\ UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
EPA 823-B-95-001
APR 2 8 f995
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 (USAGE) with experience
related to dredged material discharge activities.
EPA and USAGE 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 USAGE
1994), and "Evaluation of Dredged Material Proposed for Ocean
Disposal—Testing Manual" (the Ocean Testing Manual) (U.S. EPA and
USAGE 1991). Results of tests conducted using the testing
manuals are the basis of independent evaluations made by EPA and
USAGE 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
Recycled/Recyclable
Primed with Soy/Canola Ink on paper that
contains at least 50% recycled fiber
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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
Director
Office of Science
and Technology
Robert H. Wayland III
Director
Office of Wetlands,
Oceans and Watersheds
Enclosure
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QA/QC Guidance for Sampling and Analysis of Sediments,
Water, and Tissues for Dredged Material Evaluations
Chemical Evaluations
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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
TOG
USAGE
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-p-dioxin
polychlorinated dibenzofuran
quality assurance management plan
quality assurance project plan
quality assurance and quality control
standard reference material
tetrachlorodibenzo-p-dioxin
target detection limit
toxiclty equivalency factor
total organic carbon
U.S. Army Corps of Engineers
XI
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f/EPA
United States
Environmental Protection
Agency
Office of Water
(4305)
EPA 823-B-95-001
April 1995
QA/QC Guidance for Sampling
and Analysis of Sediments,
Water, and Tissues for Dredged
Material Evaluations
Chemical Evaluations
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v>EPA
United States
Environmental Protection Agency
(4305)
Washington, DC 20460
Official Business
Penalty for Private Use
$300
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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
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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.
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CONTENTS
Page
LIST OF FIGURES vii
LIST OF TABLES ix
ACRONYMS AND ABBREVIATIONS xi
ACKNOWLEDGMENTS xiii
1. INTRODUCTION 1
1.1 GOVERNMENT (DATA USER) PROGRAM 3
1.2 CONTRACTOR (DATA GENERATOR) PROGRAM 3
2. DRAFTING A QUALITY ASSURANCE PROJECT PLAN 6
2.1 INTRODUCTORY MATERIAL 6
2.2 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
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2.5.7 Sample Collection Methods 50
2.5.8 Sample Handling, Preservation, and Storage 53
2.5.9 Logistical Considerations and Safety Precautions 59
2.6 SAMPLE CUSTODY 60
2.6.1 Sample Custody and Documentation ; 60
2.6.2 Storage and Disposal of Samples 64
2.7 CALIBRATION PROCEDURES AND FREQUENCY 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 70
2.8.2 Chemical Analysis of Sediment 71
2.8.3 Chemical Analysis of Water . i 78
2.8.4 Chemical Analysis of Tissue 83
2.9 DATA VALIDATION, REDUCTION, AND REPORTING 87
. i
2.9.1 Data Validation 88
2.9.2 Data Reduction and Reporting 91
2.10 INTERNAL QUALITY CONTROL CHECKS 91
2.10.1 Priority and Frequency of Quality Control Checks 93
2.10.2 Specifying Quality Control Limits • 96
2.10.3 Quality Control Considerations for Physical Analysis
of Sediments 99
2.10.4 Quality Control Considerations for Chemical Analysis of
Sediments 99
2.10.5 Quality Control Considerations for Chemical Analysis of
Water 100
2.10.6 Quality Control Considerations for Chemical Analysis of
Tissue "100
IV
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2.11 PERFORMANCE AND SYSTEM AUDITS 101
2,11.1 Procedures for Pre-Award Inspections of Laboratories 101
2.11.2 Interlaboratory Comparisons 102
2.11.3 Routine System Audits 104
2.12 FACILITIES 104
2.13 PREVENTIVE MAINTENANCE 105
2.14 CALCULATION OF DATA QUALITY INDICATORS 105
2.15 CORRECTIVE ACTIONS 107
2.16 QUALITY ASSURANCE REPORTS TO MANAGEMENT 108
2.16.1 Preparing Basic Quality Assurance Reports 108
2.16.2 Preparing Detailed Quality Assurance Reports 109
2.17 REFERENCES 110
3. REFERENCES 111
4. GLOSSARY 123
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
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
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LIST OF FIGURES
Page
Figure 1. Guidance for data assessment and screening
for data quality 92
vii
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LIST OF TABLES
Table 1. Checklist of laboratory deliverables for the analysis
of organic compounds
Table 2. Checklist of laboratory deliverables for the analysis
of metals
Table 3. Routine analytical methods and target detection
limits for sediment, water, and tissue
Table 4. Levels of data quality for historical data
Table 5. Summary of recommended procedures for sample
collection, preservation, and storage
Table 6. Example calibration procedures
Table 7. PCDD and PCDF compounds determined by
Method 1613
Table 8. Polychlorinated biphenyl congeners recommended
for quantitation as potential contaminants of
concern
Table 9. Methodology for toxicity equivalency factors
Table 10. Octanol/water partition coefficients for organic
compound priority pollutants and 301 (h) pesticides
Table 11. Bioconcentration factors of inorganic priority
pollutants
Table 12, Levels of data validation
Table 13. Example warning and control limits for calibration
and quality control samples
Table 14. Sources of standard reference materials
Paqe
11
13
17
41
54
66
74
76
79
81
85
90
98
103
IX
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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
TOG
USAGE
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-p-dioxin
polychlorinated dibenzofuran
quality assurance management plan
quality assurance project plan
quality assurance and quality control
standard reference material
tetrachlorodibenzo-p-dioxin
target detection limit
toxiclty equivalency factor
total organic carbon
U.S. Army Corps of Engineers
XI
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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 (USAGE) with experience related to dredged
material discharge activities.
Members; Jim Barron EPA/OERR (Superfund)
Patricia Boone EPA/Region 5
Suzy Cantor-McKinney EPA/Region 6
Tom Chase EPA/OWOW
Pat Cotter EPA/Region 9
Tom Dixon EPA/QAMS
Bob Engler USACEE/WES
Rick Fox EPA/GLNPO
Catherine Fox EPA/Rsgion 4
Bob Graves EPA/EMSL 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 EPA/Region 10
William Muir EPA/Region 3
Rich Pruell EPA/ORD-N
Norm Rubinstein EPA/ORD-N
Brian Schumacher EPA/EMSL Las Vegas
George Schupp EPA/Region 5
Ann Strong USACEE/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 (USAGE 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 10), and Tom Wright
(USAGE WES).
XIII
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1. INTRODUCTION
This document provides programmatic and technical guidance on quality
assurance and quality control (QA/QC) issues related to dredged material
evaluations. The U.S. Army Corps of Engineers (USAGE) 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 USAGE 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 Predged Material Proposed for Discharge in Waters of the
U.S.—Testing Manual (Draft)" (the Inland Testing Manual) (U.S. EPA and
USAGE 1994), and "Evaluation of Dredged Material Proposed for Ocean
Disposal—Testing Manual" (the Ocean Testing Manual) (U.S. EPA and USAGE
1991). Results of tests conducted using the testing manuals are the basis of
independent evaluations made by EPA and USAGE 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 decision-
making. The EPA has developed a two-tiered quality management structure
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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 project-
specific 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 andjaboratory 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
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document also incorporates information contained in U.S. EPA (1984a, 1991d)
and U.S. EPA and USAGE (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 USAGE,
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 USAGE. 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 (1991 d).
The guidance in this document is intended to assist EPA and USAGE 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 USAGE. 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.
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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 USAGE to
make a decision about the suitability of dredged material for aquatic disposal
with the specified degree of confidence).
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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)1, 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. EPA1989a);
• Introductory material, including title and signature pages, table of
contents, and project description
• 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.
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• 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 primariiy
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.
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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 decision-
making.
The QA project plan should include the following certification statement signed
by a duly authorized representative of the permittee:
/ 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 ORGANIZA TION 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
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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 QA 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 USAGE personnel performing the analyses or
to the laboratory selected by USAGE'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
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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 tf le analysis of most
chemicals in the most commonly analyzed sample matrices is provided in
Appendix B, and is based on the following outline:
« 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.
• 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-eustody, and sample logbook procedures.
• Methods to be followed for processing and analyzing samples.
» QA/QC requirements, including the data quality objectives
specified in the QA project plan and appropriate warning and
control limits.
» 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,
-------
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 USAGE 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:
• 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.
• Conditions for rejection or non-analysis of samples and reanalysis
of samples.
• Required storage time for records and samples prior to disposal.
• 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
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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.
C] Tabulated results, including final dilution volume of sample Detracts, sample
size, wet-to-dry ratios for solid samples (if requested), concentrations of com-
pounds of interest (reported in units identified to two significant figures unless
otherwise justified), and equations used to perform calculations.
Concentration units should be jig/kg (dry weight) for sediment, and jig/L for
water, jig/kg (wet weight) for tissue. These results should be checked for
accuracy and the report signed by the laboratory manager or designee.
n Target detection limits (see discussion in Section 2.3.2 of this; document),
instrument detection limits, and detection limits achieved for the samples.
n Original data quantification reports for each sample.
Q Method blanks associated with each sample, quantifying all compounds of
interest identified in these blanks.
[] 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 deca-
fluorotriphenylphosphine (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.
fj 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.
fj All data qualification codes assigned by the laboratory, their description, and
explanations for all departures from the analytical protocols.
11
-------
TABLE 1. (cont.)
Additional Deliverabies for Volatile or Semivolatile Organic Compound Analyses8
L~] 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).
L~] Reconstructed ion chromatograms for gas chromatography/mass
spectrometry (GC/MS) analyses for each sample.
Q Mass spectra of detected compounds for each sample.
Q Internal standard area summary to show whether internal standard areas
were stable.
Q] 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 Deliverabies for Pesticide and Polychlorinated Biphenyl Analyses8
Q . Gas chromatography/electron capture detection (GC/ECD) chromatograms for
quantification column and confirmation columns for each sample and for all
standards analyzed.
Q GPC chromatograms (if GPC was performed).
Q] An evaluation summary for 4,4'-DDT/endrin breakdown.
H] A pesticide standard evaluation to summarize retention time shifts of internal
standards or surrogate spike compounds.
' 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
L~] A cover letter discussing analytical problems (if any) and referencing or
describing the digestion procedures and instrumentation used.
L~] 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 (4,g/kg (dry weight) for sediment, (ig/L
for water, and ng/kg (wet weight) for tissue.3 These results should be
checked for accuracy and the report signed by the laboratory manager or
designee.
L~] Target detection limits (see discussion in Section 2.3.2 of this document),
instrument detection limits, and detection limits achieved for the samples.
n Method blanks for each batch of samples.
Q 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 mg/kg for solid samples. Tine specification here
of (xg/kg is for consistency with organic chemical analyses, which are typically reported as
|o.g/kg for solid samples. If different units are used, care should be taken to ensure that results
are not confused.
13
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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 < 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
14
-------
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 USAGE 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 iin 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 10 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
15
-------
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 QA 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.
2.4 STANDARD OPERATING 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 QA project plan. Only modifications to standard operating procedures or
non-standard procedures need to be explained in the main body of the QA
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
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TABLE 3. ROUTINE ANALYTICAL METHODS AND TARGET DETECTION LIMITS
FOR SEDIMENT, WATER, AND TISSUE (parts per billion, unless otherwise noted)
Example Recommended Example Recommended Example Recommended
Sediment Sediment Tissue Tissue Water Water
Chemical Method8 TDL Method8 TDLb Method" TDL"
Inorganic Chemicals
Aluminum
Antimony
Arsenic
Beryllium
Cadmium
Chromium
3050A/6010A;
U.S. EPA(1993a)
3050A;
7040/7041;
U.S. EPA(1993a);
PSEP (1990a)
7061;7060A;
3050A;
U.S. EPA(1993a);
PSEP(1990a);
EPRI (1986)
200.8;
7090/7091;
U.S. EPA(1993a)
3050A; 601 OA;
71 31 A/71 30;
U.S. EPA(1993a);
PSEP (1990a)
3050A/7191;
7190; 601 OA;
U.S. EPA (1993a);
50,000C
2,500
5,000
2,500d
300
5,000
200.8;
U.S. EPA(1993a);
200.8;
7040/7041;
U.S. EPA(1993a);
200.8/7061;
7060A;
U.S. EPA (1993a)
200.8;
7090/7091;
U.S. EPA(1993a)
200.8; 7131A;
7130;
U.S. EPA(1993a)
200.8/7191;
7190;
U.S. EPA(1993a)
1,000
100
100
100
100
100
202.2;
6010A/200.7
7041; 204.2
3010;7061;
206.2; 206.3;
EPRI (1986)
7091; 210.2;
6010A/200.7;
200.8
213.2; 7131A;
3010;
6010A/200.7;
200.8
71 91; 200.8;
218.2; 3010;
6010A/200.7
40
3
1
0.2
1
1
-------
TABLES, (cont.)
Chemical
Example
Sediment
Method1
Recommended
Sediment
TDL
Example
Tissue
Method1
Recommended
Tissue
TDLb
Example
Water
Method1
Recommended
Water
TDLb
Cobalt
Copper
Hexavalent chromium
Iron
Lead
Manganese
Mercury
Nickel
Selenium
7201
3050A/7211;
7210; 6010A;
U.S. EPA (1993a);
PSEP (1990a)
_i
3050A/7381;
U.S. EPA (1993a)
3050A/7421;
7420; 601 OA;
U.S. EPA (1993a);
PSEP (19903)
3050A/7461;
U.S. EPA (1993a)
7471;
U.S. EPA (1993a)
3050 A/601 OA;
7521; 7520;
U.S. EPA(1993a);
PSEP (1990a)
7741:7740;
U.S. EPA (19933);
EPRI (1986)
100
S.OOO1
-
50,000*
5,000
5,000C
200
5,000
1,000e
200.8; 7201
200.8/7211;
7210;
U.S. EPA (1993a)
-'
200.8; 7381;
601 OA;
U.S. EPA (1993a)
200.8/7421;
7420;
U.S. EPA(1993a)
200.8/7461;
U.S. EPA (1993a)
7471;
U.S. EPA (1993a)
200.8/601 OA;
7521;7520;
U.S. EPA (1993a)
200.8/7741;
7740;
U.S. EPA (1993a)
100
100
-
10,000
100
500
10
100
200
219.2
721 1; 200.8;
220.1; 220.2;
3010;
60 10 A/200.7
71 97; 21 8.5
6010A/200.7;
3010; 7381;
236.2
7421;239.2
6010A/200.7;
243.2; 3010
7471; 245.1;
245.2
601 OA; 7521;
249.2
7740;7741;
270.2; 270.3;
EPRI (1986)
4
1
50
10
1
1
0.2
1
2
-------
TABLE 3. (cont.)
Chemical
Example
Sediment
Method1
Recommended
Sediment
TDL
Example
Tissue
Method"
Recommended
Tissue
TDLb
Example
Water
Method8
Recommended
Water
TDLb
Silver
Thallium
Tin
Zinc
3050A/7761;
7760;
U.S. EPA (1993a);
PSEP (1990a)
7840/7841;
U.S. EPA (1993a)
U.S. EPA (1993a)
3050A/7951;
7950;
U.S. EPA (1993a);
PSEP (1990a)
200"
200"
500e'e
15,000
200.8/7761:7760;
U.S. EPA (1993a)
200.8; 7840; 7841;
U.S. EPA (1993a)
200.8;
U.S. EPA(1993a)
200.8/7951; 7950;
U.S. EPA(1993a)
100
100
100
2,000
7761:272.2
7840; 7841;
279.2
282.2
7951;289.2;
200.7;3010;
601 OA
1
1
5
1
Organotin
NCASI(1986);
Uhler and Durrel
(1989);
Rice et al. (1987)
10
NCASI (1986);
Riceetal. (1987);
Uhler etal. (1989)
10
NCAS!(1986);
Rice et al.
(1987); Uhler
and Durrel
(1989)
o.o-
-------
IMOUC O. IUUIIUJ
Example Recommended Example Recommended Example Recommended
Sediment Sediment Tissue Tissue Water Water
Chemical Method* TDL Method* TDL" Method* TDL"
Nonlonlc Organic Compounds
LPAH Compounds
Naphthalene
Acenaphlhylene
Acenaphlhene
1625C;3540A;
3550A/8100;
8250; 8270A;
8310;
NOAA (1989);
U.S. EPA (1993a)
1625C;3540A;
3550A/8100;
8250; 8270A;
8310;
U.S. EPA(1993a)
1625C;3540A;
3550A/8100;
8250; 8270A;
8310;
U.S. EPA (1993a)
20
20
20
16250; 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 etal. (1993);
NOAA (1989)
20
20
20
16250; 351 OA;
3520A/8100;
8250; 8270A;
8310
16250; 351 OA;
3520A/8100;
8250; 8270A;
8310
16250; 351 OA;
3520A/8100;
8250; 8270A;
8310
10
10
10
-------
TABLES, (cont.)
Chemical
Example
Sediment
Method*
Recommended
Sediment
TDL
Example
Tissue
Method8
Recommended
Tissue
TDL"
Example
Water
Method8
Recommended
Water
TDL"
Fluorene
Phenanthrene
Anthracene
1 -Methylnaphthalene
1625C; 3540A;
3550A/8100;
8250; 8270A;
8310;
U.S. EPA (1993a)
1625C; 3540A;
3550A/8100;
8250; 8270A;
8310;
U.S. EPA (1993a)
1625C; 3540A;
3550A/8100;
8250; 8270A;
8310;
U.S. EPA (19933)
1625C; 3540A;
3550A/8100;
8250; 8270A;
8310;
U.S. EPA(1993a)
20
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)
1625C; 8100;
8250; 8270A;
8310;
U.S. EPA (1993a);
Sloan et al.
(1993);
NOAA (1989)
20
20
20
20
1625C; 3510A;
3520A/8100;
8250; 8270A;
8310
1625C; 351 OA;
3520A/8100;
1 8250;8270A;
8310
1625C; 3510A;
3520A/8100;
8250; 8270A;
8310
1625C; 3510A;
3520A/8100;
8250; 8270A;
8310
10
10
10
10
-------
TABLES, (cont.)
Exampte Recommended Example Recommended Example Recommended
Sediment Sediment Tissue Tissue Water Water
Chemical Method* TDL Method1 TDLb Method* TDLb
2-MethyInaphthalene
1625C; 3540A;
3550A/8100;
8250; 8270A;
8310;
U.S. EPA (1993a)
20
1625C; 8100;
8250; 8270A;
8310;
U.S. EPA (1993a);
Sloan et al. (1993);
NOAA (1989)
20
1625C; 351 OA;
3520A/8100;
8250; 8270A;
8310
10
HPAH Compounds
Fluoranthene
Pyrene
Benz[a]anthracene
1625C;3540A;
3550A/8100;
8250; 8270A;
8310;
U.S. EPA (1993a)
1625C; 3540A;
3550A/8100;
8250; 8270A;
8310;
U.S. EPA (1993a)
1625C; 3540A;
3550A/8100;
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 at al. (1993);
NOAA (1989)
20
20
20
1625C; 351 OA;
3520A/8100;
8250; 8270A;
8310
1625C;3510A;
3520A/8100;
8250; 8270A;
8310
1625C; 3510A;
3520A/8100;
8250; 8270A;
8310
10
10
10
-------
1ME3. fcont.)
