of chemicals, 

c-5 
accurately determined by a variety of technically valid procedures, and are issued by the 

National Institute of Standards and Technology. Currently, SRMs are not available for 

the physical measurements or all pollutants in sediments; however, where possible, 

available SRMs or other regional reference materials that have been repeatedly tested 

should be analyzed with every 20 samples processed. Further information on SRMs is 

provided in the main text (see Section 2.11.2). 

Replicates 

Replicates are two or more identical samples that are analyzed to provide an estimate of 

the overall precision of sampling or analytical procedures. When two separate samples 

are taken from the same field station, or when one sample is split into two separate 

samples, these replicate samples are specifically called duplicates. Duplicates are usually 

sufficient when using an analytical procedure that is well proven in the laboratory. 

Analyzing three replicate samples (called triplicates) yields more meaningful statistical 

measures of variability than analyzing duplicate samples. However, statistically 

combining the variance of duplicate sample results across several sets of duplicates is also 

an effective way of evaluating variability. 

Replicate samples are commonly used for the following purposes: 

n Analytical (or laboratory) replicates measure the precision of sample 

analyses. To prepare analytical replicates, the sample is homogenized by 

the laboratory and divided into two subsamples. The subsamples are then 

independently analyzed. If five or fewer samples are submitted for 

analysis, a minimum of one analytical replicate is recommended, the exact 

number to be determined by the project manager. If more than 5 but less 

than 20 samples are submitted, at least 1 analytical replicate should be 

analyzed. A general rule is 1 analytical replicate for every batch of up to 

20 samples analyzed together (e.g., U.S. EPA 1990d). 

l Field replicates measure sampling variability. These samples are collected at the same time and location as other samples and are submitted for 

analysis along with the other samples. Field replicates should be coordinated with analysis of laboratory replicates so that both sampling variability and analytical variability can be measured for the same station. The 

project manager or coordinator usually determines the frequency with 

which field replicates are collected and sent to the laboratory. If funds are 

limited, a single laboratory replicate to measure analytical variability is 

preferred over a field replicate. 

m Blind replicates are samples submitted to the laboratory without the 

laboratory’s prior knowledge. Data from these blind replicates can be 

used to detect potential laboratory bias when compared with data from the 

analysis of analytical replicates. In this manner, blind replicates can serve 

C-6 
as laboratory quality control samples. However, the results for these 

samples are subject to errors introduced by the process of splitting the 

sample and by preservation, transportation, and storage procedures as well 

as analytical errors. Analysis of 1 set of blind replicates should be 

performed whenever 20 or more samples are submitted. At least one 

triplicate set is recommended for analysis of more than 20 samples. 

COMMON ANALYTICAL METHODS 

Gas Chrwnatograph y 

Gas chromatography is a technique used to separate a complex mixture of organic 

materials into its components (for example, an extract of oil or smoke, which may 

contain hundreds, even thousands, of compounds). To do this, the sample extract is 

injected into a heated chamber, in which the mixture of compounds is concentrated at the 

head of a separating column. The mixture is then carried through the column by an inert 

gas (called the mobile phase). As the column is heated, the analytes pass through 

absorbent materials (called the stationary phase). Different analytes move at different 

rates and appear one after another, along with any interfering substances for a particular 

analyte, at the effluent end of the column. Here they are measured by a detector. The 

detector sends information as an electronic signal to an integrator, chart recorder, or 

computer. The signals are then interpreted and presented graphically in the form of a 

chromutogram and digitally as a quantzjication report. 

Using the chromatogram and the digital information contained in the quantification 

report, many analytes contained in the sample can be accurately identified and quantified. 

Several different gas chromatograph/detector combinations are commonly used for the 

analysis of volatile and semivolatile organic compounds, which include pesticides and 

PCBs. Three of these combinations are described in the following sections. 

Gas Chmatograph y/Mass Spectmnetry 

GC/MS enables positive identification of a compound that has eluted from a gas 

chromatographic column. In the GC/MS chamber, separated compounds are bombarded 

by electrons and broken into characteristic fragments called ions. The mass of the 

charged ions (i.e., their molecular weight) can be sensed by a detector that accumulates 

data on ionization current over a wide range of masses. The more ions of a particular 

mass, the greater the ionization current that is recorded for that mass. At any one time, 

the relative intensity of this current over all the different masses recorded for a particular 

compound gives rise to its mass spectrum (Figure C-l). The pattern of fragmentation 

ions in a mass spectrum is used to distinguish one compound from another. In addition, 

the intensity of the current recorded for one characteristic ion over time gives rise to its 

mass chromatogram, which is used to quantify the concentration of the analyte as it 

c-7 
LIBRARY 

SAtlPLE 

Figure C-l. Example mass spectrum for benz(a)anthracene identified in a sample sediment extract (upper) and 

authentic spectrum stored in computerized GUMS library (lower). I 

C-8 
elutes from the gas chromatograph. This characteristic ion is called the quantification 

ion. The mass chromatograms for all ions detected can be superimposed into a 

reconstructed ion chromatogram (RIC), also called a total ion chromatogram. The RX 

is a graphic display of the total ionization current resulting from all mass fragments for 

all compounds detected from the start to the finish of the analysis. The EUC can be 

compared with the chromatograms produced by other detectors and provides an indication 

of the relative composition of components in the sample mixture analyzed by GUMS. 

The mass spectrometer is a selective detector that allows for the positive identification 

of many compounds. Other kinds of detectors may be more sensitive in detecting PCBs 

and other chlorinated compounds. 

Gas Chmmatograph yElectrvn Capture Detection 

Gas chromatography/electron capture detection (GUECD) is useful for detecting analytes 

such as pesticides, PCBs, and other similarly structured chemical compounds that contain 

chlorine. The ECD measures the total concentration of a chemical in a sample, but it 

cannot distinguish one individual chemical from others. Verification of individual 

chemicals is accomplished by comparing the order in which the chemicals appear (called 

the elution order) and the time that passed before they appeared (called the retention 

time) with the elution orders and retention times of certain analytical standards. The 

identity of a chemical is verified when the elution orders and retention times match on 

two columns of different stationary phases. This verification technique, called dual 

dissimilar column confirmation, is useful because two chemicals that may have the same 

elution orders and retention times on one column will have different characteristics on 

the second column. 

Gas Chromatography/Flame Ionization Detectibn 

Gas chromatography/flame ionization detection (GUFID) can be used to detect organic 

compounds that can be converted to ions during exposure to flame. This kind of detector 

is especially sensitive to molecules that contain carbon and hydrogen, just as the 

GC/ECD is especially sensitive to molecules containing chlorine. Because the GC/FID, 

like the GC/ECD, cannot distinguish between individual chemicals, dual dissimilar 

column confirmation must also be performed for each sample analyzed. Related 

detectors that use flame for analyzing organic samples include the nitrogen flame ionization detector (NFID), which is especially sensitive to nitrogen- and phosphorus-containing 

molecules, and the flame photometric detector (FPD), which is especially sensitive to 

organophosphorus pesticides and other compounds containing sulfur. 

c-9 
PACKED VS. CAPILLARY COLWVNS 

Different kinds of separating columns will 

yield different results. Packed columns 

have been used routinely in the past for 

the analysis of PCBs, pesticides, and 

volatile organic compounds. Packed columns produce chromatograms of fairly 

low resolution, although the results may 

be reproducible (i.e., precise). However, 

a large quantity of the sample extract can 

be analyzed without overloading the 

instrument. More exacting analysis is 

afforded by either megabore capillary of 

fused silica capillary columns. Pesticides 

and PCBs can now be routinely analyzed 

using megabora columns, Analysis of 

volatile organic compounds can be conducted on capillary columns. However, 

because the entire sampie purge is used 

for vofatile ana@es, a packed column 

with high loading capacity may still be 

preferred if high resolution is not esbntial. If project results are dapandent on 

detailed recognition of contaminant mixtures (as is the cage with PCBs and toxaphenef, laboratories equipped with capillary columns should be aelected to 

perform analytical tasks . 

H&h Pressure Liquid Chmmatography 

Like gas chromatography, high pressure liquid chromatography (HPLC) is a technique 

used to separate a complex mixture into its component compounds. The compounds are 

carried as a liquid through solid absorbent phases and are sensed at the effluent end of 

the column by a specialized detector sensitive to, for example, ultraviolet, fluorescent, 

or infrared signals. This technique (described in EPA’s laboratory manual Test Methods 

for Evaluating Solid Waste [U.S. EPA 1986a) is useful for analyzing polycyclic aromatic 

hydrocarbon (PAH) compounds in samples because many interferents on other instruments do not emit ultraviolet or fluorescent spectra, thereby increasing the sensitivity of 

the ultraviolet/fluorescent detector to many PAH compounds. However, some compounds of interest also do not emit these characteristic spectra. It is for this reason that 

EPA’s Contract Laboratory Program statement of work for organic analysis recommends 

GC/MS over HPLC using ultraviolet/fluorescent detectors. However, HPLC can be 

useful as a way to screen samples for PAH contamination. Because it removes some 

interferents and separates the sample into components that can be individually collected 

and analyzed, HPLC can also be used as a powerful cleanup technique. 

Atomic Absorption Spectmmetry 

Two basic methods of spectrometry are commonly used to identify and measure 

concentrations of metals in a sample. Using the first method, atomic absorption 

spectrometry, the digested sample is first vaporized and then exposed to a light source 

emitting a spectrum characteristic of the target analyte. A portion of the light is 

absorbed by the analyte in the sample. The remaining light is measured by a photoelectric detector and assigned a numerical value. Because the intensity of light absorbed by 

the sample is proportional to the quantity of the target analyte present in the light’s path, 
this value represents the concentration of a metal in the sample. Several different forms 

of atomic absorption are frequently used: 

Graphite furnace atomic absorption spectrometry (GFAA) determinations 

are completed as single element analyses. With this technique, sample 

digestates are vaporized in an electrically heated graphite furnace. The 

furnace is designed to gradually heat the digestates in several stages, 

allowing an experienced analyst to remove unwanted matrix components 

and select the optimum final temperature for the metal being analyzed. 

The major advantage of this technique is that it affords extremely low 

detection limits, which are particularly essential in the analysis of arsenic, 

cadmium, selenium, or lead. Samples must be relatively clean for GFAA 

to produce usable data. 

Hydride generation atomic absorption (HGAA) spectrometry uses a chemical reaction to separate arsenic or selenium selectively from a sample 

digestate. This technique removes these two elements from the sample 

matrix, minimizing interferences and improving instrument sensitivity. 

Cold vapor atomic absorption (CVAA) spectrometry uses a chemical 

reaction to release mercury from the digestate as a vapor, which is then 

analyzed by atomic absorption. This method should be used whenever 

analysis of mercury in samples is required. 

Flame atomic absorption (FLAA) spectrometry determinations are normally completed as single element analyses, following exposure of the 

vaporized samples to either a nitrous oxide/acetylene or air/acetylene 

flame. Data produced using this technique are relatively free of interferents, however instrument sensitivity is not as great as with other forms of 

atomic absorption. 

Inductively Coupled Plasma-Atomic Emission Spectrometry 

The second widely used and cost-effective form of spectrometry is inductively coupled 

plasma-atomic emission spectrometry (ICP). Using ICP, the digested sample is first 

turned into an aerosol, then subjected to extremely high temperatures within the 

instrument. The high temperature ionizes the atoms, which produce ionic emission 

spectra uniquely characteristic of specific metals. The wavelengths of these spectra can 

then be used to identify one or many different metals in the sample, while the intensity 

of Iight can be used to determine metals concentrations. 

The primary advantage of ICP is that it allows simultaneous or rapid sequential determination of many different metals, reducing the time and cost of individual metals analyses. 

The primary disadvantage of ICP, however, is its lower degree of sensitivity. The 

detection limit associated with ICP analysis is often higher than the detection limit that 

can be obtained through the use of a graphite furnace or several other forms of atomic 

C-11 
absorption spectrometry. Although all ICP instruments use high-resolution optics and 

background corrections to minimize interferences, analysis for traces of metals in the 

presence of a large excess of a single metal can be difficult. Spectrometric data are 

reliable only if the analyte concentrations in the digestate are 5-10 times greater than the 

instrument detection limit. When concentrations are lower than this value for ICP 

analysis (as is often the case, for example, with samples containing arsenic or lead), then 

GFAA should be used. A relatively new method of detection is the use of combined 

inductively coupled plasma-mass spectrometry (ICP/MS), which not only allows for 

simultaneous determination of many different metals, but can also achieve lower 

detection limits comparable to those using graphite furnace techniques. 

c-12 
APPENDIX D 

Example Standard 

Operating Procedures 
CONTENTS 

Page 

GENERAL STANDARD OPERATING PROCEDURES 

SAMPLE PACKAGING AND SHIPPING 

EQUIPMENT DECONTAMINATION 

SPECIFIC ANALYTICAL STANDARD OPERATING PROCEDURES 

SEMIVOLATILE ORGANIC ANALYTES IN SEDIMENT AND 

TISSUE EXTRACTS 

ANALYSIS OF PAHs BY GC/MS 

ANALYSIS OF PCBs AND CHLORINATED PESTICIDES 

INSTRUMENTAL ANALYSIS OF METALS IN SEDIMENT AND 

TISSUE EXTRACTS 

SEDIMENT EXTRACTION OF SEMIVOLATILE ORGANIC 

ANALYSES 

DIGESTION OF MARINE ORGANISM SAMPLES FOR METALS 

ANALYSIS 

TOTAL DIGESTION OF SEDIMENT SAMPLES 

TISSUE EXTRACTION OF SEMIVOLATILE ORGANIC ANALYTES 

D-1 

D-3 

D-8 

D-11 

D-14 

D-18 

D-22 

D-25 

D-30 

D-34 

D-iii 
General Standard Operating Procedures 
STANDARD OPERATING PROCEDURE 

SAMPLE PACKAGING AND SHIPPING 

For samples collected during field operations that will be classified as “environmental.” 

Specific sample packaging and shipping requirements are described below. 

ENVIRONMENTAL SAMPLES 

All samples identified as Environmental Samples should be packaged and/or shipped 

utilizing the following procedures. 

Packaging 

1. Place samples into a strong container, such as a lined cooler or a U.S. Department 

of Transportation (DOT)-approved fiberboard box. The inside of the container 

should be lined with a polyethylene bag. Wrap glass jars with bubble-pack and 

surround the samples with noncombustible, absorbent, cushioning material for 

stability during transport. 

2. Seal the large polyethylene bag with two chain-of-custody seals. 

3. Place the laboratory/sampling (including chain-of-custody) paperwork in a large 

envelope and tape it to the inside lid of the shipping container (see Shipping Papers). 

4. Close and seal the outside container with several chain-of-custody seals. Tape it shut 

using fiberglass tape. 

D-1 
Marking/Labeling 

1. Use abbreviations only where specified. 

2. Place the following information, either hand-printed or in label form, on the outside 

container: 

H Laboratory name and address 

n Return name and address. 

3. Print “Environmental Samples” and “This End Up” clearly on top of the shipping 

container. Put upward pointing arrows on all four sides of the container. No other 

marking or labeling is required. 

Shipping Papers 

No DOT shipping papers are required. The following sample custody and analytical 

laboratory request forms should accompany the sample shipment. These documents 

should be taped to the inside lid of the outside sample container: 

n Chain-of-custody form 

l Sample analytical request form 

n Sample packing list. 

See the quality assurance project plan for procedures in filling out these forms. 

D-2 
STANDARD OPERATING PROCEDURE 

EQUIPMENT DECONTA MINA T/ON 

The purpose of this standard operating procedure (SOP) is to define decontamination 

procedures for field equipment used for collecting soil, sediment, and water samples. 

Techniques for ridding equipment of both metals and organic contaminants are discussed. 

Sampling equipment is decontaminated between each sampling event to avoid cross 

contamination of samples and to help maintain a healthy working environment. Protective 

clothing is worn by all field technicians during sampling and decontamination as 

described in the health and safety plan. 

It is the responsibility of the field sampling coordinator to assure that proper decontamination procedures are followed and that all waste materials produced by decontamination 

are properly managed. It is the responsibility of the project safety officer to draft and 

enforce safety measures that provide the best protection for all persons involved directly 

with sampling or decontamination. All subcontractors (e.g., drilling contractors) are 

required to follow the decontamination procedures specified in the contract, the health and 

safety plan, and this SOP. Individuals involved in sampling and/or decontamination are 

responsible for maintaining a clean working environment and ensuring that contaminants 

are not introduced to the environment. 

All equipment will be decontaminated using a series of washes and rinses designed to 

remove materials of interest without leaving residues that will in any way interfere with 

analysis of the samples taken with that equipment. In addition, the decontamination site 

will be set up at a location separate from the sampling area in order to isolate these two 

activities. 

-.-.-___ _____ 

D-3 
Field equipment blanks will be taken at a frequency of 5 percent of samples and sent to 

the laboratory(s) for analysis along with the regular samples. These blanks will serve as 

a quality assurance indicator of possible cross contamination of samples. When feasible, 

samples to be taken with the same equipment will be taken in order from lowest to 

highest suspected contaminant levels to minimize the chances of cross contamination. 

The following is a list of materials that are required on site to support decontamination. 

The quantity and actual use of each item wilI be dependent on the overall size and nature 

of the sampling effort. 

Cleaning liquids and dispensers: soap and/or phosphate free detergent 

solutions, tap water, methanol, 10 percent nitric acid, distilled/deionized 

water 

Personal safety gear as defined in the project health and safety plan 

Chemical-free paper towels and/or tissues 

Powder-free disposable latex gloves 

Waste storage containers: drums, boxes, plastic bags 

Plastic ground cloth on which to lay clean equipment 

Cleaning containers: plastic and/or galvanized steel tubs and buckets 

Cleaning brushes with non-contaminating stiff bristles 

Steam cleaning apparatus (supplied by drilling contractor). 

The materials used in decontamination activities are located a minimum of 15-30 feet 

downwind of the sampling site as designated by the task leader. Decontamination will 

be carried out before moving to the next sampling site to avoid transporting contaminants. 

.- -.--. -.- - __- - .--_ - .-.-- .- 

D-4 
PROCEDURES 

Regardless of the type of contamination that requires removal, the basic steps involved 

are the same. Procedures unique to organic, metal, and organic/metal combined 

contamination are discussed in their respective sections that follow. 

Step 1: Gross Removal of Material 

Steam Cleaning 

Depending on the availability of apparatus (e.g., drilling operations), steam cleaning 

combined with brushing is the preferred method of initial material removal. Using steam 

alone introduces little further contamination, and is a very efficient way of removing 

materials. Equipment such as spatulas, split spoons, and drill flights are placed in and/or 

suspended over tubs that catch contaminated wash waters for proper disposal. 

Detergent Wash 

In cases where steam apparatus is not available, a phosphate free detergent wash and tap 

water rinse may be used. A detergent bath is formulated in a tub large enough to hold 

the equipment to be washed leaving enough volume to hold the tap water rinses. All 

material is brushed from the equipment into the tub. The equipment is rinsed with tap 

water while suspended over the wash tub. Because detergents can contain low leveIs of 

interfering contaminants for both organic and metals analysis, the thoroughness of the 

final rinse in this step is of utmost importance. When the analyte levels in the samples 

to be taken by the decontaminated equipment are suspected to be very low (e.g., 

background level), it is recommended that the detergent wash be replaced by a distilled 

water wash or steam cleaning when available, followed by a decontamination equipment 

blank as described below. 
Step 2: Specific Contaminant Removal 

Organic Cont8rninant-s 

For removal of general organic contaminants, the solvent of choice is methanol because 

a) it dissolves all contaminants of concern and b) it is miscible with water which means 

it can be removed with a water rinse. The equipment is suspended over a tub and rinsed 

from the top down with high purity methanol delivered by peristaltic pump for large 

pieces, or a squirt bottle for smaller pieces. Rinse wastes are disposed of according to 

the project health and safety plan. 