Chemical
Example
Sediment
Method"
Recommended
Sediment
TDL
Example
Tissue
Method-
Recommended
Tissue
TDL"
Example
Water
Method*
Recommended
Water
TDL"
Chrysene
Benzo(b&k)ftuoranthenes
Benzo[a]pyrene
Ind8no[1 ,2,3-c,d]pyrene
Dibenz[a,h]anthracene
1625C; 3540A;
3550A/8100;
8250; 8270A;
8310;
U.S. EPA (1993a)
1625C; 3540A;
3550A/8100;
8250; 8270A;
8310;
U.S. EPA (19933)
1625C; 3540A;
3550A/8100;
8250; 8270A;
8310;
U.S. EPA (1993a)
1625C; 3540A;
3550A/8100;
8250; 8270A;
8310;
U.S. EPA (1993a)
1625C; 3540A;
3550A/8100;
oizou; OZ/UM;
8310;
U.S. EPA (1993a)
20
20
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 ai. (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; 8310;
U.5. th"A naaaaK
Sloan et al. (1993);
NOAA (1989)
20
20
20
20
20
1625C; 3510A;
3520A/8100;
8250; 8270A;
8310
1625C; 3510A;
3520A/8100;
8250; 8270A;
8310
1625C; 3510A;
3520A/8100;
8250; 8270A;
8310
1625C; 351 OA;
3520A/8100;
8250; 8270A;
8310
1625C; 3510A;
3520A/8100;
8250; 8270A;
8310
10
10
10
10
10
Co
-------
TABLES, (cont)
Example Recommended Example Recommended Example Recommended
Sediment Sediment Tissue Tissue Water Water
Chemical Method* TDL Method* TDL" Method* TDL"
Benzo{g,h,i]peiylene
Chlorinated Benzenes
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene
1 ,2-Dfchlorobenzene
1 ,2,4-TrichIorobenzene
Hexachlorobenzene
1625C; 3540A;
3550A/8100;
8250; 8270A;
8310;
U.S. EPA (1993a)
1625C; 3540A;
3550A/8100;
8240A; 8250;
8260; 8270A
1625C; 3540A;
3550A/8100;
8240A; 8250;
8260; 8270A
1625C; 3540A;
3550A/8100;
8240A; 8250;
8260; 8270A
1625C; 3540A;
3550A/8250;
8260; 8270A
1625C; 3540A;
3550A/8250;
8260; 8270A
20
20
20
20
10'
10'
1625C;8100;
8250; 8270A; 8310;
U.S. EPA (19938);
Sloan et al. (1993);
NOAA (1989)
1625C; 8240A:
8250; 8270A;
Sloan etal. (1993)
1625C: 8100;
8240A; 8250;
8270A;
Sloan etal. (1993);
NOAA (1989)
1625C; 8240A:
8250; 8270A;
Sloan etal. (1993)
1625C; 8250;
8260; 8270A;
Sloan etal. (1993)
1625C; 8250;
8260; 8270A;
Sloan etal. (1993)
20
20
20
i
20
20
20
1625C;3510A;
3520A/8100;
8250; 8270A;
8310
1625C; 3510A;
3520A/8100;
8240A; 8250;
8260; 8270A
1625C; 3510A;
3520A/8100;
8240A; 8250;
8260; 8270A
1625C; 3510A;
3520A/8100;
8240A; 8250;
8260; 8270A
1625C; 3510A;
3520A/8250;
8260; 8270A
1625C; 3510A;
3520A/8250;
8260; 8270A
10
10
10
10
10
10
-------
TABLES, (cont.)
Ol
Example Recommended Example Recommended Example Recommended
Sediment Sediment Tissue Tissue Water Water
Chemical Method" TDL Method" TDL" Method" TDL"
Phthalate Esters
Dimethyl phthalate
Diethyl phthalate
Di-n-butyl phthalate
Butyl benzyl phthalate
Bis[2-ethylhexyl]phthalate
1625C; 3540A;
3550A/8060; 8100;
8250; 8270A
1625C; 3540A;
3550A/8060; 8100;
8250; 8270A
1625C; 3540A;
3550A/8060; 8100;
8250; 8270A
1625C;3540A;
3550A/8060; 8100;
8250; 8270A
1625C;3540A;
3550A/8060; 8100;
8250; 8270A
50
50
50
50
50
1625C; 8060;
8100; 8250; 8270A;
Sloan et al.
(1993);
NOAA (1989)
1625C; 8060;
8100;8250;8270A;
Sloan et al.
(1993);
NOAA (1989)
1625C; 8060;
8100; 8250; 8270A;
Sloan et al.
(1993);
NOAA (1989)
1625C; 8060;
8100; 8250; 8270A;
Sloan et al.
(1993);
NOAA (1989)
1625C;8060;
8100;8250;8270A;
Sloan et al.
(1993);
NOAA (1989)
20
20
20
20
20
1625C;3510A;
3520A/8060;
8100; 8250;
8270A
1625C;3510A;
3520A/8100;
8060; 8250;
8270A
1625C; 3510A;
3520A/8100;
8060; 8250;
8270A
1625C; 3510A;
3520A/8100;
8060; 8250;
8270A
1625C;3510A;
3520A/8100;
8060; 8250;
8270A
10
10
10
10
10
-------
TABLES, (cont.)
Example Recommended Example Recommended Example Recommended
Sediment Sediment Tissue Tissue Water Water
Chemical Method* TDL Method* TDL" Method* TDL"
Di-n-octyl phthalate
Miscellaneous Retractable Compo
Benzyl alcohol
Benzole acid
Dibenzofuran
Hexachloroethane
Hexachlorobutadiene
1625C; 3540A;
3550A/8060; 8100;
8250; 8270A
jnds
1625C;3540A;
3550A/8250;
8270A
1625C; 3540A;
3550A/8250;
8270A
1625C; 3540A;
3550A/8250;
8270A
1 625C; 3540A;
3550A/8250;
8270A
1625C;3540A;
3550A/8250;
8270A
50
50
100
50
100
20
1625C; 8060;
8100;8250;8270A;
Sloan el at.
(1993);
NOAA(1989)
1625C;8250;
8270A
1625C; 8250;
8270A
1625C; 8100;
8250; 8270A;
Sloan et al. (1993);
NOAA (1989)
1625C; 8250;
8270A
1625C; 8250;
8270A
20
100
100
20
40
40
1625C;3510A;
3520A/8100;
8060; 8250;
8270A
1625C;3510A;
3520A/8250;
8270A
1625C;3510A;
3520A/8250;
8270A
1625C; 3510A;
3520A/8250;
8270A
1625C;3510A;
3520A/8250;
8270A
1625C;3510A;
3520A/8250;
8270A
10
50
50
10
50
50
-------
TABLE 3. (cont)
M
N
Example Recommended Example Recommended Example Recommended
Sediment Sediment Tissue Tissue Water Water
Chemical Method" TDL Method" TDL" Method" TDLb
N-Nitrosodiphenylamine
Methylethyl ketone
Polychlorlnated Dlbenzofurans
Tetrachlorinated furans
Pentachlorinated furans
Hexachlorinated furans
Heptachlorinated furans
Octachlorinated furans
Polychlorlnated Dibenzo-p-dloxlns
2,3.7,8-TCDD
Other tetrachlorinated dioxins
Pentachtorinated dioxins
Hexachlorinated dioxins
1625C; 3540A;
3550A/8250;
8270A
1624C; 3540A;
3550A/8250;
8240A; 8260;
8270A
1613;8290
1613; 8290
1613; 8290
1613;8290
1613; 8290
1613; 8290
1613; 8290
1613; 8290
1613; 8290
20
20
0.001
0.0025
0.005
0.005
0.01
0.001
0.001
0.0025
0.005
1625C; 8250;
8270A
1624C; 8250;
8270A
8290
8290
8290
8290
8290
8290
8290
8290
8290
20
20
0.001
0.0025
0.005
0.005
0.01
0.001
0.001
0.0025
0.005
1625C; 3510A;
3520A/8250;
8270A
1624C;
351 OA;
3520A/8250;
8240A; 8260;
8270A
1613; 8290
1613;8290
1613:8290
1613; 8290
1613;8290
1613; 8290
1613;8290
1613; 8290
1613; 8290
50
50
0.00001
0.000025
0.00005
0.00005
0.0001
0.00001
0.00001
0.000025
0.00005
-------
TABLES, (cont.)
Qo
Example Recommended Example Recommended Example Recommended
Sediment Sediment Tissue Tissue Water Water
Chemical Method" TDL Method" . TDLb Method* TDL"
Heptachlorinated dioxins
Octachlorinated dioxins
PCBs
PCB congeners
Pesticides
Aldrin
Chlordane and derivatives
Dieldrin
4,4'-DDD
4,4'-DDE
1613; 8290
1613; 8290
0.005
0.01
Sloan et al. (1993);
NOAA (1989);
U.S. EPA (1993a)
3540A;
3550A/8080; NOAA
(1985)
3540A;
3550A/8080; NOAA
(1985)
3540A;
3550A/8080; NOAA
(1985)
3540A;
3550A/8080; NOAA
(1985)
3540A;
3550A/8080; NOAA
(1985)
1
10
10
10
10
10
8290
8290
0.005
0.01
1613; 8290
1613; 8290
0.00005
0.0001
NOAA (1989);
U.S. EPA (1993a)
8080;
NOAA (1985)
8080;
NOAA (1985)
8080;
NOAA (1985)
8080;
NOAA (1985)
8080;
NOAA (1985)
2
NOAA (1989)
10
10
10
10
10
608;
351 OA;
3520A/8080
608;
351 OA;
3520A/8080
608;
351 OA;
3520A/8080
608;
351 OA;
3520A/8080
608;
351 OA;
3520A/8080
0.01
0.04
0.14
0.02
0.1
0.1
-------
TABLE 3. (cont.)
Chemical
Example
Sediment
Method"
Recommended
Sediment
TDL
Example
Tissue
Method"
Recommended
Tissue
TDLb
Example
Water
Method"
Recommended
Water
TDL"
4,4'-DDT
Endosulfan and derivatives
Endrin and derivatives
Heptachlor and derivatives
fHexachlorocyclohexane
(lindane)
Toxaphene
Methoxycnior
Chlorbenside
3540A;
3550A/8080; NOAA
(1985)
3540A;
3550A/8080; NOAA
(1985)
3540A;
3550A/8080; NOAA
(1985)
3540A;
3550A/8080; NOAA
(1985)
3540A;
3550A/8080; NOAA
(1985)
3540A;
3550A/8080
3540A;
3550A/8080
3540A;
3550A/8080; NOAA
(1985)
10
10
5
10
10
50
10
2
8080;
NOAA (1985)
8080;
NOAA (1985)
8080;
NOAA (1985)
8080;
NOAA (1985)
8080;
NOAA (1985)
8080
8080
8080;
NOAA (1i85)
10
10
10
10
10
50
10
2
608;
351 OA;
3520A/8080
608;
351 OA;
3520A/8080
608;
351 OA;
3520A/8080
608;
351 OA;
3520A/8080
608;
351 OA;
3520A/8080
608;
3510A;
3520A/8080
608;
351 OA;
3520A/8080
608;
351 OA;
3520A/8080
0.1
0.1
0.1
0.1
0.1
0.5
0.5
0.002
-------
TABLE 3. (cont)
Example Recommended Example Recommended Example Recommended
Sediment Sediment Tissue Tissue Water Water
Chemical Method* TDL Method* TDLb Method* TDLb
Dacihal
Total chlorinated pesticides
Malathion
Parathion
Volatile Organic Compounds
Benzene
Chloroform
Ethylbenzene
Toluene
Trichloroethene
Tetrachloroethene
3540A;
3550A/8080; NOAA
(1985)
3540A;
3550A/8080; NOAA
(1985)
3540A;
3550A/8141
3540A;
3550A/8141
1624C; 8240A;
8260
1624C; 8240A;
8260
1624C; 8240A;
8260
1624C; 8240A;
8260
1624C; 8240A;
8260
1624C; 8240A;
8260
2
20
5
6
10
10
10
10
10
10
8080;
NOAA (1985)
8080;
NOAA (1985)
8141
8141
1624C; 8240A;
8260
1624C; 8240A;
8260
1624C; 8240A;
8260
1624C; 8240A;
8260
1624C; 8240A;
8260
1624C; 8240A;
8260
2
20
5
6
10
10
10
10
10
10
608;
351 OA;
3520A/8080
608;
351 OA;
3520A/8080
351 OA;
3520A/8141
351 OA;
3520A/8141
1624C; 8240A;
8260
1624C; 8240A;
8260
1624C; 8240A;
8260
1624C; 8240A;
8260
1624C; 8240A;
8260
1624C; 8240A;
8260
0.03
0.02
0.8
0.8
5
5
5
5
5
5
-------
TABLES, (cont.)
Example Recommended Example Recommended Example Recommended
Sediment Sediment Tissue Tissue Water Water
Chemical Method' TDL Method8 TDLb Method' TDLb
Total xylenes
lonlzable Organic Compounds
Phenols
Phenol
2-Methylpheno!
4-Methylphenol
2,4-Dimethylphenol
Pentachlorophenol
Resin Acids and Gualacols
1624C; 8240A;
8260
1625C; 3540A;
3550A/8040A;
8250; 8270A; 9066
1625C;3540A;
3550A/8040A;
8250; 8270A
1625C;3540A;
3550A/8040A;
8250; 8270A
1625C;3540A;
3550A/8040A;
8250; 8270A
1625C; 3540A;
3550A/8040A;
8250; 8270A
1625C;3540A;
3550A; 8250;
8270A
10
100
50
100
20
100
10
1624C;8240A;
8260
1625C;8040A;
8270A
1625C;8040A;
8270A
1625C;8040A;
8270A
1625C; 8040A;
8270A
1625C;8040A;
8270A
__g
10
20
20
20
20
100
1624C;8240A;
8260
1625C;3510A;
3520A/8040A;
8250; 8270A
1625C;3510A;
3520A/8040A;
8250; 8270A
1625C; 3510A;
3520A/8040A;
8250; 8270A
1625C;3510A;
3520A/8040A;
8250; 8270A
1625C;3510A;
3520A/8040A;
8250; 8270A
5
10
10
10
10
50
-------
Chemical
Example
Sediment
Method*
Recommended
Sediment
TDL
Example
Tissue
Method*
Recommended
Tissue
TDL"
Example
Water
Method*
Recommended
Water
TDL"
f\i
Other Analyses
Ammonia
Cyanides
Total organic carbon
Total petroleum hydrocarbons
Total recoverable petroleum
hydrocarbons
Total phenols
Acid-volatile sullides
Total sulfides
Grain size
Total suspended solids
Total settleable solids
350.1;350.2;
Plumb (1981)
901 OA; 9012
PSEP (1986);
U.S. EPA(1987a,
1992b)
9070; 418.1;
418.1
8040A
Cutter and
Dates (1987);
U.S. EPA (1991 a);
DiToroetal. (1990)
9030;
Plumb (1981)
Plumb (1981);
ASTM (1992)
—
—
100
2,000
0.1%
5,000
5,000
1,000
0.1jimole/g
100
1%
--
—
-
901 OA; 9012
418.1
-
8040A
—
-•
—
•—
-
1,000
100,000
—
10,000
~
—
—
•"•
350.1; 350.2;
350.3
335.2
9060; 415.1;
APHA 53100
418.1
418.1
420.1; 625;
8040A
376.2
—
160.2; APHA
25100
160.5; APHA
2540B
30
5,000
0.1%
100
500
50
100
—
1.0mg/L
0.05 ml/L
-------
TABLE 3. (cent.)
Chemical
Example
Sediment
Method*
Recommended
Sediment
TDL
Example
Tissue
Method8
Recommended
Tissue
TDL"
Example
Water
Method8
Recommended
Water
TDL"
Total solids/dry weight
Total volatile solids
Specific gravity
PH
= Total water content of test
species
Total lipid
160.3;
Plumb (1981);
PSEP (1986)
160.4;
Plumb (1981);
APHA 2540E;
PSEP (1986)
Plumb (1981)
9045;
Plumb (1981)
—
0.1%
0.1%
0.01 mg/L
0.1 pH units
—
"
--
—
U.S. EPA (1986b,
1987a)
Bligh and Dyer
(1959);
Folch et al. (1957)
_
—
0.1%
0.1%
"
-
Plumb (1981)
—
—
0.1 pH units
— •
Note: HPAH - high molecular weight polyeyclfc aromatic hydrocarbon
LFAK - iOw rrtoiecuiar weiyhi poiyCyctic aromatic hydroCarbort
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 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, 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.
Determined by work group discussion; no or few effects guidelines are available for comparison.
-------
TABLES. (conL)
e No sediment screening or adverse effects guidelines are available for comparison.
d Less than 1/10 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 restrict use of some routine analytical methods, but reflects work group consensus.
1 Sediment TDL slightly exceeds one available sediment guideline (Washingtorj Sediment Management Standards) at low organic carbon content (< 2 percent TOG).
9 -- Not applicable.
-------
REFERENCES CONTAINING NUMBERED METHODS IN TAEILE 3.
Reference
Method
t
US EPA 1983
US EPA 1982
US EPA
19895
US EPA 19901
US EPA 1989c
US EPA
1986a
APHA 1989
160.2
160.3
160.4
160.5
200.7
200.8
202.2
204.2
608
8290
1613
1624C
3010
3050A
351 OA
3520A
3540A
3550A
601 OA
7040
7041
7060A
7061
APHA2510D
206.2
206.3
210.2
213.2
218.2
218.5
219.2
220.1
625
1625C
7090
7091
7130
7131A
7190
7191
7197
7201
7210
7211
7381
APHA 2540B
220.2
236.2
239.2
243.2
245.1
245.2
249.2
7420
7421
7461
7471
7520
7521
7740
7741
7760
7761
7840
APHA 2540E
270.2
270.3
272.2
279.2
282.2
289.2
335.2
7841
7950
7951
8040A
8060
8080
8100
8141
8240A
8250
8260
APHA
531 OD
350.1
350.2
350.3
376.2
415.1
418.1
420.1
8270A
8310
901 OA
9012
9030
9045
9060
9066
9070
35
-------
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 QA 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 compositing 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:
• Geochemical and hydrodynamic data—The grain size, specific
density, water content, total organic carbon (TOG), 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.
• 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.
• Spill data—Evidence of a contaminant spill within or near the
dredging area may be an important consideration in identifying
locations for sampling.
•:. Dredging history—Knowledge of prior dredging may dramatically
affect sampling plans. If the area is frequently dredged (every 1-2
years) or If the area is subject to frequent ship traffic, the
sediments are likely to be relatively homogenous. Assuming that
therejs nq. major 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 QA/QC requirements, should be in
place before sampling begins. Regional guidance from governmental agencies
(i.e., EPA and USAGE) 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:
• Collecting representative samples
• Collecting an appropriate number of samples
• Using appropriate sampling techniques
• Protecting or preserving 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:
• Defining the objectives of the sampling program
• Ensuring communication among participating groups
• 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.
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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.
2.5.1 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,
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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:
• The analytical methods used and their associated detection limits—
Analytical methods often improve over time. For example, as late
as the 1970s, 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.
• 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 well-
documented 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).
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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 tech-
nique. 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.
Level 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 tec mica!
reports that suggest the data may not be comparable to
corresponding data to be collected in the current project.
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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 composited prior to analysis (with attention
to the discussion in Section 2.5.4.8). The appropriate number of samples and
the proper use of compositing 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.