Metal Contaminants 

Metals require acid solvents for efficient removal. Nitric acid is the acid of choice 

because of its ability to dissolve all of the metals of concern. The equipment is 

suspended over a tub and rinsed from the top down with 10 percent nitric acid delivered 

by peristaltic pump for large pieces, or a squirt bottle for smaller pieces. Rinse wastes 

are disposed of according to the project health and safety plan. 

Combined Organic/Metals Contaminants 

When equipment will be used to take samples that will be analyzed for both metal and 

organic constituents, the acid rinse is performed followed by the methanol rinse, each as 

described above. Due to the difficulty in obtaining organics free acids, and the ease of 

obtaining metals free methanol, the order of the two rinses must not be reversed. 

D-6 
Step 3: Final DistilkzdXleionized Water Rinse 

A final rinse with distilled/deionized water is carried out last to remove the contaminant 

specific solvents (i.e., nitric acid and/or methanol). Because these solvents may 

themselves interfere with sample analyses, this step is very important and must be carried 

out thoroughly. The equipment is suspended over a waste tub, and rinsed from the top 

down with distilled/deionized water delivered by pump or squirt bottle, depending on 

equipment size. In the case of metals decontamination, a simple pH monitoring 

technique (e.g., pH paper) may be used to monitor rinse water in determining rinse 

completion. 

Step 4: Air Dry 

Before an equipment blank is taken, the equipment is laid out on a clean plastic ground 

cloth and allowed to dry. The equipment should be protected from gross contamination 

during the drying process. 

Equipment Blanks 

Equipment blanks are taken between selected samplings as described in the Sampling and 

Analysis Plan. Equipment is rinsed with distilled water that is subsequently collected in 

a sample container. The rinsate sample is then labeled and shipped as a blind sample to 

the laboratory(s) with regular samples. One blank is created in this way for each 

analysis to be performed on samples taken with this equipment unless otherwise stated 

in the quality assurance plan. The equipment should be protected from contamination 

between the time the blank is taken and the time the next sample is collected. 

D-7 
Specific Analytical 

Standard Operating Procedures 

---r------- 
ERLN CHEMlSTRY GROUP 

STANDARD OPEmWING PROCEDURE FOR COLUMN CHROMATOG~ 

OF SEMIVOLATILE ORGANIC ANALYTES 

nJsEDm4ENTANDTlssuEExTRAcls 

(REVISED FEBRUARY 1993) 

1.0 0BJECnvEs 

2.0 MATERuIs AND EQUIPMENT 

9.5~mm ID x 4km gluts cw yahmnwith2oOmlr#srvoir 

Appuaaafordaerminingwcigbt 

Tqhsding b&m capabb of weighiq to 0.01 g 

n*vap (zym=k) pppntus, with ba@d water bath mainmid at 2S-3S” C 

Glass -Ihb-Vap fh&s, 200 ml 

Nitqp gas, unum, 99.9% pure 

Tumbler, ball-mill 

Glass /gndumd cylinders, 1W ad SOO-ml 
BioSil A silicic acid, 100-200 mesh 

Glass wool, SW 

3.0 METHom 

3.1 silica gel prcparaem 

3.1.1 Apprmimatcly 150 gmus of fully activated silica gel is accurately weighed 

andtnmfbmdtoaglassjar. 

3.1.2 Tbc silica gel is deactivated by adding 7.5 46 (weight basis) of pentanemcmcted dew water. TIM water is weighlDd accurately and an apppiate 

amount is added dmpwisc, - lmlatatime,tothesilicagel. Af?crcachwatcr 

addition, the jar is hand-* vigorously. 

3.1.3 TbeglaJsjaristhenplPcadoaaball-milltumbkraodallowedto~ble 

ovcmight. 

3.1.4 Aftertumbiing,timjarisranovaifromthetumbler. Tbcsilicagdis 

stmdtightlysakdinthejaratrmntun~untiluse. 

3.2 Column pnqamtioo 

3.2.1 Tbe~cohmasamsctupinringsta&inafbmehood. 

3.2.2 Glassw~l,sufficieat~~alcmthiclr;pluginthecolumn~placed 

intothcruuvoiroftbcolumn. Agla~~mdisusadtopwhtheglasswoolto 

tlK!bottoinoftbecoluma. 

3.2.3 11.5 g of the 7.5% bctiv8W silica gel is wcigbd out in a beaker. 

Appmxim8feiy3omlof~isaMwltothe~toformoslurry. The 

slunyiatbaacuaftlly~intothe~hlmn_ Tbabebriarimaiwith 

. -~,88ptlbtbbinrwW8USOf~ luaenhrto-all-is 

llalamdto~column. Thatatalvohu#of~c~shnuklbeappfo~ly 

3.3 c- class sepadma 

D-9 
level reaches the silica gel. The vial is then rinsed with an additional 1 ml of 

pentane which is also introduced to the column just before the silica gel is 

exposed. The eluate is collected in a clean round bottom flask. 

3.3.2 Asthesamplerinselevelrtachesthesilicagel,55mlofpentaneis~ 

to the column. The eluate is collectai as the F-l fraction in a clean Turbo-Vap 

flask. 

3.3.3 As the pentane level reaches the top of the silica, 36 ml of 70:30 

pentane:methylene chloride is introduced to the column. The F-2 fraction is 

collected in a separak Turbo-Vap flask from the F-l fraction. After collection, 

the flasks are kept tightly capped with aluminum foil. At no time should the 

column flow rate exceed 6 ml/min. 

3.3.4 After the F-2 fraction has been collected fkn the column, the flasks are 

placedinthemWVap. Theappantwistu~onandNitrogengasis 

introducedtotheflash. ThesolventisR!ducedtoapproximately1ml. The 

samples are then solventcxchanged to he@ane and concentnrt4dtoabout1ml. 

3.3.5 The frafztions are then transferred to bomsii glass vials fitted with 

Teflon-lined screw caps for storage until analysis. 

4.0 QUALWY ASSURANCWQU~ CONTROL 

4.1 Silica Gel Testing 

4.1.1 Silica Gel is verified to sepuate compound classes using the silica gel 

testing SOP. 

4.3 xntemd stmdud lbanmy 

4.3.1 PCB103 t addaJ to fiMl column flWion8 to caMa& recovery of the 

inteImlat8fKba 

D-10 
ERLN -TRY GROUP 

STANDARD OPERATING PROCEDURE FOR ANALYSIS 

OF PAEs BY GC/MS 

(REVISED FEBRUARY 1993) 

1.0 oBJEcTIvEs 

The objective of this document is to dd’ine the standaxd pxnceciure for analyzing marine 

environmental samples for PAHs using GUMS in electron impact/positive ion mode. 

2.0 EQUIPMENT 

HP Model 5890 Series lI Gas Chromatograph 

HP Model 5971A M&s Selective Detector 

HP Model 7673 Autosampler 

HP MS Chemstation (DOS Series) Sofbvare 

IBM Compatible Personal Computer 

3.0 OPERATION 

A. Instrument Parameters 

Column: 60 m x 0.25 mm ID x 0.25 urn DB-5 (J&W Scientific) 

Carrier: Helium at 25 psi; 0.8-l .O mVmin 

lnjectorz 270 degrees C; splitless mode, puge on at 0.8 min 

xlmfbcc: 300 degnss c; direct, soum 200 degrees c 

Temperature Pxqram: 1 min, 40 deg; 20 deg/min to 120 deg; 10 deg/min to 310 deg 

and hold 16 min. This is suitable for PolycycLic Aromatic Hymns. 

MS Parameters: Set by Autotune u&g PFTBA as the calibration compound; Manual 

TilIEisthenusedtoforcethe 131 and219abUdUxu to20to4Opercentofthe 

69basepeak;thte~mu~lierhtbensettomeathe~uinmentsofthe 

particuiarmethod. ~procbdure~&ae~aseriesofloops,aJaewparameter 

sdtings for a spacifk lens will affix% the bvior of the others. 

B. Daily perforrm#x Checks 

1) Adequate DFTPP qaztrum (see attached criteria), based on a 50 ng injection. 

2) Calibration Check - results for a mid-level standad must be within 25 percent of the 

true value for a single target compound; the average ennr for all compounds in 

themethodmustbelessthan15penzent. 

D-11 
C. Calibration 

The calibration method is a 5 point, intemal standard, least squares fit, forced through 

the origin. The levels are chosen to cover a range from 4 to 10 times the instrument 

detection limit for the lowest point, up to the point at which saturation and/or non-linear 

behavior is observed. For PAHs in marine sediment or tissue, the cumnt levels are 1 .O, 

5.0, 10.0, 15.0, and 20.0 ng/ul. Acceptance criteria for each level are the same as listed 

for the daily check. 

D. Sample Analysis 

A 250 uL aliquot of the sample extract is blown down to 20-25 UL with nitrogen or 

helium. If required, an internal injection standard is added (4-chloro-pterphenyl) . Once 

the daily performance checks are satisfied, the extracts are queued up on the 

autosampler. Periodic solvent blanks, standards, etc. axe inserted at the judgement of 

the analyst. 

E. Identifi&on 

Compounds are identified by monitoring a characteristic ion within a 12 second rdention 

time window. Additional ions may be monitoti at the discretion of the analyst. 

Confirmationisobtai&by&pectionoftheMlmassspectnun. 

4.0 QUALIW ASSURANCE 

A. Standand Reference Mate&l& Blanks, Calibration Checks 

Standard nference materials are prepusd along with each batch of samples. Calibration 

WdaKisareverifIedwithindapadeatlypRparedamtrolsta&uds. 

Method de&cth l&h m dehermi#d i&pa~WQ for a given sample matrix. 

~&@cWlimita~~mllyinthc640pgperinjectionrange, whichusually 

correspoadr~a3-5n%g@9b)merboddetactioalimitnnseinsamples. 

5.0 TROUBLESHOOTING AND MAINTENANCE 

Ona~ybasis,theinjectionportandliaet~c~;tbeseptumaadglasswoolin 

theliaerarec~~.Itisperiodicallynaassarytobr#lroffthe~fewinc~ofthe 

column (this is done daily for heavy workloads of dirty samples; compounds most 

affkted are the high molecular weight compounds). 

D-12 
Mass Abundance 

51 3040% of mass 198 

68 Lesstban296ofmass69 

70 Lessthan2%ofmass69 

127 4040% of mass 198 

197 Lessthanl%ofmass198 

198 Base peak, 100% relative abundance 

199 5-946 of mass 198 

275 lO-30% of rmws 198 

365 Gnater than 1% of mass 198 

441 Lbssthlmass443 

442 4040% of mass 198 

443 17-23% of mass 442 

DFTPP ACCEPTANCE CRlTERIA (by CLF 3/90) 

D-13 
l.iI 

2.0 

3.0 

ERLN CHEMISTRY GROUP 

STANDARD OPERATING PROCEDURE FOR GAS CEIROMATOGRAPHIC 

ANALYSIS OF PCBS AND CBORINATED PESTICIDES 

(REVISED FEBRUARY 1993) 

The objective of this document is to define the standard procedure for analyzing marine 

environmental samples for polychlorinated biphenyls (PCBs) and chlorinated hydrocarbon 

&cides using gas chromatography and electron capture detectors. 

EQIJImmT USED 

Hewlett Packard 5890 Gas Chromatogmphs equipped with electron capture detectors (Ni 

63), automatic samplers, 30 m DB-5 fwad silica qillary columns (0.25 p film 

thickness, 0.25 mm i.d.). Perkin-Elmer/Nelson so&are (ACCESSTHROM) provides 

for collection and storage of raw chn)nWographic data, and for selection and quantitatio& 

of analyte paks. Ultra high purity helium and 95/5% Argon/Methane gases are used 

as the carrier ad auxiliuy gas reqectively. 

OPERATION 

3.1 Instrum~checks~priortodatacollection 

3.1.1 Gas supply 

3.1.1.1 Check gas cylinder pressums. Rcplacetankifpressu&sless 

than1oopsig. 

3.1.1.2 Ckckheadpressuregaugeonfrontpa&ofinstrumeat. Gauge 

sharldrsrd18psig;adiusttocorrsctscttinsifndingishigh;chackfor 

lcakaifp1~8~~islow. Thissettingpnwiduforacarriergasflowof 

. appirnumrtely 1.5 ml/min. 

3.1.1.3 Replace injection port sqtum. C&k septum nut and column 

fittinss~leabwithlakderectorandtightmasnecessary. 

3.1.1.4 Chacktheauxiliarygwflow.Aflowof35mVminisnquired. 

3.1.1.5 Cbeckseptumpuqeabdsplitflows. Adjustto 1 and35 dmin, 

Eqectively, as lnxxssq. 

D-14 
3.1.2 Instrument output signal 

3.1.2.1 Display the analog output signal from the detector on the LED 

panel of the GC. Record the value in the instrument log book, and check 

for consistency with previous readings. On instntments with dual 

detectors, ensure the signal is correctly assigned to the detector sekted 

for the analysis. 

3.1.3 Insuument operating parameters 

3.1.3.1 Temperature programs and run times are stored as workfiles in 

each GC’s integrator. The following conditions are required for the 

analysis of PC& and pesticides: 

Injection port temperature 

Detector temperature 

Initial column temperature 

Initial bold time 

Rate1 

Ramp 1 finaltemperature 

Ramp 1 hold time 

Rate2 

Ramp 2 fural tcmpcIaturc 

Ramp 2 hold time 

Rat.83 

Final column temperature 

Final hold tbne 

stop time 

Injection port purge open time 

275°C 

325 “C 

100°C 

lmin 

5°c/min 

140°C 

lmill 

1.5”cYmin 

230°C 

20 mill 

10°C/min 

3OOOC 

5alin 

1OOUIiCJ 

lmin 

3.1.3.2 Load an appropriate workfile into the integrator. 

3.1.3.3 Enter the autosampler pu8meten into the intqator via Option 

11. Micatu which injection port is being used, the number and positions 

0ftb8 sungha in the autoaampler tny, the number of injections per bottle, 

andtb8.8mount~~(l ul). 

3.1.3.4 Check the signal asaignmcats and levels again. If they are 

comet, store the workfile in the btqxator. 

3.2 Data system setup 

3.2.1 Scheduling of standad ad samples 

O-75 
3.2.1.1 Setting up the instrument queue is accomplished by following 

instructions laid out in the Perk&Elmer Nelson manual. 

3.2.1.2 Order the samples, standards, and rinses according to the 

following guidelines: 

-place hexane rinses before and after standards 

-bracket groups of no more than five (5) samples with standards. 

-arrange multiple level standards so that a high and a low standard 

piece& as well as follow samples 

-procedural and field blanks should be run prior to samples to 

minimize risk of carryover contamination. 

3.2.1.3 Type in sample weight and internal standard amounts for each 

sample to be used in final concentration calculations. Double check all 

manually entered values for accuracy. 

3.3 Instnlment startup and data collection 

3.3.1 Aftertheiostnrmenthasbeenschactulad,arrangetbesampleJandstandatds 

to be run in the autosampler trays. Check the order for accuracy against a copy 

of the queue. Load the trays into the autosampler. 

3.3.2 Visually recheck tank regulator gauges and instrument settings to ensure 

proper settings. 

3.3.3 StartGCoperation~~collectionbyprtssing’start’onttseintegrator. 

3.4 Peak identification and qua&&ion 

3.4.1 Peak i-on is accomplished by automated routines. Identifications 

are~oacomparisoaofraentioatimesofactualstaadardstountrnownpeaks. 

Multilevel star&r& ate calibrated to generate a linear ngiession curve of 

mpofm acadiq to the manufacturer’s in&uctions. After a calibration curve 

haabeurge#iatad,thesampluareanalyzed. Analytesarequantitatedbasedon 

thaparkanrsforthe~~aadinte~standard,theamountoftbeinttrnal 

standad, and the response factors genetated from the calibration curve. 

Chromotoenmsanddatanporwaregclmatcdforeachsample~surndatd. 

4.0 QUALITY ASSURANCE 

4.1 Cbws of standa& are compared to posted references. Peak 

i&&fi&cmg, resolution sod shape8 are inspec&. calculated stabdard amounts are 

checkd for accuracy and documented. Other abnormalities, such as spurious or extra 

peaks, rising or falling baselines, and negative spiking are examined. Response factors 

D-16 
and overall instrument response are compared to previous runs and documented. Blanks 

are checked for the p- of interferences or analytcs of interest. Unknown samples 

axe compared to standa& to verify peak identifications. 

5.0 TROUBLESHOOTING 

5.1 Refer to the ERLN GC Troubleshooting notebook, the manufacturer’s manuals, or 

to experienced personnel for guidance in troubleshooting the GCs. 

D-17 
ERLN CHEMISTRY GROUP STANDARD OPERATING PROCEDURE 

FOR INSTRUMENTAL ANALYSIS OF METALS 

IN SEDIMENT AND TISSUE EXTRACTS 

1.0 OBJECTIVES 

The objective of this document is to outline the proper sample preparation and 

instrumental parameters for the analysis of trace metals in marine sediment or tissue acid 

digests. 

2.0 MATERIALS AND EQUIPMENT 

Atomic Absorption Spectrometer or Inductively Coupled Plasma Atomic Emission 

Spectrometer 

Reagent grade Insna-Analyzed concentrated HNO, for trace metal analysis (diluted to 2M 

concentration) 

3.0 METHODS 

3.1 Standard Calibration 

3.1.1 Estimate or determine the range of concentrations that exist within the 

sample analytes. This may require scanning several samples prior to standard 

calibration in order to approximate the range of absorbances (AA) or emission 

intensities (ICP) produced from the samples. 

3.1.2 Prepare multiple calibration standards that bracket the expected range of 

sample analyte concentrations. The composition of the standard matrices (i.e. acid 

strength and salt content) should match that in the samples as closely as possible. 

3.1.3 Analyze the standards and calculate calibration equations by regression 

(linear or polynomial) of standard concentrations against measured standard 

absorbance9 or intensities. 

3.2 Sample Dilutions 

3.2.1 In section 3.1 the expected range of sample concentrations is determined. 

If sample concentrations exceed the upper limit of the chosen analytical technique, 

then the sample analytes will need to be diluted to fall within the range of 

standard concentrations. Sample diluent should be of the same acid composition 

and strength present in the sample analytes (Keep close record of the sample 

dilutions so that raw analytical concentrations can be dilution-corrected). 

D-18 
4.0ANALYSI.s 

4.1 Sample Analysis (Unknown Concentrations) 

4. I. 1 Analyze the samples and record the absorbances (AA) or emission intensities 

(ICP). 

4.1.2 Triplicate readings should be made for every element. 

4.1.3 After approximately 10 (AA) or 20 (ICP) samples, several calibrarion 

standards should be ix-analyzed to determine instrumental drift. 

4.2 Concentration Calculation 

4.2.1 Calculate sample concentrations by applying the calibration equation 

obtained from the standard curve to the measured sample signals (absorbances or 

intensities). Calculate the mean and standard deviation of the individually 

calculated sample concentrations. 

4.3 Dilution Correction 

4.3.1 Calculated analyte concentrations must be dilution- corrected to obtain the 

true metal concentration present in the sample. The analyte concentration, in 

ug/mI, is converted to ug/g dry sampie by inputing the sample prep. information 

into the following equation: 

Anaiyte conc.(ug/ml) X Acid volume (ml.) 

Sed Cont. (ug/g dry sed.) = 

dry sed. wt. (g) 

5.0 QUALITY CONTROL 

5.1 Determination of Analytical Accuracy (Calibration check) 

5.1.1 Analyze several standards as unknown samples to check the accuracy of the 

standard ctuve regression. Recoveries should be within 10% of the standard 

concenawion. 

5.1.2 Analyze a solution of known and/or certified concentration, prepared 

independently from the calibration standards, to determine the daiiy analytical 

fluctuation. Recoveries should be within 10% of the certified concentration, 

5.2 Standard Additions (Spike Additions) 

5.2.1 Standard additions am required to investigate instrumental interferences 

arising from differing sample solution matrices. 

o-19 
5.2.2 Select a sample whose concentrations can be matched fairly closely with a 

dilution of a calibration standard. 

5.2.3 Prepare an acid spike (a dilution of a calibration standard) in the same acid 

matrix as the samples. Try to match spike concentrations as closely as possible 

with the sample chosen. 

5.2.4 Prepare a sample spike by removing a second sample aliquot and adding the 

same amount of calibration standard as was used in the acid spike. The total 

volume of sample spike should also be equal to the total volume of acid used in 

the acid spike. 

5.2.5 Analyze the sample, acid spike and sample spike as unknown samples. 

5.26 Calculate the spike recovery using the following equation: 

C SAMPLE SPIKE - CSAMPLe 

R(%) = 

C ACID SMKE 

5.2.7 Acceptable spike recoveries fall between 80-120% 

5.2.8 One out of every 20 samples should be chosen for a standard addition. 

6.0 DETECTION LIMITS 

6.1 Instrument Detection Limits 

61.1 Instrument detection limits are determined as the concentration equivalent 

to a signal three times the standard deviation of a blank. The limits should either 

be determined previously for given instrumental conditions or as part of the 

instrumental data analysis, and should be comparable to those listed below: 

o-20 
cu 

Zn 

Cr 

Pb 

Ni 

Mn 

Fe 

Cd 

Al 

Sn 

Sb 

As 

42 

ICP GFAA 

(ug/ml) a/u 

.020 

.oQ5 

,020 

.050 

.050 

.OlO 

.020 

.005 

.075 

.050 

.lOO 

.lOO 

.020 

1.0 

0.1 

1.0 

3.0 

2.0 

0.5 

2.0 

0.5 

2.0 

2.0 

2.0 

0.5 

61.2 Sample Detection Limits, assuming a dry weight of 2 grams and a total 

volume of 50 mls. (ie. sediment ultrasonic extraction mthod), art 25 times higher 

than the instrument D.L.‘s. Method detection limits should be calculated following 

the rigorous statistical procedure detailed in 40 CF’R Part 136. 

o-2 1 
ERLN -TRY GROUP 

STANDARD OPERATING PROCEDURE FOB SEDIMENT EXTRACTION 

OF SEMIVOLATXLE ORGANIC ANALYTES 

(REVISED FEBRUARY 1991)) 

2.0 MA- AND EQUIPMENT 

Appmtus for homogenizing scdimca 

wrist-action !ilukcr 

1OOmiglMSCXXUifUgMUbCS 

AppalaWforckterminingwcightanddryw~ 

Toploading balance capabbe of weighiq to 0.01 g 

. 

AlUWUttWeighing~ 

S~stccl~ 

Drying oven tlulinw at 10s120°C 

Tinbvap (ZytMrk) agpuatus, with katal w8ter m8ink.d 8t 2s3S”C 

Nim &rs, c-m=4 !WM plrs 

Glass lIdNap flaaka, 200 ml 

Glassgmdutdcy~,100-and~ml 

Erbnmeycr fl88k8,2m all 

Microliter syringes or micm, sohmt rimal 

Borosiliatc gkw viala with Tefloa-lid ~CIBW capa, 2-ml 

3.0 METEODS 

3.1 Find the umcct caps for each ccntd@ tube to be ud by filling tkm with 

o-22 
approximateAy 25 mls of methylenc chloride, putting the caps on and rolling the tube on 

the lab bench on a paper towei and look for leaks. Once the correct tubes and caps have 

been matched, weigh approximately 10.0 g of homogenized sample into a solvent rinsed 

centrifuge tube. Homogenization is accomplished by physical mixing of the sediment with 

stainless steel or Teflon coated utensils, or by a polye&ylene propeller attached to an 

electric drill. The amount of sample may be adjusted basai on expected contaminant 

concentrations or detection limits required. Weigh approximately 2.0 grams into a 

preweighcd aluminum pan for dry/wet determination. 

3.2 Add Internal Standards as required: CBl% for PCB analysis, 2,5dichlom-mterphenyl for pesticides, and d12 Bcnzo(a)anthrace& d10 wenanthrene mix for PAHs. 

The amount of IS added is dependent on the expected con&minant concentrations and 

should be equivalent to those ConcentIations. 

3.3 Add30gSodiumsulfateandmixwithatcfloncoatcdspatulaverywell. Thenadd 

50 ml 20:80 acetonc:mcthylcne chloride. 

3.4 Seal the cmtxifbge tubes with teflon tape and caps, and sh&c - 15 hrs. (overnight). 

Shake tubes at approximately a 60” angb, at an intensity sdting of “5”. Cectt&ge for 

20minutesat17501pmandpouroffthe sqmatantinEoanerlenmeyerflask. 

3.5 Add 50 ml of 20:80 acctone:methylene chloride, seal and shake a8 above for - 6 

hn. Centrifuge for 20 minutes at 1750 rpm and add the supernatant to the erlenmeyer 

flask. Add some additional sodium sulf’ate to the combinai extracts to ensure all water 

is excluded. 

3.6 Gravity filter the extract thmugh a pmrinsed (methylenc chloride) glass fiber filter. 

Rinse the erknmeyer 2 x with methykme chhide, and the filter itself once. Collect the 

f~trattinacleanrinsed200ml~Vaptu~.~theflaskintothe~Vap 

apparatus, aadnrmonttrewit.Openth6valveontbenitrogentankardadjusttbe 

regulator to ensure a prusum of 15 psi. Raluce tba sampb volt to approximately 1 

ml, with solvent exchange to pentane. 

3.9 Adjust ttm voluaw to 1 ml with barn.. 

3.10 Fractionate the sample following the Column chmrmtognphy SOP. 

4.0 OPTIONAL cLEANuPPRocEDuREs 

Activated copper powder (activated by the addition of 8 M hydrochloric acid and rinsa! 

with the following solvents in succession: deionized water, methanol, mcthylcne 

chloride, and bane) may be a&hi to the extract to remove any f&e ebmetttd sufir. 

The copper is added until the formation of black copper suffide no longer occurs. 

O-23 
5.0 QUW A!SSURANCWQUALEY CONTROL 

5.1 standard Refexence lmaials 

5.1.1 A certified SRM is prepared with each batch of samples to validate 

analytical recovery. Results are compared to certified concentrations and 

corrective action is required if tbc accuracy is outside of the squired 

SpCCifhltiOIlS. 

5.1.2 SRMs should be prepand in the exact same manner as the unknowns. 

5.2 Analytical Repnxhlcibility 

5.2.1 Replicate samples should be prepared to assess the reproducibility of the 

extraction procedure. 

5.2.2 For every batch of sampks, one sample should be chosen to extract and 

analyze in triplicate. Deviation between replicate samples should be ~30%. 

5.3 Pmuxhd Blanka 

5.3.1 Procedural blanks should be carried tko@out the entire extraction 

p~toverifytheabseaceofcoataoninatioaofthemethod. 

5.3.2Taceam~ofaarmlytesintheblnnb(lessthpathr#timutbem~ 

detection limit) may be ignored aad have no dfact on the subsequent sample 

analyses, but samples should be rejected ifsigniiicantconcentrations (greater than 

five times the MDL) arc present in pruahzal blanks. 

5.3.3 One blank should be pqared for each batch of samplea (minimum 

frequency of 5%). 

D-24 
ERLN CHEMISTRY GROUP STANDARD OPERATING PROCEDURE 

FOR DIGESTION OF MARINE ORGANISM SAMPLES 

FOR METALS ANALYSIS 

1.0 OBJECTIVES 

The objective of this document is to establish the standard operating procedure for the 

total digestion of marine tissue samples. Sample extracts aie routinely analyzed by Flame 

Atomic Absorption Specrrometry (FAA), Graphite Furnace Atomic Absorption 

Spectromeay (GFAAS) or Inductively Coupled Plasma Atomic Emission Spectrometry 

(ICP-AES). 

2.0 MATERIALS AND EQUIPMENT 

Top-loading balance (0.01 gram precision) 

Vacuum Freeze Dryer 

CEM Microwave Digestion System (Including 100 ml. Teflon vessel liners and pressure 

control capability) 

50 ml. class A volumetric flasks 

60 ml. polyethylene screw-cap bottles 

Instra-Analyzed grade concentrated HNO, for trace metal analysis (70-71 960) 

Hydrogen Peroxide - H,OZ (30%) 

Vacuum filtering apparatus with Whatman 42 filter paper 

3.0 METHODS 

3.1 Sample Preparation 

3.1.1 Organism samples shouid be thawed, and handled only with plastic or 

stainless steel utensils. When neccessary, organism tissues should be 

homogenized. If chromium or nickel is to be analyzed in the samples, the 

homogenizer tip should be constructed of titanium to avoid contamination of 

sample tissues. 

3.1.2 Obtain the tare weight of labeled, acid-washed 100 ml. Teflon microwave 

digestion vessel liners. 

3.1.3 Weigh approximately 3-5 grams wet tissue into each vessel (-0.5 grams 

dry). Obtain the wet gross weight of each tube. 

3.1.4 Freeze dry samples and obtain the dry gross weight for each sample. 

Subtract the tare weight and record the weight of dry tissue in each tube. 

D-25 
3.2 Closed Vessel Microwave Digestion (1st Stage) 

3.2.1 Add 10 ml. of concentrated HNO, (70-71 %) to each digestion vessel. 

3.2.2 Make sure the tissue sample is fully saturated and allow to sit for a 

minimum of 1 hour, or until all foaming subsides. 

3.2.3 Place each liner into a microwave vessel. 

3.2.4 Insert a pressure relief membrane into each cap assembly and place on top 

of the vessels. (use the modified cap assembly for the vessel to be used for 

pressure monitoring) 

3.2.5 Place a top on each vessel and hand tighten. 

3.2.6 Place the vessels into the carousel. 

3.2.7 Insert a vent tube into each vessel, place the free end in the center trap, 

then place the carousel into the oven. 

3.2.8 Connect the pressure sensing line to the modified cap assembly. (make sure 

the valve on the side of the oven is in the “neutral” position) 

3.2.9 Program the oven following the parameters below: 

STAGE 2 5 

%POWER 85 85 85 85 85 

PSI 20 40 85 150 190 

TIME 15:OO 15:OO 15100 15:Oo 15:OO 

TAP 5:OO 5:oo 5:Oo 5:00 5:00 

FAN SPEED 100 loo 100 loo 100 

** Note - Power settings an for 12 vessels. If a different 

# of vessels is desired, subtract or add 5% power 

per vessel. 

3.2.10 AfIer completion of the program, allow the pressun in the control vessel 

to drop below 20 PSI, then manually vent the control vessel, remove the pressure 

sensing line and place the carousel into the fume hood. 

3.3 Closed Vessel Microwave Digestion (2nd Stage) 

3.3.1 Manually vent each vessel, remove the caps and add 2 ml. of 30% I$02. 

3.3.2 Allow the reaction to subside, then reassemble the vessels as described in 

D-26 
sections 3.2.4-3.2.6. 

3.3.3 Place the carousel into the oven and reconnect the pressure sensing line to 

the control vessel. Check to ensure the exhaust fan is operating. 

3.3.5 Program the oven foilowing the parameters below: 

STAGE 

‘%POWER 85 100 

PSI 100 100 

TIME 1590 15100 

TAP 590 590 

FAN SPEED 100 100 

** Note - Power settings are for 12 vessels. If a different 

# of vessels is desired, subtract or add 5% power 

per vessel. 

3.3.6 Although the oven is automated, individual tissue samples will react 

differently, so all steps should be monitored in case venting should occur. If 

venting does occur, remove the vented vessels and lower the power accordingly. 

3.3.7 After completion of the program, allow the vessels to cool in the oven until 

the pressure in the control vessel is below 20 PSI. 

3.3.8 Manually vent the control vessel, then remove the carousel and place in a 

fume hood until the liquid reaches room temperature. 

3.3.9 Remove the vent tubes and manually vent the remaining vessels. 

3.4 Sample Filtration 

3.4.1 Remove the tops and rinse the lids with deionizecl water, catching the rinse 

in the vessel liner. 

3.4.2 Add -15 ml. of deionized water to each vessel. 

3.4.3 Using plastic tweezers, place a sheet of Whatman 42 filter paper in a 

vacuum filtration funnel and wet the paper with 2M HNO,. 

3.4.4 Place a 60 ml. acid-cleaned polyethylene bottle and vacuum gasket under 

the filter funnel and apply vacuum. 

3.4.5 Filter the digested sample through the paper and collect the filtrate in the 

D-2 7 
bottle. 

3.4.6 Rinse the digestion vessel with deionized water, filter and collect the filtrate 

in the bottle. 

3.4.7 Pour the combined filtrates into a 50 ml. acid-cleaned volumetric flask, and 

dilute to the mark with deionized water. 

3.4.8 Shake the solution thoroughly and transfer back to the acid-cleaned 60 

ml. polyethylene bottle. Label the bottle appropriately. 

4.0 QUALITY ASSURANCE 

4.1 Standard Reference Materials (SRM) 

4.1.1 A certified SRM should be prepared with every batch of samples to validate 

analytical recovery. 

4.1.2 SRMs should be prepared in the exact manner as the unknown samples, 

including drying, even if the material is already dry. 

4.1.3 The frequency of SRM preparation should be approximately 1 for every 20 

unknown samples prepared. 

4.1.4 The outlined extraction technique should yield close to 1009b recoveries for 

organism SRMs, as outlined in the ERLN QA/QC guidelines. 

4.2 Analytical Reproducibility 

4.2.1 Replicate samples should be prepared to assess the reproducibility of the 

digestion procedure. 

4.2.2 For every 20 samples ptepared, one sample should be chosen to digest and 

analyze in triplicate. The relative standard deviation between replicate analyses 

should be ~20%. 

4.3 Procedural Blanks 

4.3.1 Procedural blanks should be carried throughout the entire extraction 

procedure to verify that contaminants are not present in the reagents and that no 

contamination has occurred throughout the procedure. 

4.3.2 Trace amounts of metals in the blanks can be subtracted from subsequent 

sample analyses (blank subtraction), but a sample batch should be rejected if 

concentrations in the blank are >1096 of “average” sample concentrations. 

D-28 
4.3.3 One procedural blank should be prepared for every 20 samples extracted. 

D-29 
ERLN CHEMISTRY GROUP 

STANDARD OPERATING PROCEDURE FOR TOTAL DIGESTION 

OF SEDIMENT SAMPLES 

1.0 OBJECTIVES 

The objective of this document is to establish the standard operating procedure for the 

total digestion of bulk sediments. Sample digests are routinely analyzed by Flame Atomic 

Absorption Specuometry (FAA), Graphite Furnace Atomic Absorption Specnomtny 

(GFAAS) or Inductively Coupled Plasma Atomic Emission Spectrometry (ICP). 

2.0 MATERIALS AND EQUIPMENT 

Top-loading balance (0.01 gram precision) 

Vacuum Freeze Dryer 

CEM Microwave Digestion System (Including 100 ml. Teflon digestion vessel liners with 

pressure control capability) 

Protective Clothing (Polyethylene apron, Neoprene gloves, Safety goggles, Face shield) 

100 ml. class A volumetric flasks 

125 ml. polyethylene screw-cap bonles 

Instra- Analyzed grade concentrated HNO, for trace metal anaiysis (70-71 %) 

Reagent gra& concentrated HF (49%) 

Reagent gra& concentrated HCL (36.5-38%) 

Boric Acid (5%) prepared from H,BO, crystals 

Deionized water 

3.0 METHODS 

3.1 Sample Preparation 

3.1.1 Sediment samples should be thawed and homogenized with plastic or 

stainless steel utensils. 

3.1.2 Obtain the tare weight of labeled, acid-washed 100 ml. Teflon microwave 

digestion vessels liners. 

3.1.3 Weigh approximately 1.5 grams wet sediment into each vessel (-0.5 grams 

dry). Obtain the wet gross weight of each liner. 

3.1.4 Freeze dry samples and obtain the dry gross weight for each sample. 

Subtract the tart weight and record the weight of dry sediment in each liner. 

3.2 Microwave digestion 

** NOTE- Be sure to wear proper safety clothing when working with the 

concentrated HF. 

D-30 
3.21 Add 5 ml. of concentrated HNO, (70-71 %), 4 ml. of concentrated I-IF (49%) 

and 1 ml. concentrated HCI (36538%) to the vessel liners. 

3.2.2 Make sure the sediment is fully saturated and allow to sit for a minimum of 

1 hour. 

3.2.3 Place the liners into their corresponding vessels. 

3.2.4 Insert a rupture membrane into each lid and secure into place with a cap. @ 

not overtighten. 

3.2.5 Place the vessels into the carousel. 

3.2.6 Insert a vent tube into each vessel and place the free end into the center 

trap. 

3.2.7 Attach the pressure sensing line to thhe control vessel, making sure the lever 

on the side of the oven is in the “neutral” position. 

3.2.8 Program the oven following the parameters below: 

STAGE 1 2 

%POWER 100 100 

PSI 120 150 

TIME 30:oo 15:oo 

TAP 20:oo lo:OO 

FAN SPEED 100 loo 

or add 5% power per vessel. 

**Note - Power settings are for 12 vessels. If a 

different # of vessels is desired, subtract 

3.2.9 Although the oven is automated, individual sediments will react differently, 

so all steps should be monitored in case venting should occur, If venting does 

occur, remove the vented vessels and lower the power accordingly. 

3.2.10 When the program is finished, allow the pressure in the control vessel to 

drop below 20 PSI. 

3.2.11 Manually vent the control vessel, detach the pressure sensing line and place 

the carousel in a fume hood. 

3.2.12 Remove the vent tubes and vent the remaining vessels manually. 

3.2.13 In a fume hood, remove the caps and rinse the lids with deionized water, 

catching the rinse in the vessel liner. 

D-3 7 
3.2.14 Add 30 ml. of 5% Boric acid to each sample. 

3.3 Sample Filtration (This step may not be necessary) 

3.3.1 Add -15 mi. of deionized water to each vessel. 

3.4.2 Using plastic tweezers, place a sheet of Whatman 42 filter paper in a 

vacuum filtration funnel and wet the paper with 2M HNO,. 

3.3.3 Place a 120 ml. acid-cleaned polyethylene bottle and vacuum gasket under 

the filter funnel and apply vacuum. 

3.3.4 Filter the digested sample through the paper and coilect the filtrate in the 

bottle. 

3.3.5 Rinse the digestion vessel with deionized water, filter and collect the ftitrate 

in the bottle. 

3.3.6 Pour the combined filtrates into a 100 ml. acid-cleaned volumeuic flask, and 

dilute to the mark with deionized water. 

3.3.7 Shake the solution thoroughly and transfer back to the acid-cleaned 120 

ml. polyethylene bottle. Label the bottle appropriately. 

3.4 Sample Dilution (Required only if filtration step was omitted) 

3.4.1 Transfer the contents of the vessel liner to a clean 100 ml. volumetric flask 

and rinse the vessel with deionized water, also adding the rinse to the flask. 

3.4.2 Dilute to the volume mark with deionized water. 

3.4.3 Shake the extracts thoroughly and transfer into acid-cleaned 125 ml. 

polyethylene screw-cap bottles. 

3.4.4 Label the bottles appropriately and store at room temperature until analysis. 

4.0 QUALITY ASSURANCE 

4.1 Standard Reference Materials (SRMs) 

4.1.1 A certified SE&i should be prepared with every batch of samples to validate 

analytical recovery. 

4.1.2 SRMs should be prepared in the exact manner as the unknown samples, 

including drying, even if the material is already dry. 

D-32 
4.L3 The frequency of SRM preparation should be approximately 1 for every 20 

unknown samples prepared. 

4.1.4 The outlined extraction technique should yield close to 100% recoveries for 

sediment SRMs. 

4.2 Analytical Reproducibility 

4.2.1 Replicate samples should be prepared to assess the reproducibility of the 

digestion procedure. 

4.2.2 For every 20 samples prepared, one sample should be chosen to digest and 

analyze in triplicate. The relative standard deviation between replicate analyses 

should be ~20%. 

4.3 Procedural Blanks 

4.3.1 Procedural blanks should be carried throughout the entire digestion 

procedure to verify that contaminants are not present in me reagents and that 

contamination has not occurred throughout the procedure. 

4.3.2 Trace amounts of metals in the blanks can be subtracted from subsequent 

sample analyses (blank subtraction), but a sample batch should be rejected if 

concentrations in the blank are >lO% of “average” sample concentrations. 