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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. Information that should help
to define the representativeness of stations within a dredging area includes:
• Clearly defined distribution of sediments to be dredged (i.e., project
depth, overdredged depth, and side slopes)
• Clearly defined area to be sampled
• 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 ol contamination.
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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:
• The greater the number of samples collected, the better the areal
and vertical definition
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Single measurements are inadequate to describe variability
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 bicause 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 Compositing
The objective of obtaining an accurate representation and definition of the
dredging area has to be satisfied when compositing samples. Compositing
provides a way to control cost while analyzing sediments from a large number
of stations. Compositing results in a less detailed description of the variability
within the area sampled than would individual analysis at each station. How-
ever 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. Compositing
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.
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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 compositing, 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 System
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: BHS01 C.
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.
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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 USAGE (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), USAGE (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 ±15 seconds for a
single angle measurement at an intercept angle of approximately 45° and a
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range of 5 km, could potentially yield a positioning error of < ±1 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 LORAN-
C 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 earth-
based 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 0.5-5 m by
differential GPS (U.S. EPA 1987b). In differential GPS, two receivers are used.
The master receiver is placed on a known location. If s location is computed
based on satellite data, and a correction is applied to account for the errors in
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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 angle
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:
• 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
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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.
• 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.
• 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 comer of
pier, buoy) should be recorded. If photographs are to be used for
a posteriori 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
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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 bioaccumulation tests may also be field-
collected.
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 bo sampled first. At
a station where water and sediment are to be collected, watcsr samples should
be collected 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 USAGE. ASTM (1991b) 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 sampling 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 1-2 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
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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
sedimenl/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 surficial 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
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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 (1:1 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.
53
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TABLE 5. SUMMARY OF RECOMMENDED PROCEDURES FOR SAMPLE
COLLECTION, PRESERVATION, AND STORAGE
Analyses
Sediment
Chemical/Physical Analyses
Metals
Organic compounds
(e.g., PCBs, pesticides,
polycycllc aromatic
hydrocarbons)
Particle size
Total organic carbon
Total solids/specific
gravity
Miscellaneous
Sediment from which
elutriate is prepared
Biological Tests
Dredged material
Reference sediment
Control sediment
Collection
Method*
Grab/corer
Grab/corer
Grab/corer
Grab/corer
Grab/corer
Grab/corer
Grab/corer
Grab/corer
Grab/corer
Grab/corer
Sample
Volume"
100 g
250 g
100 g
50 g
50 g
SSOg
Depends on tests
being performed
12-15 L per
sample
45-50 L per test
21-25 L per test
Container0
Precleaned polyethy-
lene jar*
Solvent-rinsed glass
jar with Teflon* lid'
Whirl-pac bag"
Heat treated glass
vial with Teflon*-lined
lid0
Whirl-pac bag
Whirl-pac bag
Glass with Teflon*-
lined lid
Plastic bag or con-
tainer"
Plastic bag or con-
tainer"
Plastic bag or con-
tainer"
Preservation Storage
Technique Conditions
Dry ice* or freezer £ 4°C
storage for extended
storages; otherwise
refrigerate
Dry ice" or freezer £ 4°C°/dark'
storage for extended
storage; otherwise
refrigerate
Refrigerate < 4°C
Dry ice" or freezer £ 4°C*
storage for extended
storages; otherwise
refrigerate
Refrigerate < 4°C
Refrigerate < 4°C
Completely fill and 4°C/dark/airtight
refrigerate
Completely fill and 4°C/dark/airtight
refrigerate; sieve
Completely fill and 4°C/dark/airtight
refrigerate; sieve
Completely fill and 4°C/dark/airtight
refrigerate; sieve
Holding Times'1
Hg - 28 days
Others - 6 months'
14 days8
Undetermined
14 days
Undetermined
Undetermined
14 days
14 days'
14 days'
14 days'
-------
TABLE 5. (cont.)
Ul
Ol
Analyses
Water and Elutriate
Chemical/Physical Analyses
Participate analysis
Metals
Total Kjeldahl nitrogen
Chemical oxygen
demand
Total organic carbon
Total inorganic carbon
Phenolic compounds
Soluble reactive
phosphates
Extractabte organic
compounds (e.g., semi-
volatile compounds)
Volatile organic
compounds
Total phosphorus
Collection Sample
Method' Volume"
Discrete sampler 500-2,000 mL
or pump
Discrete sampler 1 L
or pump
Discrete sampler 100-200 mL
or pump
Discrete sampler 200 mL
or pump
Discrete sampler 100 mL
or pump
Discrete sampler 100 mL
or pump
Discrete sampler 1 L
or pump
Discrete sampler
or pump
Discrete sampler 4 L
or pump
Discrete sampler 80 mL
or pump
Discrete sampler
or pump
Container11
Plastic or glass
Acid-rinsed polyethy-
lene or glass jaH
Plastic or glass"
Plastic or glass"
Plastic or g!assk
Plastic or glass1*
Glass"
Plastic or glass"
Amber glass bottle1
Glass vial1
Plastic or glassh
Preservation Storage
Technique Conditions
Lugols solution and 4°C
refrigerate
pH < 2 with HNO3; 4°C 2°C'
refrigerate1
H2SO4 to pH < 2; 4°C"
refrigerate
H2SO4 to pH < 2; 4°C"
refrigerate
H2SO< to pH < 2; 4°C"
refrigerate
Airtight seal; refrig- 4°C"
erate"
0.1-I.OgCuSO,; 4°C"
H2SO< to pH < 2;
refrigerate
Filter; refrigerate" 4°C"
pH < 2, 6N HCI; 4°C'
airtight seal; refrigerate
pH<2with 1:1 HCL; 4°C'
refrigerate in airtight,
completely filled con-
tainer1
H2SO4 to pH < 2; 4°C"
refrigerate
Holding Times"
Undetermined
Hg - 14 days
Others - 6 months"
24 h"
7 days"
<48 hours"
6 months"
24 hours"
24 hours"
7 days for extrac-
tion; 40 days for
sample extract
analyses'
14 days for sample
analysis, if pre-
served'
7 days"
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TABLE 5. (conL)
Analyses
Total solids
Volatile solids
Sulfides
Biological Tests
Site water
Dilution water
Tissue
Metals
PCBs and chlorinated
pesticides
Volatile organic
compounds
Semh/olatile organic
compounds
Lipids
Collection
Method*
Discrete sampler
or pump
Discrete sampler
or pump
Discrete sampler
or pump
Grab
Grab or makeup
Trawl/Teflon*-
coated grab
TrawVTeflon*-
coated grab
Trawl/Teflon*-
coated grab
Trawl/Teflone-
coated grab
Trawl/Teflon"-
coated grab
Sample
Volume"
200 mL
200 mL
—
Depends on tests
being performed
Depends on tests
being performed
5-10 g
10-25 g
10-25 g
10-25 g
Part of organic
analyses
Container8
Plastic or glass11
Plastic or glass"
Plastic or glass*
Plastic carboy
Plastic carboy
Double Ziploc*0
Hexane-rinsed double
aluminum foil and
double Ziploc*0
Heat-cleaned alum-
inum foil and water-
tight plastic bag1
Hexane-rinsed double
aluminum foil and
double Ziploc*0
Hexane-rinsed alumi-
num foil
Preservation
Technique
Refrigerate
Refrigerate
pH > 9 NaOH (ZnAc);
refrigerate*
Refrigerate
Refrigerate
Handle with non-
metallic forceps; plastic
gloves; dry ice'
Handle with hexane-
rinsed stainless steel
forceps; dry fee"
Covered ice chest'
Handle with hexane-
rinsed stainless steel
forceps; dry ice8
Handle with hexane-
rinsed stainless steel
forceps; quick freeze
Storage
Conditions
4°C11
4°C*
4°C>
<4°C
<4°C
<, -20°C° or freezer
storage
£ -20°C° or freezer
storage
< -20°Cm or
freezer storage
<, -2Q°V or freezer
storage
<, -20°C or freezer
storage
Holding Times'*
7 days*
7 days*
24 hours*
14 days
14 days
Hg - 28 days
Others - 6 months™
14 days"
14 days'"
14 days"
14 days9
: Note: This table contains only a summary of collection, preservation, and storage procedures for samples. The cited references should be consulted for a more detailed
description of these procedures.
-------
TABLE 5. (cent.)
PCS - polychlorinated biphenyl
8 Collection method should include appropriate liners.
" 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 less tissue may be required depending on the analytes, matrices, detection limits, and particular analytical laboratory.
c All containers should be certified as clean according to U.S. EPA (1990c).
* These holding times are for sediment, water, and tissue based on guidance that is sometimes administrative rather than technical in nature. There are no promulgated,
scientifically based holding time criteria for sediments, tissues, or elutriates. References should be consulted if holding times for sample extracts are desired. Holding
times are from the time of sample collection.
8 NOAA (1989).
1 Tetra Tech (1986a).
9 Sample may be held for up to 1 year if«»-20°C.
h 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.
' U.S. EPA (1987a); 40 CFR Part 136, Table III.
" Plumb (1981).
' If samples are not preserved to pH < 2, then aromatic compounds must be analyzed within 7 days.
m Tetra Tech (1986b).
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2.5.8.1 Sample Handling
Sufficient sample volume should be collected to:
• Perform the necessary analyses
• 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 for
bioassays)
• Archive portions of the sample for possible later analysis.
• 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 should 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
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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, should 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 collection.
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) bescause 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.
59
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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 QA 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:
• Site location and history
• Scope of work
• Site control
• Hazard assessment (chemical and physical hazards)
• Levels of protection and required safety equipment
• Field monitoring requirements
• Decontamination
• Training and medical monitoring requirements
• 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
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documentation provides a means to track samples from the Held 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,
should 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
• Sample collection date (and time if more than one sample may be
collected at a location in a day)
• Any special notations on sample characteristics or problems
• Initials of the person collecting the sample
• Date sample sent to the laboratory
• 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:
, • The sample is possessed by an individual and secured so that no
one can tamper with it
• The location and condition of the sample is known and
documented at all times
• 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
61
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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:
• Project title
• Sample identification number
62
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• 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.
2.6.1.2 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:
• 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
• Separate custody procedures for sample handling, storage, and
disbursement for analysis in the laboratory
• 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 arid archiving
procedure should indicate the storage requirements, location, indexing codes,
retention time, and security requirements for samples and data.
63
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2.6.2 Storage and Disposal of Samples
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 sample-
disposal 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 100-177 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.
2.7 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
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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.
2.7.7 Calibration Frequency
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
analytical method provides guidance for the frequency at which continuing
-------
TABLE 6. EXAMPLE CALIBRATION PROCEDURES
Calibration Criteria
SW-846 Methods for
Organic Compounds8
EPA CLP Methods for
Organic Compounds"
Number of standards for
initial calibration
Concentration of lowest
initial calibration standard
Concentrations for initial
calibration to establish the
instrument's working linear
range
Concentration of continu-
ing calibration standards
Frequency of calibrations
Acceptance criteria for
initial calibration0
Acceptance criteria for
continuing calibration0
Minimum of five for all methods
All target analytes near,
above, the TDL
but
1. Bracket the expected concen-
tration range of analytes ex-
pected in samples
Five for all GC/MS analyses
Three for pesticides
One for PCBs and multicompo-
nent pesticides
Contractually set (e.g., 10 ng/L for
volatile organic compounds)
Contractually set (e.g., 10, 50,
100,150, and 200 ug/L for volatile
organic compounds)
2. Bracket the full instrument/
• detector linear range
Not specified, except for GC/MS Contractually set (e.g., 50 ng/L for
methods all GC/MS analyses)
Repeat when acceptance criteria Repeat when acceptance criteria
not met not met
Calculate analyte RRFs or RFs,
then RSD should be < 30 percent
for GC/MS methods and < 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
< 25 percent for GC/MS methods
and < 15 percent for all other
methods
Alternative: none
Calculate analyte RRFs or RFs,
then RSD should be < 30 percent
for GC/MS methods and < 20
percent for pesticides
Alternative: none
Calculate analyte RRFs or RFs,
then difference to mean RRF or
RF of initial calibration should be
< 25 percent for GC/MS methods
and < 15 percent for pesticides
Alternative: none
te: 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
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TABLE 6. (cont.)
* U.S. EPA (1986a).
b U.S. EPA (1990b).
c 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., < 50 percent RSD).
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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 calibration 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
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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 tie initial calibration sequence in terms of
the relationship between the intercept of the calibration 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. AH specific acceptance criteria for calibrations should be stated in
the QA project plan and the laboratory statement of work.
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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 USAGE
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
70
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temperature. The total solids values generally are used to convert
concentrations of contaminants from a wet-weight to a dry-v/eight basis.
The specific gravity of a sample is the ratio of the mass of 21 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 helps 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
disposal 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
bioaccumulated. 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 riot 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.
71
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Sediments should be analyzed for TOG. This is particularly important if there
are hydrophobia 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 al. 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
1991 a). 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).
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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 (1CP) 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 (GC/MS) 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 GC/MS. 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-tetrachlorodiben2:o-p-dioxin [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
limitations 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 analyles. The most
selective methods using GC/MS techniques are recommended for all
nonchlorinated organic compounds because such analysis can often avoid
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TABLE 7. PCDD and PCDF Compounds Determined by Method 1613
Native Compound1
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-HxCDF
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
1 Polychlorinated Dioxins and Furans
TCDD = Tetrachlorodibenzp-p-dioxin
TCDF = Tetrachlorodibenzofuran
PeCDD = Pentachlorodibenzo-p-dioxin
PeCDF = Pentachlorodibenzofuran
HxCDD = Hexachlorodibenzo-p-dioxin
HxCDF = Hexachlorodibenzofuran
HpCDD = Heptachlorodibenzo-p-dioxin
HpCDF = Heptachlorodibenzofuran
OCDD = OctachlorcxJibenzo-p-dioxin
OCDF = Octachlorodibenzofuran
74
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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 GC/ECD 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 saimples. 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 GC/ECD systems (Schwartz et al.
1993).
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TABLE 8. POLYCHLORINATED BIPHENYL CONGENERS
RECOMMENDED FOR QUANTITATION AS POTENTIAL
CONTAMINANTS OF CONCERN
Congener Number"
PCS Congener8
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
213I,4,4'-Tetrachlorobiphenyl
2,3',4',5-Tetrachlorobiphenyl
2,4,4',5-Tetrachlorobiphenyl
3,3',4,4'-Tetrachlorobiphenyl
3,4,4',5-Tetrachlorobiphenyl
212>,3,4,5'-Pentachlorobiphenyl
2,2',3,4',5-Pentachlorobiphenyl
2,2',4,5,5'-Pentachlorobiphenyl
2,3,3',4,4'-Pentachlorobiphenyl
2,3,4,4',5-Pentachlorobiphenyl
2,3',4,4',5-Pentachlorobiphenyl
2,3',4,4',6-Pentachlorobiphenyl
2',3,4,4',5-Pentachlorobiphenyl
3,3',4,4',5-Pentachlo robiphenyl
2',3,3',4,4'-Hexachlorobiphenyl
2,2',3,4,4',5'-Hexachlorobiphenyl
2,2',3,5,5',6-Hexachlorobiphenyl
2,2',4,4'15,5I-Hexachlorobiphenyl
2,3,3',4,4',5-Hexachlorobiphenyl
2,3,3',4,4',5-Hexachlorobiphenyl
2,3,3',4,4',6-Hexachlorobiphenyl
2,3',4,4',5I5I-HexachlorobiphenyI
2,3',4,4',5',6-Hexachlorobiphenyl
Summation0
8
18
28
44
52
66
77
101
105
118
126f
128
138
153
Highest
Priority"
77
87
49
101
105
118
126f
128
138
153
156
Second
Priority6
18
37
44
99
52
70
74
81
114
119
123
151
157
158
167
168
76
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TABLE 8. (cont.)
PCB Congener0
S.S'.M'.S.S'-Hexachlorobiphenyl
2,2',3,3',4,4',5-Heptachlorobiphenyl
2,2>,3,4,4',5)51-Heptachlorobiphenyl
2,2',3,4,4',5',6-Heptachlorobiphenyl
2,21,3,4,4II6,6I-Heptachlorobiphenyl
2,2',3,4',5,5',6-Heptachlorobiphenyl
2,3,3',4,41,5I5I Heptachiorobiphenyl
2,2',3,3',4,4',5,6-Octachlorobiphenyl
2I2II3,3II4I5,5',6I-Octachlorobiphenyl
2,2I,3,3>,4I4'I5I5',6-Nonachlorobiphenyl
2I2',3,3I,4,4',5)5')6I6'-Decachlorobiphenyl
Congener Number11
Highest
Summation0 Priority"
169f 169f
170 170
180 180
183
184
187
195
206
209
Second
Priority0
187
189
201
Note: PCB - polychlorinated biphenyl
a PCB congeners recommended for quantitation, from dichlorobiphenyl through decachlorobiphenyl.
b Congeners are identified by their International Union of Pure and Applied Chemistry (IUPAC) number,
as referenced in Ballschmiter and Zell (1980) and Mullin et al. (1984).
0 These congeners are summed to determine total PCB concentration using the approach In
NOAA(1989).
d 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).
9 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).
f To separate PCBs 126 and 169, It is necessary to Initially utilize an enrichment step with an activated
carbon column (Smith 1981).
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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 1989d; Table 9).
EPA and the USAGE 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 USAGE 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.
2.8.3.1 Selection of Target Analytes
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
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TABLE 9. Methodology for Toxlciity 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
2,3,7,8-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
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potential to bioaccumulate in animals (i.e., have a high Kow 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 analyte.
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 octa-
PCDDs 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
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TABLE 10. OCTANOL/WATER PARTITION COEFFICIENTS
FOR ORGANIC COMPOUND PRIORITY POLLUTANTS
AND 301(h) PESTICIDES
Octanol/Water
Partition Coefficient
Octanol/Water
Partition Coefficient
Pollutant
Pollutant
Di-n-octyl phthalate
lndeno[1,2,3-cd]pyrene
Benzo[ghi]perylene
PCB-1260
Mirex"
Benzo[k]fluoranthene
Benzo[b]fluoranthene
PCB-1248
2,3,7,8-TCDD (dioxin)
Benzo[a]pyrene
Chlordane
PCB-1242
4,4'-DDD
Dibenz[a,h]anthracene
PCB-1016
4,4'-DDT
4.4--DDE
Benz[a]anthracene
Chrysene
Endrin aldehyde
Fluoranthene
Hexachlorocyclopentadiene
Dieldrin
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Di-n-butyl phthalate
4-Bromophenyl phenyl ether
Pentachlorophenol
4-Chloropheny! phenyl ether
Pyrene
2-Chloronaphthalene
Endrin
PCB-1232
Phenanthrene
Fluorene
Anthracene
Methoxychlor*
Hexachlorobutadiene
1,2,4-Trichlorobenzene
Bis[2-ethylhexyl]phthalate
Acenaphthylene
Butyl benzyl phthalate
PCB-1221
Hexachloroethane
Acenaphthene
a-Hexachlorocyclohexane
5-Hexachlorocyclohexane
Q-Hexachlorocyclohexane
•y-Hexachlorocyctohexane
9.2
7.7
7.0
6.9
6.9
6.8
6.6
6.1
6.1
6.0
6.0
6.0
6.0
6.0
5.9
5.7
5.7
5.6
5.6
5.6
5.5
5.5
5.5
5.4
5.4
5.2
5.1
5.1
5.0
4.9
4.9
4.7
4.6
4.5
4.5
4.4
4.3
4.3
4.3
4.2
4.2
4.1
4.0
4.0
3.9
3.9
3.8
3.8
3.8
3.8
Parathion"
Chlorobenzene
2,4,6-Trichlorophenol
6-Endosulfan
Endosulfan sulfate
a-Endosulfan
Naphthalene
Fluorotrichloromethanet"
1,4-Dichlorobenzene
1,3-Dichlorobenzene
1,2-Dichlorobenzene
Toxaphene
Ethylbenzene
A/-Nitrosodiphenylamine
P-Chloro-m cresol
2,4-Dichlorophenol
3,3'-Dichlorobenzene
Aldrin
1,2-Diphenylhydrazine
4-Nitrophenol
Malathion*
Tetrachloroethene
4,6-Dinitro-ocresol
Tetrachloroethene
Bis[2-chloroisopropyl]ether
1,1,1 -Trichloroethane
Trichloroethene
2,4-Dimethylphenol
1,1,2,2-Tetrachloroethaine
Bromoform
1,2-Dichloropropane
Toluene
1,1,2-Trichloroethane
Guthion"
Dichlorodiflouromethane"
2-Chlorophenol
Benzene
Chlorodibromomethanei
2,4-Dinitrotoluene
2,6-Dinitrotoluene
:rans-1,2-Dichloropropone
c/s-1,3-DichIoropropeno
Demeton"
Chloroform
Dichlorobromomethane! .