4.3.3 One procedural blank should be prepared for every 20 samples digested. 

D-33 
ERLN tZHEMISTRY GROUP 

STANDARD OPERATING PROCEDURE IeoR TMUE EXTMCTION 

OF SEMI’VOLATILE ORGANIC ANALYTES 

tREvI!sED FEBRUARY l!m 

1.0 0BJEcnvEs 

Theobjactiveofthisdocument~to~thestandardogarpainsp~nforthe 

extraction of semi-volatik organic compaunds from rmrine tissue samples. The extracts 

will be further &anal up by silia gel cbromatogqhy pruduns prior to analysis by 

ga!3 chro~hy (Gc) or gas chromatography/masspammay (GCMS). 

2.0 MATERIALS AND EQUIPMENT 

Appaau3fordeberminingweightddryweig&t 

Tap-loading tmh~ capable of weighing to 0.01 g 

Aluminum weighing pans 

S~StCCispatuk 

Drying oven uuhhmhd at 10s12O’C 

D-34 
temperature. 

Internal Standa&, to be added to each sample prior to extraction. 

3.0 MElmoDs 

3.1 Weigh approximately 10.0 g of sample into a solvent rinsed centrifuge tube. Weigh 

approximately 1.0 gram into a preweighed aluminum pan for dry/wet determination. 

3.2 Add Internal Star&r& as required: CB198 for PCB analysis, 2,5dichloro-mterphenyl for pesticides, and d12 Benzo(a)Anthmcene and d10 Phenanthrene mix for 

PAHs. The amount of IS added is depen&nt on the expected co-t concentrations 

and should be equivalent to those concent&ons. 

3.3 Add 50 ml acetonittile. 

3.4 Polytron the samples for 20 seconds, at a speed setting of - 5. Centrifuge for 10 

minutesat1750rpmaadpouroffthesupernatPntintoasepauotolyfwntlcoatPining500 

mlpentaneextmcteddeioni&water(DI). Rcpeatthissteptwomorctimes. 

3.5 Pack extract the DI/ACEI’ONITRIIB phaseinthesepamtoryfunne1with3x50 

mlpentane. Aftereachadditionofpentaaehasbaen.phalrcn,dnwofftheboaomlayer 

into a 500 ml erlenmeyer flask. Decant the &Mane layer into a 250 ml erlenmeyer fIask 

by pouring it out the top of the sepamtory funnel. This way the tmnsfer of water into 

the pentane extract will be avoided. 

3.6 Transfer the water layer from the 500 ml ericnmeyer flask back into the sqmratory 

funnelforeverya&litionofpentane. Rinsethe5oOmlflask3xwithPentarEandadd 

therinsestothesepUatoryfuMc1. 

3.7 Combinethepentaneextxactsand&yoverSodiumSulf&e. 

3.8 Ttansferthesampletoa200mlI‘u~Vapflask. Rinaethefhuk3xwithpentane 

andaddtlerinseato~flask. Placethcflaskintothe~vapagparatus,andturn 

ontheunit. Opent&valveonthenitrogentankandsetthequlatortoensurea 

ptessulBof15psigisn!!achingtheTulbHapunit. Reducethovolumeofsampleto 

appIhmately 1 ml. 

3.9 Adjust the volume to 1 .O ml with pentane. Remove 0.1 ml of sample into a 

preweighed aluminum pan for lipid weight de&mm&n. Allow it to dry at mm 

temperature for at least 24 hours. Record the weight of the pan plus the sample. 

3.10 Fractionate the sample following the Column ChlxmMqqhy SOP. 

4.0 QUALITY MSUMNCE/QUALl’IY CONTROL 

D-35 
4.1.1 A ccrtifki SRM is pxqarcd with each batch of samples to validate 

analytial-cry. Analyticalr#ultsshouldthcabecom~tothecertified 

concentrations. Corrective action is quid if the quircd accuracy goals are 

not met. 

4.2 Analytical Rep-i 

4.2.2 For every batch of samples, one sample should be cbosea to extract and 

analyze in triplicate. Dcviathbetweea @iate samples shouldbc <30%. 

4.3 Prodwal Blanks 

4.3.1 I’mdual blanks should ti car&d Wqbuat the entim extra&on 

proccdurctovcrifythcabselwof~ofthemethod. 

4.3.2 Trace amountaofanalytdntbebla&(kathanthatimeathemethod 

ckWionlimit)nuybeis#)frbdandhvcno~o11th8subscqualtsample 

andysca,butsample8shouldberjactadif~coacestratioas~rthan 

fivetimcstheMDL)areptacatinpaucdudblanka. 

4.3.3 Ow blank slxdd be prqmd for each batch of sampbw (minimum 

fnclueacy 5%). 

D-36 
APPENDIX E 

EPA Priority Pollutants and 

Additional Hazardous 

Substance list Compounds 
CHEMICAL STRUCTURES AND MOLECULAR WEIGHTS OF U.S. EPA 

PRIORITY POLLUTANT AND ADDITIONAL HAZARDOUS SUBSTANCE LIST COMPOUNDS 

EPA # - EPA priority pollutant number defined for toxic pollutants in 40 CFR 401.15 that are a 

subset of the hazardous substances listed in Appendix VIII of 40 CFR 261. 

mw - molecular weight of an organic compound. 

HSL- hazardous substance list. E-1 
HIgi 

a 

b 

C 

d 

e 

f 

9 

h 

i 

j 

72 

76 

74 

75 

73 

a3 

a2 

79 

EPA # Compound 

mEcuLARuEIsKTPM 

39 f luoranthene 

a4 pyrene 

benro(a)anthtacene 

chtyscne 

benro(b)fluotanthene 

benro(k)fluotanthene 

benzo(a)pyrene 

indeno( 1,2,3-c ,d)pyrene 

dfbenro(a,h)anthracene 

bento(g,h,l)perylene 

I 

cHLmnwED nmwxc mlMcARBQlf 

a 26 1.3,dichlorobenzene 

b 27 1.4.dichlotobenzene 

C 25 1.2.dlchlorobenzene 

d a 1,2,4-trichlorobenzene 

e 20 2-chloronaphthalene 

f 9 hcxachlorobenzene 

structure 

a 0 

0% 0 0 

C 

0 

ax9 000 

e 

@ 

o” 

O 0 

9 

00 

a59 000 

&P 

o”ooo 

a cl 

b O” 

c cl 

6 0 c’ 

e 

a7 0 0 c’ 

b 

d 

h 

j 

Cl 

d Cl 

Cl 

nw 

202 

202 

228 

228 

252 

252 

252 

276 

278 

276 

147 

I47 

147 

181 

163 

285 

E-2 
EPA t Compound Stucture 

Ctu.oRIWED ALIp)(ATIC HYDROCARBOIIS a 

Cl CI 

a 12 hexachloroethane r,-t-t-c1 

iI ;I 

b xx trichlorobutadiene isomers 

l n OR Cl 

C xx tetrachlorobutadiene isomers b,c,d: I#' 

b: 

d xx pentachlorobutadfene isomers . E, c, 

'C-C / Cl 

Cl' \ f 

PC \ Cl Cl 

Cl Cl 

f 'c4,,ct 

/t-t. ’ -cl 

e 52 hcxachlorobutadiene e 

f 53 hexachlorocyclopentadiene 

Cl Cl 

HALOGEIUTEP ETHERS 

a 18 bfs(Z-chloroethyl)ether 

b 42 bis(Z-chloroisopropyl)ether 

c 43 bit(2-chloroethoxy)methane 

d 40 40chlorophenyl phenyl ether 

e 41 4-brunophenyl phenyl ether 

PtflxAulEs 

a 71 

b 70 

C 60 

d 67 

e 66 

f 69 

mu 

168 

158 

192 

226 

261 

273 

143 

171 

173 

dimethyl phthalate 

diethyl phthalate 

a ? 

a 

0 c-o-y 

c-o- %b ! 

194 

6 

C ? 

a 0 ;q 222 

di-n-butyl phthalate 

a 0 c-4n, 6 

f-A 

0 

butylbenzylphthalate 

e t 

bls(2-ethylhexyl) phthalate o :zzi$)z “, a 

278 

391 

di-n-octylphthalate 6 fO a t-857 391 

f--&t 

0 

E-3 
EPA I Compound Structure mu 

MIscEuA#aK OXY6mATm c-s 0 

a 

a 54 irophorone %J$ 43 9 

b ML benzyl alcohol mo,po 

C HSL bcnzoic actd C 6 0 

d 129 2.3.7.8.tetrach~oTobtbenzo-pgdioxin 

e HSL dlbtnzofuran *m 

oR6AnwrlRoGM CwPams Y 

a HSL 

D 56 

C 63 

d HSL 

e HSL 

f HSL 

Q HSL 

h 36 

i 35 

j 62 

k 5 

1 28 

1 

aniline 0 d 

nitrobenzene 0 

c t 

N-nitroso-di-n-propylamine A:?/ 

4-chloroanilfne 

2-nitroaniline 

e 9 

6 0% 

3-hitrom~\Ine 

4-nitroanitine 9 - 

0 0 

2.6.dinitrotoluene 

2,4-dfnitrotoluenc 

% i 44 

0 O’ot 

N-nitrosodiphcnyl amine bt 

k 

benzldine 9-114 1 

3.3'.dlchlorobenzidlnt !J!fw$w, 

138 

108 

122 

322 

168 

98 

123 

130 

128 

138 

138 

138 

182 

182 

198 

184 

253 

E-4 
EPA A Compound Structure fw 

PESTICfDES 

p,p'-ODE 

cc’2 

a 

db 3 C" b CWO 

cl I2 a 93 

b 94 

C 92 

d 89 

e 90 

f 91 

g 95 

h 96 

i 97 

j 90 

k 99 

1 100 

m 101 

n 102 

0 103 

P 104 

9 105 

r 113 

pens 

a 106 

b 110 

C 107 

d 111 

p,p'-ODD 3 

cc,&+3 Ocl 

c,-Cl 

p,p'-DDT 

aldrin 

djeldrin 

e 

Cf 0 cl 

chlordane gsh 

I 

Cl 

alpha-endosulfan . t\ 

Cl 

beta-endosulfan i 

endosulfan sulfate i 

cl 

endrin k 

cndrin aldehyde iF!E 

heptachlor la 

haptachlorepoxide i 0 

alpha-HCH 

beta-HCH 

delta-HCH j 

gwma-HCH 

toxaphene 

Aroclor 1242 

Aroclor 1248 

I 

Aroclor 1254 

Aroclor 1260 , 

cl Cl 

w 

0 0 

ci cl 

d L’z 

Cl 

cl xb 

f cl c12 

cl 

6 

Cl 

cl cl 

Cl 

j C2 cl 6 0 

cl 

1 ,” a2 

cl 

n 6 

etcl 

318 

320 

356 

365 

381 

410 

407 

407 

423 

381 

381. 

373 

389 

290 

M?auEmTIv2 fumaA 

E-5 
EPA I Compound 

YaATnE HAL-ml ALKMS 

a 45 

b 46 

C 16 

d 44 

e 13 

f 23 

9 10 

h 11 

i 6 

j 48 

k 32 

1 51 

m 14 

n 47 

0 15 

chlotancthane 

branoethane 

chl oroethane 

methylene chloride 

l,l’-dlchloroethane 

chloroform 

1.2.dlchloroethane 

l,l,l-trichloroethane 

carbon tetrachloride 

btanodichloranethane 

1.2.dlchloropropanc 

chlotodlbrananethane 

1.1.2~trichloroethane 

bromof om 

a 

-+I 

C 

+-Cl 

e 

cl 

+-a 

9 

“+-Cl 

i cl 

d-cl 

ci 

k 

-i;;- 

I I cl 

m 

v 

4-f -Cl 

0 

Struttwe 

clcl 1,1,2,2-tetrachloroethane n-t-(-c1 

YaAlnE HKopllATEo - a 

a aa vinyl chloride #fl 

3-Q 

b 29 l,l’-dichloroethene C 

C 30 tram-1.2.dlchloroethene ,a:” 

b 

:m'c' 'cl 

d 

62.5 

97 

97 

I 

d 33 cis- and trawl ,3-dichloropropene ")A<~ $C=C,I ,:-a 111 

a\ 4 clr- We a7 trichloroethene l P ‘cl f 131 

b 

++r 

d 

:' 

-f-Cl 

f cl 

AC1 

A 

h Cl 

+ 

Cl 

j 

+ 

1 

L 

c 

n 

': -c-& 

G 

mu 

50.6 

109 

64.5 

85 

99 

119 

99 

133 

lS4 

164 

133 

208 

133 

253 

168 

cl 

f 85 tetrachlorocthene 

/Cl 

":-.c, 166 

E-6 
EPA b Compound 

YoumE ARmmc lmmocARB= 

Structure 

a 4 benzene 

b 86 toluene 

C 30 ethylbenzene 

d HSL styrene 

e NSL total xyl l nes 

YaAmE Q(LoRIIAm mRamlc 

a 7 chlorobenrene 

YaATu lmmmlm CARmYL 

a 2 acrctleln 

b 3 actylanittfle 

YMlnEmERf 

a 

0 G bg '* 

C 5% 6 92 

0 0 d 2 106 

e +I b 104 

Q.Q. 0 0% murm1r 106 

llmucm8M 

a Cl 

0 0 112 

a 19 20chlorocthylvinylether 

YOLATILE KmEs 

a HSL acetone 

b HSL Z-butanonc 

C HSl 2-hexanone 

d HSL I-methyl-2-pentanonc 

lmcELueM YOUTILE CmPfnms 

a HSL carbon dlsulffde 

b HSL vinyl acetate 

a .o :c& 

a 

cl 

-++a-Lcc 

a 

++ 

0 

b 56 

:w: 

cm 53 

b 

106 

58 

b 76 

0. I 

:=~~,cf- 86 

E-7 
APPENDIX F 

Example Quality Assurance 

Reports 
PREFACE 

The following examples of detailed quality assurance (QA) reviews for a metals data 

package and a polychlorinated biphenyl (PCB) data package demonstrate the kind of 

information provided by QA specialists. The sections of these example reports address 

each of the components of a QA review discussed in Section 2.16 in the main text of this 

document. 

These reviews were conducted in accordance with EPA Contract Laboratory Program procedures. QA reviews for other programs may use alternative criteria for evaluation and 

different detection limits. For example, the target detection limits discussed for dredging 

programs differ from the detection limits described in this QA review. 

F-iii 
CONTENTS 

PREFACE 

QUALITY ASSURANCE REVIEW OF METALS IN WATER SAMPLES 

INTRODUCTION 

QUALITY ASSURANCE REVIEW 

Overall Case Assessment 

Completeness 

Holding Times 

Analytical Methods 

Accuracy 

Precision 

Blanks 

REFERENCES 

QUALITY ASSURANCE REVIEW OF POLYCHLORINATED 

BIPHENYLS IN SEDIMENT 

INTRODUCTION 

OVERALL CASE ASSESSMENT 

Summary of Completeness 

Summary of Data Qualifications 

HOLDING TIMES 

ANALYTICAL METHODS 

CALIBRATION 

Initial Calibration 

Continuing Calibration 

F-v 

Page 

F-iii 

F-1 

F-1 

F-1 

F-1 

F-3 

F-5 

F-5 

F-8 

F-11 

F-11 

F-13 

F-14 

F-14 

F-15 

F-15 

F-15 

F-16 

F-16 

F-17 

F-17 

F-18 
METHOD BLANK ANALYSIS 

ACCURACY 

Surrogate Compound Recoveries 

Matrix Spike Recoveries 

PRECISION 

IDENTIFICATION OF COMPOUNDS 

COMPOUND QUANTIFICATION AND REPORTED 

DETECTION LIMITS 

REFERENCES 

Page 

F-18 

F-18 

F-19 

F-19 

F-19 

F-19 

F-20 

F-20 

F-vi 
QUALITY ASSURANCE REVIEW OF METALS IN 

WATER SAMPLES 

INTRODUCTION 

This report documents the results of a quality assurance review of analytical data for 

metals in water samples from Project X. This quality assurance report is provided in 

support of the quality assurance project plan for this project. 

All laboratory analyses were performed by Analysis Laboratory in City, State, All 

samples were analyzed in accordance with the U.S. Environmental Protection Agency 

(EPA) Contract Laboratory Program Statement of Work for Inorganic Analyses (U.S. EPA 

1987). Data validation was performed according to EPA’s Laboratory Data Validation: 

Functional Guidelines for Evaluating Inorganics Analyses (U.S. EPA 1988). 

The quality assurance review included examination and validation of the following 

laboratory data: 

• Sample digestion and extraction logs 

• All instrument printouts, except for mercury (the instrument printout was 

not available from the laboratory) 

• Instrument calibration and calibration verification procedures and results 

• Sample holding times and custody records 

• Manual data transcriptions and computer algorithms. 

Data qualifiers were assigned as necessary during this review. Following the validation 

procedures, data quality was assessed with respect to accuracy, precision, and completeness. All qualifier codes used in this report are defined in Table F-l. 

QUALITY ASSURANCE REVIEW 

Overall Case Assessment 

All data for metals in the five water samples are acceptable as qualified in this review for 

the uses specified in the quality assurance project plan except for the matrix spike result 

for silver, which was rejected. Data for all samples analyzed for cadmium, calcium, lead, 

mercury, silver, and zinc are acceptable as estimates. Data qualified as J (estimated) are 

F-1 
TABLE F-l. DATA QUALIFIER CODES 

Qualifiers Applied During Quality Assurance Review 

U The analyte was not present above the level of the associated value. The associated numerical value 

indicates the approximate concentration necessary to detect the analyte in this sample. 

J The analyte was positively identified, but the associated numerical value may not be consistent with 

the amount actually present in the field sample. The data should be seriously considered for decisionmaking and are usable for many purposes. 

UJ The analyte was not present above the level of the associated numerical value. The associated 

numerical value may not accurately or precisely representhe concentration necessary to detect the 

analyte in this sample. 

R The data are unusable for all purposes. The presence or absence of the analyte has not been 

verified. Resampling and reanalysis are necessary to confirm or deny the presence of the analyte. 

Qualifiers Applied During Laboratory Validation’ 

E 

M 

N 

S 

W 

* 

+ 

The reported value is estimated because of the presence of interference. This qualifier is commonly 

used when the serial dilution result for analyses by inductively coupled plasma-atomic emission 

spectrometry (ICP) does not meet control limits. 

Duplicate injection precision was not met. 

Predigestion matrix recovery was not within control limits. 

The reported value was determined by the method of standard additions (MSA). The associated 

value is as reliable as unqualified results. 

The postdigestion spike recovery for GFAAb analysis was not within control limits (85-115 percent), 

and the sample absorbance was less than 50 percent of the spike absorbance. 

Duplicate analysis was not within control limits. 

The reported value was determined by MSA. The correlation coefficient for MSA is <0.995. 

a Adapted from U.S. EPA (1987). 

b Graphite furnace atomic absorption spectrometry. 

F-2 
acceptable, but a greater degree of uncertainty is associated with these values than with 

unqualified data. 

The matrix spike result for silver was rejected because the postdigestion spike recovery 

(58 percent) was well below the EPA Contract Laboratory Program (CLP) control limit 

(85 to 115percent recovery). Analysis of the sample by the method of standard 

additions (MSA) is required in this case, but was not performed. 

Calcium values received J qualifiers because the CLP control limit (U.S. EPA 1987) was 

exceeded slightly for the serial dilution sample analyzed by inductively coupled plasmaatomic emission spectrometry (ICP). Reported results may be underestimated by approximately 10 percent. 

Cadmium and lead results received J qualifiers because CLP control limits for matrix 

spike recoveries and for duplicate analyses were exceeded. In addition, the result for lead 

in Sample 2 was restated as undetected (U) at the reported concentration because the 

associated digestion blank was contaminated. Cadmium and lead data should be 

considered order-of-magnitude estimates. 

Mercury results were qualified J because the matrix spike recovery was below the CLP 

control limit. These results may be 100-200 percent higher than reported. 