Nitrobenzene
Benzidine
1,1-Dichloroethane
2-Nitrophenol i
Isophorone
3.8
3.8
3.7
3.6
3.6
3.6
3.6
3.5
3.5
3.4
3.4
3.3
3.1
3.1
3.1
3.1
3.0
3.0
2.9
2.9
2.9
2.9
2.8
2.6
2.6
2.5
2.4
2.4
2.4
2.3
2.3
2.2
2.2
2.2
2.2
2.2
2.1
2.1
2.1
2.0
2.0
2.0
1.9
1.9
1.9
1.9
1.8
1.8
1.8
1.7
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TABLE 10. (cent.)
Octanol/Water Octanoi/Water
Partition Coefficient parti,ion Coefficlent
Pollutant (log KQ,) Pollutant (log
Dimethyl phthalate
Chloroethane
2,4-Dlnitrophenol
1,1-Dichloroethylene
Phenol
1,2-DIchloroethane
Diethyl phthalate
AJ-nUrosodlpropylamlne
Dichloromethane
1.6
1.5
1.5
1.5
1.5
1.4
1.4
1.3
1.3
2-Chloroethylvinylether
Bis[2-chloroethoxy]methane
Acrylonitrile
Bis[2-chloroethyl]ether
Bromomethane
Acrolein
Chloromethane
Vinyl chloride
W-nitrosodimethylamine
1.3
1.3
1.2
1.1
1.0
0.9
0.9
0.6
0.6
Source: Tetra Teoh (1985)
Note: Mixtures, such as PCB Aroclors ®, cannot have discrete Km values; however, the value given is a rough estimate for
tha 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.
" No longer on priority pollutant or 301 (h) list.
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subsequently be compared against applicable water quality standards or cri-
teria, 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 of 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 iDioaccumulation
potential of those analytes have to be interpreted to establish target analytes.
The n-octanol/water partition coefficient (Kow) 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 Kow 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 Kow. 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 Kow 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
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include the chlorinated benzenes and the chlorinated phenols. Table'10
provides data for organic priority pollutants based on K^,. 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:
» The target analyte is a contaminant of concern and is present in
the sediment as determined by sediment chemical analyses
» The target analyte has a high potential to accumulate and persist
in tissues
» 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
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TABLE 11. BIOCONCENTRATION FACTORS (BCF)
OF INORGANIC PRIORITY POLLUTANTS
Inorganic Pollutant
Metals
Methylmercury
Phenylmercury
Mercuric acetate
Copper
Zinc
. Arsenic
Cadmium
Lead
Chromium IV
Chromium III
Mercury
Nickel
Thallium
Antimony
Silver
Selenium
Beryllium
Nonmetals
Cyanide
Asbestos
Log BCF
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
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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^jsers.
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 Mehrle 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 octa-
PCDDs 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 spectro-
meter 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
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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:
• 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)
• 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
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• 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
• The data flow or reporting scheme from collection of original data
through storage of validated concentrations (a flowchart is usually
necessary)
• Statistical formulas and sample calculations planned for collected
data
• 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 contam-
inated 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
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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 dif-
ferent 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 meot 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
collectiocLand prior to use. These include screening, editing, verifying, and re-
viewing through external performance evaluation audits. Dsita 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. Theses four data validation
levels range from complete, 100-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:
• Perform a brief assessment and rely on specialists to resolve
outstanding concerns. This assessment is equivalont to Level 3
(Table 12).
• Perform a complete review for Level 1 or 2 using qualified staff
and technical guidelines for QA specialists (see Footnote a in
Table 12).
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TABLE 12. LEVELS OF DATA VALIDATION
Level 1 100 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.8
Level 2 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 10-20 percent of the samples
should be reviewed. If numerous errors are found, then the entire data
package should be reviewed.
Level 3 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.
Level 4 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 1991d). 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 Selected 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 Quality Evaluation for
Proposed Dredged Material Disposal Projects (PTI 1989a), another report released by the
Sediment Management Unit in June 1989.
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• 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 Evaluating Inorganics Analyses (U.S. EPA
1988a) and Laboratory 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 [1991d]) 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:
• Blanks
91
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INFORMATION
SOURCE
Information •"*****
Complete
?
Accept
Data for Use
Accept Data with
Appropriate
Qualifications
Analytical
Data and Supporting
Documentation
Marginally
Outside Limits
Consult Expert
Severely
Outside Limits
Reject Data
(and consider
reanalysis)
Figure 1. Guidance for data assessment and screening for data quality.
92
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• Matrix spike samples
• Surrogate spike compounds
• Check standards, including:
- Spiked method blanks
- Laboratory control samples
- Reference materials
• Matrix replicates (split in the laboratory from one field sample)
• 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 USAGE 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).
2.10.1 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 v/hen existing data
indicate elevated chemical concentrations such that remova.l or other actions
may be required. In such cases, the need for increased precision may justify
the cost of extra QC samples.
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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. 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 contam-
ination), 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 project-
specific 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.
2. 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.
3. 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
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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 high-
priority 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
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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 medium-
priority 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.
2.10.2 Specifying Quality Control Limits
Prior to performing a chemical analysis, recognized limits on analytical per-
formance 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
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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 labor-
atories. For example, the following two kinds of limits are used by PSEP
(1990c) 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 ±2 times the standard deviation (U.S. 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 sipecify 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
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TABLE 13. EXAMPLE WARNING AND CONTROL LIMITS FOR
CALIBRATION AND QUALITY CONTROL SAMPLES*
Analysis Type
Recommended Warning Limit Recommended Control Limit
Ongoing calibration Project manager decision"
Surrogate spikes
Method blanks
Reference materials
Matrix spikes
Spiked method
blanks
(check standards)
Matrix replicates
Field replicates
< 50 percent recovery0
Exceeds the TDL
95 percent confidence interval, if
certified
50-150 percent recovery
50-150 percent recovery
35 percent coefficient of variation
Project manager decision
> ±25 percent of the average
response measured in the
initial calibration
Follow EPA Contract
Laboratory Program guidelines
Exceeds 5 times the TDL
To be determined
To be determinedd
To be determined
> ±50 percent coefficient of
variation (or a factor of 2 for
duplicates)
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 1990c).
b See U.S. EPA (1991d) for specific examples of project manager decisions for warning or
control limits.
0 Except when using the isotope dilution technique.
d Zero percent spike recovery requires rejection of data.
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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 tie appropriate control limit, it is
recommended that the associated warning limit be 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 because 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 reported for TOG analysis. Standards used for TOC determinations
should be verified by independent check standards to confirm tie bias of the
results. Quality control limits should be agreed upon for each analytical
procedure, and should be consistent with the overall QA project plan.
2.70.4 Quality Control Considerations for Chemical Analysis of
Sediments
i
Methods for the chemical analysis of priority pollutants in sediments should
include detailed QC procedures and requirements that should be followed
rigorously throughout the evaluation. General procedures include the analysis
of a procedural 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.
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Analytical 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 processed, 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 GC/MS 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 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 with the appropriate SRMs.
Precision and bias determinations should be performed with the same
frequency as the blanks and matrix spikes.
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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
(1991e) 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
USAGE will 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.
2.11.1 Procedures for Pre-A ward Inspections of Laboratories
The pre-award inspection is a kind of system audit for assessing the labor-
atory'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:
• The laboratory has an independent QA/QC program
• Written work plans are available for each test that describe the
approach to be used in storing, handling, and analyzing samples
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• Technically sound, written standard operating procedures are
available for all study activities
• Qualifications and training of staff are appropriate and documented
• All equipment is properly calibrated and maintained
• 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. Analytes 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
interiaboratory 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 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.
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
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TABLE 14. SOURCES OF STANDARD REFERENCE MATERIALS
PCBs
National Research Council of Canada
PAHs
National Research Council of Canada
National Institute for Standards and
Technology
Metals
National Bureau of Standards
National Research Council of Canada
Marine sediment
Marine sediment
Sediment
International Atomic Energy Agency
Estuarine sediment
Marine sediment
Dogfish liver
Dogfish muscle
Lobster hapatopan-
creas
Marine sediment
Rsh flesh
Mussel tissue
HS-1 and HS-2
HS-3, HS-4, HS-5, HS-6
SRM #1647 and SRM #1597
SRM #1646
MESS-1, BCSS-1, PACS-1
DOLT-1
DORM-1
TORT-1
SD-N-1/2(TM)
MA-A-2(TM)
MAL-1(TM)
Standard reference materials (SRMs) may be obtained from the following organizations:
Organic Constituents
U.S. Department of Commerce
National Institute for Standards and Technology
Office of Standard Reference Materials
Room B3111 Chemistry Building
Gaithersburg, Maryland 20899
Telephone: (301)975-6776
Marine Analytical Chemistry Standards Program
National Research Council of Canada
Atlantic Research Laboratory
1411 Oxford Street
Halifax, Nova Scotia, Canada B3H 3Z1
Telephone: (902) 426-3280
Inorganic Constituents
U.S. Department of Commerce
National Institute for Standards and Technology
Office of Standard Reference Materials
Room B3111 Chemistry Building
Gaithersburg, Maryland 20899
Telephone: (301)975-6776
Marine Analytical Chemistry Standards Program
National Research Council of Canada
Division of Chemistry
Montreal Road • - . •
Ottawa, Ontario, Canada K1A OR9
Telephone: (613)993-12359
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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.
2.11.3 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 labor-
atory'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:
• Receiving
• Sample storage
• Sample preparation
• Sample testing
• Reagent storage
• Data reduction and analysis.
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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 CALCULA TION OF DA TA QUALITY INDICA TORS
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:
abs[D, - Do]
Relative percent difference = - — • - - x 100
where:
D1 = sample value
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D2 = duplicate sample value
abs = absolute value.
Precision for the replicate will be calculated as the relative standard
deviation:
Percent relative standard deviation = — x 100
x
where:
x = mean of three or more results
a = standard deviation of three or more results.
o =
n-1
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 10Q
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 1QO
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:
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Completeness = valid data points obtained x 10Q
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.
2.15 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:
• Procedures for corrective actions when predetermined limits for
data acceptability are exceeded (see DQO discussion in Section
2.3)
• 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.
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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:
• Periodic assessment of measurement data accuracy (precision and
bias) and completeness
• Results of performance and system audits
• 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 Preparing Basic Quality Assurance Reports
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:
• 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.
• Holding times—The holding time section should briefly discuss the
holding time requirements and holding time exceedances.
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• 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.
• 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.
• 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 blank and replicate results for the sample
survey.
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• Intel-laboratory 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.
• 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.
2.17 REFERENCES
References cited in the QA project plan should be provided at the end of the
plan.
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3, REFERENCES
Ankley, G.T., G.J. Niemi, K.B. Lodge, H.J. Harris, D.L. Beaver, D.E. Tillitt, T.R.
Schwartz, J.P. Giesy, P.O. Jones, and C. Hagley. 1993. Uptake of planar
polychlorinated biphenyls and 2,3,7,8-substituted polychlorinated dibenzofurans
and dibenzo-p-dioxins by birds nesting in the lower Fox River and Green Bay,
Wisconsin. Submitted to Arch. Environ. Contam. Toxicol.
APHA. 1989. Standard methods for the analysis of water and wastewater.
17th ed. American Public Health Association, American Water Works
Association, Water Pollution Control Federation, Washington, DC.
ASTM. 1991 a. Annual book of standards. Volume II, Water. American Society
for Testing and Materials, Philadelphia, PA.
ASTM. 1991b. Standard guide for collection, storage, characterization, and
manipulation of sediment for toxicological testing. Method El391-90. In:
Annual Book of ASTM Standards, Water, and Environmental Technology,
Volume 11.04. American Society for Testing and Materials, Philadelphia, PA.
ASTM. 1992. Standard test method for classification of soils for engineering
purposes. In: Annual Book of ASTM Standards, D 2487, Volume 04.08.
American Society for Testing and Materials, Philadelphia, PA.
Ballschmiter, K., and M. Zell. 1980. Analysis of polychlorinated biphenyls
(PCBs) by glass capillary gas chromatography, composition of technical Aroclor-
and Clophen-PCB mixtures. Fresenius Anal. Chem. 302:20-31.
Battelle. 1985. Method for semivolatile organic priority pollutants in fish. Final
report prepared for the U.S. Environmental Protection Agency under Contract
No. 68-03-1760.
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4. GLOSSARY
Accuracy
Acid Volatile Sulfide
Analyte
Bias
Bioaccumulation
Bioassay
Bioconcentration Factor
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).
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.
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).
The degree to which an organism uptakes a
substance from water.
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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
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Control Limit
Control Sediment
Data Package
Data Quality Indicators
Data Quality Objectives
(DQOs)
substances on the 307(a)(1) list of toxic pollutants
promulgated on January 31, 1978 (43 Federal
Register 4109).
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 takon. When control
limits are exceeded, analyses should be halted;
samples analyzed since the las;t QC sample may
need reanalysis.
A sediment used to confirm the.1 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 reque:sting 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.
Surrogate spike recoveries, matrix spike
recoveries, analytical values obtained for blanks,
standard reference material, and performance
evaluation samples for each parameter in each
matrix.
Qualitative and quantitative statements of the
overall uncertainty that a decision maker is willing
to accept in results or decisions derived from
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Detector
Digestion
Disposal Site
Dredged Material
Dredged Material
Discharge
Elutriate
Evaluation
Extraction
Interference
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.
Unwanted elements or compounds in a sample
126
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Ion
Matrix
Matrix Effects
Matrix Spike Samples
Metals
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.
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.
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.
727
-------
Organic Compounds
Performance Audit
Precision
Quality Assurance
Quality Assurance
Management Plan
Quality Assurance
Project Plan
Quality Control
Quality Control
Checks
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.
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.
128
-------
Reference Materials
Reference Sediment
Replicates
Representativeness
Sediment
Semi volatile
Organic
Compound
Spectrornetry
Materials or substances with well-characterized
properties that are useful for assessing the
accuracy of an analysis and comparing analytical
performances among laboratories.
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).
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.
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.
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 (se« 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 speetrographie 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
-------
Spiked Method
Blanks
Standard Operating
Procedure
Standard Reference
Material
Statement of Work
Surrogate Spike
Compounds
Target Detection Limit
(TDL)
fluorescence emission or excitation spectrometry
for organic compounds.
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.
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.
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 mefriods.
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
130
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Tests/Testing
Toxicity Test
Volatile Organic
Compound
Warning Limit
Water Quality Standard
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, cidor, organism
behavior).
A bioassay which measures an effect (e.g., acute
toxicity, sublethal/chronic toxicity). Not a
bioaccumulation 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 date 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.
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
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APPENDIX A
Example QA/QC Checklists,
Forms, and Records
-------
CONTENTS
Page
QA PROGRAM ORGANIZATION FLOW DIAGRAM A-1
EXAMPLE DATA QUALITY OBJECTIVES FOR ACCURACY
AND COMPLETENESS A-2
ALTERATION CHECKLIST A-3
CHAIN-OF-CUSTODY RECORD A-4
FIELD TRACKING REPORT FORM A-5
LABORATORY TRACKING REPORT FORM A-5
GENERAL SAMPLE LABEL A-6
STATION LOCATION LOG A-7
SYSTEMS AUDIT CHECKLIST A-8
CORRECTIVE ACTIONS CHECKLIST A-9
A-iii
-------
QA PROGRAM ORGANIZATION FLOW DIAGRAM
PROGRAM MANAGER
REGULATORY
OFFICER
REGULATORY
OFFICER
PROJECT
MANAGER
ASSISTANT
PROJECT MANAGER
PROJECT
QA COORDINATOR
QA
CHEMISTRY
REGULATORY
OFFICER
QA DATA
ANALYSIS
A-1
-------
EXAMPLE DATA QUALITY OBJECTIVES FOR
ACCURACY AND COMPLETENESS
Variable
Volatiles
Grain Size
Matrix
Sediment
Sediment
Units
Mg/kg
Percent
Target
Detection Bias
Limit (%)
10 ±50%
0.01 —
Precision
±30%
±5%
Completeness
99%
99%
Method
Purge & Trap/GC-MS
Sieve & Pipet
Reference
EPA abc/x-cc-yy(1975)
Maximum
Holding
Time
14 days
Undetermined
-------
ALTERATION CHECKLIST
Sample Program Identification:
Material to be Sampled:
Measurement Parameter:
Standard Procedure for Analysis:
Reference:
Variation from Standard Procedure:
Reason for Variation:
Resultant Change in Field Sampling Procedure:
Special Equipment, Material, or Personnel Required:
Author's Name: _ _ Date:
Approval: _ _ Title:
Date: _
A-3
-------
CHAIN OF CUSTODY RECORD
MOJLNO.
PROJECT NAME
SAMPLERS:
STA.NO
DATE
TIME
STATION LOCATION
NO.
OF
CON-
TAHWM
REMARKS
RiKnquiihtd by:
Dttt/TUiw
Rented by :
R«llnqutth«i by:
Ottt/TbiM
RiMnquiihid by:
DIM/HUM
Rmhad by:
!*Hnquiih«l by:
Datt/TliM
Rtlinquittitd by:
Itatt/Tinw
or Uboraiory by:
Dtte /Tim RMiurfci
Oiiifibulim. Orifbul »icocnp»il« SMpnMM: Copy «o CaoiiflnMor PWd Pltat
-------
FIELD TRACKING REPORT FORM
W/0 No.
FIELD TRACKING REPORT:
FIELD SAMPLE CODE
(FSC)
BRIEF
DESCRIPTION
(LOC-SN)
DATE
i
TIME
Pace
SAMPLER
LABORATORY TRACKING REPORT FORM
W/0 No.