A J qualifier was applied to silver results because recovery of silver was poor for the 

laboratory control sample (LCS). Silver results may be approximately 100 percent higher 

than reported. Additional individual results were qualified J because the correlation 

coefficient for the results determined by MSA did not meet the CLP control limit of 0.995 

The overall data quality achieved by the laboratory for analyses completed by ICP 

(Table F-2) is typical for metals analyses in water samples. The overall data quality for 

analyses by graphite furnace atomic absorption (GFAA) is typical for arsenic, chromium, 

and silver. Data quality for cadmium, lead, and mercury is less than may be expected for 

these analytes in similar samples. Data quality may have been affected by unstable 

instrument performance. 

Completeness 

A complete data package was submitted by the laboratory for five water samples, one 

matrix duplicate and one matrix spike, and one laboratory control sample and one method 

blank for each digestion batch. A list of analytes is included in Table F-2. During the 

quality assurance review, 33 results were qualified J as discussed above. Data completeness for metals was 100 percent of total requested analytes. 

F-3 
TABLE F-2. ANALYTICAL METHODS AND INSTRUMENT 

DETECTION LIMITS 

Anatyte Method of Analysis 

Instrument 

Detection Limit 

wu 

Aluminum 

Arsenic 

Cadmium 

Calcium 

Chromium 

Copper 

Iron 

Lead 

Magnesium 

Manganese 

Mercury 

Nickel 

Silver 

Zinc 

ICP 55 

GFAAb 5 

GFAA 5 

ICP 28 

GFAA 10 

ICP 11 

ICP 9.6 

GFAA 5 

ICP 140 

ICP 1.6 

CVAA” 0.2 

ICP 18 

GFAA 5 

ICP 4 

’ Inductively coupled plasma-atomic emission spectrometry. 

b Graphite furnace atomic absorption spectrometry. 

’ Cold vapor atomic absorption spectrometry. 

d Manual spectrophotometry. 

F-4 
Holding Times 

Holding times required by EPA CLP protocols were met for all metals analyses. 

Analytical Methods 

All sample digestion and analysis procedures, instrument calibration procedures, and 

quality control checks conformed to EPA CLP requirements except as noted below. 

Sample Preparation and Analysis 

Water samples were digested according to requirements specified for CLP (U.S. EPA 

1987). Sample digestates were analyzed by ICP, GFAA, and cold vapor atomic 

absorption spectrometry (CVAA), as indicated in Table F-2. Multiple digestions were 

prepared for Samples 1 and 2 and the duplicate and the spike of Sample 2, because 

unacceptably high levels of lead were present in the second preparation blank and because 

volumes of digestate were initially insufficient for all analyses. A preparation blank and 

a laboratory control sample were digested and analyzed with each batch. Only lead and 

arsenic results were obtained from the second and third digestion batches. Results for all 

applicable quality control samples, except the method blank for lead for the third 

digestion group, were provided on the appropriate CLP forms by the laboratory or were 

added during the quality assurance review. 

Instrument Calibration 

Instrument calibration was completed according to EPA CLP protocols (U.S. EPA 1987). 

Four calibration standards and one blank were used for all analyses by GFAA. The 

correlation coefficient of a least squares linear regression met the CLP control limit of 

20.995 in all cases except one. The correlation coefficient was 0.993 for the initial 

calibration for analysis of cadmium in Samples 3 and 5. Consequently, the cadmium 

results for these samples were qualified J. 

ICP instruments were calibrated according to manufacturer instructions, using one 

standard and one blank. A low-IeveI standard was used to verify accuracy of the 

calibration curve at low analyte concentrations for all metals except mercury and aluminum. 

Initial (ICV) and continuing (CCV) calibration check standards and initial (ICB) and 

continuing (CCB) calibration blanks were analyzed immediately after instrument 

calibration, after every 10 samples or more frequently, and at the conclusion of each 

analytical run, with the following exception: no CCVKCB pair was analyzed at the 

conclusion of the ICP run. However, only interference check samples were analyzed after 

the final CCVKCB pair, and data quality was not affected. Results for all CCVs fell 

within 90-I 10 percent of the expected value (80-120 percent for mercury), as required 

- -- 

F-5 
by EPA CLP. Instrument calibration remained within control limits for all samples 

thorughout each sample run and for all other analytes. 

instrument-Specific Quality Control Procedures 

ICP-A serial dilution sample is required by EPA CLP protocols to check for matrix 

interference in samples analyzed by ICP. All samples analyzed by ICP were diluted to 

one fifth of their initial concentration to bring manganese concentrations within the linear 

range of the ICP. The laboratory chose to report the results of diluted Sample 3 on CLP 

Form 9, ICP Serial Dilutions. A further serial dilution was required by CLP protocols 

to obtain a diluted result for manganese, but was not performed. Results of the serial 

dilution for iron, magnesium, nickel, and zinc were within the CLP control limit of 

lo-percent difference from the undiluted result. The results for aluminum and copper 

were not applicable because the undiluted concentration of these metals was not 

sufficiently high. The result for calcium (1 l-percent difference) exceeded control limits, 

with the diluted result (corrected for dilution) exceeding the undiluted result. All calcium 

data were qualified E by the laboratory and J during the quality assurance review. 

Reported calcium results may have a small negative bias of approximately 10 percent due 

to matrix interference. 

Interference check samples (ICSs) were analyzed at the beginning and end of the ICP 

sample run to check for interference by other metals. Results met CLP control limits in 

all cases. To extend the linear range of the ICP to accommodate the high analyte 

concentrations present in the ICSs, a second calibration curve was obtained for some of 

the ICS analytes using higher standards than were used for the sample analyses. The 

analytical wavelength and all instrument parameters remained the same. Calibration was 

verified at the higher calibration curve as well. Data relating to the higher calibration 

curve were labeled “secondary lines” in the original data. 

GFAA--Quality control procedures for GFAA analyses included duplicate injection 

of all samples and analysis of a postdigestion analytical spike with each sample. Results 

of duplicate injections were spot-checked at a frequency of approximately 10 percent. All 

examined duplicate injection results agreed within 20-percent coefficient of variation, as 

required by CLP protocols. 

Recoveries of the analytical spike for numerous samples and analytes did not meet CLP 

control limits of 85-l 15 percent. In most cases, these data were qualified W (analytical 

spike recovery did not meet control limits and sample absorbance is less than 50 percent 

of spike absorbance) by the laboratory, or MSA was used to analyze the samples as 

required by CLP protocols. SampIe results obtained by MSA were qualified S by the 

laboratory if the correlation coefficient obtained with the MSA results was 20.995. 

Results qualified S are reliable and are not considered to be estimates. Sample results 

obtained by MSA with correlation coefficients co.995 were qualified + by the laboratory 

and J during the quality assurance review. These results are estimates. 

F-6 
A systematic calculation error was made by the laboratory for all sample results obtained 

by MSA. The error consisted of the misassignment of axes to the sample concentration 

values and to the instrument response values, resulting in an incorrect value for the slope 

of the instrument response per added concentration and consequently for the analyte 

concentration in the sample. Results obtained with a poor correlation coefficient showed 

the greatest magnitude in the error. All results were corrected during quality assurance 

review. 

Several errors were made by the laboratory in following the CLP sample analysis 

sequence for analyses by GFAA. The analytical spike recoveries of silver and lead in the 

first method blank (122- and 119~percent recovery, respectively) exceeded CLP control 

limits (85-l 15 percent). According to U.S. EPA (1987), the problems should have been 

corrected and acceptable results should have been generated for the method blank prior 

to sample analysis. A qualifier (@ was applied to the silver result for Sample 5 (the only 

result not obtained by MSA) by the laboratory because of the high analytical spike 

recovery from the blank, but was removed during the quality assurance review because 

data qualification is not automatically warranted in this case. All samples results for lead 

from the first digestion group were obtained by MSA and were not qualified by the 

laboratory or during the quality assurance review. 

The matrix spike samples for lead and silver should have been analyzed by MSA because 

the analytical spike recoveries were low (74- and %-percent recovery, respectively) for 

these analytes. The initial sample and duplicate (Sample 2) for silver were analyzed by 

MSA. The spike results for silver and lead are estimates. 

The analytical spike recovery for lead in Sample 3 was 34 percent. This sample should 

have heen diluted and reanalyzed (U.S. EPA 1987); however, MSA was performed 

instead. Samples 2 (duplicate), 5, and 6 were analyzed by MSA for arsenic and had 

correlation coefficients below the control limit. These samples should have been 

reanalyzed, but were not. The correlation coefficient for arsenic by MSA in Sample 2 

(duplicate) was 0.909, well below the control limit of 0.995, and the curve generated by 

the standard additions was exponential in appearance. This result (45.5 pg/L) was 

rejected during the quality assurance review because of the poor correlation coefficient, 

and the initial result (26.2 pg/L) was accepted as an estimate. 

Detection Limits 

All reported instrument detection limits (IDLs) were below or equal to the CLP contractrequired detection limits (CRDLs) (Table F-2). The IDL for lead by GFAA was omitted 

from CLP Form 11, but was subsequently provided by the laboratory. The IDLs reported 

for GFAA analytes were estimated by laboratory personnel based on their experience with 

the instrument and were not determined statistically as required by CLP protocols (U.S. 

EPA 1987). Data were not qualified for this omission. Based on the quality assurance 

_ . _ - .- - .- .~ .~ ..- -~ - 

F-7 
review of original laboratory data, in the reviewer’s judgment the laboratory estimates of 

detection limits tended to be high. Use of statistically determined detection limits may 

result in lower values than the reported IDL in many cases. 

Accuracy 

The laboratory performed one LCS analysis (using a commercially available standard 

prepared specifically for CLP analyses) and one predigestion matrix spike analysis 

{Sample 1 for mercury, and Sample 2 for all other analytes). Recovery of all analytes 

except silver from the LCS ranged from 84 to 112 percent. Silver recovery was 

52 percent (Table F-3). CLP control limits for metals in the LCS are 80- to 120percent 

recovery (except for silver, which has no contractual control limit [U.S. EPA 19871). All 

results for silver were qualified J during the quality assurance review because of the poor 

LCS recovery (U.S. EPA 1988). 

Predigestion matrix spike recovery was within control limits (75-125 percent; U.S. EPA 

1987) for all metals except cadmium, lead, mercury, and silver (Table F-4). Results for 

cadmium and lead (194- and 261-percent recovery, respectively) were greater than the 

control limit, and all sample results greater than the IDL were qualified J during the 

quality assurance review (U.S. EPA 1988). Only Sample 2 was not qualified for 

cadmium because none was detected. The spike results for both lead and cadmium are 

questionable because the matrix duplicate results for Sample 2 exceeded control limits, 

so a reliable sample concentration is not available. The spike sample result for lead is 

also questionable because the sample should have been analyzed by MSA, but was not. 

In addition, at least one method blank for lead was contaminated (as discussed in the 

Blanks section); nonsystematic lead contamination may also have contributed to the poor 

replicability of the duplicates and the high spike recovery for lead. All data were 

qualified as estimated despite the uncertainty in the matrix spike results because the 

magnitude of the control limit exceedance was large for both analytes. 

All mercury data were qualified J during the quality assurance review because predigestion spike recoveries (40 and 39 percent, respectively) were much lower than control 

limits. Recovery for a postdigestion mercury spike analyzed for Sample 1 was 38 percent, similar to the predigestion spike result. This result indicates that a matrix interference at the spectrophotometer was probably responsible for poor recovery. Reported 

results for mercury may be lower than the actual sample concentrations. 

The matrix spike result reported for silver was lower than the result reported for the 

unspiked sample. The analytical spike result of the matrix spike sample was low 

(58percent recovery), and therefore the matrix spike sample should have been analyzed 

by MSA, but was not. The original and duplicate Sample 2 were both analyzed by MSA. 

The matrix spike result for silver was rejected during the quality assurance review. The 

matrix spike result for chromium was not applicable because the sample concentration 

exceeded 4 times the spike concentration. The magnitude of the precision error (the 

control limit is 120 relative percent difference [RPD]) may be significant with respect to 

_ - _ .- 

F-8 
TASLE F-3. PERCENT RECOVERY FOR METALS 

IN LABORATORY CONTROL SAMPLE 

Analyte 

Percent 

Recovery’ 

Aluminum 98 

Arsenic 105 

Cadmium 112 

Calcium 99 

Chromium 109 

Copper 101 

Iron 99 

Lead 98 

Magnesium 99, 84, 93 

Manganese 100 

Mercury 111 

Nickel 97 

Silver 52 

Zinc 98 

* percent recovery = measured va’ue x loo. 

true value 

- 

F-9 
TABLE F-4. MATRIX SPIKE RECOVERY FOR METALS 

IN SAMPLE 2 

Anatyte 

Aluminum 

Arsenic 

Cadmium 

Calcium 

Chromium 

Copper 

Iron 

Lead 

Magnesium 

Manganese 

Mercuv 

Nickel 

Sitver 

Zinc 

Sample Result Spike Added Percent 

N.m bw) Recoverf 

310 

25 

5 Ub 

zoo0 

40 

5 

69 10 

27 250 

7,090 l,ooO 

29 20 

6,560 

0.2 u 

180 

28 R’ 

180 

500 

1.0 

500 

10 

500 

97 

89 

194 

NW 

NAd 

103 

77 

261 

NR 

76 

40 

106 

-’ 

95 

’ Percent recovery = 

spoked result- unsprked resutt x 1OO. 

spike added 

b U - the anaiyte was not detected at the indicated concentration. 

’ A matrix spike was not required for this analyte (U.S. EPA 

1987). 

d The result is not applicable because the sample concentration 

is greater than 4 times the spike concentration. 

l Sample 1 was spiked for mercury only. 

’ R - the spike sample result was rejected; the resutt is not 

meaningful. 

F-IO 
the spike concentration in this situation, and spike recovery results cannot be clearly 

interpreted. Assessment of analytical accuracy was based on the LCS for both silver and 

chromium. 

Precision 

Duplicate subsamples of Sample 2 for all metals and Sample 1 for mercury only were 

analyzed by the laboratory. Results are summarized in Table F-5. All results except 

cadmium and lead were within the control limit of 25 RPD (for sampie results >5 times 

the CRDL) or f the CRDL (for results 15 times the CRDL) specified by the EPA. A 

qualifier (*) was applied to all cadmium and lead values by the laboratory or during the 

quality assurance review to indicate EPA CLP duplicate control limit exceedance, and all 

cadmium and lead values were qualified J during the quality assurance review. 

The result for arsenic for Sample 2 (duplicate) as obtained by MSA and reported by the 

laboratory was rejected during the quality assurance review, but the result obtained 

initially by direct comparison to the instrument calibration curve was accepted as 

estimated (details in the Calibration section). The latter value was well within control 

limits, and the former value exceeded the control limit by less than 1 pg/L. The data 

qualifier (*) applied by the laboratory to the arsenic value for Sample 2 was removed 

during the quality assurance review. No arsenic data were qualified J. 

Blanks 

A method blank and several calibration blanks were analyzed with the sampIes for each 

metal. No contaminant was found in any method blank with one exception: lead was 

present (6.1 pg/L) in the method blank prepared with the second digestion batch. Results 

for Sample 2 and the duplicate and spike samples for Sample 2 were reported from this 

digestion batch. Sample 2 was qualified U (undetected at the reported concentration) 

during the quality assurance review because the sample result (29.4 pg/L) was <5 times 

the concentration in the method blank (U.S. EPA 1988). According to the laboratory 

worksheets for lead, the method blank prepared with the third digestion batch also 

contained lead (105 pg/L); however, data corresponding to this result were absent from 

the instrument printout, and the result was not entered onto the appropriate CLP form. 

The entry on the worksheet was apparently a transcription error, and no result is available 

for this method blank. The result reported for Sample 1 was obtained from this digestion 

batch and was qualified J during the quality assurance review. 

Several results for CCBs exceeded the detection limits for calcium, manganese, and zinc. 

However, all associated sample results exceeded 5 times the concentration of the 

respective analyte found in any CCB, and were therefore not significant with respect to 

the expected analytical variability of sample results. No sample results were qualified as 

a result of detected analyte concentrations in associated CCBs. 

---.- -__- 

F-71 
TABLE F-5. DUPLICATE ANALYSIS RESULTS FOR METALS 

IN SAMPLE 2 

Analyte 

Sample Result Duplicate Result Control Relative Percent 

WL) (P4/L) LimV Ditferenceb 

Aluminum 310 308 

Arsenic 25 26 

Cadmium 5 U’ 17 

Calcium 184,000 180,000 

Chromium 69 78 

Copper 27 29 

Iron 7,100 6,700 

Lead 29 47 

Magnesium 200,000 190,000 

Manganese 6,600 6,400 

Mercury’ 0.2 u 0.2 u 

Nickel 180 190 

Silver 28 31 

Zinc 180 190 

200 

10 

5 l d 

15 

0.2 

40 

10 

2 

8 

46’ 

3 

2 

3 

’ For results less than 5 times the CRDL, the difference between replicate sample 

results must be < the CRDL. 

b RPD = 

1 sample - duplicate I 

(sample + duplicate)/2 ’ 

’ U - the analyte was not detected at the indicated concentration. 

d Results followed by “*’ exceed CLP control limits. 

’ Sample 1 was analyzed in duplicate for mercury only. 

~-_~ ___- 

F-12 
U.S. EPA. 1987. U.S. EPA Contract Laboratory Program statement of work for 

inorganics analysis, multi-media, multi-concentration. SOW No. 788. U.S. Environmental Protection Agency, Washington, DC. 

U.S. EPA. 1988. Laboratory data validation: functional guidelines for evaluating 

inorganics analyses. U.S. Environmental Protection Agency, Office of Emergency and 

Remedial Response, Washington, DC. 

F-73 
QUALITY ASSURANCE REVIEW OF 

POLYCHLORINATED BIPHENYLS 

IN SEDIMENT 

1AfTROOiJCTION 

This report documents the results of a quality assurance review of data for polychlorinated 

biphenyls (PCBs) in sediment samples as part of the sediment characterization of the 

Project Y site. The sampling and analysis plan (SAP) and the quality assurance project 

plan (QAPP) are described in the study proposal. 

All laboratory analyses were performed by the laboratory in accordance with procedures 

specified in the SAP. Sample analyses were performed using modified versions of U.S. 

Environmental Protection Agency (EPA) SW-846 Method 8080 (U.S. EPA 1986); the 

modifications are detailed in the laboratory statement of work (SOW). Data validation 

was performed in accordance with the U.S. EPA (1988) functional guidelines for 

evaluating organic compound analyses, guidelines established in U.S. EPA (1986) 

SW-846 Method 8080, the data quality objectives specified in the SAP, and the requirements specified in the laboratory SOW. 

The quality assurance review included examination and validation of the following data: 

Sample holding times and chain-of-custody records 

Initial and continuing calibration analyses, including calculations by least 

squares linear regression 

Reported detection limits 

Method blank analyses 

Matrix spike and matrix spike duplicate recoveries 

Surrogate compound recoveries 

All reported sample results, including verification of quantification, 

examination of chromatograms, and PCB identification. 

F-74 
OVERALL CASE ASSESSMENT 

The results of the quality assurance review for the analysis of PCBs in the 64 sediment 

samples are presented below in two sections. These sections address completeness of the 

data package and the qualifiers assigned to individual measurements. 

Summary of Completeness 

A complete data package was submitted by the laboratory for 64 sediment samples, 

4 method blanks, 4 matrix spikes, and 4 matrix spike duplicates. Data completeness is 

100 percent of the total requested analyses; no results were rejected. 

Summary of Data Qualifications 

The results of analyses for PCBs in the 64 sediment samples associated with this project 

are acceptabIe for the intended purposes specified in the SAP. Some data were assigned 

a J qualifier to indicate that the values reported are estimates. The data are acceptable, 

but have a greater degree of uncertainty than nonqualified data. 