LABORATORY TRACKING REPORT:
FRACTION CODE
X
PREP/ANAL
REQUIRED
(LOC-SN)
RESPONSIBLE
INDIVIDUAL
DATE
DELIVERED
Pape
DATE
COMPLETED
A-S
-------
GENERAL SAMPLE LABEL
(NAME OF SAMPLING ORGANIZATION)
PROJECT:
DATE:
TIME: —;
SAMPLE ID NO.:
MEDIA:
STATION NUMBER:
DEPTH:
PRESERVATION:
ANALYSES TO BE PERFORMED:
SAMPLED BY:
LAB NO.:
REMARKS:
A-6
-------
STATION LOCATION LOG
DATE:
PROJECT:
STATION LOCATION:
DESCRIPTION OF SAMPLES COLLECTED:
SPC ZONE: (N/S) EAST: NORTH:
LOCATION:
Bottom Depth: (ft) (m) Tide: ± (m) MLLW: (ft) (m)
LORANC: LOP1 LOP2
Variable Radar Range: . •
Visual Fixes: (Note: Please tape any drawings to back of this sheet)
Photos - Roll: Pictures:
PID Reading ("»"£»)•
Comments:
RECORDER: SIGNATURE: ORG. CORE DATE:
A-7
-------
SYSTEMS AUDIT CHECKLIST
SAMPLE PROGRAM IDENTIFICATION:
SAMPLING DATES:
MATERIAL TO BE SAMPLED:
MEASUREMENT PARAMETER:
SAMPLING AND MONITORING EQUIPMENT IN USE:
AUDIT PROCEDURES AND FREQUENCY:
FIELD CALIBRATION PROCEDURES AND FREQUENCY:
SIGNATURE OF QA COORDINATOR:
DATE:
-------
CORRECTIVE ACTIONS CHECKLIST
SAMPLE PROGRAM IDENTIFICATION:
SAMPLING DATES:
MATERIAL TO BE SAMPLED:
MEASUREMENT PARAMETER:
ACCEPTABLE DATA RANGE:
CORRECTIVE ACTIONS INITIATED BY:
•TITLE: ,
DATE:
PROBLEM AREAS REQUIRING CORRECTIVE ACTION:
MEASURES TO CORRECT PROBLEMS:
MEANS OF DETECTING PROBLEMS (FIELD OBSERVATIONS, SYSTI-MS AUDIT, ETC):
APPROVAL FOR CORRECTIVE ACTIONS:
TITLE:
SIGNATURE:
DATE:
A-9
-------
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 B-iii
STATEMENT OF WORK B-1
SUMMARY OF ANALYSES AND SERVICES B-1
SAMPLE DELIVERY AND STORAGE B-1
METHODS B-1
QUALITY ASSURANCE AND QUALITY CONTROL REQUIREMENTS B-5
DELIVERABLES B-6
Laboratory Data Reports B-6
TURNAROUND TIME B-9
PROGRESS REPORTS, PROBLEM NOTIFICATION, AND
PROJECT AUDITS 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 ANAL YSES 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 sample-is 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 vizi 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 shsill be maintained under
strict chain of custody at all times, including documentation o:f 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.
e-y
-------
TABLE B-1. SUMMARY OF ANALYSES AND DATA QUALITY OBJECTIVES
Analyte
Target
Detection Bias
Matrix Units Limit (%)
Precision
(%)
Completeness
(%)
Method Reference
Holding
Time
(days)
Organic Analyses
TCL' semivolatlle
organic compounds
TCL volatile organic
compounds
TCL pesticides and
PCBs*
Lipids
Metals Analyses
Copper
Mercury
TALC metals
Solids
Water
Tissue
Solids
Water
Tissue
Solids
Water
Tissue
Tissue
Solids
Water
Solids
Water
Tissue
Solids
Water
Tissue
tig/kg
Conventional and Nutrient-Related Analyses
Acid-volatile sulfide Solids ^moles/g
Total organic carbon
Dissolved organic carbon Water
Solids
Water
% carbon
mg/L
mg/L
-------
TABLE B-1. (cont.)
Analyte
Physical Analyses
Grain size
Percent moisture
Total suspended solids
Matrix
Solids
Solids
Water
Units
g dry wt.
% moisture
mg/L
Target
Detection Bias Precision Completeness
Limit (%) (%) (%) Method Reference
Holding
Time
(days)
* Target compound list.
6 Polychlorinated biphenyl.
c Target analyte list.
-------
TABLE B-2. ESTIMATED MAXIMUM NUMBER OF SAMPLES BY MONTH AND ANALYTE TYPE
(date) (date) (date) (date) Total
Maximum Maximum Maximum Maximum Maximum
Analyte SoHds Water Tissue Solids Water Tissue Solids Water Tissue Solids Water Tissue Solids Water Tissue
Organic Analyses
TCL' serrfvolatile organic compounds
TCL volatile organic compounds
TCL pesticides and RGBs6
Uplds
Metals Analyses
Copper
Mercury
TALC metals
DO
Conventional and Nutrient-Related Analyses
Acid-volatile sulfide
Total Inorganic carbon
Dissolved organic carbon
Physical Analyses
Grain size
Percent moisture
Total suspended solids
" Target compound list.
* Polychlorinated biphenyl.
c Target analyte list.
-------
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 per-
formed at the start of the project and when any ongoing calibration does
not meet control criteria. The number of points used in the initial calibra-
tion 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 bhink 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, whichev-
er 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 metiils, 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, whichev-
er is more frequent.
B-5
-------
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
shall 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.
Laboratory Data Reports
All data reports shall include the following:
A. General
1. A cover letter documenting all sample preparation and analytical protocols used
and explaining any variance from protocols contained in the appropriate EPA
statement of work (SOW) or this SOW.
2. Copies of completed chain-of-custody records and sample analysis request
forms.
3. 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.
4. Tabulated results in units specified in the appropriate EPA SOW or this SOW.
5. 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.
B-6
-------
B. Quality Control Results
1. For the analyses of inorganic compounds, the foEowing summary results should
be tabulated in the format of the appropriate indicated EPA form:
a. Initial and ongoing calibration verifications
b. Initial and ongoing calibration blanks and preparation blanks
c. Inductively coupled plasma-atomic emission specti'ometry (ICP) interfer-
ence checks
d. Matrix spike sample recoveries
e. Duplicate samples
f. Laboratory control sample recoveries
g. Method of standard additions, if performed
h. ICP serial dilution
i. Mercury holding times, if performed
j. Instrument detection limits
k. ICP interelemental correction factors
1. 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
B-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 documenta-
tion must be available at the request of the Contractor QA/QC Coordinator as part of the
Laboratory's standard QA/QC procedures:
• All original data
" Sample receipt and storage logbooks
• Record of sample holding time
• Storage temperature logbooks
• Conductivity of distilled/deionized water
" Analytical balance annual and routine (Class S weights) calibration
logbooks
B-8
-------
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 shall 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 inquired each week for
the duration of the project. Immediate notification of the Contractor QA/QC Coordinator
is required when the Laboratory identifies a problem that could prevent all QA/QC
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,
Quality Control Checks, and
Widely Used Analytical Methods
-------
CONTHVTS
Page
DESCRIPTION OF CALIBRATION, QUALITY CONTROL SAMPLES, AND
WIDELY USED ANALYTICAL METHODS C-1
INTRODUCTION C-1
CALIBRATION C-1
QUALITY CONTROL SAMPLES C-3
Blanks C-3
Matrix Spikes C-4
Surrogate Spikes C-4
Check Standards C-5
Laboratory Control Samples C-5
Spiked Method Blanks C-5
Reference Materials C-5
Replicates C-6
COMMON ANALYTICAL METHODS C-7
Gas Chromatography C-7
Gas Chromatography/Mass Spectrometry C-7
Gas Chromatography/Electron Capture Detection C-9
Gas Chromatography/Flame lonization Detection C-9
High Pressure Liquid Chromatography C-10
Atomic Absorption Spectrometry C-10
Inductively Coupled Plasma-Atomic Emission Spectrometry 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 concen-
trations may be established from this analytical curve. The degree with which incremen-
tal 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:
C-1
-------
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. Environ-
mental 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 through-
out 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 fre-
quent), 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 calibra-
tion of these instruments is 10 percent of the samples or every 2 hours
during an analysis run, whichever is more frequent.
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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. Contamina-
tion can arise from sources such as the reagents themselves, sample or reagent contain-
ers, 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:
• Method blanks (also called preparation blanks or reagent blanks) are used
to identify any contamination that may have been contributed by laborato-
ries 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.
• 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 compared 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.
• Transport blanks (also called trip blanks) are used to delect 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.
• Field 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.
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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.
Surrogate 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 com-
pounds 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 labeled 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.
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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.
Laboratory Control 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
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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:
« 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 role is 1 analytical replicate for every batch of up to
20 samples analyzed together (e.g., U.S. EPA 1990d).
" Field replicates measure sampling variability. These samples are collect-
ed at the same time and location as other samples and are submitted for
analysis along with the other samples. Field replicates should be coordi-
nated with analysis of laboratory replicates so that both sampling varia-
bility 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.
« 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
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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 ANAL YTICAL METHODS
Gas Chromatography
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
chromatogram and digitally as a quantification 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 chroraatograph/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 Chromatography/Mass Spectrometry
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
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9
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Figure C-1. Example mass spectrum for benz(a)anthracene identified in a sample sediment extract (upper) and
authentic spectrum stored in computerized GC/MS library (lower).
-------
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 chiromatogram. The RIC
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 RIC 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 GC/MS.
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 Chromatography/Electron Capture Detection
Gas chromatography/electron capture detection (GC/ECD) is useful for detecting analytes
such as pesticides, PCBs, and other similarly structured chemical compounds that contain
chlorine. The BCD 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 Detection
Gas chromatography/flame ionization detection (GC/FID) 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 ioniza-
tion 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
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PACKED VS. CAPILLARY COLUMNS
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, col-
umns produce chromatograms of fairly
low resolution, although the results may
be reproducible (i.e., preciseK However,!:
a large quantity of the sample extract can
be analyzed without overloading the
instrument. More exacting analysis Is
afforded by either megabore capillary or .
fused silica capillary columns. Pesticides
and PCBs can now be routinely analyzed
usingi megaBore columns, ^Analysis of
volatile organic compounds cart be con-
ducted on capillary columns.--. Howeveiv
" because ;.the:.«fitir0:99mpfe purge Is u$«J
. for volatile 'analyses, a packed column
with high loading capacity may sKll be
preferred if high resolution is'aot esserv-
:; tialv If project results are dependent of*
detailed recognition of contaminant mix-
tures (a$ is the case with PCBs a.rjd .toxa*
pheneh laboratories equipped withcapil-
..lary columns should be selected,: to
perform analytical tasks. <• r. ;^--
High Pressure Liquid Chromatography
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 instru-
ments do not emit ultraviolet or fluorescent spectra, thereby increasing the sensitivity of
the ultraviolet/fluorescent detector to many PAH compounds. However, some com-
pounds 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 Spectrometry
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 photoelec-
tric 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,
C-10
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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 metid being analyzed.
The major advantage of this technique is that it affords extremely low
detection limits, which are particularly essential in the jualysis 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 chemi-
cal reaction to separate arsenic or selenium selectively from a sample
digestate. This technique removes these two element; 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 nor-
mally 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 interfer-
ents, 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 light can be used to determine metals concentrations.
The primary advantage of ICP is that it allows simultaneous or rapid sequential determi-
nation 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-ll
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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. Spectroraetric 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
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APPENDIX D
Example Standard
Operating Procedures
-------
CONTENTS
Page
GENERAL STANDARD OPERATING PROCEDURES
SAMPLE PACKAGING AND SHIPPING D-1
EQUIPMENT DECONTAMINATION D-3
SPECIFIC ANALYTICAL STANDARD OPERATING PROCEDURES
SEMIVOLATILE ORGANIC ANALYTES IN SEDIMENT AND
TISSUE EXTRACTS D-8
ANALYSIS OF PAHs BY GC/MS D-11
ANALYSIS OF PCBs AND CHLORINATED PESTICIDES D-14
INSTRUMENTAL ANALYSIS OF METALS IN SEDIMENT AND
TISSUE EXTRACTS D-18
SEDIMENT EXTRACTION OF SEMIVOLATILE ORGANIC
ANALYSES D-22
DIGESTION OF MARINE ORGANISM SAMPLES FOR METALS
ANALYSIS D-25
TOTAL DIGESTION OF SEDIMENT SAMPLES D-30
TISSUE EXTRACTION OF SEMIVOLATILE ORGANIC ANALYTES D-34
D-ili
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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
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Marking/Labeling
1, Use abbreviations only where specified.
2. Place the following information, either hand-printed or in label form, on the outside
container:
• Laboratory name and address
• 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:
« Chain-of-custody form
• Sample analytical request form
« Sample packing list.
See the quality assurance project plan for procedures in filling out these forms.
D-2
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STANDARD OPERATING PROCEDURE
EQUIPMENT DECONTAMINATION
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 decontami-
nation 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
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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 will 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
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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 levels 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.
D-5
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Step 2: Specific Contaminant Removal
Organic Contaminants
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
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Step 3: Final Distilled/Deionized 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
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Specific Analytical
Standard Operating Procedures
-------
ERLN CHEMISTRY GROUP
STANDARD OPERATING PROCEDURE FOR COLUMN CHROMATOGRAPHY
OF SEMTVOLATILE ORGANIC ANALYTES
IN SEDIMENT AND TISSUE EXTRACTS
(REVISED FEBRUARY 1993)
1.0 OBJECTIVES
The objective of this document is to define die standard operating procedure for the
preparation of columns for the cleanup and chemical class separation of semi-volatile
organic compounds from marine samples. The extract tractions will be analyzed by gas
chromatography (GQ or gas chromatography/mass spectrometry (GC/MS).
2.0 MATERIALS AND EQUIPMENT
9.5-mm ID X 45-cm glass chromatography column with 200 ml reservoir
Apparatus for determining weight
Top-loading balance capable of weighing to 0.01 g
Turbo-Vap (Zymark) apparatus, with heated water bath maintained at 25-35° C
Glass Turbo-Vap flasks, 200 ml
Nitrogen gas, compressed, 99.9% pure
Tumbler, ball-mill
Glass graduated cylinders, 100- and 500-ml
Glass beakers, 50-ml
Borosilicate glass vials with Teflon-lined screw caps, 2-ml
Micropipets, solvent rinsed or muffled at 400°C
Reagents
Pentane, pesticide grade or equivalent
Methylene Chloride (CH^Clj), pesticide grade or
equivalent
Hexane, pesticide grade or equivalent
Heptane, pesticide grade or equivalent
Deionized water, pentane-extracted
D-8
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BioSil A silicic acid, 100-200 mesh
Glass wool,
1.0 METHODS
3.1 Silica gel preparation
3.1.1 Approximately 150 grams of fully activated silica gel is accurately weighed
and transferred to a glass jar.
3.1.2 The silica gel is deactivated by adding 7.5% (weight basis) of pentane-
extracted deionized water. The water is weighed accurately and an appropriate
amount is added dropwise, — 1 ml at a time, to the silica ijel. After each water
addition, the jar is hand-shaken vigorously.
3. 1.3 The glass jar is then placed on a ball-mill nimbler zind allowed to tumble
overnight.
3.1.4 After tumbling, the jar is removed from the tumbler. The silica gel is
stoned tightly sealed in the jar at room temperature until use.
3.2 Column preparation
3.2.1 The glass columns are set up in ring stands in a fume hood.
3.2.2 Glass wool, sufficient to create a 1 cm thick plug in the column is placed
into the reservoir of the column. A glass rod is used to push the glass wool to
the bottom of the column.
3.2.3 11.5 g of die 7.5% deactivated silica gel is weighed out in a beaker.
Approximately 30 ml of CHjClj is added to the beaker to form a slurry. The
slurry is then carefully poured into the column. The beaker is rinsed with
additional CHjCl], as are the inner walls of the reservoir to ensure all silica is
introduced to the column. The total volume of CHjClj should be approximately
50 mi
3.2.4 The column is allowed to drip, and the ehiate is collected and discarded.
When the level of the CH^Clj just retches the top of the silica gel, 50 ml of
pentane is slowly added to the column. This ehiate is also collected and
discarded.
3.3 Chemical class separations
3.3.1 The sample extract is introduced to the column just as the pentane rinse
0-9
-------
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 As the sample rinse level reaches the silica gel, 55 ml of pentane is added
to the column. The eluate is collected 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 separate Turbo-Vap flask from the F-l traction. 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 from the column, the flasks are
placed in the Turbo-Vap. The apparatus is turned on and Nitrogen gas is
introduced to the flasks. The solvent is reduced to approximately 1 ml. The
samples are then solvent-exchanged to heptane and concentrated to about 1 ml.
3.3.S The fractions are then transferred to borosilicate glass vials fitted with
Teflon-lined screw caps for storage until analysis.
4.0 QUALITY ASSURANCE/QUALITY CONTROL
4.1 Silica Gel Testing
4.1.1 Silica Gel is verified to separate compound classes using the silica gel
testing SOP.
4.2 Method Blanks
4.2.1 Method (procedural) blanks are included in each sample set to provide an
estimate of contamination from the reagents.
4.3 Internal Standard Recovery
4.3.1 PCB103 is added to final column fractions to calculate recovery of the
internal standard.
D-1O
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ERLN CHEMISTRY GROUP
STANDARD OPERATING PROCEDURE FOR ANALYSIS
OF PAHs BY GC/MS
(REVISED FEBRUARY 1993)
1.0 OBJECTIVES
The objective of this document is to define the standard procedure for analyzing marine
environmental samples for PAHs using GC/MS in electron impact/positive ion mode,
2.0 EQUIPMENT
HP Model 5890 Series H Gas Chromatograph
HP Model 5971A Mass Selective Detector
HP Model 7673 Autosampler
HP MS Chemstation (DOS Series) Software
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; 0.8-1.0 ml/min
Injector: 270 degrees C; splitless mode, purge on at 0.8 min
Interface: 300 degrees C; direct, source 200 degrees C
Temperature Program: 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 Hydrocarbons.
MS Parameters: Set by Autotune using PFTBA as the calibration compound; Manual
Tune is then used to force the 131 and 219 abundances to 20 to 40 percent of the
69 base peak; die electron multiplier is then set to meet the requirements of the
particular method. This procedure is done in a series of loops, as new parameter
settings for a specific lens will affect the behavior of this others.
B. Daily Performance Checks
1) Adequate DFTPP spectrum (see attached criteria), based on a SO ng injection.
2) Calibration Check - results for a mid-level standard must be within 25 percent of the
true value for a single target compound; the average error for all compounds in
the method must be less than IS percent.
D-11
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C. Calibration
The calibration method is a 5 point, internal 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 current levels are 1.0,
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 2SO 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-p-terphenyl). Once
the daily performance checks are satisfied, the extracts are queued up on the
autosampler. Periodic solvent blanks, standards, etc. are inserted at the judgement of
the analyst.
E. Identification
Compounds are identified by monitoring a characteristic ion within a 12 second retention
time window. Additional ions may be monitored at the discretion of the analyst.
Confirmation is obtained by inspection of the full mass spectrum.
4.0 QUALITY ASSURANCE
A. Standard Reference Materials, Blanks, Calibration Checks
Standard reference materials are prepared along with each batch of samples. Calibration
standards are verified with independently prepared control standards.
B. Method Detection Limits
Method detection limits are determined independently for a given sample matrix.
Instrument detection limits are generally in the 6-10 pg per injection range, which usually
corresponds to a 3-5 ng/g (ppb) method detection limit range in samples.
5.0 TROUBLESHOOTING AND MAINTENANCE
On a daily basis, the injection port and liner are cleaned; the septum and glass wool in
the liner are changed. It is periodically necessary to break off the first few inches of the
column (this is done daily for heavy workloads of dirty samples; compounds most
affected are the high molecular weight compounds).
D-12
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DFTPP ACCEPTANCE CRITERIA (by CLP 3/90)
Mass Abundance
51 30-60% of mass 198
68 Less than 2% of mass 69
70 Less than 2% of mass 69
127 40-60% of mass 198
197 Less than 1 % of mass 198
198 Base peak, 100% relative abundance
199 5-9% of mass 198
275 10-30% of mass 198
365 Greater than 1% of mass 193
441 Less than mass 443
442 40-60% of mass 198
443 17-23% of mass 442
D-13
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ERLN CHEMISTRY GROUP
STANDARD OPERATING PROCEDURE FOR GAS CHROMATOGRAPfflC
ANALYSIS OF PCBs AND CHLORINATED PESTICIDES
(REVISED FEBRUARY 1993)
1.0 OBJECTIVES
The objective of this document is to define the standard procedure for analyzing marine
environmental samples for poly chlorinated biphenyls (PCBs) and chlorinated hydrocarbon
pesticides using gas chromatography and electron capture detectors.
2.0 EQUIPMENT USED
Hewlett Packard 5890 Gas Chromatographs equipped with electron capture detectors (Ni
63), automatic samplers, 30 m DB-5 fused silica capillary columns (0.25 ft, film
thickness, 0.25 mm i.d.). Peridn-Elmer/Nelson software (ACCBSS*CHROM) provides
for collection and storage of raw chromatographic data, and for selection and quantitation
of analyte peaks. Ultra high purity helium and 95/5% Argon/Methane gases are used
as the carrier and auxiliary gas respectively.
3.0 OPERATION
3.1 Instrument checks made prior to data collection
3.1.1 Gas supply
3.1.1.1 Check gas cylinder pressures. Replace tank if pressure is less
than 100 psig.
3.1.1.2 Check head pressure gauge on front panel of instrument. Gauge
should read 18 psig; adjust to correct setting if reading is high; check for
leaks if pressure is low. This setting provides for a carrier gas flow of
approximately 1.5 ml/min.
3.1.1.3 Replace injection port septum. Check septum nut and column
fittings for leaks with leak detector and tighten as necessary.
3.1.1.4 Check the auxiliary gas flow. A flow of 35 ml/min is required.
3.1.1.5 Check septum purge and split flows. Adjust to 1 and 35 ml/min,
respectively, as necessary.
D-14
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3.1.2 Instrument output signal
3.1.2.1 Display the analog output signal from the detector on the
panel of the GC. Record the value in the instrument log book, and check
for consistency with previous readings. On instruments with dual
detectors, ensure the signal is correctly assigned to the detector selected
for the analysis.
3.1.3 Instrument 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 PCBs and pesticides:
Injection port temperature 275 °C
Detector temperature 325 °C
Initial column temperature 100°C
Initial hold time 1 min
Rate 1 5°C/min
Ramp 1 final temperature 140°C
Ramp 1 hold time 1 min
Rate 2 1.5°C/rain
Ramp 2 final temperature 230°C
Ramp 2 hold time 20 min
Rate 3 ICPC/min
Final column temperature 300°C
Final hold time 5 min
Stop time 100 mill
Injection port purge open time 1 min
3,1.3.2 Load an appropriate workfile into the integrator.
3.1.3.3 Enter the autosampler parameters into the integrator via Option
11. Indicate which injection port is being used, the number and positions
of the samples in the autosampler tray, the number of injections per bottle,
and the amount injected (1 ul).
3.1.3.4 Check the signal assignments and level} again. If they are
correct, store the workfile in the integrator.
3.2 Data system setup
3.2.1 Scheduling of standards and samples
D-15
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3.2.1.1 Setting up the instrument queue is accomplished by following
instructions laid out in the Perkin-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
precede 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 Instrument startup and data collection
3.3.1 After the instrument has been scheduled, arrange the samples and standards
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 Start GC operation and data collection by pressing 'start' on the integrator.
3.4 Peak identification and quantitation
3.4.1 Peak identification is accomplished by automated routines. Identifications
are based on comparison of retention times of actual standards to unknown peaks.
Multilevel standards are calibrated to generate a linear regression curve of
response according to the manufacturer's instructions. After a calibration curve
has been generated, the samples are analyzed. Analytes are quantitated based on
the peak areas for the analytes and internal standard, the amount of the internal
standard, and the response factors generated from the calibration curve.
Chromatograms and data reports are generated for each sample and standard.
4.0 QUALITY ASSURANCE
4.1 Chromatograms of standards are compared to posted references. Peak
identifications, resolution and shapes are inspected. Calculated standard amounts are
checked 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
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and overall instrument response are compared to previous runs and documented. Blanks
are checked for the presence of interferences or analytes of interest. Unknown samples
are compared to standards 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 GCn.
0-77
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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 Instra-Analyzed concentrated HNO3 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 anaiytes. 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 die 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
absorbances 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 anaiytes 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 anaiytes (Keep close record of the sample
dilutions so that raw analytical concentrations can be dilution-corrected).
D-18
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4.0 ANALYSIS
4.1 Sample Analysis (Unknown Concentrations)
4,1.1 Analyze the samples and record the absorbances (A A) 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 calibration
standards should be re-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/ml, is converted to ug/g dry sample by inputing the sample prep, information
into the following equation:
Analyte conc.(ug/ml) X Acid volume (ml.)
Sed. Cone, (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 die
standard curve regression. Recoveries should be within 10% of the standard
concentration.
5.1.2 Analyze a solution of known and/or certified concentration, prepared
independently from the calibration standards, to determine the daily analytical
fluctuation. Recoveries should be within 10% of the certified concentration.
5.2 Standard Additions (Spike Additions)
5.2.1 Standard additions are required to investigate instrumental interferences
arising from differing sample solution matrices.
D-19
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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.
5.2.6 Calculate the spike recovery using the following equation:
CSAMPLESPKE "
ACID SPKE
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
6.1.1 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:
£7-20
-------
ICP GFAA
(ug/ml) (ug/L)
1.0
0.1
1.0
3.0
2.0
0.5
2.0
0.5
2.0
2.0
2.0
0.5
6.1.2 Sample Detection Limits, assuming a dry weight of 2 grams and a total
volume of 50 mis. (ie. sediment ultrasonic extraction method), are 25 times higher
than the instrument D.L.'s. Method detection limits should be calculated following
the rigorous statistical procedure detailed in 40 CFR Part 136.
Cu
Zn
Cr
Pb
Ni
Mn
Fe
Cd
Al
Sn
Sb
As
Ag
.020
.005
.020
.050
.050
.010
.020
.005
.075
.050
.100
.100
.020
D-21
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ERLN CHEMISTRY GROUP
STANDARD OPERATING PROCEDURE FOR SEDIMENT EXTRACTION
OF SEMIVOLATILE ORGANIC ANALYTES
(REVISED FEBRUARY
1.0 OBJECTIVES
The objective of this document is to define the standard operating procedure for the
extraction of semi-volatile organic compounds from marine sediment samples. The
extracts will be further cleaned up by silica gel chromatography procedures prior to
analysis by gas chromatography (GQ or gas chromatography/mass spectrometry
(GC/MS).
2.0 MATERIALS AND EQUIPMENT
Apparatus for homogenizing sediment
Wrist-action shaker
100 ml glass centrifuge tubes
Apparatus for determining weight and dry weight
Top-loading balance capable of weighing to 0.01 g
Aluminum weighing pans
Stainless steel spatula
Drying oven maintained at 105-120°C
Turbo-Vap (Zymark) apparatus, with heated water maintained at 25-35 °C
Nitrogen gas, compressed, 99.9% pure
Glass Turbo-Vap flasks, 200 ml
Glass graduated cylinders, 100- and SOO-ml
Erienmeyer flasks, 250 ml
Microliter syringes or micropipets, solvent rinsed
Borosilicate glass vials with Teflon-lined screw caps, 2-ml
Reagents
Methylenc chloride, pesticide grade or equivalent
Deionized water, pentane-extracted
Acetone, pesticide grade or equivalent
Sodium sulfate-anhydrous, reagent grade. Heated to 400°C tor at least 4 hours,
then cooled and stored in a tightly sealed glass container at room
temperature.
Internal Standards, to be added to each sample prior to extraction.
3.0 METHODS
3.1 Find the correct caps for each centrifuge tube to be used by filling them with
D-22
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approximately 25 mis of methylene chloride, putting the caps on and rolling the tube on
the lab bench on a paper towel 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 muring of the sediment with
stainless steel or Teflon coated utensils, or by a polyethylene propeller attached to an
electric drill. The amount of sample may be adjusted based on expected contaminant
concentrations or detection limits required. Weigh approximately 2.0 grams into a
preweighed aluminum pan for dry/wet determination.
3.2 Add Internal Standards as required: CB198 for PCB analysis, 2,5-dichloro-m-
terphenyl for pesticides, and d!2 Benzo(a)anthracene/ dlO Phenanthrene mix for PAHs.
The amount of IS added is dependent on the expected contaminant concentrations and
should be equivalent to those concentrations.
3.3 Add 30 g Sodium sulfate and mix with a teflon coated spatula very well. Then add
50 ml 20:80 acetone: methylene chloride.
3.4 Seal the centrifuge tubes with teflon tape and caps, and shalce -15 hrs. (overnight).
Shake tubes at approximately a 60° angle, at an intensity setting of "5". Centrifuge for
20 minutes at 1750 rpm and pour off the supernatant into an erienmeyer flask.
3.5 Add 50 ml of 20:80 acetone:methylene chloride, seal and shake as above for -6
hrs. Centrifuge for 20 minutes at 1750 rpm and add the supernatant to the erienmeyer
flask. Add some additional sodium sulfate to the combined extracts to ensure all water
is excluded.
3.6 Gravity filter the extract through a pre-rinsed (methylene cldloride) glass fiber filter.
Rinse the erienmeyer 2 x with methylene chloride, and the filter itself once. Collect the
filtrate in a clean rinsed 200 ml Turbo-Vap tube. Place the flask into the Turbo-Vap
apparatus, and turn on the unit. Open the valve on the nitrogen tank and adjust the
regulator to ensure a pressure of 15 psi. Reduce the sample volume to approximately 1
ml, with solvent exchange to pentane.
3.9 Adjust the volume to 1 ml with hexane.
3.10 Fractionate the sample following the Column Chromatography SOP.
4.0 OPTIONAL CLEANUP PROCEDURES
Activated copper powder (activated by the addition of 8 M hydrochloric acid and rinsed
with the following solvents in succession: deionized water, methanol, methylene
chloride, and hexane) may be added to the extract to remove Jiny free elemental sulfur.
The copper is added until the formation of black copper sulfkle no longer occurs.
D-23
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5.0 QUAIJTY ASSURANCE/QUALITY CONTROL
5.1 Standard Reference Materials
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 the accuracy is outside of the required
specifications.
5.1.2 SRMs should be prepared in the exact same manner as the unknowns.
5.2 Analytical Reproducibility
5.2.1 Replicate samples should be prepared to assess the reproducibility of the
extraction procedure.
5.2.2 For every batch of samples, one sample should be chosen to extract and
analyze in triplicate. Deviation between replicate samples should be <30%.
5.3 Procedural Blanks
5.3.1 Procedural blanks should be carried throughout the entire extraction
procedure to verify the absence of contamination of the method.
5.3.2 Trace amounts of analytes in the blanks (less than three times the method
detection limit) may be ignored and have no effect on the subsequent sample
analyses, but samples should be rejected if significant concentrations (greater than
five times the MDL) are present in procedural blanks.
5.3.3 One blank should be prepared for each batch of samples (minimum
frequency of 5%).
D-24
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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 are routinely analyzed by Flame
Atomic Absorption Spectrometry (FAA), Graphite Furnace Atomic Absorption
Spectrometry (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 HNO3 for trace metal analysis (70-71 %)
Hydrogen Peroxide - H£>2 (30%)
Vacuum filtering apparatus with Whatman 42 filter paper
3.0 METHODS
3.1 Sample Preparation
3.1.1 Organism samples should be thawed, and handled only with plastic or
stainless steel utensils. Where 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.
0-25
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3.2 Closed Vessel Microwave Digestion (1st Stage)
3.2.1 Add 10 ml. of concentrated HNO3 (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 12345
%POWER 85 85 85 85 85
PSI 20 40. 85 150 190
TIME 15:00 15:00 15:00 15:00 15:00
TAP 5:00 5:00 5:00 5:00 5:00
FAN SPEED 100 100 100 100 100
** Note - Power settings are for 12 vessels. If a different
# of vessels is desired, subtract or add 5% power
per vessel.
3.2.10 After completion of the program, allow the pressure in the control vessel
to drop below 20 PSl, 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% Hf>2.
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 following the parameters below:
STAGE 1 2
%POWER 85
PSI 100
TIME 15:00
TAP 5:00
FAN SPEED 100
100
100
15:00
5:00
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 deionized 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 HNO3.
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-27
-------
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 100% 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 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 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 >10% of "average" sample concentrations.
£3-28
-------
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 Spectrometry (FAA), Graphite Furnace Atomic Absorption Spectrometry
(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 bottles
Instra-Analyzed grade concentrated HNO3 for trace metal analysis (70-71 %)
Reagent grade concentrated HF (49%)
Reagent grade concentrated HCL (36.5-38%)
Boric Acid (5%) prepared from H3BO3 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 tare 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
-------
3.2,1 Add 5 ml. of concentrated HNO3 (70-71 %), 4 ml. of concentrated HF (49%)
and 1 ml. concentrated HC1 (36.5-38%) 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. fi>
lot 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 30:00 15:00
TAP 20:00 10:00
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.
3.2.9 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-31
-------
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 ml. 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 HNO3.
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 collect the filtrate in the
bottle.
3.3.5 Rinse the digestion vessel with deionized water, filter and collect the filtrate
in the bottle.
3.3.6 Pour the combined filtrates into a 100 ml. acid-cleaned volumetric 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 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.
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 the reagents and that
contamination has not occurred throughout the procedure!.
4.3.2 Trace amounts of metals in the blanks can be suboracted from subsequent
sample analyses (blank subtraction), but a sample batch should be rejected if
concentrations in the blank are >10% of "average" sample concentrations.
4.3.3 One procedural blank should be prepared for every 20 samples digested.
D-33
-------
ERLN CHEMISTRY GROUP
STANDARD OPERATING PROCEDURE FOR TISSUE EXTRACTION
OF SEMTVOLATILE ORGANIC ANALYTES
(REVISED FEBRUARY 1993)
1.0 OBJECTIVES
The objective of this document is to define the standard operating procedure for the
extraction of semi-volatile organic compounds from marine tissue samples. The extracts
will be further cleaned up by silica gel cinematography procedures prior to analysis by
gas chromatography (GC) or gas chromatography/mass spectrometry (GC/MS).
2.0 MATERIALS AND EQUIPMENT
Apparatus for homogenizing tissue
Brinkman Polytron
100- or 150-ml glass centrifuge tubes
Apparatus for determining weight and dry weight
Top-loading balance capable of weighing to 0.01 g
Aluminum weighing pans
Stainless steel spatula
Drying oven maintained at 105-120SC
Turbo-Vap (Zymark) apparatus, with heated water bath maintained at 25-35° C
Nitrogen gas, compressed, 99.9% pure
Glass Turbo-vap flasks, 200 ml
Glass graduated cylinders, 100- and 500-ml
Glass separatory funnels, 1 L.
Glass erlenmeyer flasks, 250 and 500 mL
Borosilicate glass vials with Teflon-lined screw cast, 2-ml
Microliter syringes or mkropipets, solvent rinsed
Reagents
Pentane, pesticide grade or equivalent
Acetonitrile, pesticide grade or equivalent
Deionized water, pentane-extracted
Sodium sulfate-anhydrous, reagent grade. Heated to 400°C for at least 4 hours,
then cooled and stored in a tightly-sealed glass container at room
D-34
-------
temperature.
Internal Standards, to be added to each sample prior to extraction.
3.0 METHODS
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 Standards as required: CB198 for PCB analysis, 2,5-dichloro-m-
terphenyl for pesticides, and d!2 Benzo(a)Anthracene and dlO Phenanthrene mix for
PAHs. The amount of IS added is dependent on the expected contuninant concentrations
and should be equivalent to those concentrations.
3.3 Add SO ml acetonitrile.
3.4 Polytron the samples for 20 seconds, at a speed setting of - 5. Centrifuge for 10
minutes at 1750 rpm and pour off the supernatant into a separator) funnel containing 500
ml pentane extracted deionized water (DI). Repeat this step two more times.
3.5 Back extract the DI/ACETONITRILE phase in the scparatory funnel with 3 X 50
ml pentane. After each addition of pentane has been shaken, draw off the bottom layer
into a 500 ml erlenmeyer flask. Decant the Pentane layer into a 250 ml ertenmeyer flask
by pouring it out the top of the separatory funnel. This way the transfer of water into
the pentane extract will be avoided.
3.6 Transfer the water layer from the 500 ml erlenmeyer flask buck into the separatory
funnel for every addition of pentane. Rinse the 500 ml flask 3 x with Pentane and add
the rinses to the separatory funnel.
3.7 Combine the pentane extracts and dry over Sodium Sulfate.
3.8 Transfer the sample to a 200 ml Turbo-Vap flask. Rinse the flask 3 x with pentane
and add the rinses to the flask. Place the flask into the Turbo-Vap apparatus, and turn
on the unit. Open the valve on the nitrogen tank and set the regulator to ensure a
pressure of 15 psig is reaching the Turbo-Vap unit. Reduce this volume of sample to
approximately 1 ml.
3.9 Adjust the volume to 1.0 ml with pentane. Remove 0.1 ml of sample into a
prcweighed aluminum pan for lipid weight determination. Allow it to dry at room
temperature for at least 24 hours. Record the weight of the pan plus the sample.
3.10 Fractionate the sample following the Column Chromatography SOP.
4.0 QUALITY ASSURANCE/QUALITY CONTROL
D-35
-------
4.1 Standard Reference Materials
4.1.1 A certified SRM is prepared with each batch of samples to validate
analytical recovery. Analytical results should then be compared to the certified
concentrations. Corrective action is required if the required accuracy goals are
not met.
4.1.2 SRMs should be prepared in the exact same manner as the unknowns.
4.2 Analytical Reproducibility
4.2.1 Replicate samples should be prepared to assess the reproducibility of the
extraction procedure.
4.2.2 For every batch of samples, one sample should be chosen to extract and
analyze in triplicate. Deviation between replicate samples should be <30%. ,
4.3 Procedural Blanks
4.3.1 Procedural blanks should be carried throughout the entire extraction
procedure to verify the absence of contamination of the method.
4.3.2 Trace amounts of analytes in the blanks (less than three times the method
detection limit) may be ignored and have no effect on the subsequent sample
analyses, but samples should be rejected if significant concentrations (greater than
five times the MDL) are present in procedural blanks.
4.3.3 One blank should be prepared for each batch of samples (minimum
frequency 536).