A summary of the technical factors resulting in the qualification of the PCB data is as 

follows: 

n The laboratory did not fully establish linearity for the initial calibration 

near the lower end of the standard curve. Demonstration of linearity near 

the lower end of the curve is important for validating to demonstrate the 

limits of detection and practical quantification limits specified in the 

laboratory SOW. 

n The laboratory quantified all sample results using a single-point standard 

(i.e., the continuing calibration standard). However, quantification using 

a single-point standard is only acceptable if linearity is established throughout the calibration range in the initial calibration. 

n The criterion for continuing calibration was not met for three of the eight 

total standard analyses. 

n Surrogate recoveries for 13 samples did not meet quality control limits; the 

associated data were qualified as estimates. 

In addition, all PCB values were recalculated because coeluting chromatographic peaks 

were used by the laboratory to identify PCBs; therefore, the peak heights used for 

quantification resulted in biased values. The recalculated vaIues were typically one-half 

of the original concentrations reported by the laboratory. In addition, the laboratory 

occasionally incorrectly identified and reported results for specific PCBs. During the 

quality assurance review, these data were corrected. 

-. .-. -. . 

F-15 
A complete discussion of the results of the data validation and specific problems 

identified during the quality assurance review is provided below. 

HOLDING TIMES 

All storage conditions and sample holding times were properly met by the laboratory. 

The holding time requirements for PCB analyses specified in the SAP are as follows: 

n All samples must be shipped on ice to the laboratory and stored at -18°C 

until sample extractions are performed 

n Sample extracts must be analyzed within 40 days 

n Sediment samples must be kept frozen and extracted within 6 months from 

the date and time of sample collection. 

The 64 sediment samples were collected between and ; the 

samples were received at on . Samples were extracted 

between and , and the sample extracts were analyzed 

between and 

ANALYTICAL METHODS 

Samples were analyzed for PCBs using a modified version of U.S. EPA (1986) SW-846 

Method 8080. The modifications are specified in the SAP and the laboratory SOW and 

include the following: 

Larger sample size for extraction (i.e., approximately 100 grams, wet 

weight) 

In addition to the Contract Laboratory Program (CLP) surrogate compound 

dibutylchlorendate (DBC), the use of an additional surrogate compound 

(4,4’-dibromooctafluorobiphenyl [DBOFB]) to monitor recovery on a 

sample-by-sample basis 

Sample extract cleanup procedures as required using alumina column 

chromatography by EPA Method 3610, florisil column chromatography by 

EPA Method 3620, and elemental sulfur cleanup by EPA Method 3660 

Megabore capillary gas chromatography/electron capture detection (GC/ECD) analysis to enhance resolution and reduce potential interferences 

Use of a multipoint calibration for all Aroclor@ mixtures and analysis of a 

check standard of 0.1 ng (on-column) for verification of instrument 

sensitivity to assess the validity of the required detection limits. 

F-16 
The laboratory generally performed the recommended modifications. Florisil cohunn 

chromatography was used for a limited number of samples. EPA Method 3660 (mercury 

cleanup) and a sulfuric acid cleanup step were used to remove elemental sulfur; the 

sulfuric acid cleanup step was used on all samples associated with this project. The use 

of sulfuric acid was approved by the project manager during sample processing. 

CALIBRATION 

The results of all initial and continuing instrument calibrations performed by the 

laboratory are generaIly acceptable. Specific problems identified during this quality 

assurance review are discussed in the section below. 

Instrument calibration is performed to establish and ensure that the chromatographic 

system is capable of producing acceptable and reliable analytical data. An initial 

calibration is performed prior to sample analysis to establish the linearity of the 

chromatographic system, including demonstrating that all target compounds can be 

detected. Continuing calibrations are performed to verify that instrument performance is 

stable and reproducible on a day-to-day basis. The initial and continuing calibrations are 

to be performed according to procedures established by CLP protocols and modified in 

the SAP and the laboratory SOW. 

A detailed description of the results for initial and continuing calibrations is presented 

below. 

Initial Calibration 

The laboratory performed an initial three-point calibration using concentrations of 0.4, 1 .O, 

and 5.0 ng (on-column) for the five Aroclor@ mixtures (Aroclor” 1016, 122 1, 1232, 1248, 

and 1260). A five-point initial calibration (0.4, 1.0, 2.0, 3.0, and 5.0 ng) was performed 

for PCB 1242 and PCB 1254. 

Linearity of the initial calibration to zero concentration is assumed when the percent 

relative standard deviation (RSD) of the calibration factors is 120 percent over the entire 

calibration range (U.S. EPA 1986). Additionally, the correlation coefficients (r2) 

generated by least squares linear regression should be greater than 0.9950 to demonstrate 

linearity. 

The laboratory calculated the 3 values for the initial calibrations using the sum of all 

chromatographic peaks that were integrated (i.e., from the first peak integrated, the 

injection peak, to the last peak integrated) to perform the calcuIations. Only the 

chromatographic peaks representative of a specific PCB mixture should be used for 

performing these calculations. Therefore, all standard chromatograms were reviewed 

during the quality assurance review and the 3 values were recalculated. 
The recalculated results generated using least squares linear regression indicate that 

linearity through the origin was not established. While linearity through the origin is not 

uncommon for this type of analysis, most PCB concentrations that were recalculated are 

in this low concentration range. Therefore, the results for PCBs were assigned a J 

qualifier to indicate estimated values. 

Continuing Calibration 

The number of continuing calibrations is acceptable; however, the frequency of calibrations is not acceptable. The data were not qualified for unacceptable frequency of 

antimony calibration because of the numerous other problems identified and discussed in 

other sections of this report. 

The criteria for acceptable continuing calibration require that the calibration factors for 

all target compounds have a difference of 115 percent from the average calibration factor 

calculated for the associated initial calibration (U.S. EPA 1986). The 15percent 

difference value is required for results calculated using the chromatographic column that 

is used for quantitative purposes. In addition, the percent difference of the calibration 

factors calculated for the cbromatographic column used for confirmation must be 

120 percent (US. EPA 1986). If the criteria for the percent differences are not met, then 

a new initial calibration sequence must be prepared. 

The laboratory performed 8 continuing calibration analyses during the analysis of the 64 

sediment samples. The criteria for continuing calibration were not met for three of eight 

calibrations performed (ranging from 32- to 92-percent difference). In addition, the 

laboratory typically performed continuing calibrations at the end of a given daily 

analytical sequence or the calibrations were clustered together. 

METHOD BLANK ANALYSIS 

Method blank analysis is performed to determine the extent of laboratory contamination 

of samples. The four method blank analyses for this project are acceptable; PCBs were 

not detected. 

ACCURACY 

Accuracy of the analytical results is expressed in terms of the bias and precision of 

measurements. Bias is assessed by evaluating the recoveries of the surrogate compounds 

and the matrix spike recoveries calculated for sample analyses. Precision is assessed by 

evaluating the differences between duplicate matrix spike analyses. These results are 

presented below. 

F-18 -- - -- - 
Surrogate Compound Recoveries 

The surrogate compound recoveries reported for the 64 sediment sample analyzed are 

acceptable, except 13 surrogate recoveries did not meet the quality control limits and the 

associated data are accepted as estimates. The data quality objective for acceptable 

recovery for surrogate recovery is lOOGO percent. 

The recoveries for DBC ranged from 0 to 160 percent, with an average recovery of 

70 percent. The recoveries for DBOFB ranged from 0 to 128 percent, with an average 

recovery of 71 percent. Thirteen surrogate recoveries exceeded the quality control limits; 

four recoveries were reported at zero percent, and nine recoveries were less than 

50 percent but greater than zero percent. No data were rejected because only one 

unacceptable surrogate recovery was reported for a given sample and the other surrogate 

recovery value was acceptable. The values for PCBs reported in these samples were 

assigned a J qualifier to indicate the values are estimates. 

Matrix Spike Recoveries 

The results for the matrix spike recoveries are acceptable for the four sets of duplicate 

matrix spike analyses that were performed, except for three results that are acceptable as 

estimates. All matrix spike analyses were performed using Aroclor’ 1254 and the 

samples chosen by the laboratory for the matrix spikes had detectable amounts of PCBs. 

The criteria for acceptable matrix spike recovery is 100&50 percent. All recoveries were 

recalculated during the quality assurance review. The recalculated matrix spike recoveries 

ranged from 0 to 90 percent. Only three results did not meet the quality control limits. 

No data were rejected in accordance with procedures detailed by EPA CLP protocols 

(U.S. EPA 1988). 

PRECISION 

Two of the four total relative percent difference (RPD) values did not meet the quality 

control criteria for precision, Precision is expressed as the RPD between the recoveries 

of the matrix spike and the matrix spike duplicate analyses performed on a sample. The 

quality control criterion for precision is *50 percent. The RPDs calculated from the 

duplicate matrix spike recoveries ranged from 13 to 90 percent. 

IDENTIFICATION OF COMPOUNDS 

All chromatograms were examined during the quality assurance review to verify that PCB 

identifications and confirmations (where applicable) are correct. The confirmation of the 

PCB identification during the quality assurance review focuses on false positives. 

However, PCBs reported as not detected are also evaluated to investigate the possibility 

of false negatives. Confirmation of possible faIse negatives is addressed by reviewing 

F-79 
other factors relating to analytical sensitivity (e.g., detection limits, instrument Linearity, 

and analytical recovery). 

Either Aroclor@ 1254 or Aroclor@ 1260, or a mixture of the two, was identified in 55 of 

64 samples associated with this study. Absolute identification for the presence of 

Aroclors@ 1254 or 1260 could not be confirmed during the quality assurance review 

because all chromatograms generated with the confirmational chromatographic column 

drifted off scale (i.e., 100 percent, full-scale deflection). Additional sample dilutions were 

not performed for these samples. Therefore, results generated using data obtained from 

only one chromatographic column were used to perform quantification and identify the 

PCBs. As a result, all results were assigned a J qualifier to indicate the values reported 

are estimates. 

COMPOUND QUANTlFlCATlON AND REPORTED DETECTION LIMITS 

All quantifications performed by the laboratory were corrected during the quality 

assurance review. The laboratory had not accounted for coeluting peaks when Aroclors@ 1254 and 1260 were present in a given sample; the inclusion of coeluting peaks 

resulted in biased values. Quantification of the reported data and the reported detection 

limits were recalculated to ensure all results are accurate and consistent with the 

requirements established in U.S. EPA (1986) SW-846 Method 8080, the SAP, and the 

laboratory SOW. 

During the quality assurance review, chromatographic peaks characteristic to each PCB 

mixture were chosen to check quantifications and their identity. The heights of selected 

integrated peaks for a specific PCB mixture used for calibration were summed to 

recalculate the 8 values, and concentrations of PCBs detected in the samples were 

recalculated using least squares linear regression. The results for PCBs quantitated in the 

samples were typically one-half of the values originally reported by the laboratory; all 

results were assigned a J qualifier to indicate estimated values. 

The laboratory reported limits of detection of 5 @kg (wet-weight basis) for Aroclor? 

1016, 1254, and 1260 and 10 &kg (wet-weight basis) for Aroclor? 1221, 1232, 1242, 

and 1248 in most samples. Overall, the laboratory reported limits of detection that range 

from 5 to 100 &kg (all values are adjusted for dilutions that may have been performed). 

U.S. EPA. 1986. Test methods for evaluating solid waste (SW-846): physical/chemical 

methods. U.S. Environmental Protection Agency, Office of Solid Waste and Emergency 

Response, Washington, DC. 

U.S. EPA. 1988. Laboratory data validation: functional guidelines for evaluating 

organics analyses. U.S. Environmental Protection Agency, Office of Emergency and 

Remedial Response, Washington, DC. 

- - _-. -- .-. -.-.-- - .-. .- 

F-20 
APPENDIX G 

Analytical/Environmental 

Laboratory Audit 

Standard Operating Procedure 
CONTENTS 

Page 

ANALYTICAL/ENVIRONMENTAL LABORATORY AUDIT 

STANDARD OPERATING PROCEDURE 

1. PURPOSE AND INTRODUCTION 

2. AUDITOR QUALIFICATIONS 

3. REQUEST FOR AUDIT 

4. CLARIFICATION OF AUDIT OBJECTIVES 

5. ESTIMATE OF AUDIT COSTS 

6. PREPARATION FOR THE AUDIT 

6.1 Identification of Laboratory Contact Person 

6.2 Initial Discussion with Laboratory Management 

6.3 Pre-Site Visit Activities 

6.4 Schedule of the Site Visit 

7. PERFORMANCE OF THE SITE VISIT 

8. USE OF THE AUDIT CHECKLIST FORM 

9. USE OF THE AUDIT SCORING GUIDELINES 

10. AUDIT REPORT 

G-1 

G-1 

G-1 

G-1 

G-1 

G-2 

G-2 

G-2 

G-3 

G-3 

G-4 

G-5 

G-6 

G-7 

G-7 
ANALYTICAL/ENVIRONMENTAL 

LABORATORY AUDIT 

STANDARD OPERATING PROCEDURE 

1. PURPOSE AND INTRODUCTION 

The purpose of this standard operating procedure (SOP) is to provide guidance to EZ 

Consultants (EZ) staff in auditing analytical or environmental testing laboratories. The 

audit requires evaluation of information collected during the review of laboratory 

documents, performance of site interviews, and observation of normal laboratory 

operations. Basic procedures for arranging and performing a site visit are provided, as 

well as a checklist for items to be considered during the audit process, and an evaluation 

guide. Portions of the audit checklist form (Attachment 1) are based upon laboratory 

evaluation checksheets developed by the U.S. EPA Industrial Technology Division. 

There are two typical reasons why an audit is requested to be performed: to determine 

the capability of a laboratory to perform (future) testing for EZ; or to evaluate the quality 

of data submitted, usually on behalf of a third party. The SOP outlined below is 

applicable in both cases. 

2. AUDITOR QUALIFICATIONS 

The auditor should have the technical experience necessary to perform the audit, i.e., 

familiarity with the analytical methods of interest, instrumentation used, standard QA 

practices, and general good laboratory practices. The auditor should also be familiar with 

this SOP. 

3. REQUEST FOR AUDIT 

A staff member desiring a laboratory audit be performed can contact the EZ chemistry 

group and request an auditor be assigned for this task. 

4. CLARIFICATION OF AUDIT OBJECTIVES 

The auditor should consult the staff member requesting the audit to determine the purpose 

of the audit and the rigor with which the audit must be performed. The extent of the 

audit and the intensity of scrutiny will vary, according to the type of laboratory, analyses, 

---------- 

G-l 
5. 

and type of project which are involved. The auditor should get clear direction from the 

individual requesting the audit to determine the intensity of review which is desired. 

Information necessary to make this decision include: 

• Reason for audit 

• Rigorousness of the data requirements 

• Type of project for which data are (to be) collected 

• Analytical methods required. 

ESTIMATE OF AUDIT COSTS 

The labor costs involved for the audit will depend on the intensity of the audit, which in 

turn depends upon factors such as the following: 

• Type and size of project involved 

• Type of laboratory involved 

• Rigorousness of information requirements 

• Required analytical methods 

• Size and organization of the laboratory 

• Accessibility of documents for review 

• Type of audit report necessary. 

For a rough estimate, the audit of a small, subcontract laboratory with 10 staff members, 

producing standard CLP data packages for inorganics, with all necessary documents 

available in the EZ contract files would take approximately 18 hours of the auditor’s time: 

eight hours for audit preparation, four hours for the site visit (excluding travel), and six 

hours for evaluation and report generation. Additional labor costs would include clerical, 

word processing, and editing staff time. Other direct costs such as travel expenses and 

computer time would also need to be included. 

6. PREPARATION FOR THE AUDIT 

6.1 Identification of Laboratory Contact Person 

If a laboratory (which will be) performing analyses for EZ is to be audited, then the 

auditor should contact the laboratory directly. Usually the best person with whom to 

establish contact is the technical director or lab manager, if such a position exists. 

G-2 
If the laboratory to be audited is (or will be) performing analyses for a third party, that 

party should first be contacted, and their assistance should be enlisted to establish contact 

with the laboratory. 

6.2 Initial Discussion with Laboratory Management 

Initiate preliminary discussions with the laboratory contact person to: 

n Obtain a profile of laboratory. e.g., what types of samples and analyses are 

handled, what clients are served, what level and types of services are 

available, how lab is managed, identification of the managerial chain, 

management’s overall philosophy of quality, type of quality program in 

place. 

n Identify the primary concerns. e.g., potential or perceived problems, 

perceived strengths. 

n Identify the expectations, e.g., reason for desiring an audit, expected use of 

the outcome. 

n Identify any problems the laboratory may have with EZ. 

If at all possible, do not take an adversarial attitude, but instead try to foster a 

cooperative relationship with the laboratory. This is especially important when there 

have been previous problems or concerns regarding the quality of data produced by 

the laboratory. It is much easier to obtain necessary information and to resolve 

problems if an open, cooperative relationship can be established for the audit process. 

6.3 Pre-Site Visit Activities 

n Review the audit checklist form (Attachment 1): determine what information will be necessary to complete the form and prepare for the site 

visit. The topics generally covered during the site visit include organization and personnel training, client requests, sample receipt and storage 

areas, sample preparation areas, general laboratory facilities, documents, 

standards, procedures, instrumentation, quality control, data review, data 

management, and report generation, 

n Collect relevant information: gather applicable laboratory or project 

documents which will be helpful in filIing out portions of the audit 

checklist in advance, or aid in completing the audit report. Such documents could include the laboratory statement of qualifications (SOQ), 

statement of work (SOW), contract or bid package, relevant analytical or 

sampling methods, EPA or state performance evaluations performed within 

the past year, and the laboratory QA/QC manual. If the laboratory is 

currently under contract with EZ, or a third party for whom EZ is performing the audit, obtain the applicable documents from our contract files or 

G-3 
6.4 

from the third party. If the laboratory is being considered for performance 

of future work, obtain copies of the documents from the laboratory, if 

possible. 

m Review the assembled information and begin filling out the audit checklist 

form following the instructions in Section 8. Make notes of additional 

questions regarding the laboratory which will need to be answered. Note 

that the audit checklist form (Attachment 1) contains general guidelines for 

laboratories testing hazardous materials, therefore, not all of the questions 

may be applicable. The audit procedure will proceed more quickly if those 

sections which are not applicable are marked with “N/A” in advance. 

Schedule of the Site Visit 

Remind the laboratory contact person of the purpose of the audit when you make the 

arrangements for a site visit. Since the most useful information can be gained while the 

laboratory is operating under typical conditions, only two to three days’ advance warning 

should be allowed prior to the site visit. This should allow enough time for the laboratory 

to arrange that key individuals are available for site interviews. 

It is helpful to the laboratory staff if the auditor provides the laboratory with information 

on the audit and explains how the site visit will be conducted. See Section 7 for a typical 

agenda for a site visit. Information which should be discussed in making arrangements 

for the site visit should include: 

m Purpose of the audit (e.g., potential contract, resolution of problems) 

n Estimate of time the site visit will take (typically, three to four hours for 

a small laboratory performing one type of analysis) 

n Areas of the laboratory to be audited 

n Topics to be covered during the site visit (e.g., organization and personnel 

training, client requests, sample receipt and storage areas, sample tracking, 

sample preparation areas, general laboratory facilities, documents, standards, procedures, instrumentation, quality control, data review, data 

management, and report generation) 

n Staff requested to be available to the auditor during the site visit (e.g., lab 

manager or director, QA/QC officer, sample management supervisor, 

sample custodian, sample processing supervisor, inorganic and/or organic 

section supervisors, bench chemists and technicians, data management); 

there should be a specific laboratory staff member identified to provide 

information on each of the topics listed above 

---- - - - - -. .- - . -. . ._ . 

G-4 
n Documents requested to be available to the auditor during the site visit 

(e.g., QA program documents, policies and procedures, manuals, control 

charts, corrective action reports) 

m Proposed site visit schedule (see Section 7 for a typical schedule) 

m Specific problems, if any. 

PERFORMANCE OF THE SITE V./S/T 

It is important to perform the site visit in a professional, efficient manner, and to 

minimize disruption of the normal laboratory activities. Try to have a cooperative 

attitude, and emphasize that this site visit is an information gathering activity that may 

provide helpful information to their organization as well. Do not make critical remarks 

or point out flaws, but include such remarks in written notes. One way to conduct a site 

visit is as follows: 

n Initial briefing: meet the key personnel (managers and supervisors) in the 

laboratory as a group and briefly explain the purpose of the audit. Have 

one of the laboratory staff present a general overview of the laboratory 

organization and capabilities, and introduce personnel. Ask that a history 

be presented on a sample. beginning with the initial request for analysis, 

receipt of the sample from the client, through internal procedures and 

analysis, generation of data and submittal of the final data report to the 

client. Set the format for this initial briefing with the laboratory contact 

person prior to the site visit. Try to arrange to keep this initial briefing to 

approximately half an hour. 

n Document review: have arrangements made ahead of time for an opportunity to review the laboratory documents you requested be available. 

This can be done at this point, during the interview, or near the end of the 

interview, just prior to the final briefing. 

n Observation of the various areas of the laboratory: make arrangements 

ahead of time with the laboratory contact person to visit each area of 

interest in the laboratory to make observations. Cover each of the applicable topics on the audit checklist. Follow the sample history, as presented 

earlier by the laboratory. The audit checklist is organized to facilitate this 

task. 

n Information gathering: collect information on the audit checklist as the site 

visit progresses. Make checks in the appropriate places, or write in the 

information necessary for each question as responses are given. It is 

difficult to remember all the information provided, and is important to be 

as accurate as possible in recording responses at the time they are provided. 

G-5 
If possible, arrange to speak with bench level technicians and analysts 

during the observation process. Specific instructions for filling out the 

audit checklist are provided in Section 8. 

m Final briefing: meet with the key personnel, or at a minimum with the 

laboratory director or QA manager, at the end of the interviews to ask any 

questions which may not have been answered. If additional information is 

necessary, ask that it be forwarded. Since it is not possible to tell the 

laboratory at this time whether the audit was passed or not, because a 

detailed review of the information provided on the checklist will be 

required, make no comment on whether the laboratory has passed the audit. 

However, give an indication of when the laboratory may expect an audit 

report, and to whom this report will be made available. Always thank the 

laboratory staff for their time and for allowing you to disrupt their schedules. 

8. USE OF THE AUDIT CHECKLIST FORM 

The audit checklist form (Attachment 1) provides general guideline questions for 

laboratories performing hazardous materials analysis. The EZ chemistry group leader 

should be consulted by the auditor, if it is felt that a project-specific form must be 

generated. 

The checklist is divided into several sections: 

n Organization and Personnel 

n Sample Receipt and Storage Area 

n Sample Preparation Area/Facilities 

n Instrumentation 

n Quality Control 

n Data Handling and Review 

n QC Manual Checklist 

n Summary. 

It is assumed that appropriate staff (who have been previously identified) will be made 

available to the auditor to answer the questions in each of these sections. Make checks 

in the appropriate boxes, or write in the information necessary for each question as the 

answers are provided. Do not make critical remarks or point out flaws, but include such 

information in written notes. Either write all notes on the checklist form or attach notes 

to the form. Ask to inspect documents, when appropriate, to verify answers. 

G-6 
9. USE OF THE AUDIT SCORING GUIDELINES 

Once the site visit has been completed and any additional information has been provided 

to the auditor, the evaluation of the laboratory can be completed. 

Point distributions for each response which can be answered “yes” or “no” are given in 

the scoring guideline in Attachment 2. In some cases, it may be necessary to check both, 

as not all requirements may be fulfilled. All points are then totaled and the percentage 

of the maximum possible points is then calculated. Questions which are not applicable 

to a particular facility are not scored, and are not counted toward the maximum possible 

points, thereby neither rewarding or penalizing the laboratory. Responses to questions 

which have no point value will be used to determine marginal cases of pass or fail. The 

following criteria are given for acceptability or nonacceptability: 

86-100% of maximum possible points 

76-85% of maximum possible points 

= acceptable audit 

= provisionally acceptable audit 

(based on responses to nonpoint 

questions) 

below 76% of maximum possible points = unacceptable audit 

IO. AUDIT REPORT 

An internal memo summarizing the results should be provided to the EZ staff who 

requested the audit be performed. In many cases, the third party may wish to receive 

copies of the completed audit report for their records. An example memo is provided as 

Attachment 3 of this procedure. If it has been requested, a copy should also be provided 

to the audited laboratory. 

.-__ -- --.- __ ___.____ ---_--_--- -----..---..---- 

G-7 
Attachment I 
ANALTTICAL CHEMISTRY LABORATORY AUDIT GUIDELINES 

Laboratory: 

Address: 

Date: 

Telephone: 

Auditor(s): 

Laboratory Personnel Interviewed: 

Name Title 

Laboratory Accreditation/Certification: 

Expiration 

Comments: 

Score: 
LABORATORY AUDIT GUIDELINES 

Page 2 

Yes No Points Comments 

A. Organization and Personnel 

1. Is there an organizational chart available? 

2. Is everyone in the organization familiar with it? 

3. Is an up-to-date file maintained in the laboratory describing the educational background and/or related 

work experience of all laboratory personnel? 

4. Is there a formal training program for personnel? 

5. Are employees required to demonstrate proficiency 

with analytical instrument operation, methods, or 

techniques prior to working on client samples? 

6. Is this proficiency testing documented? 

7. Is the organization adequately staffed to meet commitments in a timely manner? 

0. Is there a designated QA/QC Officer? 

9. To whom does the lab QA/QC Officer report? 

10. Was the lab QA/QC Officer available during the audit? 

11. Was a program manager or laboratory manager available during the evaluation? 

Comments: 

B. Sample Receipt and Storage Area 

1. 

2. 

3. 

4. 

5. 

6. 

7. 

Is a sample custodian designated? 

Are the responsibilities clearly defined? 

In writing? 

Is there a standard sample login procedure followed? 

Does the procedure include adequate inspection of 

samples and accompanying documents to verify that 

they are intact, complete, and consistent? 

Is there an inspection checklist? 

Does it document adequately the nature and condition of samples and documentation? 

Is the integrity of samples and shipping containers 

being documented? 

--- 

vm- 

--- 

--- 

em- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 
Lni30~A TAR Y a UDIT GUIDELINES 

Page 3 

Yes No Points Comments 

a. Are samples logged into a bound notebook? 

a. Computerized lab management system? 

b. Other? (describe: ) 

9. Does the login record document: 

a. Field and laboratory ID 

b. Analyses requested 

c. Storage location 

d. Signature of custodian 

e. Collection date 

f. Receipt date 

g. Analysis due date 

h. Sample holding time 

i. Special instructions 

10. Is there a daily summary of information such as samples received, analyses requested, date sampled, or 

date received? 

11. To whom is this summary distributed? 

12. Are login records filed and readily retrievable? 

13. How far back in time can records be retrieved? 

14. Are written SOPS developed for receipt and storage 

of samples? 

15. Are they available to and understood by laboratory 

personnel? 

16. Is a clean area available for receiving and opening 

sample shipments? 

17. Is this area separated from other lab operations (consider not only spatial separations, but air flow, personnel, traffic, etc.)? 

18. Does the custodian understand the importance of 

preventing lab contamination? 

19. If appropriate, are the pl-fs of samples measured and 

recorded to verify that they are preserved? 

20. What percentage of samples is checked? 

21. Are records of these checks retained? 

22. Are facilities adequate for the storage of samples? 

23. Are samples stored so as to maintain their preservation? 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 
LABORATORY AUDIT GUIDELINES 

Page 4 

Yes No Points Comments 

24. Are volatile samples stored separately from semivolatile samples? 

--- 

25. Is the temperature of the cold storage area recorded 

daily? 

--- 

a. Are excursions noted, along with descriptions of 

corrective action taken? 

--- 

b. Is this being reviewed periodically by a supervisor 

or the QC unit? 

--- 

26. Is the sample storage area secure? 

--- 

27. How is sample identification maintained? 

28. Is positive sample chain-of-custody maintained within 

the lab? 

--- 

29. How are samples tracked through the lab? 

30. How long are samples retained? 

Sample extracts? 

31. How are special instructions regarding preparation, 

analysis, or turnaround times transmitted within the 

laboratory? 

Comments: 

C. Sample Preparation Area/Facilities 

1. Is the laboratory maintained in a clean and organized 

manner? 

--- 

2. Does the lab appear to have adequate work space 

(120 f? per analyst)? 

--- 

3. Are the toxic chemical handling areas either stainless 

steel benches or an impervious material covered with 

absorbent paper? 

--- 

4. Are contamination-free work areas provided for the 

handling of toxic materials? 

--- 
LABORATORY AUDIT GUIDELINES 

Page 5 

Yes No Points Comments 

5. Are adequate exhaust hoods available to prevent 

contamination of personnel and the laboratory facility? 

--- 

6. Are the flow rates and/or face velocities of these 

hoods periodically checked and recorded? 

--- 

7. How frequently are they checked? 

a. Are the procedures and records adequate to demonstrate the proper face velocity profile for each hood 

over the period of record? 

--- 

9. Is the near-face interior of each hood clear of objects 

that might interfere with the proper face velocity profile and thereby reduce hood efficiency? 

--- 

10. Are chemical waste disposal policies/procedures welldefined and followed by the laboratory? 

--- 

11. Are records of waste containerization and disposal 

(lab logs, manifest, etc.) filed and retrievable? 

--- 

12. Are voltage control devices installed on major instrumentation? 

--- 

13. What is the laboratory’s source of distilled/deionized 

water? 

14. Is the conductivity of this water checked daily and 

data recorded (acceptable conductivity is 2.0-5.0 

pmhos/cm at 25X)? 

-- 

15. Is the analytical balance located away from draft and 

areas subject to rapid temperature fluctuations? 

-- 

16. is it protected from vibration associated with activities 

in the facility (i.e., it should be on a heavy table, on a 

floor that does not bounce when walked on, etc.)? 

-- 

17. Is the balance maintained by a certified technician? 

--- 

18. Is the balance routinely calibrated with Class S 

weights and are the calibration data recorded? P-P 

19. Are the Class S weights handled properly to prevent 

contamination/damage? 

--- 

20. How often are the Class S weights certified? 

21. Are pH and ion selective meters properly calibrated 

and maintained: and are these activities recorded? 

--- 

22. Are laboratory thermometers (including mercury-inglass) calibrated at least yearly against an NIST 

traceable thermometer and documented? 

--- 
LABORATORY AUDIT GUIDELINES 

Page 6 

Yes No Points Comments 

23. 

24. 

25. 

26. 

27. 

28. 

29. 

30. 

31. 

32. 

33. 

34. 

35. 

36. 

37. 

38. 

39. 

Are reagents dated upon receipt by labeling each 

container with the date received? 

Is there a complete log of reagent and solvent supply 

giving the quantity, batch number, receipt date, percent activity, or purity? 

Are reagents and standards checked prior to use? 

Are solvent lots checked and documented prior to 

use? 

Are reference materials properly labeled? 

Is each spiking/calibration standard completely traceable to documented neat material or a documented 

purchased standard? 

Is each logbook entry signed and dated by the individual who prepared the solution? 

Are logbooks periodically reviewed and signed by a 

manager/supervisor? 

Are logbooks maintained in a manner which allows 

complete traceability? 

Are standards stored separately from samples and 

sample extracts? 

Are volatile and semivolatile standard compounds 

properly segregated? 

Are SOPS readify available to laboratory personnel? 

Are glassware cleaning procedures documented? 

Are the cleaning procedures consistent with EPA 

recommended procedures? 

Is the temperature of the drying ovens recorded daib? 

Is cleaned glassware properly handled and stored to 

prevent contamination? 

l-low do lab personnel recognize glassware that has 

been prepared for specific function (e.g., organic vs. 

inorganic)? 

--- 

--- 

--- 

--- 

--- 

A-- 

--- 

--- 

--- 

--- 

--- 

--- 

40. Is the laboratory secured? 

Comments: 

--- 

D. Instrumentation 

1. Are instrument operating manuals available? 
LABORATORY AUDIT GUIDELINES 

Page 7 

Yes No Points Comments 

2. 

3. 

4. 

5. 

Do the operators demonstrate a good familiarity with 

the manuals? 

Are there service contracts on the instrumentation 

(and is a record maintained of the service)? 

Are in-house replacement parts available? 

Have the instruments been modified in any way? 

Describe the modifications and discuss ramifications: 

6. 

7. 

8. 

9. 

10. 

11. 

12. 

Are instruments properly vented or are appropriate 

traps in place? 

Is a logbook maintained for each instrument? 

Is a complete list of laboratory instrumentation available? 

Are all calibration data hard-copied and retained? 

When calibrating an AA: 

a. How many standards are run to generate the 

calibration curve? 

b. Is a new curve generated for each run? 

c. Is a standard blank always run? 

d. Is calibration checked immediately after completing as well as periodically throughout the run? 

When calibrating an ICP: 

a. How many standards are run to generate the 

calibration curve? 

b. Is a new curve generated for each run? 

c. Is a standard blank always run? 

d. Is calibration checked immediatefy after completing as well as periodically throughout the run? 

When calibrating a GC: 

a. How many standards are run to generate the 

calibration curve? 

b. Is a calibration check standard run daily? 

c. What are the performance criteria for this standard? 

d. Is the instrument typically calibrated for every 

compound of interest? 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 
LABORATORY AUDIT GUIDELINES 

Page 8 

Yes No Points Comments 

e. How are retention times monitored for each compound of interest, and when is corrective action 

taken? 

13. When calibrating a GC/MS: 

a. 

b. 

C. 

d. 

e. 

f. 

h. 

i. 

j. 

How many standards are run to generate the 

calibration curve? 

Is a calibration check standard run daily? 

What are the performance criteria for this stanIs the instrument typically calibrated for every 

compound of interest? 

Is the instrument tuned at least daily? 

-- 

Do the tuning procedures conform to the methods 

for which the instrument is being used? 

What compound and performance criteria are 

Are surrogates and internal standards used? 

Are surrogate and internal standard recoveries 

monitored? 

What are the action limits? 

Comments: 

E. Quality Control 

1. Are method blanks prepared and analyzed with each 

batch of samples, for each analytical procedure, or 

some percentage? 

What percentage: 

a. For GC/MS analyses? 

b. For GC analyses? 

c. For ANICP analyses? 

d. For wet chemistry? 

2. At what frequency are lab duplicates prepared and 

analyzed: 

a. For GUMS analyses? 

b. For GC analyses? 

c. For AA/ICP analyses? 
LABORATORY AUDIT GUDELINES 

Page 9 

Yes No Points Comments 

d. For wet chemistry? 

3. How are duplicate sample results tracked and used: 

a. For GUMS analyses? 

b. For GC analyses? 

c. For AAIICP analyses? 

d. For wet chemistry? 

4. At what frequency are lab spikes (e.g., spiked deionized water or clean soil) prepared and analyzed: 

a. For GUMS analyses? 

b. For GC analyses? 

c. For AA/ICP analyses? 

d. For wet chemistry? 

5. At what stage of processing are samples spiked: 

a. For GUMS analyses? 

b. For GC analyses? 

c. For AAKP analyses? 

d. For wet chemistry? 

6. Are matrix spiked samples employed: 

a. For GC/MS analyses? --- 

b. For GC analyses? --- 

c. For AA/ICP analyses? --- 

d. For wet chemistry? 

-- 

7. What action is taken when results exceed control 

limits: 

a. For GUMS analyses? 

b. For GC analyses? 

c. For ANICP analyses? 

d. For wet chemistry? 

8. Are surrogate compounds utilized for GC/MS anatyses? 

9. When are the surrogates added to the samples? 

--- 

10. How many surrogate compounds are introduced? 

il. Is the percent recovery for each surrogate calculated? 

--- 

12. Are those data reported? 

--- 

13. Are performance criteria established for surrogates? 

--- 

14. Are percent recoveries plotted on control charts? 

--- 
LABORATORY AUDIT GUIDELINES 

Page 10 

Yes No Points Comments 

15. What action is taken when results exceed limits? 

16. Are surrogate compounds utilized for GC analyses? 

17. When are the surrogates added to the samples? 

18. How many surrogate compounds are introduced? 

19. Is the percent recovery for each surrogate calculated? 

20. Are those data reported? 

21. Are performance criteria established for surrogates? 

22. Are percent recoveries plotted on control charts? 

23. What action is taken when results exceed limits? 

F. Data Handling and Review 

1. Are computer programs validated prior to use? 

2. Are records of the validation maintained? 

3. Are user instructions complete and available to all 

users? 

4. Do analysts/technicians record data in a neat and 

accurate manner? 

5. Are all handwritten data recorded in nonerasable ink? 

6. Have entries been obliterated (e.g., through crossouts or “whiteout”)? 

7. Are data calculations spot-checked by a second person? 

What percentage? 

8. Are these checks documented on the hard-copy data 

record, and dated and initialed by the reviewer? 

9. Are raw data being identified with client name, project 

number, date, and other pertinent tracking information? 

10. Are raw data (notebooks, data sheets, computer files, 

strip chart recordings) being retained for 5 years? 

11. Is there a system for report, record, or data retrieval? 

12. Do supervisory personnel review the data or QC 

results? 

What percentage? 

--- 

--- 

--- 

--- 

--- 
LABORATORY AUDIT GUIDELINES 

Page 11 

Yes No Points Comments 

13. Are these reviews documented? 

14. Are in-house QC charts maintained and available for 

onsite inspection for: 

a. Matrix spikes? 

b. Laboratory duplicates? 

c. Surrogate recoveries? 

d. Calibration check standards? 

15. Have method detection limit studies been performed 

for each method in use? 

a. How recently? 

b. Any procedural or configurational changes since 

then? 

16. Do records indicate that appropriate corrective action 

has been taken when analytical results fail to meet 

the QC criteria? 

Comments: 

G. QC Manual Checklist 

1. Does the laboratory have a QC manual? 

2. Does the manual address the following: 

a. Personnel? 

b. Facilities or equipment? 

c. Operation of instruments? 

d. Method validation 

e. Calibration frequency 

f. Standards preparation 

g. Documentation of procedures 

h. Preventive maintenance 

i. Reliability of data 

j. Data validation 

k. Feedback and corrective action 

I. Record-keeping 

m. Internal audits 

Comments: 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 

--- 
LABORATORY AUDIT GUIDELINES 

Page 12 

Yes No Points Comments 

H. Summary 

1. Do responses to the evaluation indicate that laboratory personnel are aware of QA/QC and its potential 

impact on the data? 

-- 

2. Is a positive emphasis placed on QA/QC by laboratory management? 

--- 

3. Have the responses been open and direct? 

-- 

4. Has the attitude been cooperative? 

--- 

5. Is the proper emphasis placed on quality assurance? 

--- 

Comments: 
Attachment 2 

---m 
ANA L YTICA L AUDIT SCORING GUIDELINES 

Point distributions for each response that can be answered yes” or ‘no” are given in the 

following guideline. In cases of incomplete fulfillment of requirements, both responses 

may be checked. All points are then totaled and the percentage of the maximum possible 

points is then calculated. Questions that are not applicable to a particular facility are not 

scored, and are not counted toward the maximum possible points, thereby neither 

rewarding nor penalizing the laboratory. Responses to questions which have no point 

value will be used to determine marginal cases of pass or fail. The following criteria are 

given for acceptability or nonacceptability: 

86400% of maximum possible points = acceptable audit 

76435% of maximum possible points = provisionally acceptable audit 

(based on responses to nonpoint 

questions) 

below 76% of maximum possible points = unacceptable audit 
AUDIT SCORING GUIDELINES 

Page 2 

Yes No Comments 

A. Organization and Personnel 

1. 

2. 

3. 

4. 

5. 

6. 

7. 

8. 

9. 

10. 

11. 

Is there an organizational chart available? 

Is everyone in the organization familiar with it? 

Is an up-to-date file maintained in the laboratory describing the educational background and/or related 

work experience of all laboratory personnel? 

Is there a formal training program for personnel? 

Are employees required to demonstrate proficiency 

with analytical instrument operation, methods, or 

techniques prior to working on client samples? 

Is this proficiency testing documented? 

Is the organization adequately staffed to meet commitments in a timely manner? 

Is there a designated QAKX Officer? 

To whom does the lab QNQC Officer report? 

Was the lab QAIQC Officer available during the audit? 