0-36
-------
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 1
Compound Structure
mw
PHENOLS
a
b
c
d
65
HSL
HSL
34
SUBSTITUTED
a
b
c
d
e
f
9
h
LOW
a
b
c
d
e
f
24
31
22
21
HSL
64
57
59
OH
phenol (ch
^*^ OH
2-methyl phenol b [or"3
OH ^
4-methyl phenol c (CD)
2, 4-d1methyl phenol °^ d^T"3
PHENOLS
OH
2-chlorophenol (oj"
, ON
2,4-d1chloropnenol (oj"
OH TT
4-chloro-3-methyl phenol c (pi
ci ^ d eiJLn
2,4,6-trlchlorophenol T(3T
OH ^-r
2,4,5-trlchlorophenol Jot"
o*>r f . on
pentachlorophenol n "^^C"
OH tl* ^f^Cl
2-n1trophenol ($T"°*
ON
2,4-d1n1trophenol h (ch"1*1
94
10B
108
122
126
163
143
198
198
266
139
184
MOLECULAR WEIGHT AROMATIC S
55
77
1
80
81
78
9 ^
naphthalene C§©
b FR
acenaphthylene (pK)
acenaphthene (A®
*+*r*^ ^
fluorene ^C!I3§)
phenanthrene @~(o)
f
anthracene ©^^©
128
152
154
116
178
178
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 VUL of 40 CFR 261.
mw - molecular weight of an organic compound.
HSL - hazardous substance list.
E-1
-------
EPA * Compound
HIGH MOLECULAR WEIGHT PAH
a 39 fluoranthene
b 84 pyrene
c 72 benzo(a)anthracene
d 76 chrysene
e 74 benzo(b)fluoranthene
f 75 benzo(k)fluoranthene
g 73 benzo(a)pyrene
h 83 indeno(l,2,3-c,d)pyrene
1 82 dibenzo( a, h)anthracene
j 79 benzo(g,h,1)pery1ene
CHLORIKATED AROMATIC HYDROCARBONS
a 26 1,3-dlchlorobenzene
b 27 1,4-dichlorobenzene
c 25 It2-d1ch1orobenzene
d 8 1,2,4-trichlorobenzene
e 20 2-chloronaphthalene
f 9 hexachlorobenzene
Structure
a
(§3
n
ci
ci
n
f n
C1
mw
202
202
228
228
252
252
252
276
278
276
147
147
147
181
163
285
E-2
-------
EPA I Compound
CHLORINATED ALIPHATIC HYDROCARBONS
i 12 hexachloroethane
trlchlorobutadiene isomers
tetrachlorobutadlene isomers
pentachlorobutadiene isomers
hexachlorobutadiene e
hexachlorocyclopentadiene
HALQ6EiATED ETHERS
a 18 bis(2-chloroethyl)ether
b 42 b1s(2-chloro1sopropyl)ether
c 43 b1s(2-chloroethoxy)methane
d 40 4-chlorophenyl phenyl ether
e 41 4-bromophenyl phenyl ether
Stucture
b
c
d
e
f
XX
XX
XX
52
53
ci ci
ci-c-c-ci
CI Cl
b,c,d:
.
H OR Cl
ci
«
Cl
Cl
•o
Cl
Cl
Cl
Cl
CH
168
158
192
226
261
273
143
173
204
249
PHTHALATES
a 71 dimethyl phthalate
b 70 diethy1 phthalate
c 68 d1-n-butyl phthalate
d 67 butylbenzylphthalate
e 66 b1s(2-ethylhexyl) phthalate
f 69 d1-n-octylphthalate
e
tor'
0
*
194
278
312
391
£-3-
-------
EPA I Compound Structure mm
MISCELLANEOUS OXYGENATED CONFOUNDS
a
b
c
d
e
54
HSL
HSL
129
HSL
isophorone «,-ixJL.. i
^CHj a!J fa jk
benzyl alcohol to)
benzole acid c rf^j 4
2f3,7»8-tetrachlorod1benzo-p-d1ox1n . ei^^O^C
dlbenzofuran (S£^
-------
EPA *
PESTICIDES
a
b
c
d
e
f
5
h
i
j
k
1
m
n
0
P
q
r
93
94
92
89
90
91
95
96
97
98
99
100
101
102
103
104
105
113
PCBs
a 106
b 110
c 107
d 111
Compound
pfp'-DDE
p,p'-OOD
pfp'-OOT
aldrin
dleldrin
chlordane
alpht-endosulfin
beta-endosulfan
endosulfan sulfate
endrin
endrin aldehyde
heptachlor
heptach1orepox ide
alpha-HCH
beta-HCH
delta-HCH
gamma-HCH
toxaphene
Structure
mw
(man copoHBtis. «mniMTE
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
FMWU
a a
£-5
-------
EPA f Compound
VOLATILE HALOGENATEO AUAHES
a 45 chloromethane
b 46 brorroethane
c 16 chloroethane
d 44 methylene chloride
e 13 l.l'-dichloroethane
f 23 chloroform
g 10 1,2-dichloroethane
h 11 1,1,1-trichloroethane
1 6 carbon tetrachloride
j 48 bromodi chloromethane
k 32 1,2-dichloropropane
1 51 chlorodlbrcmomethane
m 14 1,1,2-trichloroethane
n 47 bromoform
o 15 1,1,2,2-tetrachloroethane
VOLATILE HALOGEMATEO AUEMES
a 88 vinyl chloride
b 29 I,l'-d1chl oroethene
c 30 trans-1 ,2-dichloroethent
Structure
a (
-fa b
i i
_ — «— C— Ir
C | i
I I
— C— C— Cl j
it a
ci
-La
,7 '
— C— c—ci f a
1 1 ?
g -U.CI
a
i i
11 ci
i i
i ~^-a
a ci
ci-c-a
a a a
k -H
a a
-M-c-ei 1
-«_^-6-a ,
m -c-a ^
ci a ir
-{-H1 n
o -f«p
b-
Cl Cl
n— i- e-a
i i
a
% ,^a h
^c-cx b
C|^B^
X Vp
>-<* d
i i
d 33 c1s- and trans-1 ,3-dichloropropene "^c-e^f" „>•& eli* Own-
^°^x0 f
°XC1
mw
50.6
109
64.5
85
99
119
99
133
154
164
133
208
133
253
168
62.5
97
97
1 111
131
166
E-6
-------
EPA f Compound
VOLATILE AROMATIC HYDROCARBONS
a 4 benzene
b 86 toluene
c 38 ethylbenzene
d HSL styrene
e HSL total xylenes
Structure
e
o.f. fb
•«3
b o^
(1 a
CM
AW 011O ISONTO
mw
78
92
106
104
106
VOLATILE CHLORINATED AROMATIC HYDROCARBONS
i
a 7 chlorobenzene
ci
112
VOUTILE UGATURATED CARBOKTL COMPOUNDS
a 2 acrolein
b 3 acrylonltrlle
:«c%
56
53
VQUTILE ETHBIS
i 19 2-ch1oroethylv1ny1ethtr
• ,
106
VOLATILE KETOKES
a HSL acetone
b HSL 2-butanone
c HSL 2-hexanone
d HSL 4-methyl-2-pentanone
MISCELLANEOUS VOLATILE COMPOUNDS
a HSL carbon dlsulflde
| b HSL vinyl acetate
i 111 i
—c—e—c—e—«—c—
a
*-c*s
76
86
£-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 pro-
cedures. 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
Page
PREFACE F-iii
QUALITY ASSURANCE REVIEW OF METALS IN WATER SAMPLES F-1
INTRODUCTION F-1
QUALITY ASSURANCE REVIEW F-1
Overall Case Assessment F-1
Completeness F-3
Holding Times F-5
Analytical Methods F-5
Accuracy F-8
Precision F-11
Blanks F-11
REFERENCES F-13
QUALITY ASSURANCE REVIEW OF POLYCHLORINATED
BIPHENYLS IN SEDIMENT F-14
INTRODUCTION F-14
OVERALL CASE ASSESSMENT F-15
Summary of Completeness F-15
Summary of Data Qualifications F-15
HOLDING TIMES F-16
ANALYTICAL METHODS F-16
CALIBRATION F-17
Initial Calibration F-17
Continuing Calibration F-18
F-v
-------
Page
METHOD BLANK ANALYSIS F-18
ACCURACY F-18
Surrogate Compound Recoveries F-19
Matrix Spike Recoveries F-19
PRECISION F-19
IDENTIFICATION OF COMPOUNDS F-19
COMPOUND QUANTIFICATION AND REPORTED
DETECTION LIMITS F-20
REFERENCES 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. Ah*
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 complete-
ness. 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 / (estimated) are
F-1
-------
TABLE F-1. 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 decision-
making 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 represent the concentration necessary to detect the
analyte in this sample.
/? 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 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.
M Duplicate injection precision was not met. •
N Predigestion matrix recovery was not within control limits. .......
S The reported value was determined by the method of standard additions (MSA). The associated
value is as reliable as unqualified results.
W The postdigestion spike recovery for GFAA" 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.
1 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 115-percent recovery). Analysis of the sample by the method of standard
additions (MSA) is required in this case, but was not performed.
Calcium values received / qualifiers because the CLP control limit (U.S. EPA 1987) was
exceeded slightly for the serial dilution sample analyzed by inductively coupled plasma-
atomic emission spectrometry (ICP). Reported results may be underestimated by approxi-
mately 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 th
-------
TABLE F-2. ANALYTICAL METHODS AND INSTRUMENT
DETECTION LIMITS
Analyte
Aluminum
Arsenic
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Silver
Zinc
Method of Analysis
ICP"
GFAA"
GFAA
ICP
GFAA
ICP
ICP
GFAA
ICP
ICP
CVAAC
ICP
GFAA
ICP
Instrument
Detection Limit
(H9/L)
55
5
5
28
10
11
9.6
5
140
1.8
0.2
18
5
4
1 Inductively coupled plasma-atomic emission spectrometry.
" Graphite furnace atomic absorption spectrometry.
° Cold vapor atomic absorption spectrometry.
d Manual spectrophotometry.
F-4
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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
>0.995 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-level standard was used to verify accuracy of the
calibration curve at low analyte concentrations for all metals except mercury and alumi-
num.
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 CCV/CCB pair was analyzed at the
conclusion of the ICP run. However, only interference check samples were analyzed after
the final CCV/CCB pair, and data quality was not affected. Results for all CCVs fell
within 90-110 percent of the expected value (80-120 percent for mercury), as required
F-5
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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
10-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 (11-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 85-115 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. Sample results obtained by MSA were qualified S by the
laboratory if the correlation coefficient obtained with the MSA results was >0.995.
Results qualified S are reliable and are not considered to be estimates. Sample results
obtained by MSA with correlation coefficients <0.995 were qualified + by the laboratory
and / during the quality assurance review. These results are estimates.
F-6
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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 cif silver and lead in the
first method blank (122- and 119-percent recovery, respectively) exceeded CLP control
limits (85-115 percent). According to U.S. EPA (1987), the problems should have been
corrected and acceptable results should have been generated for Ihe 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 58-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 been 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 ithe curve generated by
the standard additions was exponential in appearance. This nisult (45.5 |ig/L) was
rejected during the quality assurance review because of the poor correlation coefficient,
and the initial result (26.2 fag/L) was accepted as an estimate.
Detection Limits
All reported instrument detection limits (DDLs) were below or equal to the CLP contract-
required detection limits (CRDLs) (Table F-2). The DDL for lead by GFAA was omitted
from CLP Form 11, but was subsequently provided by the laboratory. The DDLs 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 120-percent
recovery (except for silver, which has no contractual control limit [U.S. EPA 1987]). All
results for silver were qualified / 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 / 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 / during the quality assurance review because prediges-
tion 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 per-
cent, similar to the predigestion spike result. This result indicates that a matrix interfer-
ence 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
(58-percent 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 ^20 relative percent difference [RPD]) may be significant with respect to
F-8
-------
TABLE F-3. PERCENT RECOVERY FOR METALS
IN LABORATORY CONTROL SAMPLE
Analyte
Aluminum
Arsenic
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Silver
Zinc
8 Percent recovei
Percent
Recovery"
98
105
112
99
109
101
99
98
99, 84, 93
100
111
97
52
98
measured value v inn
true value
F-9
-------
TABLE F-4. MATRIX SPIKE RECOVERY FOR METALS
IN SAMPLE 2
Sample Result Spike Added
Analyte (u.g/L) (u,g/L)
Aluminum
Arsenic
Cadmium
Calcium
Chromium
• Copper
Iron
Lead
Magnesium
Manganese
Mercury9
Nickel
Silver
Zinc
* Percent recov
310
25
5 I/
—
69
27
7,090
29
~
6,560
0.2 U
180
28 fl'
180
spiked
2,000
40
' 5
~
10
250
1,000
20
~
500
1.0
500
10
500
result- unspiked
Percent
Recovery*
97
89
194
NRC
NAd
103
77
261
NR
76
40
106
-'
95
result x 100.
spike added
b U - the analyte was not detected at the indicated concentra-
tion.
c 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.
* Sample 1 was spiked for mercury only.
1 R - the spike sample result was rejected; the result is not
meaningful.
F-10
-------
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 siimple results >5 times
the CRDL) or ± the CRDL (for results <5 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 / during the quality assuxance 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 (ag/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 /.
Blanks
A method blank and several calibration blanks were analyzed with the samples for each
metal. No contaminant was found in any method blank with one exception: lead was
present (6.1 (ag/L) in the method blank prepared with the second digestion batch. Results
for Sample 2 and the duplicate and spike samples for Sample 2 v/ere 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 (ag/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 [Jg/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, arid no result is available
for this method blank. The result reported for Sample 1 was obtained from this digestion
batch and was qualified / 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-11
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TABLE F-5. DUPLICATE ANALYSIS RESULTS FOR METALS
IN SAMPLE 2
Analyte
Aluminum
Arsenic
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Mercury*
Nickel
Silver
Zinc
Sample Result Duplicate Result
(ug/L) (ug/L)
310
25
5U°
184,000
69
27
7,100
29
200,000
6,600
0.2 U
180
28
180
308
26
17
180,000
78
29
6,700
47
190,000
6,400
0.2 U
190
31
190
Control Relative Percent
Limit* Difference"
200
10
5*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 _ | sample - duplicate |
(sample * dupiicate)/2'
c 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
-------
REFERENCES
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. Environ-
mental 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-13
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QUALITY ASSURANCE REVIEW OF
POL YCHLORINA TED BIPHENYLS
IN SEDIMENT
INTRODUCTION
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 require-
ments specified in the laboratory SOW.
The quality assurance review included examination and validation of the following data:
• Sample holding tunes 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-14
-------
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 acceptable 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:
• 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.
• 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 through-
out the calibration range in the initial calibration.
• The criterion for continuing calibration was not met for three of the eight
total standard analyses.
• 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 values were typically one-half
of the original concentrations reported by the laboratory. In addition, the laboratory
occasionally incorrectly identified and reported results for speciiic 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:
• All samples must be shipped on ice to the laboratory and stored at -18°C
until sample extractions are performed
• Sample extracts must be analyzed within 40 days
• 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/EC-
D) 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 column
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 generally 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, 1.0,
and 5.0 ng (on-column) for the five Aroclor® mixtures (Aroclor® 1016, 1221, 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 PCS 1254.
Linearity of the initial calibration to zero concentration is assumed when the percent
relative standard deviation (RSD) of the calibration factors is <20 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 r2 values for the initial calibrations using the sum of all
chromatographic peaks that were integrated (i.e., from the fiist peak integrated, the
injection peak, to the last peak integrated) to perform the calculations. 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 r2 values were recalculated.
F-17
-------
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 calibra-
tions 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 <15 percent from the average calibration factor
calculated for the associated initial calibration (U.S. EPA 1986). The 15-percent
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 chromatographic column used for confirmation must be
^20 percent (U.S. 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
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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 100±50 percent.
The recoveries for DEC 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 di:.d 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 false negatives is addressed by reviewing
F-19
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other factors relating to analytical sensitivity (e.g., detection limits, instrument linearity,
and analytical recovery).
Ether 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 QUANTIFICATION 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 Aro-
clors* 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 r2 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 ug/kg (wet-weight basis) for Aroclors®
1016, 1254, and 1260 and 10 |ig/kg (wet-weight basis) for Aroclors® 1221, 1232, 1242,
and 1248 in most samples. Overall, the laboratory reported limits of detection that range
from 5 to 100 |ig/kg (all values are adjusted for dilutions that may have been performed).
REFERENCES
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
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APPENDIX G
Analytical/Environmen tal
Laboratory Audit
Standard Operating Procedure
-------
CONTENTS
ANALYTICAL/ENVIRONMENTAL LABORATORY AUDIT
STANDARD OPERATING PROCEDURE G-1
1. PURPOSE AND INTRODUCTION G-1
2. AUDITOR QUALIFICATIONS G-1
3. REQUEST FOR AUDIT G-1
4. CLARIFICATION OF AUDIT OBJECTIVES G-1
5. ESTIMATE OF AUDIT COSTS G-2
6. PREPARATION FOR THE AUDIT G-2
6.1 Identification of Laboratory Contact Person G-2
6.2 Initial Discussion with Laboratory Management G-3
6.3 Pre-Site Visit Activities G-3
6.4 Schedule of the Site Visit G-4
7. PERFORMANCE OF THE SITE VISIT G-5
8. USE OF THE AUDIT CHECKLIST FORM G-6
9. USE OF THE AUDIT SCORING GUIDELINES G-7
10. AUDIT REPORT G-7
G-iii
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ANAL YTICAL/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-1
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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.
5. 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
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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:
• 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.
• Identify the primary concerns, e.g., potential or perceived problems,
perceived strengths.
• Identify the expectations, e.g., reason for desiring an audit; expected use of
the outcome.
• 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
• Review the audit checklist form (Attachment 1): determine what infor-
mation will be necessary to complete the form and prepare for the site
visit. The topics generally covered during the site visit include organi-
zation 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.
• Collect relevant information: gather applicable laboratory or project
documents which will be helpful in filling out portions of the audit
checklist in advance, or aid in completing the audit report. Such docu-
ments 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 perform-
ing the audit, obtain the applicable documents from our contract files or
G-3
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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.
• 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.
6.4 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:
• Purpose of the audit (e.g., potential contract, resolution of problems)
• Estimate of time the site visit will take (typically, three to four hours for
a small laboratory performing one type of analysis)
• Areas of the laboratory to be audited
• 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, stan-
dards, procedures, instrumentation, quality control, data review, data
management, and report generation)
• 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
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• 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)
• Proposed site visit schedule (see Section 7 for a typical schedule)
• Specific problems, if any.
7. PERFORMANCE OF THE SITE VISIT
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:
• 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.
• Document review: have arrangements made ahead of time for an op-
portunity 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.
• 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 applica-
ble topics on the audit checklist. Follow the sample history, as presented
earlier by the laboratory. The audit checklist is organized to facilitate this
task.
• 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
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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.
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 sched-
ules.
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:
• Organization and Personnel
• Sample Receipt and Storage Area
• Sample Preparation Area/Facilities
• Instrumentation
• Quality Control
• Data Handling and Review
• QC Manual Checklist
• 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
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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 = acceptable audit
76-85% of maximum possible points = provisionally acceptable audit
(based on responses to nonpoint
questions)
below 76% of maximum possible points = unacceptable audit
10. AUDIT REPORT
An internal memo summarizing the results should be provided i:o 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
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Attachment 1
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ANALYTICAL CHEMISTRY LABORATORY AUDIT GUIDELINES
Laboratory: Date:
Address: Telephone:
Auditor(s):
Laboratory Personnel Interviewed:
Name Title
Laboratory Accreditation/Certification:
Expiration
Comments:
Score:
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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 de-
scribing 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 com-
mitments in a timely manner?