Was a program manager or laboratory manager available during the evaluation? 

Comments: 

8. Sample Receipt and Storage Area 

1. 

2. 

3. 

4. 

5. 

6. 

7. 

8. 

Is a sample custodian designated? 

Are the responsibilities clearly defined? 

In writing? 

Is there a standard sample login procedure followed? 

Does the procedure include adequate inspection of 

samples and accompanying documents to verify that 

they are intact, complete, and consistent? 

Is there an inspection checklist? 

Does it document adequately the nature and condition of samples and documentation? 

Is the integrity of samples and shipping containers 

being documented? 

Are samples logged into a bound notebook? 

a. Computerized lab management system? 

b. Other? (describe: ) 

1 

1 

1 

1 

2 

2 

5 

2 

1 

1 

2 

1 

1 

1 

2 

1 

1 

1 

5 

5 

5 

-1 

-1 

-1 

-2 

-2 

-1 

-1 

-1 

-1 

-1 

-1 

-1 

-1 

-1 

-1 

-1 

-1 

-1 

-2 

-2 

-2 
AUDIT SCORING GUIDELINES 

Page 3 

Yes No Comments 

9. Does the login record document: 

a. Field and laboratory ID 

b. Analyses requested 

c. Storage location 

d. Signature of custodian 

e. Collection date 

f. Receipt date 

g. Analysis due date 

10. 

h. Sample holding time 

i. Special instructions 

Is there a daily summary of information such as samples received, analyses requested, date sampled, or 

date received? 

11. To whom is this summary distributed? 

12. Are login records filed and readily retrievable? 

13. How far back in time can records be retrieved? 

14. Are written SOPS developed for receipt and storage 

of samples? 

15. Are they available to and understood by laboratory 

personnel? 

16. Is a clean area available for receiving and opening 

sample shipments? 

17. Is this area separated from other lab operations (consider not only spatial separations, but air flow, personnel, traffic, etc.)7 

la. 

19. 

20. 

Does the custodian understand the importance of 

preventing lab contamination? 

If appropriate, are the pHs of samples measured and 

recorded to verify that they are preserved? 

What percentage of samples is checked? 

21. 

22. 

23. 

Are records of these checks retained? 

Are facilities adequate for the storage of samples? 

Are samples stored so as to maintain their preservation? 

24. 

25. 

Are volatile samples stored separately from semivolatile samples? 

Is the temperature of the cold storage area recorded 

daily? 

2 

2 

2 

2 

2 

2 

2 

2 

2 

2 

-2 

-2 

-2 

-2 

-2 

-2 

-2 

-2 

-2 

-2 

2 -2 

-1 

-1 

-1 

-1 

-1 

-1 

-1 

-1 

-1 

-2 

-1 
AUDIT SCORING GUIDELINES 

Page 4 

Yes No Comments 

26. Is the sample storage area secure? 1 

27. How is sample identification maintained? 1 

28. Is positive sample chain-of-custody maintained within 1 

the lab? 

29. 

30. 

31. 

How are samples tracked through the lab? 

How long are samples retained? 

Sample extracts? 

How are special instructions regarding preparation, 

analysis, or turnaround times transmitted within the 

laboratory? 

a. Are excursions noted, along with descriptions of 2 

corrective action taken? 

b. Is this being reviewed periodically by a supervisor 2 

or the QC unit? 

Comments: 

C. Sample Preparation Ares/Facilities 

1. Is the laboratory maintained in a clean and organized 2 

manner? 

2. Does the lab appear to have adequate work space 1 

(120 ft2 per analyst)? 

3. Are the toxic chemical handling areas either stainless 1 

steel benches or an impervious material covered with 

absorbent paper? 

4. Are contamination-free work areas provided for the 1 

handling of toxic materials? 

5. Are adequate exhaust hoods available to prevent 2 

contamination of personnel and the laboratory facility? 

6. Are the flow rates and/or face velocities of these 1 

hoods periodically checked and recorded? 

-1 

-1 

-1 

-1 

-1 

-2 

-1 

-1 

-1 

-1 

-1 
AUDIT SCORING GUIDELINES 

Page 5 

Yes No Comments 

7. How frequently are they checked? 

8. Are the procedures and records adequate to demonstrate the proper face velocity profile for each hood 

over the period of record? 

9. 

10. 

11. 

12. 

Is the near-face interior of each hood clear of objects 

that might interfere with the proper face velocity profile and thereby reduce hood efficiency? 

Are chemical waste disposal policies/procedures welldefined and followed by the laboratory? 

Are records of waste containerization and disposal 

(lab logs, manifest, etc.) filed and retrievable? 

Are voltage control devices installed on major instrumentation? 

13. What is the laboratory’s source of distilled/deionized 

water? 

14. Is the conductivity of this water checked daily and 

data recorded (acceptable conductivity is 2.0-5.0 

umhos/cm at 25X)? 

15. 

16. 

17. 

18. 

19. 

Is the analytical balance located away from draft and 

areas subject to rapid temperature fluctuations? 

Is it protected from vibration associated with activities 

in the facility (i.e., it should be on a heavy table, on a 

floor that does not bounce when walked on, etc.)? 

Is the balance maintained by a certified technician? 

Is the balance routinely calibrated with Class S 

weights and are the calibration data recorded? 

Are the Class S weights handled properly to prevent 

contamination/damage? 

20. How often are the Class S weights certified? 

21. Are pH and ion selective meters properly calibrated 

and maintained; and are these activities recorded? 

22. Are laboratory thermometers (including mercury-inglass) calibrated at least yearly against an NIST 

traceable thermometer and documented? 

23. Are reagents dated upon receipt by labeling each 

container with the date received? 

1 

1 

1 

1 

1 

2 

1 

1 

2 

2 

2 

1 

1 

1 

-1 

-1 

-1 

-1 

-1 

-2 

-1 

-1 

-2 

-2 

-2 

-1 

-1 

-1 
AUDIT SCORING GMDELINES 

Page 6 

Yes No Comments 

24. 

25. 

26. 

27. 

28. 

29. 

30. 

31. 

32. 

33. 

34. 

35. 

36. 

37. 

38. 

39. 

40. 

Is there a complete log of reagent and solvent supply 

giving the quantity, batch number, receipt date, percent activity, or purity? 

Are reagents and standards checked prior to use? 

Are solvent lots checked and documented prior to 

use? 

Are reference materials properly labeled? 

Is each spiking/calibration standard completely traceable to documented neat material or a documented 

purchased standard? 

Is each logbook entry signed and dated by the individual who prepared the solution? 

Are logbooks periodically reviewed and signed by a 

manager/supervisor? 

Are logbooks maintained in a manner which allows 

complete traceability? 

Are standards stored separately from samples and 

sample extracts? 

Are volatile and semivolatile standard compounds 

properly segregated? 

Are SOPS readily available to laboratory personnel? 

Are glassware cleaning procedures documented? 

Are the cleaning procedures consistent with EPA 

recommended procedures? 

Is the temperature of the drying ovens recorded daily? 

Is cleaned glassware properly handled and stored to 

prevent contamination? 

How do lab personnel recognize glassware that has 

been prepared for specific function (e.g., organic vs. 

inorganic)? 

Is the laboratory secured? 

Comments: 

D. Instrumentation 

1. Are instrument operating manuals available? 

2. Do the operators demonstrate a good familiarity with 

the manuals? 

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AUDIT SCORING GUIDELINES 

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Yes No Comments 

3. 

4. 

5. 

6. 

7. 

8. 

9. 

10. 

11. 

12. 

Are there service contracts on the instrumentation 

(and is a record maintained of the service)? 

Are in-house replacement parts available? 

Have the instruments been modified in any way? 

Describe the modifications and discuss ramifications: 

Are instruments properly vented or are appropriate 

traps in place? 

Is a logbook maintained for each instrument? 

Is a complete list of laboratory instrumentation available? 

Are all calibration data hard-copied and retained? 

When calibrating an AA: 

a. How many standards are run to generate the 

calibration curve? 

b. Is a new curve generated for each run? 

c. Is a standard blank always run? 

d. Is calibration checked immediately after completing as well as periodically throughout the run? 

When calibrating an ICP: 

a. How many standards are run to generate the 

calibration curve? 

b. Is a new curve generated for each run? 

c. Is a standard blank always run? 

d. Is calibration checked immediately after completing as well as periodically throughout the run? 

When calibrating a GC: 

a. How many standards are run to generate the 

calibration curve? 

b. Is a calibration check standard run daily? 

c. What are the performance criteria for this standard? 

d. Is the instrument typically calibrated for every 

compound of interest? 

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Yes No Comments 

e. How are retention times monitored for each compound of interest, and when is corrective action 

taken? 

13. When calibrating a GUMS: 

a. How many standards are run to generate the 

calibration curve? 

b. 

C. 

Is a calibration check standard run daily? 5 

What are the performance criteria for this standard? 

d. Is the instrument typically calibrated for every 5 

compound of interest? 

e. 

f. 

Is the instrument tuned at least daily? 5 

Do the tuning procedures conform to the methods 5 

for which the instrument is being used? 

What compound and performance criteria are 

used? 

h. 

i. 

Are surrogates and internal standards used? 5 

Are surrogate and internal standard recoveries 5 

monitored? 

i* What are the action limits? 

Comments: 

E. Quality Control 

1. Are method blanks prepared and analyzed with each 5 

batch of samples, for each analytical procedure, or 

some percentage? 

What percentage: 

a. For GUMS analyses? 

b. For GC analyses? 

c. For AA/lCP analyses? 

d. For wet chemistry? 

2. At what frequency are lab duplicates prepared and 

analyzed: 

a. For GUMS analyses? 

b. For GC analyses? 

c. For AAZP analyses? 

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AUDIT SCORING GUIDELINES 

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d. For wet chemistry? 

Yes No Comments 

3. 

4. 

5. 

6. 

7. 

8. 

9. 

10. 

11. 

12. 

13. 

14. 

How are duplicate sample results tracked and used: 

a. For GUMS analyses? 

b. For GC analyses? 

c. For AAIICP analyses? 

d. For wet chemistry? 

At what frequency are lab spikes (e.g., spiked deionized water or clean soil) prepared and analyzed: 

a. For GUMS analyses? 

b. For GC analyses? 

c. For AA/ICP analyses? 

d. For wet chemistry? 

At what stage of processing are samples spiked: 

a. For GUMS analyses? 

b. For GC analyses? 

c. For AA/ICP analyses? 

d. For wet chemistry? 

Are matrix spiked samples employed: 

a. For GUMS analyses? 

b. For GC analyses? 

c. For AAIICP analyses? 

d. For wet chemistry? 

What action is taken when results exceed control 

limits: 

a. For GUMS analyses? 

b. For GC analyses? 

c. For AA/ICP analyses? 

d. For wet chemistry? 

Are surrogate compounds utilized for GC/MS analyses? 

When are the surrogates added to the samples? 

5 

How many surrogate compounds are introduced? 

Is the percent recovery for each surrogate calculated? 

Are those data reported? 

Are performance criteria established for surrogates? 

Are percent recoveries plotted on control charts? 

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Yes No Comments 

15. What action is taken when results exceed limits? 

16. Are surrogate compounds utilized for GC analyses? 

17. When are the surrogates added to the samples? 

18. How many surrogate compounds are introduced? 

19. Is the percent recovery for each surrogate calculated? 

20. Are those data reported? 

21. Are performance criteria established for surrogates? 

22. Are percent recoveries plotted on control charts? 

23. What action is taken when results exceed limits? 

F. Data Handling and Review 

1. 

2. 

3. 

4. 

5. 

6. 

7. 

8. 

9. 

10. 

11. 

12. 

13. 

Are computer programs validated prior to use? 

Are records of the validation maintained? 

Are user instructions complete and available to all 

users? 

Do analysts/technicians record data in a neat and 

accurate manner? 

Are all handwritten data recorded in nonerasable ink? 

Have entries been obliterated (e.g., through crossouts or ‘whiteout”)? 

Are data calculations spot-checked by a second person? 

What percentage? 

Are these checks documented on the hard-copy data 

record, and dated and initialed by the reviewer? 

Are raw data being identified with client name, project 

number, date, and other pertinent tracking information? 

Are raw data (notebooks, data sheets, computer files, 

strip chart recordings) being retained for 5 years? 

Is there a system for report, record, or data retrieval? 

Do supervisory personnel review the data or UC 

results? 

What percentage? 

Are these reviews documented? 

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Yes No Comments 

14. Are in-house QC charts maintained and available for 

onsite inspection for: 

a. Matrix spikes? 

b. Laboratory duplicates? 

c. Surrogate recoveries? 

d. Calibration check standards? 

15. Have method detection limit studies been performed 

for each method in use? 

a. How recently? 

b. Any procedural or configurational changes since 

then? 

16. Do records indicate that appropriate corrective action 

has been taken when analytical results fail to meet 

the QC criteria? 

Comments: 

G. QC Manual Checklist 

1. Does the laboratory have a QC manual? 

2. Does the manual address the following: 

a. Personnel? 

b. Facilities or equipment? 

c. Operation of instruments? 

d. Method validation 

8. Calibration frequency 

f. Standards preparation 

g. Documentation of procedures 

h. Preventive maintenance 

i. Reliability of data 

j. Data validation 

k. Feedback and corrective action 

I. Record-keeping 

m. Internal audits 

Comments: 

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Yes No Comments 

H. Summary 

1. Do responses to the evaluation indicate that laboratory personnel are aware of QA/QC and its potential 

impact on the data? 

2. Is a positive emphasis placed on QNQC by laboratory management? 

3. Have the responses been open and direct? 

4. Has the attitude been cooperative? 

5. Is the proper emphasis placed on quality assurance? 

Comments: 

2 -2 

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2 -5 
Attachment 3 

This is an example memorandum for a specific laboratory for 

which there were very few negative remarks. Naturally, not 

all laboratories will be of this quality. 
(from an actual laboratory audit) 

TO: [Audit Requestor] 

FROM: [Auditor] 

DATE: [Day/Month/Year] 

SUBJECT: Laboratory Audit Visit to [Laboratory Name] 

[Street Address] 

[City, State, Zip Code] 

[Phone Number] 

An analytical chemistry laboratory observation visit was conducted on [date] at the [laboratory 

name and location]. The observation visit was performed by [auditor name] as part of the general 

QA/QC observations being conducted on behalf of [client name]. Samples were collected in the 

field by [source testing or field sampling company], and analyzed at the [laboratory name]. The 

following areas were included as a part of the observation process at [laboratory name]: 

n Personnel and organization 

n Sample receipt and storage 

n Sample preparation facilities 

I Instrumentation and equipment 

n Quality control 

I Data handling and review. 

The attached Analytical Chemistry Laboratory Audit Guidelines were followed during the visit. 

Participating [laboratory name] staff included: 

n [Names and titles]. 

The purpose of the observation visit was to determine whether [laboratory name] has the facilities, 

equipment, trained personnel, and QAIQC program in place to be capable of routinely producing 

data of known quality for site characterization programs. The completed checklist is appended. 

AUDIT FINDINGS 

Generally, the [laboratory name] was found to be capable of producing known quality, traceable 

data. There appeared to be, an adequate understanding of QAIQC procedures within the 

laboratory. The employees interviewed displayed a positive attitude and an appreciation for the 

importance of quality assurance, and understood the potential impact of QA/QC upon data. 

No major deficiencies were noted during the audit. The following recommendations are intended 

to improve a basically sound program: 

n There should be more formal in-house QA/QC and training programs instituted for 

analysts and technicians; currently, training is dependent upon the more experienced analysts 
n An inspection checklist should be generated for incoming samples, which includes 

the nature and condition of samples and documentation 

n Internal chain-of-custody procedures should be initiated 

n As part of the SOPS, a specific policy should be instituted for the rejection of 

incoming compromised samples 

n Control charts should be maintained for all types of QC samples that are run. 

The [laboratory name] staff were very helpful and cooperative. There appears to be a positive 

emphasis placed on QAJQC by laboratory management, and the responses appeared to be open 

and direct. 
APPENDIX H 

Format for the Sediment 

Testing Report 
SEDIMENT TESTING REPORT FORMAT 

The sediment testing report, including physical, chemical, bioassay, and bioaccumulation 

data, should be prepared using the format guidelines below. 

A. INTRODUCTION 

The project description should include the following information: 

1. Location of the proposed dredging project and the disposal site. 

2. A plan view map showing project design depth, side-slopes, allowable overdepth. 

3. Proposed dredging and disposal quantities. 

B. MATERIALS AND METHODS 

1. Field sediment sampling and sediment sample handling procedures should be 

described or referenced. 

2. References for laboratory protocols for physical, chemistry, bioassay, and 

bioaccumulation analyses should be included, such as: 

a. EPA method numbers and other EPA-approved methods that do not have a 

specific EPA number. 

b. Target detection limits and references used for physical, chemical and tissue 

analyses. 

C. Test species used in each test, the supplier or collection site for each test 

species, and QA/QC procedures for maintaining the test species. 

d. Locations of references and control sediment samples. 

e. Source of water used in all biological tests and documentation that the water is 

free of contaminants. 

f. Bioassay and bioaccumulation testing procedures and QA/QC information. 

g. Statistical analysis procedures. 

C. LOCATION OF SAMPLING AREAS 

1. The exact position of the dredging site sampling areas and each core taken within 

each sampling area should be mapped. 

H-1 
2. A table should be prepared with the coordinates for each station in latitude and 

longitude (North America Datum 1983). 

3. A table should be included showing the required sampling depth at each sampling 

location compared to the actual core depth achieved during field sampling. Any 

problems in collecting sediment from the required depth should be discussed. 

4. The type of positioning equipment to be used for the sampling program should be 

specified. 

5. Charts should be provided to show the location of the reference site, the control 

site(s) and the disposal site, including the coordinates of each site. 

D. DESCRIPTION OF TESTING APPROACH 

The rationale for performing specific types of tests (e.g. chemical analysis of elutiate for 

comparison to water quality standards, tissue analysis, etc.) should be presented in writing. 

E. FINAL RESULTS 

1. Summary data tables should be furnished. All data tables should be typed or 

produced as a computer printout. 

2. Copies of the final raw data sheets should be included. These tables should be 

certified to be accurate by the analytical laboratory manager. 

F. DISCUSSION AND ANALYSIS OF DATA 

1. An evaluation of historical data from the proposed dredging site should be concisely 

discussed. References to previous sediment testing should also be included. 

2. Statistical comparisons between the dredging site sediments and the reference 

sediment should be made. 

G. REFERENCES 

This list should include all references used in the field sampling program, laboratory and 

statistical data analyses, and historical data used to compare the dredging to the reference 

site. 

H. DETAILED QA/QC PLANS AND INFORMATION 

The following topics should be addressed in the QA Plan: 

• Introductory material, including title and signature pages, table of contents, and 

project description. 

H-2 
n 

n 

n 

n 

n 

n 

n 

n 

n 

n 

n 

n 

n 

n 

n 

n 

QA organization and responsibilities (the QA organization should be designed to 

operate with a degree of independence from the technical project organization to 

ensure appropriate oversight) 

QA objectives 

Standard Operating Procedures 

Sampling strategy and procedures 

Sample custody 

Calibration procedures and frequency 

Analytical procedures 

Data validation, reduction, and reporting 

Internal QC checks 

Performance and system audits 

Facilities 

Preventive maintenance 

Calculation of data quality indicators 

Corrective actions 

QA reports to management 

References. 

I. PERTINENT CORRESPONDENCE WITH SCOPING COMMENTS AND 

COORDINATION 

The report should contain copies of the correspondence related to coordination on the 

testing activities for the proposed project. 

H-3 

*U.S. GOVERNMENT PRINTINGOFFICE: IQ95 - 821 - 15.1 ! 821~81 
QA/QC Guidance for Sampling and Analysis of Sediments, 

@EPA Water, and Tissues for Dredged Material Evaluations 

Chemical Evaluations 

NOTE TO USER OF THIS MANUAL 

Please cut the furnished spine 

to fit your binder 
United States 

Environmental Protection Agency 

14305) 

Washington, DC 20460 

Official Business 

Penalty far Private Use 

$,XlO