8. 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 au-
dit?
11. Was a program manager or laboratory manager avail-
able during the evaluation?
Comments:
B. Sample Receipt and Storage Area
1. Is a sample custodian designated?
2. Are the responsibilities clearly defined?
In writing?
3. Is there a standard sample login procedure followed?
4. Does the procedure include adequate inspection of
samples and accompanying documents to verify that
they are intact, complete, and consistent?
5. Is there an inspection checklist?
6. Does it document adequately the nature and condi-
tion of samples and documentation?
7. Is the integrity of samples and shipping containers
being documented?
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LABORATORY AUDIT GUIDELINES
Page 3
Yes No Points Comments
8. 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 sam-
ples 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 (con-
sider not only spatial separations, but air flow, per-
sonnel, traffic, etc.)?
18. Does the custodian understand the importance of
preventing lab contamination?
19. If appropriate, are the pHs 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 preser-
vation?
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LABORATORY AUDIT GUIDELINES
Page 4
Yes No Points Comments
24. Are volatile samples stored separately from semivola-
tile 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 ft2 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?
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LABORA TORY 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?
8. Are the procedures and records adequate to dem-
onstrate 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 pro-
file and thereby reduce hood efficiency?
10. Are chemical waste disposal policies/procedures well-
defined 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 instru-
mentation?
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 25°C)?
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?
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-in-
glass) calibrated at least yearly against an NIST
traceable thermometer and documented?
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LABORATORY AUDIT GUIDELINES
Dage 6
Yes No Points Comments
23. Are reagents dated upon receipt by labeling each
container with the date received?
24. Is there a complete log of reagent and solvent supply
giving the quantity, batch number, receipt date, per-
cent activity, or purity?
25. Are reagents and standards checked prior to use?
26. Are solvent lots checked and documented prior to
use?
27. Are reference materials properly labeled?
28. Is each spiking/calibration standard completely trace-
able to documented neat material or a documented
purchased standard?
29. Is each logbook entry signed and dated by the indi-
vidual who prepared the solution?
30. Are logbooks periodically reviewed and signed by a
manager/supervisor?
31. Are logbooks maintained in a manner which allows
complete traceability?
32. Are standards stored separately from samples and
sample extracts?
33. Are volatile and semivolatile standard compounds
properly segregated?
34. Are SOPs readily available to laboratory personnel?
35. Are glassware cleaning procedures documented?
36. Are the cleaning procedures consistent with EPA
recommended procedures?
37. Is the temperature of the drying ovens recorded dai-
ly?
38. Is cleaned glassware properly handled and stored to
prevent contamination?
39. How do lab personnel recognize glassware that has
been prepared for specific function (e.g., organic vs.
inorganic)?
40. Is the laboratory secured?
Comments:
). Instrumentation
1. Are instrument operating manuals available?
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LABORATORY AUDIT GUIDELINES
Page 7
Yes No Points Comments
2. Do the operators demonstrate a good familiarity with
the manuals?
3. Are there service contracts on the instrumentation
(and is a record maintained of the service)?
4. Are in-house replacement parts available?
5. Have the instruments been modified in any way?
Describe the modifications and discuss ramifications:
6. Are instruments properly vented or are appropriate
traps in place?
7. Is a logbook maintained for each instrument?
8. Is a complete list of laboratory instrumentation avail-
able?
9. Are all calibration data hard-copied and retained?
10. 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 complet-
ing as well as periodically throughout the run?
11. 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 complet-
ing as well as periodically throughout the run?
12. 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 stan-
dard?
d. Is the instrument typically calibrated for every
compound of interest?
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LABORATORY AUDIT GUIDELINES
Page 8
Yes No Points Comments
e. How are retention times monitored for each com-
pound of interest, and when is corrective action
taken?
13. When calibrating a GC/MS:
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 stan-
dard?
d. Is the instrument typically calibrated for every
compound of interest?
e. Is the instrument tuned at least daily?
f. Do the tuning procedures conform to the methods
for which the instrument is being used?
g. What compound and performance criteria are
used?
h. Are surrogates and internal standards used?
I. Are surrogate and internal standard recoveries
monitored?
j. 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 AA/ICP analyses?.
d. For wet chemistry?
2. At what frequency are lab duplicates prepared and
analyzed:
a. For GC/MS analyses?
b. For GC analyses? ;
c. For AA/ICP analyses?.
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LABORATORY AUDIT GUIDELINES
Page 9
Yes No Points Comments
d. For wet chemistry?
3. How are duplicate sample results tracked and used:
a. For GC/MS analyses?
b. For GC analyses?
c. For AA/ICP analyses?.
d. For wet chemistry?
4. At what frequency are lab spikes (e.g., spiked deion-
ized water or clean soil) prepared and analyzed:
a. For GC/MS 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 GC/MS analyses?
b. For GC analyses?
c. For AA/ICP 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 GC/MS analyses?
b. For GC analyses?
c. For AA/ICP analyses?.
d. For wet chemistry?
8. Are surrogate compounds utilized for GC/MS analy-
ses?
9. When are the surrogates added to the samples?
10. How many surrogate compounds are introduced?
11. 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?
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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 cross-
outs or "whiteout")?
7. Are data calculations spot-checked by a second per-
son?
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 informa-
tion?
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?
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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:
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LABORATORY AUDIT GUIDELINES
Page 12
Yes No Points Comments
H. Summary
1. Do responses to the evaluation indicate that labora-
tory personnel are aware of QA/QC and its potential
impact on the data?
2. Is a positive emphasis placed on QA/QC by labora-
tory 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
-------
ANALYTICAL 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:
86-100% of maximum possible points = acceptable audit
76-85% of maximum possible points = provisionally acceptable audit
(based on responses to nonpoint
questions)
below 76% of maximum possible points = unacceptable audit
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AUDIT SCORING GUIDELINES
Page 2
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 de-
scribing 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 com-
mitments in a timely manner?
8. 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 au-
dit?
11. Was a program manager or laboratory manager avail-
able during the evaluation?
Onmmflnts-
B. Sample Receipt and Storage Area
1. Is a sample custodian designated?
2. Are the responsibilities clearly defined?
In writing?
3. Is there a standard sample login procedure followed?
4. Does the procedure include adequate inspection of
samples and accompanying documents to verify that
they are intact, complete, and consistent?
5. Is there an inspection checklist?
6. Does it document adequately the nature and condi-
tion of samples and documentation?
7. Is the integrity of samples and shipping containers
being documented?
8. Are samples logged into a bound notebook?
a. Computerized lab management system?
h. Other? (ri«snrihp- )
Yes
1
1
1
1
2
2
5
2
1
1
2
1
1
1
2
1
1
1
5
5
5
No Comments
-1
-1
-1
-2
-2
-1
-1
-1
-1
-1
-1
-1
-1
_•<
-1
-1
-1
-1
-2
-2
-2
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AUDIT SCORING GUIDELINES
PageS
9.
10.
11.
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
Is there a daily summary of information such as sam-
ples received, analyses requested, date sampled, or
date received?
To whom is this summary distributed?
Yes
2
2
2
2
2
2
2
2
2
2
Mo Comments
-2
-2
-2
..2
-2
-2
-2
-2
-2
-2
12. Are login records filed and readily retrievable? 2 -2
13. How far back in time can records be retrieved?
14. Are written SOPs developed for receipt and storage 2 -1
of samples?
15. Are they available to and understood by laboratory 1 -1
personnel?
16. Is a clean area available for receiving and opening 1 -1
sample shipments?
17. Is this area separated from other lab operations (con- 1 -1
sider not only spatial separations, but air flow, per-
sonnel, traffic, etc.)?
18. Does the custodian understand the importance of 1 -1
preventing lab contamination?
19. If appropriate, are the pHs of samples measured and 1 -1
recorded to verify that they are preserved?
20. What percentage of samples is checked?
21. Are records of these checks retained? 1-1
22. Are facilities adequate for the storage of samples? 1 -1
23. Are samples stored so as to maintain their preser-" 2 -1
vation?
24. Are volatile samples stored separately from semivola- 5 -2
tile samples?
25. Is the temperature of the cold storage area recorded 2 -1
daily?
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AUDIT SCORING GUIDELINES
Page 4
Yes No Comments
a. Are excursions noted, along with descriptions of 2 -1
corrective action taken?
b. Is this being reviewed periodically by a supervisor 2 -1
or the QC unit?
26. Is the sample storage area secure? 1 -1
27. How is sample identification maintained? 1 -1
28. Is positive sample chain-of-custody maintained within 1 -1
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 2 -2
manner?
2. Does the lab appear to have adequate work space 1 -1
(120 ft2 per analyst)?
3. Are the toxic chemical handling areas either stainless 1 -1
steel benches or an impervious material covered with
absorbent paper?
4. Are contamination-free work areas provided for the 1 -1
handling of toxic materials?
5. Are adequate exhaust hoods available to prevent 2 -1
contamination of personnel and the laboratory facility?
6. Are the flow rates and/or face velocities of these 1 -1
hoods periodically checked and recorded?
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AUDIT SCORING GUIDELINES
Page 5
Yes Mo Comments
7. How frequently are they checked?
8. Are the procedures and records adequate to dem- 1 -1
onstrate 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 1 -1
that might interfere with the proper face velocity pro-
file and thereby reduce hood efficiency?
10. Are chemical waste disposal policies/procedures well- 1 -1
defined and followed by the laboratory?
11. Are records of waste containerization and disposal 1 -1
(lab logs, manifest, etc.) filed and retrievable?
12. Are voltage control devices installed on major instru- 1 -1
mentation?
13. What is the laboratory's source of distilled/deionized
water?
14. Is the conductivity of this water checked daily and 2 -2
data recorded (acceptable conductivity is 2.0-5.0
u,mhos/cm at 25°C)?
15. Is the analytical balance located away from draft and 1 -1
areas subject to rapid temperature fluctuations?
16. Is it protected from vibration associated with activities 1 -1
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? 2 -2
18. Is the balance routinely calibrated with Class S 2 -2
weights and are the calibration data recorded?
19. Are the Class S weights handled properly to prevent 2 -2
contamination/damage?
20. How often are the Class S weights certified?
21. Are pH and ion selective meters properly calibrated 1 -1
and maintained; and are these activities recorded?
22. Are laboratory thermometers (including mercury-in- 1 -1
glass) calibrated at least yearly against an NISI
traceable thermometer and documented?
23. Are reagents dated upon receipt by labeling each 1 -1
container with the date received?
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AUDIT SCORING GUIDELINES
Page 6
Yes No Comments
24. Is there a complete log of reagent and solvent supply 1 -1
giving the quantity, batch number, receipt date, per-
cent activity, or purity?
25. Are reagents and standards checked prior to use? 1 -1
26. Are solvent lots checked and documented prior to 1 -1
use?
27. Are reference materials properly labeled? 1 -1
28. Is each spiking/calibration standard completely trace- 2 -1
able to documented neat material or a documented
purchased standard?
29. Is each logbook entry signed and dated by the indi- 1 -1
vldual who prepared the solution?
30. Are logbooks periodically reviewed and signed by a 1 -1
manager/supervisor?
31. Are logbooks maintained in a manner which allows 2 -2
complete traceability?
32. Are standards stored separately from samples and 1 -1
sample extracts?
33. Are volatile and semivolatile standard compounds 1 -1
properly segregated?
34. Are SOPs readily available to laboratory personnel? 1 -1
35. Are glassware cleaning procedures documented? 2 -2
36. Are the cleaning procedures consistent with EPA 5 -2
recommended procedures?
37. Is the temperature of the drying ovens recorded dai- 1 -1
ly?
38. Is cleaned glassware properly handled and stored to 2 -2
prevent contamination?
39. How do lab personnel recognize glassware that has
been prepared for specific function (e.g., organic vs.
inorganic)?
40. Is the laboratory secured? 1 -1
Comments:
D. Instrumentation
1. Are instrument operating manuals available? 1 -1
2. Do the operators demonstrate a good familiarity with 1 -1
the manuals?
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AUDIT SCORING GUIDELINES
Page?
Yes No Comments
3. Are there service contracts on the instrumentation 1 -J
(and is a record maintained of the service)?
4. Are in-house replacement parts available? 1 -1
5. Have the instruments been modified in any way? -1 1
Describe the modifications and discuss ramifications:
6. Are instruments properly vented or are appropriate 1 -1
traps in place?
7. Is a logbook maintained for each instrument? 1 -1
8. Is a complete list of laboratory instrumentation avail- 1 -1
able?
9. Are all calibration data hard-copied and retained? 5 -2
10. When calibrating an AA:
a. How many standards are run to generate the
calibration curve?
b. Is a new curve generated for each run? 5 -2
c. Is a standard blank always run? 5 -2
d. Is calibration checked immediately after complet- 5 -2
ing as well as periodically throughout the run?
11. When calibrating an ICP:
a. How many standards are run to generate the
calibration curve?
b. Is a new curve generated for each run? 5 -2
c. Is a standard blank always run? 5 -2
d. Is calibration checked immediately after complet- 5 -2
ing as well as periodically throughout the run?
12. When calibrating a GC:
a. How many standards are run to generate the
calibration curve?
b. Is a calibration check standard run daily? 5 -2
c. What are the performance criteria for this stan-
dard?
d. Is the instrument typically calibrated for every 5 -2
compound of interest?
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AUDIT SCORING GUIDELINES
Page 8
Yes No Comments
e. How are retention times monitored for each com-
pound of interest, and when is corrective action
taken?
13. When calibrating a GC/MS:
a. How many standards are run to generate the
calibration curve?
b. Is a calibration check standard run daily? 5 -2
c. What are the performance criteria for this stan-
dard? :
d. Is the instrument typically calibrated for every 5 -2
compound of interest?
e. Is the instrument tuned at least daily? 5 -2
f. Do the tuning procedures conform to the methods 5 -2
for which the instrument is being used?
g. What compound and performance criteria are
used?
h. Are surrogates and internal standards used? 5 -2
i. Are surrogate and internal standard recoveries 5 -2
monitored?
j. What are the action limits?
Comments:
E. Quality Control
1. Are method blanks prepared and analyzed with each 5 -2
batch of samples, for each analytical procedure, or
some percentage?
What percentage:
a. For GC/MS analyses?
b. For GC analyses?
c. For AA/ICP analyses?
d. For wet chemistry? _
2. At what frequency are lab duplicates prepared and
analyzed:
a. For GC/MS analyses?
b. For GC analyses?
c. For AA/ICP analyses?
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AUDIT SCORING GUIDELINES
Page 9
Yes No Comments
d. For wet chemistry?
3. How are duplicate sample results tracked and used:
a. For GC/MS analyses?
b. For GC analyses?
c. For AA/ICP analyses?
d. For wet chemistry? _
4. At what frequency are lab spikes (e.g., spiked deion-
ized water or clean soil) prepared and analyzed:
a. For GC/MS 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 GC/MS analyses?
b. For GC analyses?
c. For AA/ICP analyses?
d. For wet chemistry? _
6. Are matrix spiked samples employed:
a. For GC/MS analyses? 1 -1
b. For GC analyses? 1 -1
c. For AA/ICP analyses? 1 -1
d. For wet chemistry? 1 -1
7. What action is taken when results exceed control
limits:
a. For GC/MS analyses?
b. For GC analyses?
c. For AA/ICP analyses?
d. For wet chemistry? _
8. Are surrogate compounds utilized for GC/MS analy-
ses?
9. When are the surrogates added to the samples?
10. How many surrogate compounds are introduced?
11. Is the percent recovery for each surrogate calculated? 5 -2
12. Are those data reported? 2 -2
13. Are performance criteria established for surrogates? 2 -2
14. Are percent recoveries plotted on control charts? 2 -2
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AUDIT SCORING GUIDELINES
Page 10
Yes No Comments
15. What action is taken when results exceed limits?
16. Are surrogate compounds utilized for GC analyses? 1 -1
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? 1 -1
20. Are those data reported? 1-1
21. Are performance criteria established for surrogates? 1 -1
22. Are percent recoveries plotted on control charts? 1 -1
23. What action is taken when results exceed limits?
F. Data Handling and Review
1. Are computer programs validated prior to use? 2 -1
2. Are records of the validation maintained? 2 -1
3. Are user instructions complete and available to ail 2 -1
users?
4. Do analysts/technicians record data in a neat and 2 -1
accurate manner?
5. Are all handwritten data recorded in nonerasable ink? 2 -2
6. Have entries been obliterated (e.g., through cross- -2 2
outs or "whiteout")?
7. Are data calculations spot-checked by a second per- 2 . -2
son?
What percentage?
8. Are these checks documented on the hard-copy data 2 -2
record, and dated and initialed by the reviewer?
9. Are raw data being identified with client name, project 2 -2
number, date, and other pertinent tracking informa-
tion?
10. Are raw data (notebooks, data sheets, computer files, 2 -2
strip chart recordings) being retained for 5 years?
11. Is there a system for report, record, or data retrieval? 2 -1
12. Do supervisory personnel review the data or QC 2 -1
results?
What percentage?
13. Are these reviews documented? 2 -1
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AUDIT SCORING GUIDELINES
Page 11
14.
15.
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?
Have method detection limit studies been performed
Yes
2
2
2
2
5
No Comments
-2
-2
-2
-2
-2
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
—2
10
-2
-10
1
1
1
1
1
1
1
1
1
1
1
1
1
-1
-1
-1
-1
-2
-1
-1
-1
-2
-2
-2
-2
-1
Comments:
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AUDIT SCORING GUIDELINES
Page 12
H.
Summary
1. Do responses to the evaluation indicate that labora-
tory personnel are aware of QA/QC and its potential
impact on the data?
2. Is a positive emphasis placed on QA/QC by labora-
tory management?
3. Have the responses been open and direct?
4. Has the attitude been cooperative?
5. Is the proper emphasis placed on quality assurance?
nnmmRnts-
Yes
2
2
2
2
2
No Comments
-2
-2
-2
-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]:
• Personnel and organization
• Sample receipt and storage
• Sample preparation facilities
• Instrumentation and equipment
• Quality control
• Data handling and review.
The attached Analytical Chemistry Laboratory Audit Guidelines were followed during the visit.
Participating [laboratory name] staff included:
« [Names and titles].
The purpose of the observation visit was to determine whether [laboratory name] has the facilities,
equipment, trained personnel, and QA/QC 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 QA/QC 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:
• There should be more formal in-house QA/QC and training programs instituted for
analysts and technicians; currently, training is dependent upon the more experi-
enced analysts
-------
» An inspection checklist should be generated for incoming samples, which includes
the nature and condition of samples and documentation
« Internal chain-of-eustody procedures should be initiated
• As part of the SOPs, a specific policy should be instituted for the rejection of
incoming compromised samples
« 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 QA/QC by laboratory management, and the responses appeared to be open
and direct.
-------
APPENDIX H
Format for the Sediment
Testing Report
-------
I
SEDIMENT TESTING REPORT FORMAT
The sediment testing report, including physical, chemical, bioa&say, 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
-------
• 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 PRINTING OFFICE: 199S- 821 - 154 / 82081
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